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2016; IJC

Available at: http://www.drbg

SR. 2(3): http://www.drbgrpublications.in/ijcsr.p

olume 2; Issue 3 [Special

IJCSR

rpublications.in/ijcsr.php

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Issue] 2016



2016; IJC

Int

A Ne

Sarah Tucke


rnational Conference on

w Horizon in MaterialsDate

11th March, 2016

Organized by

Department of Physics

r College (Autonomous), Tamilnadu, India

hp; ISSN: 2454-5422



2016; IJC

About Sarah Tucker Colleg

Sarah Tucker College, fou

minority institution of highe

the Tirunelveli Diocesan

University. The motto of the

The mission is 'Service T

through earnest academic p

society. It seeks to serve a

academic standards and its

‘with A' Grade in 5th January

About the Physics Depart

Physics was introduced as a

the Postgraduate level in 19

in laying stress on teachin

counseling. The Departmen

excellent results and univer

have had M.Sc., Physics cou

state of excellence under the

faculty.

Objective of the Internatio

To expose the recent develstudents, research scholars a


(Autonomous), Tamilnadu, India

ded in 1895 enjoys a heritage of 120 ye

r education for women. It functions under

Trust Association affiliated to Manonm

college is "So run that ye may obtain the in

rough Knowledge'. The college strives t

rsuit and aims at creative and empathetic

long with the holistic development of its

reputation were acknowledged by the NAA

2013.

ent

core subject at the Undergraduate level in 1

9. Ever since its inception, the Department

, in service education, interdisciplinary ac

t is notified for its consistently good aca

ity top ranks. Ours was the only women's

rse affiliated to M.K.U. The department has

able guidance of efficient heads and dedica

al Conference

opments, applications and innovations ind faculty members of other discipline.

hp; ISSN: 2454-5422

ars as a Christian

he management of

aniam Sundaranar

orruptible crown".

owards excellence

involvement in the

inmates. The high

C and reaccredited

68 and elevated to

has been a pioneer

tivities and carrier

emic record with

college in 1979 to

rown to its present

ted members of the

aterial science to



2016; IJC

International Conferen

Editor in Chief

B.Govindarajan

Associate Editors

Mrs. A. Effie Cordelia, As

Mrs. S.G. Pushpalatha Gra

Dr. J. Juliet Latha Jeyakum

Editors

Mrs. R. Jeyam Jebaraj, As

Mrs. P. Elizabeth Jeyarani

Mrs. D. Jegathi Jasmine,

Dr. F. Jeyamangalam, Ass

Mrs. T. Varthini, Assc. Pr

Dr. S. Lincy Mary PonmaDr. D. Jencylin Navarani,

Mrs. S. Kumutha, Asst. P

Mrs. M.P. Rameela, Asst.

Mrs. K. Sofiya Diana, Ass

Mrs. R. Juliet Jeyanthi, A

Mrs. P. Jeyaseeli, Asst. Pr

Miss. V. Bala Shunmugaj


e on “A new hori zon in mater ials” E

c. Prof.,

elin, Asst. Prof.,

ari, Asst. Prof.,

sc. Prof.,

, Assc. Prof.,

ssc. Prof.,

c. Prof.,

of.,

ni, Asst. Prof., Asst. Prof.,

of.,

Prof.,

t. Prof.,

st. Prof.,

of.,

thi, Asst. Prof.,

hp; ISSN: 2454-5422

itorial Board



2016; IJC

Patron

Dr. Usha Godwin

Convener

Mrs. R. Suganthi Christina

Organizing Secretary

Mrs. S.G. Pushpalatha Gracel

Members

Mrs. R. Jeyam Jebaraj

Mrs. P. Elizabeth Jeyarani

Mrs. D. Jegathi Jasmine

Mrs. A. Effie Cordelia

Dr. F. Jeyamangalam

Mrs. T. VarthiniDr. J. Juliet Latha Jeyakumari

Dr. S. Lincy Mary Ponmani

Dr. D. Jencylin Navarani

Mrs. S. Kumutha

Mrs. M.P. Rameela

Mrs. K. Sofiya Diana

Mrs. R. Juliet JeyanthiMrs P. Jeyaseeli

Miss V. Bala Shunmugajothi


ORGANIZING COMMITTEE

in

hp; ISSN: 2454-5422



2016; IJC

To

The Organisers,

Department of Physics,

Sarah Tucker College,

Tirunelveli.

I feel immensely please

Materials” (INHIM16 ) by our

Many of the greatest in

all made in the same way. The

sinks! Another noteworthy tree i

Einstein provided us with hicounterintuitive for many peopl

surprise people to realize how

an atom is considered to be almo

So a study on the facts o

I too appreciate to the

Teaching & Non-teaching staff

innovations in material science t


Greetings

in conducting the International Conference on

Department of Physics.

entions are due to the power of Physics. Trees,

lack Ironwood tree is so dense that it does not f

s the red wood: the bark of a red wood tree is re

classical theory of relativity. One area ofe is that as objects move faster they actually g

uch of the universe is made up of empty space.

st entirely empty space.

f Physics is really surprising

fforts taken by the Patron, the Convener, the

of our college to expose the recent developm

o students research scholars and faculty member

hp; ISSN: 2454-5422

“A New Horizon in

for example, are not

loat on water; it just

sistant to fire. Albert

the theory that is t larger. It may also

. The composition of

rganizing Secretary,

ents, applications &

of other discipline



2016; IJC

Materials h

the revolution is only just be

transportation, human health,

sources or developing stronger,

of materials used by scientists i

20th century expanded greatly

brought materials science much

wanted from engineered product

modify existing ones is still only

The possibility of influencing

opportunities that we are only

chemistry is breaking down ba

world that we live in. Worldwid

competition and advantage. Und

generous support of manageme

material science.

I congratulate the organizing coPhysics, Sarah Tucker College

industrialists and materials scie

material science. I convey m

conference.

Tirunelveli – 7

07.03.2016


Foreword

ve undergone a revolution in the past century,

inning. Innovative materials play essential ro

and industrial productivity.Whether explorin

lighter materials and sophisticated devices. In e

n products and systems was very limited. The

he number of materials and our knowledge of

more close to manufacturing as we sought to des

s. Now, in the 21st century, the ability to design

in its infancy, and the potential is limitless and e

material composition and properties at the

just starting to explore; the convergence of

rriers. Innovation in materials is transforming

, materials are seen as a priority for innovation b

erstanding the new horizon in materials in future

t, decided to conduct the conference to promot

mmittee of the conference and the entire teamfor steering the young minds. The presentation

tist expose the recent developments, applicatio

y best wishes and compliments for the succe

hp; ISSN: 2454-5422

but in many respects

les in clean energy,

alternative energy

rlier days, the range

developments of the

their properties, and

ign the properties we

new materials and to

xciting.

tomic scale creates

iology, physics and

engineering and the

ut also as a source of

, the college with the

new innovations in

of the department of from academicians,

s and innovations in

ssful conduct of the



2016; IJC

Office:

Associate Professor and Head Dept. of Physics,Sarah Tucker College,Tirunelveli - 627007,Tamil Nadu, India.

Materials Science is aof matter, Engineering appScience is very important fnuclear fusion, biomaterialsreplacement materials.

Research on materialproperties and formation ofprocesses for manufacturingmaterials: light weight compand silicon microchips for the

This International Cobrings together Scientists, Reexposure to the recent develo

following areas: Nanomaterials Biomaterials Theoretical Ph Advanced Mat Computational Applications o

The call for papers eScholars. We have receivedpresentation that reveals theINHIM’16 will be a rewardi

participants. On behalf of theSpeakers, Delegates and wisacademically refreshing inter

The blessing of the Alon “A New Horizon in Materi


Mrs. Suganthi Christina, M.Sc.,

Reside

, B 143Tirunel

Phone:Cell: 9

PREFACE

n interdisciplinary subject spanning the Phylications and Industrial manufacturing pror the development in nanotechnology, qand metallurgy as well as medical technol

s is essential to study the relationship betmaterials. It also includes development of

them. Modern society is heavily depensites for faster vehicles, optical fibres for t

information revolution which is the need of

nference on “A New Horizon in Mater

earch Scholars, Graduate and Post Graduatements, applications and innovations in Mate

ysics erial Characterization

Material Science f Materials

voked a good response from Faculty, Studpapers for the oral presentation and 27 p

enthusiasm generated by the Conference. Ing experience academically as well as scie

organizing committee I extend a warm weh them a pleasing experience, an intellectuction during the Conference.

mighty God is the prime factor for this Internals”.

(Mrs.

hp; ISSN: 2454-5422

.Phil

nce:

.G.O “B” Colony, veli - 627007. 0462-2553320

42447151

sics and Chemistry ocesses. Materials

antum computing, gies such as bone

een the structure, new materials and dent on advanced elecommunications

the hour.

als - INHIM’16”

students to provide rials Science in the

ents and Research pers for the poster

am confident that ntifically to all the

lcome to the Guest ally rewarding and

ational Conference

Suganthi Christina)

Convenor



2016; IJC

S.No

IJCSR41

Low Loss Dielectric Materials fo

Bindu Gunupudi, Christopher M

IJCSR42

Synthesis and characterization of

T.Athi Sakthi Grawya and S.Pus

IJCSR43

Synthesis and Characterization o

M.Sankareswari, R.Vidhya, A.Az

IJCSR44

Synthesis and characterization of

R.Vidhya, M.Sankareswari, A. Az

IJCSR45

Synthesis and characterization ofGROWN by solution method

D.Jencylin NavaRani, P.SelvarajIJCSR46

Investigation on the nucleation ki

N.Balasundari, P.Selvarajan, S.

IJCSR47

Investigation on structural, spectalanine oxalate single crystals

S.Lincy Mary Ponmani, P.Selvar

IJCSR48

Synthesis and characterization ofhydrate

S.G.Pushpalatha Gracelin, C.Kri

IJCSR49

Studies on the Mechanical and TCrystals

A. Effie Cordelia and S. Perumal

IJCSR50

Electrical conductivity measuremedium

M.P.Rameela, Vinu Bharathi and

IJCSR51

Systematical calculation of Alphexcited states of daughter

G. M. Carmel Vigila Bai and R.

IJCSR52

Synthesized and Characterization

R.Anitha, E.Kumar and D. Muth

IJCSR53 Studies on molecular interactionsdifferent temperatures

K. Umamakeshvari and U. Sank

IJCSR54

Z - Scan measurement and imped

R. Jothi mani, P. Selvarajan and

IJCSR55

Studies on optical and mechanica

I.Stella Jeya Christy, A. Effie Co

IJCSR56

Thermal and Dielectric Propertie

A.Roselin, A. Sumathi, A. Effie C


IndexArticles

r Metal and Superconducting Microwave Resonator Circuits

irhead and Mark Colclough

zinc oxide nano particle by sol-gel route

pam

f SiO2 Doped TiO2 Thin Films: Influence of Coating Cycles

hagu Parvathy and K.Neyvasagam

Cu-TiO2 thin films by Sol-Gel process

haghu parvathiand K.Neyvasagam

L-ALANINE DOPED GLYCINE Lithium chloride CRYSTALS

an, S.Lincy Mary Ponmani and N.Balasundari netics of urea doped Bis glycine picrate

incy Ponmani and D.JencylineNavarani

oscopic and mechanical properties of organic non-linear optical D

ajan, D.Jencylin and N.Balasundari

semi organic nonlinear optical material: Ammonium Tartrate Tetra

ishnan and P.Selvarajan

hermal Properties of Sulphamic Acid Doped Glycine NLO Single

ents of pure and nickel sulphate doped KDP crystals grown by gel

T. Asaithambi

decay half-lives of heavy nuclei from ground state to ground and

ithya Agnes

of cerium dioxide (ceria) nanoparticles by using a microwave ove

raj

of Bromoform and Ethyl bromide with Benzene at four

r

ance analysis of L-alanine alaninium nitrate single crystals (LAAN

C.Parvathiraja

l properties of DL-malic acid doped ADP single crystals

rdelia S. Perumal

s of DL-Malic Acid Doped ADP NLO Single Crystals

ordelia and S. Perumal

hp; ISSN: 2454-5422

Page No

353

359

366

379

391

403

-

411

420

428

439

447

455

460

)

472

478

487



2016; IJC

,

IJCSR57

Solvothermal Synthesis and CharNanostructures

A.Suganthi, S.John Kennady Vet

IJCSR58

Optical and Structural Characteri

S. Karpagavalli , S .John Kenna A. Suganthi


acterization of Manganese Doped Copper Oxide Flower Like

anathan,S.Perumal,D.Priscilla Koilpillai andS.Karpagavalli

zation of Cobalt Doped Manganese Oxide Nanoparticles

dy, Vethanathan, S.Perumal, D. PriscillaKoilpillai and

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497

503



Volume: 2; Issue: 3 [Special Issue]; March-2016; pp 353-358. ISSN: 2454-5422

Low Loss Dielectric Materials for Metal and Superconducting MicrowaveResonator Circuits

Bindu Gunupudi1*, Christopher Muirhead and Mark Colclough

School of Physics & Astronomy, University of Birmingham, Edgbaston, Birmingham, United Kingdom B15 2TT

*Corresponding Author Email Id: [email protected]

Abstract

The materials used for fabrication of microwave resonator circuits are vital in

determining key resonator parameters. These microwave resonator circuits have a wide

range of applications such as in the telecommunications industry, in the manufacture of

non-invasive blood glucose monitoring devices, kinetic inductance detector devices and

to build circuits for studies for quantum mechanical properties. Here we describe the use of

a low loss dielectric substrate and a superconducting material to fabricate coupled,superconducting, microwave resonator circuits. We have used oxidized silicon substrates

that have a low loss tangent and a dielectric constant of ~ 11.2. The resonator

structures were fabricated on thin film niobium which has a superconducting critical

temperature of ~ 9.2 K. The resonators were found to have high quality factors ~ 105 at 1

K, which was sufficient for our experiments. The behaviour of these circuits was

investigated thoroughly, both theoretically as well as experimentally. An in-situ tuning

mechanism was designed, constructed and implemented successfully to tune the

resonators at low temperatures. A thorough analysis was done to determine the

optimum material that could be used for our tuning probe. It was ascertained that macor,

an insulating material, that did not cause any interference in the electromagnetic

environment could be used for this purpose. Tuning of resonators was performed

without degrading the resonators’ quality factors, which is a significant experimental

achievement. These coupled resonator devices, when cooled to low temperatures ~ 20 mK

could further be used to study quantum mechanical properties of macroscopic objects.



2016; IJC

Keywords: Coupled Mi

Microwave Resonators

Introduction

The aim of the work descri

coupled, superconducting, m

temperatures. There has bee

as substrates for resonator ci

no losses within the dielec

dielectric cause the saturatio

measured signal as well as aresonant frequency [2].

The second part of the work

can be used in-situ to tune t

There are extensive repo

superconducting microwave

method was designed and

achieved. The details of this

Materials and Methods

The most commonly used s

their low loss tangent at fre

have used oxidized Silicon

film (~ 200 nm) niobium wh

on the substrates. The cou

photolithography on 10 x 5

to a copper PCB and then e

were made by placing the

temperature of ~ 1.3 K. A

Network Analyser was

measurements on the sample


rowave Resonators, Low loss substr

ed in this paper is to investigate the behav

icrowave resonators and to be able to tune t

considerable research on dielectric materia

rcuits [1]. The most important aspect being t

ric substrate. At temperatures T < 1 K, ir

n of two-level systems (TLS) and contribute

ffect the permittivity ϵ of the substrate, ther

describes the design and working of a tuni

he microwave resonant frequencies at cryog

ts in the literature about the various

resonator [3]. In this experimental proj

implemented and tuning of resonators

mechanism are explained in the subsequent s

ubstrate materials are silicon and sapphire.

uencies ~ 6 GHz and at temperatures ~ 1

substrates. In order to fabricate the resona

ich is superconducting below Tc ~ 9.2 K wa

led resonator structures were fabricated u

mm2 diced wafers. The sampled were glue

nclosed in a copper cavity. Low tempera

sample enclosure in a liquid helium cry

ector

used to make microwave transmissio

s.

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tes, Tuning of

ior of a system of

hem in-situ at low

ls that can be used

at there should be

regularities in the

to the noise in the

by the microwave

g mechanism that

enic temperatures.

ways to tune a

ct, a mechanical

was successfully

ections.

This is because of

K. In our case, we

or structures, thin

s sputter deposited

sing conventional

d and wirebonded

ure measurements

ostat with a base

and reflection



2016; IJC

In order to design a tunin

resonators, a series of tests

as insulating materials, suc

transmission was measure

microwave modes and henc

thermal contraction at low t

be a suitable material for o

tuning probe. A tuning disc,

bottom end of the macor rod

inductance was reduced and

Results and Discussion

In our coupled resonators s

weak coupling between the

and measured transmission r

K.

(a)

Fig. 1 (a) Shows a sample t

from a system of coupled re

104. This figure is taken fro


g probe that could be used to tune the s

ere performed at room temperature. Both

h as brass, nylon and macor were tested.

d it was seen that conducting materi

e could not be used. On taking into account

emperatures, it was decided that macor, a

ur

made of niobium on oxidized silicon substra

. As it was lowered over one of the resonat

hence there was an increase in its resonant fr

stem, we first studied the effect on the fre

resonators. Fig.1b shows a comparison bet

esponse from a system of coupled microwav

(b)

at is glued and wirebonded to a copper PCB

sonators at T = 1.3 K. The resonator qualit

reference [4].

hp; ISSN: 2454-5422

ystem of coupled

onducting as well

The background

als affected the

properties such as

n insulator would

te was glued to the

rs on the chip, the

quency.

quencies due to a

een the predicted

e resonators at ~ 1

. (b) Transmission

factors are ~ 6 x



2016; IJC

Fig. 2 (a) Shows the eff

enclosure. (b) Shows the

enclosure. This figure is tak

The effect of coupling on th

thoroughly investigated. A

Experiments were conducte

tuning probes on the microw

conducting and insulating p

probe caused a shift in the b

of interest. An insulating p

whilst being lowered into the

In our experiments, an insu

following reasons: firstly be

i.e., ~ 1 K; secondly, it hasthirdly, a small dielectric

capacitance of the microwav


ct of lowering a brass (conducting) rod

ffect of lowering a nylon (insulating) ro

n from reference [4].

resonant frequencies of a few coupled reso

mechanism that enabled tuning of resonato

d to study the effect of inserting conducti

ave background transmission. As shown in

obe were lowered into the sample enclosur

ackground resulting in unwanted modes in t

obe was preferred since it had no effect

sample enclosure.

lating material called macor was used. It

cause it is rigid when cooled to temperatur

a relatively small coefficient of differenti constant and hence, it would not signif

e resonators.

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into the sample

into the sample

nator samples was

rs was developed.

ng and insulating

Figs. 2a and 2b, a

e. The conducting

e frequency range

n the background

as chosen for the

es of our interest,

l contraction, and icantly affect the



2016; IJC

Fig. 3 A schematic of our t

chip. This figure is taken fro

Lastly, the effect of tuning t

the tuning probe through the

(a)

Fig. 4 (a) A photograph of

simulated and measured c

lowered over one of the reso


uning probe being lowered onto one of the

reference [4].

he resonators in-situ was studied. This was

lid of the sample enclosure as shown in Fig.

(b)

an assembled tuning mechanism set-up. (b)

ange in the resonant frequency when th

ators. This figure is taken from reference [4]

hp; ISSN: 2454-5422

resonators on the

done by lowering

4a below.

A comparison of

tuning probe is

.



2016; IJC

Fig. 4b shows the effect of t

tuning probe was lowered.

in AIM Spice and measured

Thus we were successful in

systems as well as in tuning

Acknowledgements

I would like to thank the

Gary Walsh for technical ass

References[1] Hammer, G., et al. "S

applications."Superconducto

[2] Barends, R. et al. “C

superconducting resonators”

[3] Healey, J. E., et al.

Applied Physics Letters 93.4

[4] Gunupudi, Bindu. Cou

electro- mechanical interacti


he resonant frequency of one of the resonat

There is an excellent agreement between

data.

the studies of coupled superconducting mi

ne of their resonant frequencies at low temp

niversity of Birmingham for the College

istance and Mr.Krishnarao Gunupudi for his

uperconducting coplanar waveguide reson

r Science and Technology 20.11 (2007): S40

ontribution of dielectrics to frequency an

Applied Physics Letters, 92, 223502 (2008)

Magnetic field tuning of coplanar wave

(2008): 043513

pled superconducting microwave resonato

n. Diss. University of Birmingham, 2015

hp; ISSN: 2454-5422

rs over which the

the predicted data

crowave resonator

eratures.

Elite Scholarship,

suggestions.

ators for detector

8

noise of NbTiN

uide resonators."

rs for studies of




Synthesis and characterization of zinc oxide nano particle by sol-gel route

T.Athi Sakthi Grawya and S.Pushpam*

Assistant Professor*, Department of Physics, N.M.S.S.Vellaichamy Nadar College, Nagamalai, Madurai, India.


Abstract

This detailed study is report about the synthesis and characterization of Zinc oxide nano

particle (ZnO). ZnO is an important member of semiconducting material of II, VI group. Due

to its unique properties, ZnO is the richest family of nano structure among all semiconducting

materials. This paper shows that ZnO nano particle is prepared by sol-gel method. Here, ZnO

nano particle is readily synthesized using zinc acetate dihydrate as a precursor and ethyl

alcohol as solvent. The ZnO nano particle which is obtained from this method by drying

process at 80°C in a hot air oven. And the sample were characterized by X-Ray diffraction

(XRD), Fourier transform infrared spectroscopy (FTIR), UV-Visible spectroscopy. The

particle size measurement which is done by XRD scherrer’s formula. The average particle

size of the prepared ZnO nano powder is 44.37nm. UV-Visible spectroscopy revealed the

formation of ZnO nano particles. The absorption spectrum shows a sharp absorbance onset at

275nm which indicates an almost uniform size of the nano particles. After this, FTIR

spectrum of the ZnO nano particles synthesized by sol-gel method which was acquired in the

range of 400-4000 correlated to metal oxide bond (ZnO). The FTIR spectra peak at

414.7 indicates the characteristic absorption bands of ZnO nano particles. Also the UV-

Visible absorption spectrum and XRD shows a typical spectrum for ZnO nano particles.

Keywords: ZnO nano particles, Sol-gel, XRD, UV, FTIR.

Introduction

Today, when the world is surrounding on the roof of technology and electronics, mostly

dominated by compatible electronic equipments and thereby creating the need for materials



2016; IJC

possessing versatile propertie

of material a very common

independence of India the

elements Germanium (Ge) a

property like low melting poi

surface from electrical leaka

better fabrication technology

As time passes on, the rapid

was very well fulfilled by

optoelectronic devices. GaAs

carrier mobility and highersuited for optoelectronics dev

the future world, something

world therefore now demand

band gap, higher electron mo

investigation about such a ma

is a wide gap semiconductor

only has this ZnO possessedand sensor applications.

Also ZnO has been commonl

range of applications. This

enthusiasm to develop prope

ZnO has been used in medica

ZnO is catching fire right fro[1] and optical properties

electroluminescence decay

manufacturing of simpler Zn

[3]. Also with a progress in

cathodluminescence (CL), ca

[4-7].


s. After digging the pages of history for the

ategory of material comes out that is “se

amily of semiconductors is dominated b

nd Silicon (Si). Germanium get famous du

t and lack of natural occurring germanium

ge where as silicon dominates the commer

nd application to integrated circuits for diffe

rowing world demands speed along with tec

aAs which ease the path for the design

which is a direct band gap semiconductor

ffective carrier velocity in comparison toices. But this do not leads to the completion

ore is required that is high temperature elect

s a material that should possess inherent pr

bility as well as higher breakdown field stre

terial the name of compound comes out is “

material very well satisfying the above requi

any versatile properties for UV electronics

y used in its polycrystalline form over hund

ignites many research minds all over the

r growth and processing techniques for the

l treatment for quite number of years in Chi

the beginning of 1950, with a number of r[2] like N-type conductivity, absorp

arameter. The decade of 1970 for Zn

O devices like ceramic varistors, piezoelec

the study of variety of characterization t

acitance – voltage studies (CV), electrical co

hp; ISSN: 2454-5422

search of such type

iconductor”. Since

our very known

e to possession of

xide to prevent the

cial market for its

rent purposes.

hnology. This need

of high speed and

possessing higher

Si makes it better of requirement for

ronics devices. The

operties like larger

gth. So on making

Zinc Oxide” which

red properties. Not

, spintronic devices

red years in a wide

world and creates

synthesis of ZnO.

a. The research on

views on electrical tion spectra and

passes away in

ric transducers etc

echniques such as

nduction and so on



2016; IJC

In the field of ZnO research

different growth parameters a

to production of high quality

the main focus. ZnO has now

it presents very interesting p

range synthesis.


ZnO nano particles were sy

techniques [8], wet chemical

Thermal decomposition meth

Here, the ZnO nano particles

sample was analyzed by mea

recorded on ultraviolet – vi

synthesized material was ch

mid-infra red range (400 – 400

All the chemical reagents in

guaranteed – grade, and were

In this experiment, the sol - g

NPs). In a typical procedure

distilled water with continuou

was heated to 50°C and 300

3ml of H2O2 was added drop

almost clear solution. Thiscentrifuged and washed sever

After washing the ZnO nano

of ZnO will occur during the


the last decade was mainly concerned w

nd processing techniques. Thus currently re

, reproducible P-type conducting ZnO for d

become one of most studied material in the

roperties for optoelectronics and sensing ap

nthesized by several different methods, s

l method [9], green chemistry [10], micro

od [12, 13], and chemical vapour decompo

were prepared by sol-gel method. The crys

ns of X-ray diffractometer (XRD).The absor

ible (UV-Vis) spectrometer. The composi

racterized by Fourier transform infrared s

).

this experiment were obtained from com

used as received without further treatment.

l method was used for preparation of ZnO n

6.3g of zinc acetate dihydrate was added t

s stirring to dissolve zinc acetate completely

l of absolute alcohol was added slowly with

ise to the vessel and mixed it using a magn

solution was incubated for 24 hours andal times with double distilled water to remo

articles is dried at 80°C in a hot air oven. C

rying process.

hp; ISSN: 2454-5422

ith optimization of

earch work related

vice application is

last seven years as

plications, in nano

uch as the sol-gel

ave method [11],

ition method [14].

tal structure of the

bance spectra were

tion quality of the

pectroscopy in the

mercial sources as

ano particles (ZnO-

200 ml of double

. Then the solution

stirring. After this,

tic stirrer to get an

the solution was ve the by products.

mplete conversion



2016; IJC


X-Ray Diffraction Analysis

The crystallinity was determi

an XPERT-PRO Diffractome

about 0.3 g of dried ZnO part

glass sample container, and

The phase purity and composi

XRD. Figure (1.1) shows a ty

A number of Bragg reflectio

corresponding to (100), (002

ZnO nano particles by using

powder can be calculated by

D = 0.9λ/

Where λ is the wavelength o

(FWHM) and θ is the angle o

is found to be 44.37nm.

Figure (1

UV- Optical Absorption Sp

Electromagnetic radiation suc

characterized by a wavelen

approximately 400 to 800


ed by XRD powder diffraction. Analysis is

ter system equipped with a Cukα (K=1.54

icles were deposited as a randomly oriented

the XRD patterns were recorded between

tion of the particles obtained by a sol - gel p

pical XRD pattern of ZnO nano particles, pr

ns with 2θ values of 36.12°, 31.63° and 3

), (101) planes[15,16] which shows a typic

JCPDS 36-1451. The crystallite size (D) of

sing Scherrer’s formula.

Cos θ

f X rays used (1.54060 Å), β is the fullwidt

f diffraction. The crystallite size of prepared

.1):- X-Ray Powder Diffraction patterns of Z

ctroscopy

h as visible light is commonly treated as a w

gth or frequency. Visible wavelengths co

m [17,18]. The UV – optical spectra of Z

hp; ISSN: 2454-5422

erformed by using

A°) source, Here,

powder into a plexi

0° to 80° angles.

ocess examined by

pared in this work.

.30° are observed

al XRD pattern of

the prepared nano

h at half maximum

ZnO nano powder

nO nano particles

ve phenomenon,

ver a range from

nO is recorded in



2016; IJC

SCHIMADZU UV-VISIBLE

shows the UV-Vis optical abs

dried in air at 80°C. The ab

which indicates an almost uni

Fi

FTIR

FT-IR is an effective method

Transform Infrared, the pref

were characterized by FTIRthrough a sample. Some of th

passed through (transmitted).

transmission, gives informat

spectroscopy useful for sever

• FTIR can identify unknown

• FTIR can determine the qual

• FTIR can determine the amo

Figure (1.3) shows the FTI

method, [23] which was aqui

500 correlated to me

1500 corresponds to the

bending vibrations. The pea

bending vibrations respective


SPECTRO PHOTOMETER from 200-80

orption spectrum of ZnO nano particles as sh

orption spectrum shows a sharp absorbanc

form size of the nano particles [19-22].

gure (1.2):- UV-Visible absorption of ZnO n

to reveal the composition of products. FTI

rred method of infrared spectroscopy. The

spectroscopy. In infrared spectroscopy, IRe infrared radiation is absorbed by the samp

The resulting spectrum represents the molec

ion of type of bonding in the sample. T

l types of analysis.

materials

ity or consistency of a sample

unt of components in a mixture.

spectrum of the ZnO nano particles synt

red in the range of 400-4000 . The ban

tal oxide bond (ZnO). The peaks in th

C=O bonds. The adsorbed band at 1544

k at 1340 and 1512 corresponds

ly. The peaks in the range of 1600 to 4000

hp; ISSN: 2454-5422

nm. Figure (1.2)

own in figure (1.2)

onset at 275 nm,

ano particle

stands for Fourier

prepared samples

radiation is passed le and some of it is

ular absorption and

is makes infrared

hesized by sol-gel

between the 450-

e range of 1400-

is assigned O-H

to C=O and O-H

indicates the



2016; IJC

functional group present in it

nano particles, the peak at 41

Conclusion

ZnO nanoparticles have been

average particle size of ZnO

exhibit the UV absorption p

shows stretching vibrations a

cost for producing ZnO nano

Acknowledgement

I am grateful to Dr.P.Gna

N.M.S.S.Vellaichamy Nadar

thank Dr.S.Pushpam, Assist

constant guidance and encour

References

[1] A.R. Hutson, Phys.Rev.,1

[2] G.Heiland, E.Mollwo, F.S

[3] Shyam Sundar Pareek and

[4] M.Matsuoka, J.App.Phys.,

[5] P.R.Emtage, J.App.Phys.,

[6] M.Inada, J.Phys.,17 (1978


. Also the figure (1.3) shows the typical spe

.7 is the characteristic absorption of Z

Figure (1.3):- FTIR Spectrum of ZnO nano

prepared using sol-gel method. XRD resu

nano particle is 44.37 nm. The synthesized

ak at 275nm. In FT-IR spectroscopy pure

t 400-4000 The present work proves it

articles.

adurai, Head of the Department, Depar

ollege for his encouragement of this work.

ant Professor, N.M.S.S.Vellaichamy Nada

agement.

8 (1957) 222-230

tockmann, Solid State Phys.,8 (1959) 193-19

Kapil Pareek, IOSR J.App.phy (IOSR-JAP),

10 (1971) 736

8 (1977) 4372-4384

) 1-10

hp; ISSN: 2454-5422

ctrum of pure ZnO

O bond.

articles

lt which shows the

ZnO nanoparticles

ZnO nanoparticles

is simple and low

tment of Physics,

I would also like to

r College for her

6

3(2):(2013)16-24



2016; IJC

[7] F.S.Hickerne, J.App.Phys.

[8] Ameer A, Faheem A, Nis

(2010): 399-402

[9] Yadav A, Virendra P, Kat

641-5

[10] Jayaseelan C, Abdul Ra

Bagavana A, et al, A , 90 (201

[11] Deepali S, Sapna S, Ka

(2011), 9661-72

[12] Yang Y, Li X. and Bao

[13] Tonto P. Phatanasri S. an

[14] Wu B.J. and liu S. C, Ad

[15] Liu B and Zeng H.C, J.

[16] Shen G.Z, Cho J.H, Xo

5496

[17] Ashtaputre S.S, Dephpa

Urban J, Huram S.K, Gosavi

[18] P.K. Giri, S. Bhattachary

Nanotechnology, 11, (2011),

[19] Guo L, Cheng X. Y, Ya

(2001) 123-127

[20] Marcos R.M., Daniel S.

[21] Shingo T, Atsushi N, Ta

[22] Tanujjal B, Karthik K. L

725[23] Gupta T.K, Ceramic J.


, 44 (1973)1061-1071

hat A, Chaman M, Naqvi A H, J. Alloys an

he A A, Sheela R, Deepti Y, Sundaramoorth

human A, Vishnu Kirthi A, Marimuthua S,

2) 78-84

itha B S, Jaspreet R, Mohinder K, App Su

, Chemical physics letters 373. (2003), 22-2

d P. Praserthdam, Ceramics International 34:

vanced materials 14; (2002), 215 -218

m.Chem. Soc, 125, (2003), 4430-4431

J.K, Xi G.C. and Lee C. J, Phys chem. B,

de A., Marathe S, Wankhede M.E, Chiman

.W. and Kullkarni S.K, Phys, 65,(2005), 61

ya, B.Chetia, Satchi kumari, Dilip K. Singh,

1-6

n Y. J. and Ge W. K, Materials science and

. and Antonio M. N, Material letters, 125. (

eharu T. and Hiroyuki Wada, Materials. 4, (

, Soumik S and Joydeep D, J. Nanotechnol

ater. Res., 7, (1992), 3280-3295

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d Compounds ,496,

y, et al, 29, (2006),

Santhoshkumar T,

face Science , 257,

: (2008), 57-62

109, (2005), 5491-

pure J, Parischa R,

-620

J. Nanoscience and

engineering, C16.

014) 75-77

2011), 1132-1143

gy. 4, (2013), 714-




Synthesis and Characterization of SiO2 Doped TiO2 Thin Films: Influence of

Coating Cycles

M.Sankareswari1, R.Vidhya1, A.Azhagu Parvathy2 and K.Neyvasagam3*

1 PG Department of Physics, V.V.Vanniaperumal College for Women, Virudhunagar, India.

2 UG Department of Physics, V.V.Vanniaperumal College for Women, Virudhunagar, India.*3 PG and Research Department of Physics, The Madura College, Madurai, India.


Abstract

Silica doped Titanium di oxide (SiO2-TiO2) thin films (different coating cycles 4, 6

& 8) were prepared by spin coating deposition on glass substrate. The prepared films

were pre annealed at 100oC for 10 minutes and post annealed at 400oC for 3 hours.

Structural and optical properties of the synthesized films were analyzed as a function

of coating cycle. X-Ray Diffractometer (XRD), Scanning Electron Microscope

(SEM), Energy Dispersive X-Ray Analysis (EDAX), UV – Vis spectrometer and

Photoluminescence spectrometer (PL) were used to explore the structural,

morphological, stoichiometric ratio and optical properties of the SiO2 doped TiO2

thin films. All the films exhibited the anatase phase, tetragonal structure with

preferential orientation along the (101) plane. X-Ray line profile analysis was

carried out to determine the micro structural properties such as crystallite size, microstrain, dislocation density, number of crystallites and stress of the SiO 2 doped TiO2

thin films. The crystallite size was found to increase as the coating cycle increases.

Morphological studies revealed that the fractured structure on the surface of the

films. The stoichiometric ratio of the film was confirmed by EDAX analysis.

Surface roughness of the film was characterized by Atomic Force Microscope

(AFM). Optical parameters such as band gap, extinction coefficient and refractive

index were estimated by optical absorption measurements. Optical band gap valueswere found to decrease with the increase in coating cycle. Photoluminescence



2016; IJC

studies displayed that st

560 nm. The results o

coating cycle has strong

thin films.

Key Words: Thin film,

Vis.

Introduction

TiO2 is the most attracti

its properties from fund

has three modification

brookite (orthorhombic

applications such as op

several factors which d

particle size, crystallini

structure, the TiO2 film

to understand the phase

[5]. The addition of La

improve the thermal sta

increase the adhesion a

a key issue in device st

the annealing temperatu

thin film synthesis su

chemical vapour deposi

sol-gel technique is onederiving unique metast

homogeneity [9].

In the present work,

substrates for various c

carried out to determi

structural parameters s


rong emission peaks were observed at 485

f structural and optical characteristic study

effect on structural and optical properties of

TiO2, SiO2, spin coating, XRD, SEM, ED

e materials in nano science and nano techn

amental and practical point of view [1]. C

hases which are rutile (tetragonal), anatase

). Titania nano particles received much

tical devices, sensors and solar cell applica

etermine the performance of TiO2 for appli

ty and the morphology [2 - 4]. Dependin

can be tailored for different applications. S

structure of TiO2 when it is deposited on dif

O3, CeO2, CuO, Fe2O3, SiO2 or other oxide

bility [6]. Additionally the presence of som

d mechanical stability of thin film on subst

ability [6, 7]. The phase transformation of

re and dopant [8]. Many methods have bee

h as sol-gel technique [9], hydrothermal

ion [11], physical vapour deposition [12] etc

of the most widely used methods due to iable structure at low reaction temperature

iO2 doped TiO2 thin films were deposit

oating cycles (4, 6 and 8). X-ray diffracti

e the structural properties of the deposite

uch as crystallite size, micro strain, disl

hp; ISSN: 2454-5422

m, 542 nm and

suggested that

nano crystalline

X, AFM, UV-

logy because of

ystalline titania

(tetragonal) and

interest for its

tions. There are

cations such as

g on the phase

o it is necessary

ferent substrates

s into TiO2 can

e dopants could

ates which play

iO2 depends on

established for

methods [10],

., Among them,

ts possibility of s and chemical

ed on to glass

n analysis was

d films. Micro

cation density,



2016; IJC

number of crystallites a

ray line profile analys

optical properties wer

dispersive analysis by

effect of coating cycles

of the SiO2 doped TiO2

Experimental details

SiO2 doped TiO2 thin fil

chemicals were analyti

purification. The precu(TTIP) and Tetra Ethyl

were selected as solvent

Nano structure SiO2 do

4ml TTIP was mixed w

to stabilize the solution

and the solution was s

substrates (25mmx75m

rpm/30s. The films wer

repeated to obtain 4 co

more samples of 6 and

400°C for three hours.

The deposited films we

All the measurements wof the films were obtain

0.15405 nm) in steps

examination of the fil

microscope. The optica

calculated using (Schim

– 5301) Photoluminesc

measured by using (Sur


d stress were estimated from x-ray diffracti

is technique. Surface morphology, film c

analyzed using scanning electron micr

-rays and optical absorption techniques re

on the structural, morphological and optica

thin films were studied and the results are dis

ms were prepared using sol – gel spin coatin

cal reagent grade and used directly with

sors of TiO2 and SiO2 were Titanium TetrOrtho Silicate (TEOS) respectively. Ethanol

and stabilizer of TTIP.

ed TiO2 thin films were prepared by the fol

ith 30ml ethanol. Then 1ml acetic acid was

. 0.1 ml TEOS was added into the matrix

tirred for one hour. The films were deposi

x2mm) by the spin coating method with

preannealed at 100°C for five minutes. Th

ting cycles. The same method was followed

8 coating cycles. Finally all the films were

e characterized extensively using the follow

ere performed at room temperature. X-ray did using X’ pert pro diffractometer with Cu

of 0.1 over the 2 range of 20° - 80°.

s was done using Hitachi (s-3000H) sc

l data and PL spectra of the SiO2 doped

adzu 1800) UV – Vis – NIR spectrometer and

nce spectrometer. The thickness of the pre

est SJ – 301) stylus profilometer.

hp; ISSN: 2454-5422

n data using X-

omposition and

oscopy, energy

pectively. The

l characteristics

cussed.

g technique. All

ut any further

Iso Propoxide and acetic acid

lowing method.

dropped slowly

f TiO2 solution

ted on to glass

speed of 3000

procedure was

to prepare two

ost annealed at

ing instruments.

ffraction pattern α radiation (K =

Morphological

anning electron

TiO2 films was

(Schimadzu RF

ared films was



2016; IJC

Results and discussion

Structural studies

To study the crystallin

number of coating cycle

XRD pattern recorded f

shown in Figure1.

Fig .1: XRD Pattern ofcoating cycles c) 4 co

The XRD result shows

orientation along (1 0 1)

(0 4 0), (2 0 0) peaks.

the height of peaks. It is

SiO2 doped TiO2 thin fil

were found to be in agre

The average crystal size

maximum (FWHM) dat

Where is the FWHM

(CuKα=0.15405 nm). A

increase which reveals t


quality of the SiO2 doped TiO2 thin fil

s, the films were subjected to X-ray diffracti

or SiO2 doped TiO2 thin films for different

iO2 doped TiO2 thin films for a) 8 coating cating cycles

that all the films have anatase phase wit

plane. All the prepared SiO2 doped TiO2 fil

hen the coating cycle increases, there is a s

observed that there is no change in the phase

ms. Table 1 shows the observed and calculat

ement with standard JCPDS data (File no. 8

of the deposited film was determined from

using the following Scherrer formula

0 .9( ) D n m

C o s

λ

β θ

in radians is the Bragg’s angle, λ is the x

s the coating cycle increases, the intensity o

hat the crystallinity increases due to the pre

hp; ISSN: 2454-5422

s for different

on analysis. The

oating cycles is

cles b) 6

h a preferential

ms have (1 0 1),

light increase in

structure of the

ed values which

-4203).

Full Width Half

(1)

ray wavelength

f the peaks also

ferential growth



2016; IJC

of the SiO2 doped TiO2.

found to increase from

cycles.

In addition to the chang

of coating cycles. Cryst

It needs to be addresse

doped TiO2 thin film is

where ‘D’ is the crysta

results are summarized

cycle increases.

The micro strain

=ε

From Table 1, it is obse

to 0.036 for 8 coatings.

that lattice imperfection

The number of crystallidetermined using the rel

3N =

t

D

where t is the thickness

Fig 2(a) and (b) show

variation of thickness a

Malliga et al., [13] obse

Table 1: Structural

CoatingCycles

2θ (degree)

Observed Standard

4 25.254 25.304

6 25.245 25.304

8 25.256 25.304


The crystallite size of the SiO2 doped TiO

20.22 nm for 4 coating cycles to 53.93 n

es in crystallite size, crystal defects may oc

l dislocation is the main defect related to the

d and hence the dislocation density availa

alculated from the given formula,

2

1 D

δ (2)

llite size of the SiO2 doped TiO2 thin fil

in table 1. The dislocation density decrease

of the SiO2 doped thin film was measured us

C o s θ

4 (3)

ved that the strain value decreases from 0.09

he decrease in strain with increase in coatin

is due to increase in crystallite size.

tes per unit area (N) of the SiO2 doped Tiation

(4)

of the film .The calculated values are summa

the variation of crystallite size & dislocat

d micro strain respectively with number of

rved similar results in their investigation on

parameters of SiO2 doped TiO2 thin films for various coating c

(hkl)orientation

Phase andcrystalstructure

Thickness(µm)

CrystallitesizeD (nm)

DislocatioDensityδX1014

lines /m2

101 Anatase,tetragonal

1.8 20.22 24.45


1.9 40.43 6.12


2 53.93 3.43

hp; ISSN: 2454-5422

thin films was

for 8 coating

ur by the effect

crystallite size.

ble in the SiO2

. The observed

s as the coating

ing the relation

8 for 4 coatings

g cycles implies

2 thin film was

rized in Table 1.

ion density and

coating cycles.

iO2.

cles.

n

MicrostrainµX10-3

No. of crystallitesper unitareaNX1016

0.09 21.8

0.05 2.87

0.03 1.27



2016; IJC

Fig 2 (a) variation of

Morphological and Co

Figure 3 shows the SEthin films. The films

During the drying and a

as a result of contractio

the layer and substrate

TiO2 thin films produc

suggest a high photo cat

thin film improves with

Fig.3 SEM micrograp

Figure 4(a) & (b) sho

coating cycles and 8 co

and O. The presence of

and would change it to

higher a value [14].


rystallite size & dislocation density and 2 (b

micro strain with coating cycles

positional analysis

micrographs of 4 and 8 coating cycles ofroduced by this technique indicate fractur

nnealing processes of the films, crack forma

n, stress and different thermal coefficients

[5]. The fractured surface morphology of

d by this technique which resulted in a la

alytic activity. The results also suggest that u

increasing coating cycles.

hs of SiO2 doped TiO2 thin films (a) 4 coatin

coating cycles

s the EDAX pattern of SiO2 doped TiO2

ting cycles. EDAX results indicated the mai

SiO2 in the thin film could destroy the lin

Ti – O – Si. This aspect can shift binding

hp; ISSN: 2454-5422

) thickness &

iO2 doped TiO2

d morphology.

tion takes place

of expansion of

the SiO2 doped

ge surface area

niformity of the

g cycles (b) 8

thin films of 4

peaks of Ti, Si

age of Ti-O-Ti

energy of Si to



2016; IJC

Fig.4 EDAX spectra of

Atomic Force Micros

of the thin film. AFM i

cycles is shown in Figu

doped TiO2 thin film are

Fig.5 AFM ima

Optical analysis

The transmittance and

obtain the information

transmittance spectra o

between 300 and 800n

reduction in the transmi

the effect on the surfa

described in earlier studi

Fig.6 Transmittance

(


SiO2 doped TiO2 thin films (a) 4 coating cycl

cycles

ope (AFM) was used to characterize the su

ages (2D & 3D) of SiO2 doped TiO2 thin fi

e 5. The root mean square and roughness va

16.40 nm and 10.93 nm respectively.

ge of SiO2 doped TiO2 thin film for 8 coatin

reflectance spectra were recorded at room

of optical properties of SiO2 doped TiO2

f the SiO2 doped TiO2 thin films obtain

for different number of coatings is shown i

ittance with increase in coating cycles may

e roughness and grain size boundary of t

ies [15 – 18].

pectra of SiO2 doped TiO2 thin films (a) 4 c

) 6 coating cycles (c) 8 coating cycles

hp; ISSN: 2454-5422

es (b) 8 coating

rface roughness

lm for 8 coating

lues of the SiO2

cycles

temperature to

thin films. The

d in the range

n Figure 6. The

be attributed to

e thin films as

oating cycles



2016; IJC

The reflectance spectra

coating cycles is shown

as wavelength increases

films with 4 coating cyc

Fig.7 Reflectanc

(

The nature of transition i

(h k hα ν ν

Where is the absorptenergy gap in eV and

transition present in the

the material is direct all

material is indirect allo

with photon energy (h

coating cycles are show

Fig. 8 a) Direct an

(a) 4 coatin


of the SiO2 doped TiO2 thin films for diff

in Figure 7. It shows that the reflectance th

. The highest reflectance value of about 70

les.

e spectra of SiO2 doped TiO2 thin films (a) 4

) 6 coating cycles (c) 8 coating cycles

s determined using the following equation

) m

g E (5)

ion coefficient in cm-1, hγ is the photon eA is a constant. The value of ‘m’ determi

material. If m = 1/2 indicates that the transi

owed and m = 2 indicates that the transition

ed. A plot of (αhγ)2 with photon energy (

) for SiO2 doped TiO2 thin films obtained

in Figure 8 (a) and 8 (b).

b) Indirect band gap of SiO2 doped TiO2 thi

g cycles (b) 6 coating cycles (c) 8 coating cy

hp; ISSN: 2454-5422

rent number of

e film increases

is obtained for

coatings

nergy, Eg is an nes the type of

tion involved in

involved in the

γ) and (αhγ)1/2

for 4, 6 and 8

n films for

les



2016; IJC

Extrapolation of linear

value of the material. T

in the present work are

and 8 coating cycles r

attributed to quantum si

The values of refractive

the following equations

1 ^ 0 .5n =

1 ^ 0 .5 R

R

K =4α λ

π

where n is the refractiv

is the reflectance (%).

coating cycles is show

observed at 6 for 8 coat

films for 6 coating cycl

The refractive index va

is observed in extinctio

Figure 10.

Fig.9 Refractive Inde

(a) 8 coatin


portion of the graph to X-axis (energy) giv

he direct and indirect band gap values of th

found to be 3.4, 3, & 2.8 eV and 3.2, 2.8 &

spectively.The reason for decrease in ban

e effect.

index n and extinction coefficient (K) are d

(7) and (8)

(6)

(7)

index of the material, K is the extinction c

The variation of refractive index with ene

in Figure 9. The maximum value of ref

ing cycles. Also refractive index values of t

s and 4 coating cycles are estimated at 4 an

iation may be due to the film thickness. Th

coefficient of the SiO2

doped TiO2

thin fil

x versus photon energy for SiO2 doped TiO2

g cycles (b) 6 coating cycles (c) 4 coating cy

hp; ISSN: 2454-5422

s the band gap

films obtained

2.6 eV for 4, 6

gap energy is

etermined using

efficient and R

rgy for various

ractive index is

e prepared thin

2 respectively.

same variation

ms as shown in

thin films for

les



2016; IJC

Fig.10 Extinction coef

for (a) 8 coati

To further validate the

emission spectroscopy

spectra observed at exc

doped TiO2 films exhib

visible range. The peak

[19]. The structural de

referred to as native poi

energy levels of the ban

doped TiO2 thin films a

intensities for different

TiO2 thin films increase

due to the improvement

increase in the coatin

contribute its usage as a

Fig. 11 PL spectra o


icient versus photon energy for SiO2 doped

ng cycles (b) 6 coating cycles (c) 4 coating c

crystalline quality of the thin films, ph

was used and the results are illustrated in

itation wavelength of 410 nm demonstrate t

it three peaks (485nm, 542nm and 560nm)

s in the visible region are associated with s

ects of a seed solution exhibited in the vi

nt defects and include oxygen vacancies whi

d gap [20 – 21]. It was observed that the P

re almost in the same wavelength position b

number of coating cycles. The PL intensity

with increase in number of coating cycles.

in quality and increase in oxygen vacancie

cycles could improve the structural qu

transducer in biosensing applications [22].

SiO2 doped TiO2 thin films for (a) 8 coating

coating cycles (c) 4 coating cycles

hp; ISSN: 2454-5422

iO2 thin films

ycles

toluminescence

Figure 11. PL

hat all the SiO2

which lie in the

ructural defects

sible region are

ch present deep

peaks of SiO2

ut have varying

of SiO2 doped

This increase is

. It reveals that

lity which can

cycles (b) 6



2016; IJC

Conclusion

SiO2 doped TiO2 thin fi

spin coating technique

analysis revealed that th

with preferential orienta

to be 20.22 nm, 40.43 n

coating cycles respecti

density, strain and stres

have fractured structur

elements are obtained.

film has a direct band g3.2, 2.8 & 2.6 eV for

increases with increas

suggested that thickness

topography was found

coating cycles. These r

films were considerabl

SiO2 doped TiO2 films a

Reference

1. Castillo,N., Olguin,D.,

properties of TiO2 thin f

50(4), 382, 2004

2. Mahsid,S., Askari,M.,

Nano particles preparati

589, 2009

3. Wang C.C and Ying J.

and rutile Titania and na

4. Liu,T., Wang,W., Ma,T

of titania prepared by u

3005, 2003


lms were deposited successfully onto glass

or 4, 6 and 8 coating cycles respectively.

e prepared films have anatase phase with tetr

tion along (1 0 1) plane. Also the crystallite

m and 53.93 nm for 4 coating cycles, 6 coati

ely. The micro structural parameters suc

were estimated. Surface morphology show

. EDAX analysis revealed that films wit

ptical absorption measurements indicated th

ap value of 3.4, 3 & 2.8 eV and indirect ba, 6 and 8 coating cycles respectively. PL s

in number of coating cycles. The resu

of the film increases as the coating cycle in

by using AFM. The uniformity of the film

esults showed that the properties of SiO2 d

influenced by the coating cycles and the

re desirable material for photo catalytic appli

CondeA., Gallaro Jimenez,S. Structural an

ilm prepared by spray pyrolysis. Rensta Mex

Ghamsari,M.S., Afshar,N., Lahuti,S. Mix

on using sol-gel method. J. Alloys and com

. Sol-gel synthesis and hydro thermal proce

no crystal. Chem. Mater. 11,3113-3120,199

., Tao,J., Zhang,J and Hu,T. Synthesis and

sing a photo assisted sol-gel method. Lang

hp; ISSN: 2454-5422

substrates using

-ray diffraction

agonal structure

size was found

ng cycles and 8

as dislocation

d that the films

Ti, O and Si

at the deposited

nd gap value of pectra intensity

lt of thickness

reases. Surface

increases with

oped TiO2 thin

nano crystalline

cations.

morphological

icana De Fisica.

ed – phase TiO2

ounds. 47, 586-

ssing of anatase

characterization

our. 19, 3001-



2016; IJC

5. Shanmugam,S., Muthar

TiO2 thin film on cu sub

Trends & Technology. 1

6. Lek Sikong., Jiraporn

Effect of doped SiO2 an

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8. Yuranova,T., Mosteo,

textiles surface modifie

A: Chemical. 244, 160-1

9. Bischof,B.L., and Aner

porous anatase TiO2. Ch

10. Jinghuanzhang., XinXi

photo catalytic properiti

Hazarclous Materials, 1

11. Dongjin Byun, Yong

Photocatalytie TiO2 d

Materials. 73, 199-206,

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Composite using sol g

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self reporting marerials

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zinc oxide nano structu

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,M., Pei,S. Annealing impact on the

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non polar surfaces in ZnO nano structures.

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Synthesis and characterization of Cu-TiO2 thin films by Sol-Gel process

R.Vidhya1, M.Sankareswari1, A. Azhaghu parvathi2 and K.Neyvasagam3*

1PG Department of Physics, V.V.Vanniaperumal College for Women, Virudhunagar, India.2UG Department of Physics, V.V.Vanniaperumal College for Women, Virudhunagar, India.

*3PG and Research Department of Physics, The Madura College, Madurai, India.


Abstract

Copper doped TiO2 (Cu-TiO2) thin films have been deposited onto the microscopic glass

substrate by spin coating technique. The influence of varying coating cycles (3, 5 and 7) on

the structural, surface morphological and optical properties of the films have been studied by

X-ray diffraction method (XRD), Scanning Electron Microscopy (SEM) with Energy

Dispersive X-ray Analysis (EDAX), Atomic Force microscopy (AFM), UV-Vis absorption

spectroscopy (UV-Vis-NIR), and Photoluminescence (PL) study. The X-ray diffraction

pattern of Cu-TiO2 films confirmed the tetragonal crystal structure of anatase phase with a

strong orientation along (1 0 1) plane. The X-ray line profile analyses have been carried out

to determine the micro structural parameters such as crystallite size, micro strain and

dislocation density. The thickness of the films was about 0.96 µm to 1.8 µm using stylus

profilomer. Morphological studies have revealed that grains are agglomerated, irregular with

mosaic like structure. The elemental compositions of the films were confirmed by EDAXspectrum. The UV-Visible spectral analysis showed the transmittance and band gap (direct &

indirect) were found to decrease with increase in coating cycles. The room temperature PL

spectra of Cu-TiO2 thin films show blue and green emissions at 485 nm and 545 nm with

excitation at 410 nm. These results suggest that the varying coating cycles is an important

parameter for the improvement of structural and optical quality of Cu-TiO2 thin films derived

by sol-gel spin coating technique.



2016; IJC

Keywords: Cu-TiO2 thin fi

EDAX.

Introduction

Titanium dioxide (TiO2) is o

moreover, it has been wi

catalysts/catalyst for environ

and ultra-violet absorber in s

reasonable, because TiO2 is

chemical stability, high me

different crystal structure:

(orthorhombic). The anatas

photocatalyst due to slow rec

rutile and brookite [4].

However, exploring the prop

area of research. In this regar

transition metal like Cu [5], C

copper (Cu) was found to bebecause of its notable effects

plays an important role on t

optical or electronic propertie

species on the surface of the

Cu doped TiO2 thin films, in

sputtering [14], sol-gel proces

over other synthesis techniquand crystalline phase.

In our work, we prepared the

with varying coating cycles o

been investigated.


lm, spin coating method, XRD, AFM, UV-

e of the most important semiconductor ma

dely used in fuel cell, solar energy

ental remediation process, white pigment i

unscreen cream [1-3]. Such wide range of

an inexpensive, environmentally friendly

hanical strength and photo activation. Ti

rutile (tetragonal), anatase (tetragon

crystalline TiO2 has been found to b

mbination rate of excited electron and hole

erties of TiO2 for improving its efficiency i

s, modifications of intrinsic properties of T

o, V [6], Fe [7] and Nb [8] have long been p

ne of the most considerable element amongon the activity of TiO2. The existence of

he activity, because Cu could influence th

s of TiO2 [10] as well as the number of oxy

iO2 [11]. A number of methods have been

cluding chemical vapor deposition [12], sp

s [15] etc. Among these, sol gel technique h

es for its excellent control over chemistry, h

Cu-TiO2 films by sol-gel spin coating meth

n structural, surface morphological and opti

hp; ISSN: 2454-5422

Visible, PL, SEM,

erials in daily life;

conversion, photo

n paints and paper

application is quite

material with high

2 possesses three

l) and brookite

the most active

ompared to that of

s still an emerging

iO2 by doping with

roposed. Specially,

the transition metal Cu species at TiO2

e particle size [9],

en or intermediate

reported to prepare

ray pyrolysis [13],

s many advantages

omogeneity, purity

od. Their influence

cal properties have



2016; IJC


Raw materials

Titanium (IV) isoproxide (T

(Cu (NO3)2.3H2O) were used

was used as a solvent.

Preparation of Cu-TiO2 thi

Cu – TiO2 thin films were p

technique reported previousl

was mixed with ethanol and

added and stirred for 15 min.TiO2 host lattice, required

(NO3)2.3H2O) as a dopant pr

added to the mixture and stirr

cleaned with soap solution, a

were ultrasonically cleaned fo

The gel was dropped onto the

rpm/30 s by using a spin coa

furnace. The process of spin

three-coating film. Two mor

three, five, and seven layer co

Characterizations

The XRD pattern of Cu-

characterized by X-Ray diffra

was operated at 40 KV and

surface morphological obser

SEM and S-Flash 6130 Bruk

using Surfest SJ-301 (Stylus

400-700 nm by using the

Photoluminescence (PL) spe


IP, 99.95 %, Sigma-Aldrich), and copper (I

as raw materials. Ethanol (C2H5OH, 99.9

films

repared at room temperature by using so

[16]. A stoichiometric amount of titanium

agnetically stirred for 10 min, and then gla

To achieve the desired concentration of Custoichometric amount of Copper II Nitr

cursor was dissolved in ethanol. This dopan

ed vigorously for 2 hour. Prior to deposition

cetone, chromic acid and distilled water. Fi

r 30 minute.

cleaned glass substrates which were rotated

ter. The coated layer was dried at 100°C fo

ning and drying was repeated for two mor

films of five and seven coatings were als

ated films annealed at 500°C for 3 hour were

iO2 thin films obtained for various co

ction (XRD) using X’PERT-PRO X - ray di

30 mA with CuKα1 radiation of waveleng

ations and elemental analysis were done b

r EDAX respectively. The thickness of the

rofilometer). UV-Visible spectra were reco

(Schimadzu 1800) UV-VIS-NIR spect

tra were recorded using (Schimadzu RF-5

hp; ISSN: 2454-5422

I) nitrate trihydrate

, Merck Germany)

l – gel spin coating

(IV) isopropoxide

ial acetic acid was

ion as a dopant in ate trihydrate (Cu

t solution was then

the substrates were

ally the substrates

at a speed of 3000

5 min in a muffle

times to obtain a

prepared. Finally,

also synthesized.

ating cycles were

ffractometer which

th 1.5406 A°. The

y EV018 Carlzeiss

ilms was measured

ded in the range of

ophotometer. The

301) luminescence



2016; IJC

spectrophotometer with xen

excitation wavelength of 410


XRD analysis

The XRD patterns of differen

by spin coating method is sho

Figure1: XRD pattern of C

The observed XRD patterns

anatase phase with high inten

0 0), (2 1 1) and (0 0 2) are

consistent with JCPDS fileintensity of the peaks increas

values measured using stylus

The crystallite size was deter

=

where D = particle size (nm)

beam in A° , β = full widt


on lamp as the light source at room te

nm.

t coating cycles of Cu-TiO2 thin films coated

wn in figure 1.

-TiO2 films for different coating cycles

show that the coated films have tetragonal

ity peak in (1 0 1) orientation. The other ori

also observed for all the samples with low

no. 89-4203. From the XRD pattern, it iss with increase in number of coating cycles.

profilometer are given in Table 1.

ined using the Debye- Scherrer’s formula,

( ) (1)

, k = shape factor (0.94), λ = wavelength o

h at half maximum (FWHM) of the promi

hp; ISSN: 2454-5422

perature with an

on glass substrate

BCC structure of

ntations (2 1 0), (2

intensities which is

observed that the The film thickness

the incident X-ray

ent peak, and θ =



2016; IJC

diffraction (Bragg) angle. Fr

with increase in coating cycle

et.al, [17]. Using the size of t

(µ) has been determined from

δ =

µ =

where t is the film thickness

values were summarized in T

cycle increases, the crystallit

strain decreases which reveals

Figure: 2(a) Variation of

thickness and strain with di

Table 1: Micro stru

Number of coatings

CrystalliteD (nm

3 55.3

5 65.77

7 76.1


om the calculation it is found that the cryst

s. Similar results have been shown by earlie

e crystallites, the dislocation density (δ) an

the relations given below

(2)

(3)

. The calculated crystallite size, dislocation

able 1. From the calculation it was observed

size also increases whereas the dislocation

the improved crystalline structure.

rystallite size and dislocation density &

ferent coatings of Cu-TiO2 thin films

tural parameter of Cu-TiO2 thin films wicoating cycles

size )

Thickness t(µm)

Dislocationdensity(δ) lines/m2

0.96 3.27

1.30 2.31

1.8 1.73

hp; ISSN: 2454-5422

llite size increases

r literature saranya

strain in the films

density and strain

that as the coating

density and micro

2(b) variation of

h varying

Strain µ (x10-3)

36.01

30.03

26.15



2016; IJC

Surface morphology with El

The SEM micrographs of Cu-

Figure 3.

Figure 3: SEM images for (

coating cycles of Cu-TiO2 th

From the morphological im

agglomerated, irregular grain

in nucleation over growth an

composition of the films w

shown in figure c and d whic


emental analysis

TiO2 thin films prepared at various coating c

) 5 (b) 7 coating cycles with EDAX spectr

in films

ge it is observed that the prepared Cu-Ti

size and island like structure. Increase in c

d the film surface observed to be closely p

s identified by EDAX measurement. The

demonstrates the presence of Ti, O and Cu i

hp; ISSN: 2454-5422

ycles are shown in

m for (c) 5 (d) 7

2 thin films were

ating cycle results

acked. The surface

EDAX results are

n the spectrum.



2016; IJC

Surface topography

Atomic force microscopy (A

on glass substrate for 3 coat

Figure (4a) shows the unevenshows mountain and valley li

mean square values are about

represents the homogeneity o

Figure: 4(a) AFM 2D and 4

Optical Analysis

The UV-Visible transmittanc

cycles are shown in figure 5.

Figure 5: Transmittance sp

cycles


M) images (2D and 3D) of Cu doped TiO2

ing cycles are illustrated in figure 4(a) and

distribution of spherical shaped grains over te nanostructure in some places. The surface

1.69 nm and 3.21 nm respectively. The low

the TiO2 particles on the surface [18].

(b) 3D image of Cu-TiO2 thin films for 3 c

spectra of Cu-TiO2 thin films for different

ctra of Cu-TiO2 thin films for different

hp; ISSN: 2454-5422

thin film deposited

4(b) respectively.

he surface and (4b) roughness and root

er roughness value

ating cycles

number of coating

umber of coating



2016; IJC

From UV-Visible plots, it is

increase of film thickness.

maximum for the film with th

350 nm for all the Cu-TiO2 th

in transmittance is due to a

electrons from the valence ba

The band gap energy (Eg) ca

band gap value can be obtaine

αhν =

Where A is a constant related

direct transition and n = 2 f

incident photon energy and E

(hν) is shown in Figure 6. Th

of the plot (αhν)2 versus hν t

for different number of coatin

Figure 6: (a) Direct and (

number of coating cycles


bserved that the optical transmittance is fou

he transmittance in the visible region w

ree coating cycles. The transmittance found t

in film and approaches to zero at around 30

bsorption of light caused by the excitation

d to the conduction band of TiO2 [19].

n be estimated from the optical absorption

d from the optical absorption spectra by usin

A(hν − E ) (4)

to the effective masses associated with the b

r indirect transition, α is the absorption co

g is the optical band gap. The plot of (αhν)2

optical band gap is obtained by extrapolatin

α = 0. The direct and indirect band gap of

g cycles are shown in figure 6(a) and 6(b) re

b) Indirect bandgap of Cu-TiO2 thin f

hp; ISSN: 2454-5422

d to decrease with

as observed to be

o decrease at about

nm. This decrease

and migration of

easurements. The

g Tauc’s relation

ands and n = ½ for

efficient, hν is the

with photon energy

g the linear portion

Cu-TiO2 thin films

pectively.

lms for different



2016; IJC

The direct and indirect band

to decrease with increase in n

in film density and increase

literature malliga et.al, [20].

The extinction coefficient (

calculated from

k =

n =

Figure 7: (a) Extinction coe

films for different number o

From the figure, it is obser

coating cycle and this due to

increases with respect to co

cycles is in the range of 2.5 t

film [21].

TableCoatingcycles

Di

357


ap energy values of the Cu-TiO2 thin films (

umber of coating cycles which might be the

in crystal size. Similar results have been

K) and refractive index (n) of Cu-TiO2 t

(5)

+( )

− K (6)

fficient and (b) Refractive index vs Energ

f coating cycles

ed that the extinction coefficient increase

increase in absorption. The refractive inde

ting cycle. The value of refractive index

o 3.1 which is higher than bulk anatase due

2: Optical Data of Cu-TiO2 Thin Filmsrect bandgap

(eV)Indirect bandgap

(eV)Transmit

(%)

3.2 3.0 603.0 2.8 452.8 2.6 35

hp; ISSN: 2454-5422

Table. 2) are found

esult of the change

shown by earlier

hin film has been

y of Cu-TiO2 thin

s with increase in

x of the films also

f different coating

to thickness of the

tance



2016; IJC

Photoluminescence Analysis

The most valuable informati

PL spectra. The PL spectra

temperature with excitation

characterized by three emissi

nm (2.6 eV) can be attributed

of phonons in TiO2 lattice. T

In general, it has been observ

response [20].

Figure 8: PL spectra of Cu-

Conclusion

Cu-TiO2 thin films have betechnique with different coati

films have tetragonal crystal s

also observed that the crystal

with increasing number of c

shows that the films are wit

confirms the presence of Ti,

optical band gap (both direct


n on the quality and purity of the films ma

of Cu-TiO2 thin films for different coati

avelength of 410 nm is shown in figure 8.

on bands. A blue emission with a peak cent

to indirect recombination via defect states

e peak at 545 nm (2.2 eV) corresponds to

ed that the transparency in the films advers

iO2 thin films for different number of co

n deposited onto glass substrates using sng cycles. X-ray diffraction analysis reveale

tructure with preferential orientation along (

lite size increases but dislocation density a

atings due to increase in film thickness. S

h irregular grains with flake like morpholo

O and Cu. Optical study revealed that the

and indirect) decrease but PL band emission

hp; ISSN: 2454-5422

y be obtained from

ng cycles at room

Each PL spectra is

ered at around 486

ith the interaction

iO2 anatase phase.

ly affects their PL

ting cycles

l-gel spin coating d that the prepared

1 0 1) plane. It was

nd strain decreases

urface morphology

gy. EDAX spectra

transmittance and

intensity increases



2016; IJC

with increase in number of c

has strong effect on structura

application in photo catalytic

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Synthesis and characterization of L-ALANINE DOPED GLYCINE Lithium chloride

CRYSTALS GROWN by solution method

D.Jencylin NavaRani *1, P.Selvarajan2, S.Lincy Mary Ponmani1 and N.Balasundari3

1Department of Physics, Sarah Tucker College, Tirunelveli, Tamilnadu, India.2

Department of Physics, Aditanar College of Arts and Science, Tiruchendur, India3Department of Physics, Sri K.G.S.Arts College, Srivaikundam, Tamilnadu,India.


Abstract

Nonlinear optical (NLO) crystals can be classified into organic, inorganic and semi organic

materials. L-alanine doped glycine lithium chloride crystal is a semi-organic material and it

was grown using water as the solvent by slow evaporation at room temperature. Colourless

crystals of well-defined morphology were grown in a growth period of 20 days. The

solubility of the material was measured. The grown crystals were characterized by powder X-

ray diffraction analysis and FT-IR analysis. Also UV-Vis spectral studies, dielectric studies

and microhardness measurement of the grown crystals were carried out.

Keywords: NLO, GG, Gamma-glycine

Introduction

-glycine single crystals have been grown using additives such as potassium chloride,

sodium chloride, potassium bromide, ammonium chloride, phosphrous acid, lithium nitrate,

magnesium chloride, cadmium chloride etc . In this work, -glycine (GG) crystals have been

grown using lithium chloride as the additive and to modify the various properties of

gamma-glycine, L-alanine is added as dopant. Single crystals of undoped and doped

gamma-glycine was grown by solution method with slow evaporation technique at room

temperature (31oC). The grown crystals were characterized to analyze the structural, spectral,

mechanical, electrical properties and other properties and the obtained results are presented.



2016; IJC


Sample preparation

Single crystals of gamma-gly

lithium chloride in 1:1 mola

prepared and the calculated

distilled water and by stirrin

prepared and this solution w

solution was allowed for slo

single crystals of gamma-gly

purity. To grow L-alanine d

of L-alanine were added in

obtained by slow evaporation

observed that all the grown cr

(i)

Figure 1: The grown

crystal, ii) 2 m

Measurement of solubility

The solubility is the amount

temperature and it is measur

and L-alanine doped gamma

results that the solubility valu

glycine crystals and as the c

solubility is found to decrease


cine ( -glycine) was grown by taking AR

r ratio. Initially, the aqueous solution of lit

amount of glycine was added into it. By a

g using a hot plate magnetic stirrer, satu

as filtered using high a quality filter paper

evaporation to obtain the crystals. It took a

cine (GG). The sample was re-crystallized a

ped gamma-glycine crystals, 1 mole%, 2 m

to the solutions of gamma-glycine and si

technique. The grown crystals are displayed

ystals are transparent, colourless and non-hy

(iii)

crystals: i) 1 mole% of L-alanine doped gam

ole% of L-alanine doped gamma-glycine cry

f solute present in 100 ml of saturated sol

d by gravimetrical method. The solubility

-glycine are presented in the figure 2. It is

es decrease when L-alanine is added as the d

oncentration of these dopant increase in th

.

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grade glycine and

hium chloride was

ding more double

rated solution was

.Then the filtered

bout 20 days to get

ain to improve the

ole% and 3 mole%

ngle crystals were

in the figure 1. It is

roscopic.

ma-glycine

stal

tion at a particular

urves for the pure

observed from the

opant into gamma-

host crystals, the



2016; IJC

30

28

30

32

34

36

38

40

42

44

46

48

S o l u b i l i t y ( g / 1 0 0 m l )

Figure 2: Solubility cur

Characterization technique

X-ray diffraction (XRD) pr

characterization of crystals a

bondangles, molecular orien

determined by X-ray crystallXRD method to estimate

MACH3/CAD4 single X-ra

optical transmission spectrum

a Perkin Elmer UV-vis-NIR s

For this study, an optically p

study, microhardness measu

(Leitz Weitzier hardness test

and deformation characteris

calculated using the relation

the diagonal length of indenta

crystalline samples were mea


35 40 45 50

Temperature (oC)

Pure GG Sample

GG+ L-alanine (1mole%)



es for undoped and L-alanine doped gamma

ovides an efficient and practical method

nd the molecular structure, atomic coordin

tation and packing of molecules in singl

graphy. The grown crystals were subjected tthe lattice parameters by employing

diffractometer with Mo K radiation (λ

of the samples was recorded in the 190- 11

pectrometer (model-Lambda 35).

lished single crystal of thickness 2mm was

rements were done using a Vickers micr

er). Hardness test provides useful informati

tics of materials. The Vickers microhard

Hv = 1.8544 P/d2 kg/mm2, where P is the

tion impression. Dielectric constant and diel

ured using a two probe arrangement and an

hp; ISSN: 2454-5422

glycine crystals.

for the structural

ates, bond lengths,

e crystals can be

o the single crystal a Bruker-Nonious

=0.71073 Ǻ). The

0 nm region using

sed. In the present

hardness indentor

on on the strength

ness number was

pplied load and d,

ctric loss values of

CR meter.



2016; IJC


XRD studies for identificati

From the Single crystal x-ray

doped crystals of gamma-gl

dimensions obtained by singl

The diffraction data shows a

slight changes in the values

gamma-glycine samples com

Table 1: Unit cell con

Crystal

Undoped gamma-glycin

GG crystal doped with

of L-alanine


of L-alanine


of L-alanine

Powder XRD studies for theare given in the figures 3 . Th

of crystallinity is high. The

package and the obtained Mil

(JCPDS file No. 06-0230)..

The unit cell parameters obta

almost the same with the data


n of crystal structure

diffraction study, it is noticed that all the

cine crystallize in hexagonal crystal struc

crystal XRD studies for the sample are sh

very good match with the data reported in

of lattice parameters have been noticed fo

ared to pure gamma-glycine crystal.

stants of undoped and doped gamma-glyc

Axial

dimensions (Å)

Angular

parameters

(degrees)

e (GG)a= b=7.023 (2)

c=5.4780(1)

== 90o

=120o

1 mole %

a=b=7.092(4)

c=5.501(2)

== 90o

=120o

mole %

a=b=7.102(3)

c=5.507(6)

== 90o

=120o

mole %

a=b=7.111(3)

c=5.510(1)

== 90o

=120o

grown crystals were carried out and the recoe sharp diffraction peaks in the patterns indi

diffraction peaks were indexed using the

ller indices (hkl values) were compared wit

he powder XRD data for the samples are gi

ined from powder XRD diffraction method

obtained from single crystal XRD method.

hp; ISSN: 2454-5422

rown undoped and

ture. The unit cell

own in the table 1.

the literature and

L-alanine doped

ine crystals

Unit cell

volume

Å3

234.04

239..82

240.41

241.29

rded XRD patterns cate the percentage

indexing software

the standard chart

ven in the tables 2.

are observed to be



2016; IJC

Figure 3: Powder X-ray diff

Table 2: Values of 2-theta

for GG s

Critical nucleation paramet

Nucleation kinetic studies w

gamma-glycine using a cons

S.No. 2Ө (d1 21.67

2 25.09

3 29.05

4 29.95

5 33.39

6 35.74

7 38.758 42.22

9 52.01

10 60.22

11 68.66


ractogram for GG crystal doped with 1 mole

, interplanar distance, Miller indices and

ample doped with 1 mole % of L-alanine

rs

re performed for the grown crystals of u

tant temperature bath (CTB). From these s

grees) d ( ) Hkl4.097 101

3.546 2-10

3.070 200

2.980 111

2.681 2-21

2.509 102

2.321 3-102.138 2-31

1.756 103

1.535 400

1.365 3-33

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% of L-alanine

elative intensity

ndoped and doped

tudies, the data of

I/Imax (%)37.93

43.1

100

67.2

70.6

36.2

37.927.5

27.5

31.0

24.1



2016; IJC

critical nucleation parameters

nucleation phenomena that a

plots of induction period vers

sample doped with L-alanin

understand that the inductio

induction period is observed t

800

1000

1200

1400

1600

I n d u c t i o n

p e r i o d

s e c o n d s )

Figure 4: Plots of induc

Dielectric studies

The grown crystals were c

constant and loss factor. Th

material. The dielectric loss

dielectric and an insulated p

factor (tan ) versus log of fre

and 80 oC are presented in

for the undoped and doped

conductivity of the grown

temperature of the crystals is

and this results in an enhance


were obtained and these data will be usefu

re taking place in the supersaturated soluti

us supersaturation ratio for undoped gamma

e is presented in the figures 4. From t

n period decreases with supersaturation ra

o be increased when gamma-glycine is dope

1.22 1.24 1.26 1.28 1.30

Supersaturation ratio (S)

Pure GG Sample

GG +L-alanine(1 mole%)



tion period versus supersaturation ratio for g

samples doped with L-alanine

t, polished and subjected to the measure

e lower the dielectric loss the more effec

angle is an important parameter both for

rtion . The plots of dielectric constant (ε r)

quency for the samples at different tempera

he figure5. The variations of AC conductivi

gamma-glycine crystals are shown in the

crystals increases with increase in temp

increased, there is a possibility of weakenin

d conductivity .

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l to understand the

ns of samples The

-glycine (GG), GG

e results one can

tio values and the

with L-alanine.

mma-glycine

ment of dielectric

tive is a dielectric

the material of a

and dielectric loss

ures such as 30, 50

y with temperature

figures 6. The AC

rature. When the

of hydrogen bond



2016; IJC

25

30

35

40

45

50

55

60

65

70

75

80

85

D i e l e c t r i c c o n s t a n t (

r )

Figure 5: Variation of di

added ga

40

4

6

8

10

12

14

16

18

a c

x 1 0 - 7 ( m ) - 1

Figure 6: Temperature

do


2 3 4 5 6

log f

C

C

C

ielectric constant with frequency for 1 mole

ma-glycine crystal at different temperatures

50 60 70 80

Temperature (oC)

Pure GG sample

GG+L-alanine (1 mole%)

GG+L-alanine (3 mole%)

ependence of AC conductivity for undoped

ed gamma-glycine crystals at 103 Hz

hp; ISSN: 2454-5422

of L-alanine

and L-alanine



2016; IJC

Fourier transform infrared

Functional groups and the

infrared spectroscopy. The

excite overtones and harmo

may be used to study the

structure. The recorded FTI

assignments for absorption b

reported in the literature .

3200 and 2400 cm-1 was due t

of NH2 and C – H of CH2 st

attributed to carboxylate grouto NH3 group. Thus, the carb

as ammonium ion in gamma-

stretching vibration. The ba

structure. The bending vibrat

at 1385 cm-1 is assigned to C

stretching. The presence of c

molecule exists in zwitter ioabsorption peaks/bands are sh

the dopants are added into the

Figure 7: FTIR spectru


(FTIR) spectroscopic studies

olecular structure of compounds can be i

igher-energy near-IR, approximately 140

ic vibrations. The mid-infrared, approximat

fundamental vibrations and associated ro

R spectra of the samples are shown in t

nds of infrared spectra were given in accor

he broad envelope in the higher wavenum

o hydrogen interaction with other atoms suc

retching. The bands observed at 501, 606

ps while the peaks absorbed at 1491 and 556xyl group is present as carboxylate ion and

glycine. The peak observed at 1040 cm-1 is

d at 606 cm-1 is due to the wagging

ion of CH group appears at 927 cm -1 in the

2 twisting vibration. The peak around 2885

rboxylate and ammonium ion clearly indica

nic form in gamma-glycine crystal. It isifted slightly and some bands are narrowed

lattice of gamma-glycine crystals.

m of 1 mole% of L-alanine doped gamma-gl

hp; ISSN: 2454-5422

entified using the

0 – 4000 cm−1 can

ely 4000 – 400 cm−1

tational-vibrational

he figures 7. The

ance with the data

er region between

as N – H stretching

and 683 cm-1 are

cm-1 are attributed amino group exists

assigned to C-C-N

vibration of COO-

pectrum. The peak

corresponds to CH

tes that the glycine

observed that the or broadened when

ycine sample



2016; IJC

Table 3. Values of w

Sam

Pure Gamma gl

GG +L-alanine

GG +L-alanine

GG +L-alanine

Determination of transmitt

index

Optical transmittance and tran

are important for single cryst

cut and polished and the speci

using a spectrophotometer in

spectra of the samples are p

evident that the grown crysthave UV lower cut-off wave

suggests that the crystals are

gap values are given in the ta

Figure 9: Transmittanc


rk hardening coefficient (n) for the samples

gamma-glycine

le Work hardeningcoefficient(n)

ycine(GG) 5.175

(1mole%) 5.083

(2mole%) 4.324

(3mole%) 3.914

nce, optical band gap, extinction coeffici

sparency cut-off wavelength and other linea

ls mainly used in optical applications. The

men 1.5 mm thick was subjected to transmis

the spectral region of 200 – 1100 nm. The rec

esented in the figures 9. From the transm

ls of undoped, and L-alanine doped gamlength and the transparency in the entire vi

suitable for second harmonic generation. T

le 4.

spectrum of gamma-glycine crystal doped

of L-alanine

hp; ISSN: 2454-5422

of L-alanine

nt and refractive

optical parameters

rown crystals were

sion measurements

rded transmittance

ittance spectra it is

a-glycine crystals sible region and it

he calculated band

ith 1 mole%



2016; IJC

Table.4.Band g

Undo

Gam

1 mol

Gam

3 mol

Conclusion

Pure gamma glycine and L-

studies were carried out. Sin

grown by slow evaporation

structure of the grown crystal

mechanical property of the

noticed that there is an incre

alanine. The dielectric propert

Acknowledgement

The authors thank the staff

microhardness data UVvisibl

by Crecent Engineering Colle

References

T.P. Srinivasan, R. Indirajith,

J. Zaccaro, J. Matic, A.S. My

K. Allen, R.J. Davey, E. Ferr

C.S. Towler, R.J. Davey, R.

T. Balakrishnan, R. Ramesh


ap values for Undoped and doped gamma-gl

Sample Band gap (eV)

ed gamma-glycine

a-glycine +

% of L-alanine

a-glycine +

% of L-alanine

5.62

5.12

4.95

lanine doped gamma glycine were synthes

gle crystals of un doped and L-alanine do

technique. Single crystal XRD study rev

s. The band gap of both the samples of this

grown crystals was studied by micro hard

ase in hardness when gamma glycine cryst

y also effectively studied.

embers of St.Joseph’s college, Trichy for

spectral and FTIR data. The supports exten

ge, Chennai

R. Gopalakirhnan, J. Crystal Growth 318 (2

rson, B.A. Garetz, Cryst. Growth Des.1 (20

ri, C. Towler, G.J. Tiddy, Cryst.Growth Des.

. Lancaster, C.J. Price, J. Am. Chem.Soc. 12

abu, K. Ramamurthi, Spectrochim. Acta Par

hp; ISSN: 2454-5422

ycine

ized and solubility

ed gamma-glycine

als the hexagonal

work is found. The

ness test and it is

al is doped with l-

helping us to take

ded in the research

11) 762

1) 5

. 2 (2002) 523

6 (2004) 13347

t A69 (2008)114



2016; IJC

B. Narayana Moolya, A. JaGrowth 280 (2005) 581

J. Uma, V. Rajendran, Optik 1

Sd. Zulifiqar Ali Ahamed,Raju, Arab.J. Chem. (2013) 6

M. Esthaku Peter, P. Ramasa

S.Govinda, K.V.Rao, Phys. S

B.Tareev, Physics of dielectri


yarama, M.R. Sureshkumar, S.M. Dharma

25 (2014) 816

.R. Dillip , P. Raghavaiah , K. Mallikarjun, 429

y Spectrochimica Acta Part A 75 (2010) 14

atus Solidi 27 (1975) 639

materials, Mir Publishers, Moscow (1979)

hp; ISSN: 2454-5422

rakash, J. Crystal

a, B. Deva Prasad

17




Investigation on the nucleation kinetics of urea doped Bis glycine picrate

N.Balasundari1, P.Selvarajan2, S.Lincy Ponmani3 and D.JencylineNavarani3

1Depatment of Physics, Sri KGS College of Arts and Science, Srivaikundam, India.2Department of Physics, Aditanar College of Arts and Science, Tiruchendur, India.3

Department of Physics, Sarah Tucker College, Tirunelveli, India.*Corresponding Author Email Id: [email protected]

Abstract

The present communication deals with the nucleation kinetics of urea doped Bis glycine

picrate (BGP).Induction period and interfacial energy have been determined for the aqueous

solution growth of urea doped BGP. It is observed that the induction period decreases asthe

supersaturation ratio increases and hence the nucleation rateincreases. The solubility of ureadoped BGP crystal has been estimated at different temperatures. It is observed that, BGP has

apositive temperature coefficient of solubility. Nucleation parameters such as radius of the

critical nucleus, number of molecules in the criticalnucleus and critical free energy change

have also been investigated.

Keywords: Nucleation kinetics; Induction period; Interfacial energy; solubility; BGP; doping

Introduction

Crystals of amino acid family have been grown and studiedby several researchers for their

excellent nonlinear optical (NLO) properties. The study ofamino acid crystallizes with other

organic and inorganic molecules, which presents a high non-linear opticalcoefficient has

gained much attention in the last few years because of the possibility of using them in

technological devices .Picric acid forms stablepicrates with various organic molecules like

glycine through π bonding orionic bonding. BisGlycine picrate(BGP)is an organic nonlinear

optical material that belongs to monoclinic crystalsystem and the lattice parameters are a =



2016; IJC

14.968 Å, b = 6.722 Å, c =

growth rate and the characteri

the present study, the nuclea

andcritical free energy ch

determined induction period f

Material synthesis and puri

The BGP was synthesized by

acid in the molar ratio of 2:

thoroughly dissolved in doub

magneticstirrer to yield a hountil the synthesized salt of p

of 0.5, 1 and 1.5 mole %were

Bisglycine picrate salt. The p

the recrystallization process.

Experimental procedure

The solution growth methodcrystals with well faceted mo

for the success of the soluti

aqueous solution by gravim

dissolving the solute in w

maintained at 30 °C (accurac

stirrer.

It isdone to have uniform

solution. After attaining satu

gravimetrically .The same pr

for undoped (pure) and urea

50ºC are presented in the figu


5.165 Å and β= 93.65º .Influence of urea

stics of BGP have been reported in our earli

tionparameters such as interfacial energy, v

nge were evaluated numerically using

or urea doped BGP.

ication

reacting the aqueous solutionsof high purit

1with double distilled water as the solvent.

le distilledwater and stirred well using a tem

mogeneous mixture of solution. Then the sure Bisglycine picrate was obtained. Calcula

added to the solution of Bisglycine picrate t

urity of the synthesized salts was further im

is widely used and best suited for growingrphology. Solubility measurements arean ess

n growth technique. Solubilitystudies wer

tric method. The solubility of pure BGP

ter. The solution was kept in a consta

y±0.01 °C) andcontinuously stirred using a

temperature and concentration throughoutt

ation, theequilibrium concentration of the s

cess was repeated for the urea doped BGP.

oped BGP salts at various temperatures ran

re 1.

hp; ISSN: 2454-5422

n the morphology,

er investigation .In

olume free energy

theexperimentally

glycine and picric

he reactants were

perature controlled

olution was heated ted amount of urea

obtain urea-doped

roved by repeating

goodquality single ential pre-requisite

carried out in an

as determined by

ttemperature path

otorized magnetic

he volume of the

olute was analyzed

olubility diagrams

ging from 30 ºC to



2016; IJC

15

20

25

30

35

40

45

50

55

60

65

70

75

S o l u b i l i t y ( g / 1 0 0 m l )

Figure 1: Solubili

The saturated solution of pure

the nucleation experiments.T

supersaturations by employ

saturatedsolution of BGP in

inaccordance with pre deter

placed in the constant tempe

degrees above the saturate

undissolved. The bath temper

as the solution reached 303

was observed. The total ti

nucleus of detectable size w

growth of the critical nucleu

time needed between theatta

detectable size.Hence this can

of thenucleus was seen at

calculatingthe induction peri

same process was repeated fo

function of supersaturation

supersaturation increases. Th

interfacial tensionvalues.


30 35 40 45 50 55

Temperature(oC)

Pure BGP salt

BGP + 0.5 mole% of urea

BGP + 1 mole% of urea


ty diagram for pure and urea doped BGP

and urea doped BGP were prepared using th

he induction period was measured experim

ing the isothermal method . In this

an aqueous solution of 1.1 supersaturation

ined solubility at 303 K. The prepared sat

ature water bath. The temperature of the ba

temperature to dissolve the excess sol

ature was lowered to 303K and a stop clock

, when the nucleation formedinside the solu

e elapsed between supersaturation and th

as taken as theinduction period (τ). The ti

s to adetectable size was negligibly small,

inment of supersaturated and the appearan

be taken as induction period. The appearan

the bottom of the container. This process

ds for different supersaturation ratios (1.1

r the urea doped BGPand the obtained resul

isshown in Fig. 2. The induction period

e measured induction period values were u

hp; ISSN: 2454-5422

crystals

solubility data for

entally at different

ethod, 50 ml of

ratio was prepared

urated solutionwas

th wasraised a few

ute that remained

was started as soon

tion a bright glitter

e appearance of a

e required for the

compared with the

e of a nucleus of

e of the first speck

was repeated for

3, 1.16, 1.2 ) .The

ts were plotted as a

decreased as the

sed to estimate the



2016; IJC

Figure 2.Plot of

Nucleation kinetics

The classical nucleation theor

given as ,

∆

where_Gv is the energy chan

radius of the nucleus.The firs

the second term represents t

phase and the surroundingmo

formation of a small cluste

nucleation from the saturated

∆

where∆Gv is the volume free

and k is the Bolzmann’s cocondition

d( ∆ Gv)/dr = 0. Hence, the

nucleation can be expressed a

∗ =

Here k is the Boltzmann’s c

ratio

150

200

250

300

350

400

450

500

550

600

I n d

u

c t i o n

p

e r i o

d

s e c


induction period ( ) vsSupersaturation r

y states that the energy requiredto form the

= ∆ +4 (1)

ge per unit volume, ‘ ’ is the interfacialte

t term in Eq. (1) represents the formation o

e differences in the chemicalpotential bet

ther liquor. Fluctuation in the supersaturated

of molecules known as embryos.The dri

solution isgiven as,

(2)

energy change, V is the specific volumeof t

stant.In the critical state, the free energy f

critical radius and the Gibbscritical free

s;

(3)

nstant, T is the absolute temperature, S is

∆ ∗ = ( ) (4)

1.10 1.12 1.14 1.16 1.18 1.20

pure BGP


BGP 1 mole% of urea

BGP 1.5 mole% of urea

Supersaturation ratio (S)

hp; ISSN: 2454-5422

tio (S)

uclei (spherical) is

sion and ‘r’ is the

f a newsurface and

een the crystalline

solution causesthe

ving force for the

he solute molecule

rmation obeys the

energy barrier for

the supersaturation



2016; IJC

The rate of nucleation (i.e., th

expressed by an Arrhenius-ty

where A is the pre-exponenti(approximately A= 1 x 1030 f

The number of molecules in t

According to the classical the

induction period (τ) is related

ln

where B is a constant, R is th

theinduction period at tem

S)2againstln(τ)(fig 3)from Eq

value of ln B. The slope is giv

m

20

5.0

5.2

5.4

5.6

5.8

6.0

6.2

6.4

l n


e number of nuclei formed per unit time per

e equation

= ( ∆ ∗

)(5)

l factor or solution),

e critical nucleus is expressed by

= ∗

(6)

ory of homogenous nucleation(14), the

to the interfacial tension (σ) as follows

-lnB +( )

(7)

k =

universal gasconstant and NA is the Avoga

perature T and supersaturation ratio S.

. (6) is a straight line andthe intercept on t

enas,

= (8)

40 60 80 100 120

Pure BGP BGP + 0.5 mole% of urea

BGP 1 mole% of urea

BGP 1.5 mole% of urea

1 / (ln S)2

igure.3. Plot of 1/ (ln S)2vsln (τ).

hp; ISSN: 2454-5422

unitvolume) can be

dro’s number and τ

plot of 1/ (ln

e Y-axis gives the



2016; IJC


The solubility of Pure and ur

Fig. 1. From the graph,it is

temperature and it is found t

solubility increases with tem

solubility. Fig.2 shows the

constanttemperature. The val

supersaturated concentration

theinduction period increases

induction period againstsuper

have a controlled nucleation r

Table 1: Summary of cri

Sample

Pure BGP

BGP + 0.5mole% of urea

BGP + 1mole% of

urea

BGP + 1.5mole% of urea

1.11.11.11.

1.11.11.11.

1.11.1

1.11.

1.11.11.11.

Theinterfacial tension has bee

BGP and various mole perce


a doped BGP crystals as a function of temp

bserved that solubility of the samples in w

o be more for urea doped BGP than the p

perature, the samples have positive temper

induction period as a function of super

e of τ decreases and hence the nucleation

of the aqueous solution isincreased. It c

with increase in additive concentration of

saturation gives an idea of optimized inducti

ate to grow good quality singlecrystals.

ical nucleation parameters for pure and u

samples

∆G x 10-

20

(joules )

J x 10nuclei/s /volum

e

r x 10-

m

36

36

3

6

36

0.4290.2610.1770.117

0.4250.2580.1750.116

0.3080.187

0.1270.084

0.1790.1090.0740.049

3.6085.3786.5677.573

3.6435.4176.5987.591

4.8106.412

7.3958.186

6.5357.7188.3878.901

12.69.828.086.58

12.59.768.046.54

11.28.72

7.185.85

9.327.275.984.87

21.410.15.663.05

21.110.05.623.02

15.47.27

4.062.1

8.974.252.371.28

n calculated at constant temperature(room te

tage of urea doped TGS crystals from the

hp; ISSN: 2454-5422

erature is shown in

ater increases with

re BGP. Since the

ture coefficient of

saturation ratio at

ateincreases as the

n be noticed that

urea. The study of

n period in orderto

rea doped BGP

70

25

5

1

8

mperature) for pure

raph (fig.3) drawn



2016; IJC

between ln τ and 1/ (lnS)2.

6.661 mJ/m2 .Using the interf

critical nucleus(r*), Gibbsfre

critical nucleushave been calc

summarized in the Table 1.I

increase ofsupersaturation an

supersaturation. That means t

lead to spurious nucleation. A

the increaseof supersaturation

is increased.

ConclusionThe fundamental nucleation

determined on the basisof the

have been experimentallyde

supersaturation conditions us

nucleation parameters such as

nucleus andthe number of

interfacial tension values.

Acknowlogements

The authors are thankful to

Regional Research Laborato

Joseph College (Trichy), M.K

References

X. Liu, Z. Wang, G. Zhang,(2007) 130-132.

Y. Zhang, H. Li, B. Xi, Y. C

J. Hernandez-Paredes, D. GlDuarte-Moller, J.Mol. Struct.

D. Eimerl, S. Velsko, L. Dav

Sachinkumar, Hotam sing ch

860


he calculated values of interfacial tension

acial tension value, the nucleation paramete

energy change(∆G*) and number of mo

ulated for the controlled nucleationcondition

t is notedfrom Table 1that the value of r*

consequently the nucleation rate (J) increas

he number of critical nucleiformed will be in

lso itwas observed that the values of n and

and also these parameters decrease when c

parameters of pure and urea doped B

classical nucleation theory. The solubility a

ermined. The interfacial tension was calc

ing the experimentally determinedinduction

volumefree energy, Gibbs critical free ener

molecules in the critical nucleus were d

the supported work from various resear

y (Trivandrum), Crescent Engineering Col

. University (Madurai) and Cochin Universit

. Wang, A. Duan, Z. Sun, L. Zhu, D. Xu, J

e, J. Zheng, Mater. Chem.Phys. 108 (2008)

ossman-Mitnik, H.E. Esparza-Ponce, M.E.875 (2007) 295-301.

is, F. Wang,G. Loiacona, G. Kennedy, 25 (1

oudhari, Chandrabhanseniya.Chem.Pharm.R

hp; ISSN: 2454-5422

ary from 6.473 to

rssuch as radius of

ecules (n) in the

and the results are

decreases with the

es with increase of

creased which will

G* decreases with

ncentration of urea

GP crystals were

d induction period

ulated at different

period values. The

y, radius of critical

terminedusing the

h centers such as

lege (Chennai), St

y (Cochin).

. Cryst.Growth 308

192-195.

Alvarez-Ramos, A.

89) 179 – 193.

es.,2011,3[4]. 854-



2016; IJC

ChandrabhanseniyaSumit si330-336

S. Yamaguchi, M. Goto, H.1028.

T. Kai, M. Goto, K. Furuhata,

T. Uma Devi, N. Lawrence(2008) 340.

N.Balasundari, P.Selvarajan,Science and Tech. 2011, 3(12

K.Byrappa, T.Ohachi, “Cr(Springer), Norwich, New Yo

N.P. Zaitseva, L.N. Rashkovi

A.E. Nielsen, S. Sarig, J. Crys

M. volmer, A. weber, phys. c


ng trivedia, Santoshkumarverma JChem.Ph

Takayanagi, H. Ogura, Bull. Chem. Soc. J

H. Takayanagi, Anal. Sci. 10 (1994) 359.

, R. Ramesh Babu, K. Ramamurthi, Spect

S.Lincy Mary Ponmani and D.Jencylin R): 64-67

ystal Growth Technology”, William Ark(2003)

ch, S.V. Bogatyreva, J. Cryst. Growth 148 (1

t. Growth 8 (1971) 1.

hem. 119(1926)27

hp; ISSN: 2454-5422

arm.Res.,2011,3(6)

n.61 (1988) 1026 –

rochim.Acta A 71

ecent Research in

ndrew Publishing

995) 276.



2016; IJ

Volume: 2; Iss

Investigation on structural, s

opti

S.Lincy Mary Pon

1Department of Physics, Sarah Tucke2Department of Physics, Aditanar Co3Department of Physics, Sri KGS col

*Corresponding Author Email Id *li

Over recent years, amino acid

by several researchers for their

rare amino acid racemates cry

Single crystal of DL-Alanin

evaporation technique. Trans

obtained. Formation of the n

spectra. The grown crystals hathe crystalline nature.

Single crystal X-ray diffracto

the crystal structure. The cell

XRD. DLAO belongs to mo

A°,b=6.583(3) A°, c=12.460(4

is 851.6(6) A3.The functional

SR. 2(3): http://www.drbgrpublications.in/ijcsr.

ue: 3 [Special Issue]; March-2016; pp 411-41

pectroscopic and mechanical properties of

al DL-alanine oxalate single crystals

ani1*, P.Selvarajan2, D.Jencylin1 and N.Bal

r College, Tirunelveli, India.

llege of Arts and Science, Tiruchendur, India.

lege of Arts and Science, Srivaikundam, India.

[email protected]

Abstract

family crystals have been subjected to ext

nonlinear optical (NLO) properties. DL-alan

tallizing in a noncentro symmetric space gr

Oxalate (DLAO) has been grown fro

arent colourless crystals upto10 mm x 6

w crystal has been confirmed by single cry

ve been subjected to powder X-ray diffracti

eter was utilized to measure unit cell param

arameters of the grown crystal are identifie

noclinic system with with a lattice para

) A° and α= γ=90° and β=113.58(2)° and vo

roups are confirmed in vibrational analysis.

php; ISSN: 2454-5422

9. ISSN: 2454-5422

organic non-linear

sundari3

nsive investigations

ine is one among the

oup. A new Organic

solution by slow

mm x 3 mm were

stal XRD and FTIR

n studies to identify

eters and to confirm

from single crystal

eters a=11.329(3)

lume of the unit cell

Mechanical strength



2016; IJ

of the grown material is tested

applied load is increased.

Keywords : Aminoacid; DLCrystal structure; Microhardne

Introduction

The organic materials play

modulation, optical parametric

Over recent years, amino acid

by several researchers for th

complexes are the organic or

their ability in ease of pro

understanding of the properti

requires more attention

DL-Alanine is one among the

space group. The structure of

structure is stabilized by a netcarboxyl group is present as a

literature survey, it is noticed

complexes.

Experimental studies of DL

Growth procedure

DL-alanine oxalate (DLAO) w

by slow solvent evaporation t

(AR grade) were mixed with

alanine oxalate. A saturated s

filter paper. The filtered soluti

filter paper so that the rate of

crystals were obtained after 3

distilled water in order to impr


by Hardness studies. The value of hardnes

-alanine; Crystal growth; Single crystal; X-rass

n important role in second frequency mi

oscillation, optical bi-stability, harmonic g

family crystals have been subjected to ext

ir nonlinear optical (NLO) properties. A

semi-organic materials that have attracted g

cessing in the assembly of optical devi

s of amino acid crystals, as well as other

are amino acid racemates crystallizing in a

DL-alanine was elucidated by Subha Nand

ork of characteristic head-to-tail hydrogencarboxylate ion and amino group as ammo

that a limited number of papers are avail

O crystal

as grown from the aqueous solution using d

chnique. An equimolar amount of DL-ala

sufficiently large amount of water at 50 o

lution of 150 ml was taken and the solutio

on was taken in a beaker, which was tightly

evaporation could be minimized. Good tran

weeks and the obtained material were re-

ove their purity. The recrystallized crystalsw

php; ISSN: 2454-5422

increases when the

y Diffraction;

xing, electro-optical

neration (SHG) etc.

nsive investigations

ino acids and their

reat attention due to

ces. The complete

rganic crystals, still

on-centrosymmetric

ini et al. The crystal

ond sequences. The nium ion. From the

able on DL-alanine

ouble distilled water

nine and oxalic acid

to synthesize DL-

n was filtered using

closed with a thick

sparent, small single

crystallized twice in

ere used as the seed



2016; IJ

to obtain big sized crystals

displayed in the figure 1.

Solubility measurementTo grow bulk crystals from s

solvent in which it is moderat

organic solvents like acetone,

of a crystal depends on the am

by the solubility of the materi

was determined by addinga

temperature till it was complsolubility ofDL-alanine oxalat

50°C and 55° C. The temperat

figure 2. From the result, it is

data can be used for preparin

studies.

Fig 2: Variation


ofDL-alanine oxalate. The harvested cry

Fig 1: Photograph of DLAO crystals

lution by slow evaporation technique, it is

ly soluble. It is found that DLAO sample is

ethanol and ethanol and is reasonably solub

unt of material available in the solution, whi

l in that solvent. The solubility of DL-alani

known quantity of solute in solvent mai

letely dissolved. Using this technique, thewas evaluated at various temperatures viz.

ure dependence of solubility of DL-alanine

observed that the solubility increases with

g the saturated solution and for carrying o

of solubility with temperature for DLAO

30 35 40 45 50 55

40

60

80

100

120

140

160

S o l u b i l i t y ( g / 1 0 0 m l )

Temperature (oC)

php; ISSN: 2454-5422

tals of DLAO are

desirable to select a

sparingly soluble in

le in water. The size

ch in turn is decided

ne oxalate in water

ntained at constant

e magnitude of the . 30°C, 40°C, 45°C,

oxalate is shown in

temperature. These

t nucleation kinetic

rystal



2016; IJ


X-ray diffraction studies

The cell parameters of the

diffractometer (Bruker-Nonius

monoclinic system with the ce

α= γ=90° and β=113.58(2)° a

In order to identify the diffr

subjected to powder X-ray didiffractometer. The XRD patt

were indexed using the INDE

and Steeple . The values of 2θ,

Fig 3: P

10 15

-5000

0

5000

10000

15000

20000

25000

30000

35000

( 0 1 1 )

c o u n t s


grown crystal were obtained using si

MACH3/CAD4).It is observed that the DL

ll parameters a=11.329(3)Å, b=6.583(3) Å,

d volume of the unit cell is 851.6(6)Å 3.

action planes of the crystal of DLAO, the

fraction studies with a high resolution PANrn is shown in figure 3.The reflections of

ING software package by following the

hkl values and d-values etc. are presented i

wder XRD pattern of DLAO crystal

20 25 30 35 40 45 50 55 60 65

( 3 0 3 )

( - 1 2 2 )

( 3 1 0 )

( - 2 1 3 )

( 1 1 2 )

( - 2 1 2 )

( - 1 0 3 )

( 1 0 2 )

2θ (degrees)

php; ISSN: 2454-5422

ngle crystal X-ray

O crystal belongs to

=12.460(4) Å ° and

grown sample was

alytical X’pert PRO owder XRD pattern

rocedure of Lipson

the table 1.

70



2016; IJ

Table 1: The valu

2θ

15.55

20.36

21.39

22.50

24.57

26.51

29.4530.72

41.55

FTIR analysis

The vibrational analysis of th

spectrum is recorded in the ranIn FTIR spectrum, the broad in

NH3+ vibrations. This confir

bonded with oxalic acid throu

structureofthiscompoundistake1correspond toNHstretchingvib

that at1929 cm-1 indicates C

1600cm-1

indicate the presenassigned to the peak at 146

stretching of the COO- group.

1147 cm_1 and 918 cm_1 are

lower frequency range, the sh

assigned vibrational frequenci


es of 2θ, hkl values and d-values for DLA

d(std) Hkl

5.7032 011

4.3256 102

4.1506 -103

3.9571 -212

3.6150 112

3.3575 -213

3.0634 3102.9018 -122

2.1656 303

e grown crystal was done using FTIR spec

ge of400 – 4500 cm−1 . The recorded spectrutense peak is observed between 3200 – 2800

s that the amine group presented in the

h hydrogen bonding. ToanalyzetheFTIRspe

nintoaccount.The broad bandsaround3039

rations.The peak observed at 2948 cm-1 sho

stretching.The C=O stretching band obs

e of carboxylic acid group. The CH3 bendicm-1. The peak at 1407 cm-1 was assig

TheC-O stretching wasassignedto1006 cm-1

assigned to asymmetrical coupled vibratio

rp peak observed at 520 cm-1 is assigned t

es are given in the table 2.

php; ISSN: 2454-5422

crystal

trometer. The FTIR

mis shown in Fig. 4. m−1, which is due to

L-alanine molecule

ctrum,the molecular

cm-1and 3157 cm-

sCH stretching and

rved at 1724 and

ng deformation was ned to symmetrical

.The peaks between

s of alanine. In the

COO-rocking. The



2016; IJ

Table 2: FTI

Wavenumb

5291

100114

140146

151

160172192294303315

Fig 4: F

Mechanical Properties

The mechanical strength of D

by means of Leitz Vickers m

temperature with a constant i

varying the load from 25 to 1

graph (Fig.5) is plotted betw

observed from the graph that

1

T r a n s m i t t a n c e %


frequency assignment of pure DLAO cry

r in cm- Band assignments

COO-rockingAsymmetric coupled vibrationsalanine

6 C-O stretching7 Asymmetriccoupled vibrations

alanine7 COO- symmetrical stretching0 CH3 bending deformation,

O – H symmetric stretching&C – O symmetric stretching

7 NH3

+ symmetric deformation &NH2 in-plane deformation

0 C=O stretching4 C=O stretching6 C – N stretching8 C – H stretching9 N – H stretching7 N – H stretching

IR spectrum for the grown crystal DLAO

AO crystal was checked by carrying out m

icrohardness tester. The static indentations

ndentation time of 10 s. The indentation

00 g. Vickers microhardness values have b

en Vickers hardness number (VHN) and

the hardness increases as the load increa

4500 4000 3500 3000 2500 2000 1500 1000 500

20

30

40

50

60

70

80

90

00

Wavenumber (cm-1)

php; ISSN: 2454-5422

stal

of

of

icrohardness studies

were made at room

arks were made by

en calculated and a

pplied load P. It is

es. The experiment



2016; IJ

shows that the crystal of DLA

not shown in figure 5. The for

g is due to the release of th

hardening coefficient ‘n’ of th

of the log P versus log d plot (

crystal is a soft material and th

Fig 5:

Fig 6

Second Harmonic Generatio

A high density Nd:YAG laser

the powdered sample of the D

laser beam having the green e

l o g P


breaks when a load more than 100 g is app

ation of cracks on the surface of the crystal

internal stresses generated locally by in

DLAO crystalis 3.67 and it has been deter

ig. 6). Since the work hardening coefficient i

hardness is low.

lot of Hv versus load for DLAO crystal

: Variation of log P with log d for DLAO crys

(SHG) studies

(λ=1064 nm) with a pulse duration of 6 ns

LAO. The SHG emission was confirmed fr

ission (λ=532 nm). SHG efficiency of the g

20 30 40 50 60 70 80 90 100 110

60

70

80

90

100

110

120

H v ( K

g / m m

2 )

Load (g)

1.42 1.44 1.46 1.48 1.50 1.52 1.54 1.56 1.58 1.60 1.62

1.3

1.4

1.5

1.6

1.7

1.8

1.9

2.0

log d

php; ISSN: 2454-5422

lied and this result is

beyond the load 100

entation. The work

ined from the slope

s more than 1.6, this

al

was passed through

m the output of the

rown DLAO crystal



2016; IJ

is 1.13 times that of the stan

frequency conversion.

Conclusion

Solubility studies of DL-alan

temperatures and the single c

slow evaporation method. XR

The XRD studies show that th

The presence of functional gr

mechanical strength has been

has been calculated.

Acknowledgement

The authors are thankful to the

technology, Papanamcode,

Joseph’s College (Autonom

characterization.

References

J. Badan, R. Hierle, A. Periga

(Ed.), Am Chem. Soc., Washin

M. Kitazawa, R. Higuchi, M.

L. Misoguti, A.T. Varela, F. D

Opt. Mater. 6 (1994) 147

W.S. Wang, M. D Aggarwal,

Cryst.Growth 198/199 (1999)

M. SubhaNandhini, RV. Kris

(2002) 307

R.Becker and W.Doring, Ann.

D.Turnbull and J.C. Fisher, J.


dard KDP crystal. Thus this crystal is a p

ine oxalate (DLAO) sample has been car

ystal of this sample has been grown from

studies reveal that thestructure of DLAO cr

e crystalline perfection of the grown crystal

oups in the sample has been confirmed by

hecked for the sample and the work harden

authorities of National Institute for Interdic

rivandrum, Madurai Kamaraj University,

us), Triuchirappalli for providing instru

d, J. Zyss, Am. Chem. Soc. Symp. Ser. 23

gton, 1993

akahashi, Appl. Phys. Lett. 64 (1994) 2477

Nunes, V.S. Bagnato, F.E.A. Melo, J. Men

J. Choi, T. Gebre, A.D. Shield, B.G. Pen

78

hnakumar, K. Sivakumar, S.Natarajan, Ac

Physik, 24 (1935) 719

hem.Phys., 17 (1949) 71

php; ISSN: 2454-5422

otential material for

ied out at different

aqueous solution by

ystals is monoclinic.

is reasonably good.

FTIR analysis. The

ing coefficient value

iplinary Science and

Madurai, and St.

mental facility for

, in: D.J. Williams

desFilho, S.C, Zilio,

, D.O. Frazier, J.

taCrystalogr., E 58



2016; IJ

H. Lipson, H.Steeple, “Inte

Macmillan, NewYork (1970)

Ivan Kityk, MalgorzataMakow

M. Arivanandhana, K. Sankara

N.TheresitaShanthi, P.Selvaraj


rpretation of X-ray powder Diffraction

ska-Janusik, Mol. Cryst. Liq. Cryst. 353 (20

narayanan, P. Ramasamy, J. Crystal Growth

an, C.K. Mahadevan, Curr. Appl. Physics, 9

php; ISSN: 2454-5422

Patterns”, FifthEd,

0) 513

31 (2008) 1493

(2009) 1155



2016; IJ

Volume: 2; Issue: 3 [

Synthesis and characteriza

S.G.Pushpalath

1Department of Physics, Sar2Department of Physics, Ari3Department of Physics, Adi

A semiorganic non – linear opti

using water as a solvent. The

Fourier transform infrared (F

present in the grown crysta

spectroscopy. The crystal syst

Ray diffraction analysis. And t

Key words: Semi-organic, non

Introduction

Recent research is focused on

threshold good mechanical an

growth and characterization o

crystals are grown by slow

obtained is subjected to variou


Special Issue]; March-2016; pp 420-427. IS

ion of semi organic nonlinear optical mat

Tartrate Tetra hydrate

Gracelin1, C.Krishnan2 and P.Selvarajan3

ah Tucker College, Tirunelveli, India.

ngnar Anna College, Aralvaimozhi, India.

itanar College of Ats and Science, Tiruchendur, India.

Abstract

al crystal of ATT have been grown by slow

structural and vibrational properties of the c

IR) studies confirm the vibrations of vario

l. The optical transmittance is studied t

em and lattice parameters were determined

he solubility of the crystal is determined.

-linear, slow evaporation, X-Ray diffraction.

semi organic materials due to their large lin

d thermal stability .The present investigati

f crystal of ATT(ATT) a new semi organic

evaporation technique at room temperatur

characterization studies such as XRD,FT-I

php; ISSN: 2454-5422

N: 2454-5422

rial: Ammonium

evaporation technic

rystals were studied.

s functional groups

hrough UV visible

from the crystal X-

earity, high damage

n is focused on the

material .The ATT

e.The ATT crystals

and UV-VIS.



2016; IJ

Crystal Growth

The calculated amount of A

continuous stirring to get a husing watt man filter paper t

undisturbed. The filtered soluti

optically transparent crystals w

Characterization Studies

Single crystal X-ray diffracti

hydrate was carried out using

determine the unit cell parame

ELICO SL 218 double beam

the wavelength range of 200-

infrared region 4500 - 400 cm

8400S) using a KBr pellet tec

crystal was performed by th

YAGlaser (Model:YG501C,

this study on the (001) plane o


Single Crystal X-ray diffrac

Single crystal X-ray diffracti

hydrate was carried out using

determine the unit cell paramethat the ATT crystal is monocli

8.9901(Å),b = 15.5424(Å),c =

FTIR Spectral analysis

The infrared spectroscopy i

sample.When infrared radiatio

absorbed at a specific wavel


T salt was first dissolved in 100 ml of

omogeneous mixture. The saturated solutiremove the suspended impurities. Then t

on was allowed to evaporate slowly at room

ere harvested in a growth period of three we

n analysis of the grown crystal of Ammo

Enraf-Nonius CAD-4 diffractometer using

ters and space group.Optical studies have be

V-visible spectrophotometer which records

1100nm.FTIR absorption spectrum of the-1

was recorded on a spectrometer (Model:

hnique. Second Harmonic Generation (SH

e powder technique of Kurtz and Perry

=1064 nm). Smooth, flat surface was selec

the crystal.

ion analysis

n analysis of the grown crystal of Ammo

Enraf-Nonius CAD-4 diffractometer using

ters and space group. The analysis of the cnic in structure with space group P1 and latti

6.2512(Å) α=γ=90 , β=101.507

effectively used to identify the functi

n interacts with a sample, a portion of the

ngths and the Fourier Transform Infrare

php; ISSN: 2454-5422

deionised water by

n was then filtered he solution was left

temperature. Good,

ks.

nium Tartrate Tetra

Mo Kα

radiation to

en carried out using

optical spectrum in

rown crystal in the

HIMADZU- FTIR-

) test for the grown

using a pulsed Nd:

ted and subjected to

nium Tartrate Tetra

Mo Kα radiation to

llected data reveals ce parameter are a =

nal groups of the

incident radiation is

(FTIR) absroption



2016; IJ

spectrum is a characteristic o

spectrum of the grown cry

spectrometer (Model: SHIMA

FTIR spectrum of cr

spectroscopic study was carri

aspects of crystals. The assi

accordance with the data r

wavenumber region between

atoms such as N – H stretchin

539cm-1 are attributed to carbo

to NH3 group. Thus, the carbo

ammonium ion in . The

vibration.The presence of ca

molecule exists in zwitter ion

FTIR analysis to analyze the p

assignments of crystal ar

Fig 1 FTIR Graph

Fig(1) FTIR Spectra Of Am

4000 3500 3000 2500

40

50

60

70

80

90

100

( T )

waven

3 7 8 8 . 8

9

3 4 5 3 . 0

4

3 2 6 4 . 3

2

2 9 1 5 . 6

8

2 7 4 1 . 3

5 2 3 7 8 . 3

2

FTI0 2 4


functional groups of molecules in a samp

tal in the infrared region 4500 - 400 cm-1

DZU- FTIR-8400S) using a KBr pellet tech

stal is presented in the figure 1. The

d out with a view of obtaining an insigh

nments for absorption bands of infrared s

ported in the literature.The broad enve

238 and 2700cm-1 was due to hydrogen in

of NH2 and C – H of CH2 stretching. Th

xylate groups while the peaks absorbed at 61

yl group is present as carboxylate ion and a

peaks observed at 827 cm-1 are assigned

rboxylate and ammonium ion clearly indi

ic form in crystal. The grown crystal

resence of functional groups. The observed

given.

onium Tartrate Tetrahydrate.

2000 1500 1000 500

umber (cm-1)

.

2 2 8 3 . 9

6

.

2 0 4 2 . 4

7

1 9 0 8 . 1

2

1 7 4 8 . 2

0

1 5 9 9 . 4

6

1 5 3 2 . 2

9

1 1 5 6 . 4

6 9 4 2 . 1 5

9 1 4 . 9

7

6 8 6 . 2

7

6 8 10

0

2

4

6

8

10

php; ISSN: 2454-5422

le. FTIR absorption

was recorded on a

nique. The recorded

present vibrational

t into the structural

ectra were given in

lope in the higher

teraction with other

bands observed at

2 cm-1 are attributed

mino group exists as

to C-C-N stretching

cates that the ATT

s were subjected to

requencies and their



2016; IJ

Optical properties

To determine the transparency

was recorded and is shown infor this study. The cut- off w

shows that the crystal was opt

and it is a feature that promot

sufficient transmission in the

determined using following fo

the thickness of the crystal.

crystal are important factors fo

crystals in the wavelength ran

T/100.The wave length is incr

fall to zero in the transmitta

transmittance in the entire visi

corresponds to the fundamen

theory of electronic.The band

found to be (4.97) eV.

Fig 2The wave length versus

Fig.2 The graph was drawn

increasing the wavelength also

200 400

40

50

60

70

80

90

100

P e r c e n t a g e o f t r a n s m i t t a n c e


range of the grown ATT crystal, UV-vis tra

Fig.2. Optically clear single crystal of thickavelength of the crystal occurs at 225 nm.

ically transparent in the wavelength range fr

s possible optical applications in NLO dev

isible and IR region. The optical absorptio

rmula α= ((2.303log(1/T)t).where T is the tr

ptical transmittance range and transparen

r optical applications. The recorded transmitt

ge of 200 – 1200 nm are shown fig (3).Tr

eased, transmittance is also increased. At a

ce is observed for ATT sample and the c

ble and near IR region. The sharp fall at 22

al absorption edge, which is essential in

gap of ATT is calculated using the formula

percentage of transmittance

between wave length versus percentage of

increased the percentage of T.

600 800 1000 1200

Wave length (nm)

php; ISSN: 2454-5422

nsmittance spectrum

ness 2mm was used From the figure, it

om 300 to 1100 nm

ices. The crystal has

coefficient (α) was

ansmittance and t is

y cut-off of single

ance spectra of ATT

nsmittance (T) = %

out 225 nm a sharp

rystal has sufficient

5 nm for the sample

onnection with the

Eg =1240/λmax,it is

T. From the graph



2016; IJ

Fig.3 The Wavelength Verse

Fig 3 The absorbance wave le

is increased.

Fig 4 Wave length ve

The graph was plotted betwe

relation is given by Reflect

reflectance is decreased also th

200 400

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

a b s o r b a n c e ( A )

200 400

0.00

0.05

0.10

0.15

0.20

R e f l e c t a n c e ( R )


s the Absorbance

ngth is 249nm.The absorbance is decreased,

rsus Reflectance

en Wave length (λ) andReflection(R) as s

ance(R)=1-(T+A).The Reflectance wavele

e wavelength is increased.

600 800 1000 1200

avelength in nm

600 800 1000 1200

Wave length (nm)

php; ISSN: 2454-5422

also the wave length

hown in fig (4)The

ngth is 249nm.The



2016; IJ

Fig 5 Wave length v

. The dependenc

study the band structure and

also the wave length is increas

Fig 6 Wave length v

The refractive index (n) can b

The plot between wavelength

200 400 6

0.00

0.05

0.10

0.15

0.20

A b s o r p t i o n c o e f f i c i e n t (

W

200 300 400 500 600

1.0

1.2

1.4

1.6

1.8

2.0

2.2

2.4

2.6

2.8

R e f r a c t i v e i n d e x ( n )

Wave length


ersus absorption coefficient

of optical absorption coefficient with the ph

he type of transition of electrons.The abso

d.

ersus refractive index

determined from reflectance data using n=

nd refractive index (n) of ATT crystal is sh

00 800 1000 1200

ave length (nm)

700 800 900 1000

(nm)

php; ISSN: 2454-5422

oton energy helps to

rbance is decreased;

(1+ )/(1 − √ ).

wn in fig (6). From



2016; IJ

the fig (6) it is observed that

refractive index (n) of the ATT

Fig 7 Photon of energy vers

The plot of variation of (αh ν)2

plot and it is used to find out

by the extrapolation of the line

wide bandgap,the grown cryst

Conclusion

Semi organic crystals of ATT

diffraction study shows the cr

confirms the functional grou

reveals that ATT crystals ar

transparency of about 90% wigood optical transparency an

potential candidates for NLO a

Acknowledgements

The authors are grateful to th

Anna College, Nagercoil and

encouragement given to us to

staff members of St. Jose

1 2 3

0

5

10

15

20

25

( a h v ) ^ 2


the refractive index decreases with increas

crystal is 1.57 at 297nm.

us (αhν)2

versus h ν is shown in fig (10).This plot is

the accurate optical band gap value.The ban

ar part and the value is found to be 4.97eV.

l has large transmittance in the visible regio

as grown from slow evaporation technique.

stal belongs to monoclinic crystal system.

s present in the grown crystal. UV-Visi

optically transparent in the entire uv-vi

th a lower cut off wavelength at 225 nm.d reasonably good NLO properties, these

pplications.

e managements of Sarah Tucker College,

Aditanar College of Arts and Science,

carry out the research work. Also the author

h’s College, Trichy, Cochin University,

4 5 6 7

hv

4 . 9

7

php; ISSN: 2454-5422

ing wavelength.The

known as the Tauc’s

gap was evaluated

As a consequence of

.

Single crystal X-ray

he FT-IR spectrum

le spectral analysis

ible range and has

s ATT crystal have materials could be

Tirunelveli, Arignar

iruchendur for the

s are thankful to the

Cochin, Crescent



2016; IJ

Engineering College, Chennai

experimental work.

References

G.Albrecht, R.B.Corey, J.Am.

E.Ramachandran, K.Baskaran

K. Srinivasan, J. Arumugam

Y. Iitaka, Acta Crystallogr. 11

Jan Baran , Henryk Ratajczak ,

T. Balakrishnan, R. Ramesh B

P.Selvarajan , J.Glorium Arul

R.W. Williams J. Molecular S

A. Dawson, D.R. Allan, S.A.

C.R.Pulham, L. Sawyer, Cryst.

Charles J,Pouchert, The Aldric

Company,INC,Milwaukee,Wis

P.Kalsi , Spectroscopy of Orga

J.C.Anderson, Dielectrics, Cha

J.B.Birks, J. Hart, Progress in

B.Helina, P Selvarajanand A S

1K.V. Rao, A. Samakula, J. A

E.M. Onitsch, uber die mikroh

S.K. Kurtz, T.T. Perry, J. Appl


, VIT, Vellore, IIT, Madras, who helped

Chem. Soc.61 (1939) 1087

, S. Natarajan Cryst. Res. Technol. 42(2007)

ptical Materials 30 (2007) 40

(1958) 225

pectrochimica Acta Part A 61 (2005) 1611

bu, K. Ramamurthi Spectrochimica Acta Pa

aj, S.Perumal, J. Crystal Growth 311 (2009)

tructure (Theochem) 685 (2004) 101

elmonte, S.J. Clark, W.I.F. David, P.A.McG

Growth Des. 5 (2005)1415

h library of Infrared Spectra, Third Edn., Ald

consin (1981)

nic Compounds, Wiley Eastern, New Delhi(

pman and Hall, London, (1963)

ielectrics, Heywood, London(1959)

J Lucia Rose, Phys. Scr. 85 (2012) 055803

pl. Phys. 36 (1965) 2031

arte der metalle, Mikroscopia 2 (1947) 131

. Phys. 39 (1968) 3798

php; ISSN: 2454-5422

us to carry out the

73

rt A 69 (2008) 1114

3835

regor, S.Parsons,

rich Chemical

985)



2016; IJ

Volume: 2; Iss

Studies on the Mechanical

1 Department of Physics, Sarah Tuck

2Physics Research Centre, S.T. Hind

Amino acids contain proton d

favorable pH, the natural ami

group and positively charged

nonpolar and aliphatic amino

proteins. It is not chiral and c

minimal side chain of only o

properties of crystals, here an

The dopant sulphamic acid is

Pbca, which is centrosymmcentrosymmetric crystals do n

crystals GSA had been harve

spectral analysis had been ca

harmonic nonlinear optical stu

Keywords: Single crystal X

analysis, TG-DTA, SHG effici



and Thermal Properties of Sulphamic Aci

NLO Single Crystals

A. Effie Cordelia1 and S. Perumal2

r College, Tirunelveli, India.

College, Nagercoil, India.

Abstract

nor carboxylic group and proton acceptor a

o acids exist as zwitterions with a negative

amino group. Among these, Glycine (H

cid. It is also the smallest of 20 amino acids

an fit into hydrophilic and hydrophobic env

e carbon atom. As doping can alter the ph

ttempt was made to dope Glycine crystals

classical inorganic compound which crysta

tric. According to the theoretical cont show SHG. But it was fruitful indeed, as

ted as a result of doping. X-ray diffractio

ried out. Thermal stability, hardness studi

ies of the crystals were reported in this work

RD, Powder XRD, FTIR Spectrum, Vic

ncy, Third harmonic nonlinear optical para

php; ISSN: 2454-5422

8. ISSN: 2454-5422

d Doped Glycine

mino group. Thus at

ly charged carboxyl

N2CH2COOH) is a

commonly found in

ironments due to its

ysical and chemical

ith sulphamic acid.

llizes in space group

ept of SHG, the a novel NLO single

analysis and FTIR

s, second and third

.

er’s microhardness

eters



2016; IJ

Introduction

Nonlinear optical (NLO) cryst

and opto-electronics. In recentNLO materials with improved

Ideal NLO crystals are expe

conversion, wide phase matchi

ease of fabrication and high

crystals have been grown wit

attempt to dope glycine with s

Experimental work

AR grade chemicals glycine a

crystals. To grow single cryst

amount of glycine in doubly d

highly homogeneous mixture

left undisturbed in dust free at

obtained after a period of three

F


als play a major role in the fast developing

decade, major advances have been made inoptical, mechanical characteristics and high

cted to posses large nonlinear figure of

ng angle ,high laser damage threshold, wide

echanical, thermal and chemical stability.

Glycine and sulphamic acid separately bu

lphamic acid.

nd sulphamic acid were purchased so as to

ls GSA, 1mole % of sulphamic acid was a

eionized water and put on magnetic stirrer

f uniform composition. After proper filtrati

osphere. Fine colourless transparent single

weeks.

ig.1 Photograph of the crystal GSA

php; ISSN: 2454-5422

fields like photonics

the development of damage thresholds.

erit for frequency

optical transparency,

Several NLO single

this work is a new

harvest GSA single

ded with calculated

or four hours to get

on, the solution was

crystals BASA were



2016; IJ


Single Crystal XRD analysis

The crystals GSA were analy

Nonius MACH3/CAD4 singl

tabulated as below:

Sample System

GSA Monoclinic

For GSA, the value of = 111.

Powder XRD analysis

Powder XRD patterns of the

advance diffractometer with

powder. The sample was scan

are given in fig.2. The unit ce

index the reflecting planes. In

diffraction patterns which in

variation in the intensity of dif

the dopant sulphamic acid into


ed for cell parameter values with compute

e crystal X-ray diffractometer and the

Table 1 Cell parameter values of GSA

a( ) b( ) c(

5.14 12.01 5.

77

grown crystals GSA was recorded using

uK (=1.5418Å) radiation after crushing

ed over the range 0-800 at the rate of 2 per

ll parameters determined from single crysta

the figure, we can notice the appearance o

icate the good crystalline nature of the

fracted beam at different planes accounts for

the host lattice.

ig.2 Powder XRD pattern of GSA

php; ISSN: 2454-5422

r controlled Bruker-

btained results are

) V( )

5 315

BRUKER AXS D8

the sample into fine

minute. The patterns

l XRD were used to

f sharp peaks in the

rown crystals. The

the incorporation of



2016; IJ

Fourier Transform Infrared (

FTIR absorption spectra of t

recorded on a Lambda 35 specfigures 3. The absorption band

Table

Wave num317300289261227212

16115114013211110389696050


TIR) spectral studies

he grown crystals in the infrared region

trophotometer using a KBr pellet technique as/peaks and their assignments are given in th

Fig.3 FTIR spectrum of GSA

2 Spectral assignments of sample GSA

er (cm- ) Spectral assignments3996

2

58821

NH3+ stretching

NH3+ stretching

C-H stretchingN-H-O stretchingN-H stretchingCombination band

C=O stretchingN-H bendingCOO- symmetric stretchCH2 twistingC-C stretchingC-C-N stretching(SO4)2 stretchingN-S stretchingCOO- waggingCOO- rocking

php; ISSN: 2454-5422

000-400 cm-1 were

nd it is shown in the table 2.



2016; IJ

Microhardness studies

Measurement of microhardnes

is a mechanical property that iwith various loads. The varia

GSA crystals were measured u

Fig.4.and it is noticed that the

which confirms the reverse ind

The graph plotted between log

the line gives the Meyer’s in

brought under the category of= 2.94. Hence GSA is a soft m


of a material is a measure of resistance to pl

s studied by measuring the Vickers microhion of Vicker’s hardness number (Hv) wit

sing Shimadzu HMV-2T microhardness test

Vickers hardness number (Hv) increases

entation size effect.

d and log P for the crystals GSA are shown i

ex or work hardening coefficient (n) . If n

ard materials. If n >1.6, the material is softaterial.

Fig. 4 Variation of Hv with load

Fig. 5 Graph between log d and log P

php; ISSN: 2454-5422

astic deformation. It

rdness number (Hv) different loads for

r and is presented in

ith the applied load

n fig.5. The slope of

1.6, the material is

ne. Here for GSA, n



2016; IJ

Fig.6 Plot of yield str

and brittleness index as functi

Table 3 Calculated me


ngth, elastic stiffness constant, fracture to

on of load

hanical parameters of GSA

php; ISSN: 2454-5422

ughness coefficient



2016; IJ

Thermal studies

Thermo gravimetric analysis o

Elmer Diamond instrument ino C/min upto 800 o C. The cor

GSA is thermally stable upto

sharp endothermic peak at 27

sharp exothermic peak at 580o

273 oC is also confirmed by the

Second order NLO studies

The Second Harmonic Gener

samples was performed using

ns and repetition rate 10 Hz.

confirmed from the emission

phosphate (KDP) was used as

taken in powder form. The va

210 0 .0

D T A u

V

3 0 .0 0

2 0 .0 0

10 .0 0

0 .0 0

-10 .0 0

-2 0 .0 0

-3 0 .0 0

l


n the grown crystals GSA are performed wi

itrogen atmosphere with a rate of flow of 2

responding curves are shown in fig.7.

Fig.7 TG-DTA thermogram of GSA

73oC. This is proved both by TG and DTA.

3.1oC represents the melting point of the

C may be due to volatization of the compou

TG curve also.

ation (SHG) test for the grown sulphamic

Nd: YAG laser with first harmonics output

. The second harmonic signal generated

of green radiation. In this experiment, p

the reference. Both the reference material

lues of SHG relative efficiency of the grow

T em p C el7 06 0 0 .05 0 0 .04 0 0 .03 0 0 .00 0 .0

2 7 3 . 1 C e l

- 3 4 . 9 7 u V

php; ISSN: 2454-5422

h the help of Perkin

0

The occurrence of a

omponent. A small

nd. Melting point at

acid doped Glycine

f 1064 nm, width 8

in the samples was

tassium dihydrogen

and the samples are

crystals BASA and

8 0 0 .00 .0

T G

k %

2 .5 0 0

2 .0 0 0

1.5 0 0

1.0 0 0

0 .5 0 0

0 .0 0 0

-0 .5 0 0

-1. 0 0 0

-1. 5 0 0l



2016; IJ

GSA with reference to KDP

NLO property of the samples.

applications. Due to the pres

polarizability of the molecules,

Tab

Z-Scan analysis

Third order nonlinear optical

technique. The magnitude a

absorption coefficient (β) of t

(OA) and closed aperture (CA

nonlinear absorption coefficie

experiment, Gaussian laser

direction has been taken as Z

using a convex lens and the fo

(CW) laser light 632.8 nm

optically polished 1mm thick

and the energy transmitted by

transmittance for the position

calculate the third order nonlin

is the signature for nonlinearit


re tabulated in the table 4. The powder S

This shows that doped crystals will be better

nce of dopant into the crystal lattice, the

which tends to increase the SHG efficiency.

le 4 Value of relative SHG efficiency

Sample

Relative

SHG

Efficiency

GSA 0.613

property of the grown crystals GSA was

d sign of the nonlinear refractive index

e crystals were calculated from Z-scan dat

) Z-scan methods are used for the simultane

nt and nonlinear optical refraction for optic

eam was used for molecular excitation

– axis of the optically polished crystal. Th

al point was taken as Z=0. The monochrom

ith power 3.13 MW beam from He-Ne l

rystal was fixed in the travel range of 25 m

the sample were measured using a power m

d crystal was measured at different positi

ear optical property of the crystal. The peak

of the material.

php; ISSN: 2454-5422

G test confirms the

candidates for NLO

re is an increase in

studied by Z-scan

(n2) and nonlinear

. The open aperture

ous measurement of

al materials. In this

and its propagation

beam was focused

tic continuous wave

aser was used. The

m. The input energy

ter. The normalized

ns and was used to

followed by a valley



2016; IJ

The Z-scan curves in closed a

Table 5 Third

Sample n2

10-12 cm2 /W

GSA 4.546


d open aperture modes are illustrated in fig.

ig.9 Closed aperture Z-scan curve

harmonic nonlinear optical parameters of

β

10-6 cm/W

R.P of χ(3)

10-10

I.P of χ

10-10

1.081 7.904 9.465

Fig.8 Open aperture Z-scan curve

php; ISSN: 2454-5422

and fig.9

SA

(3) χ(3)

10-9 e.s.u

1.233



2016; IJ

The values of third order nonli

the crystals GSA are given in t

the self defocusing nature of t

have saturable absorption. Thu

have now become transparent

Conclusion

Novel sulphamic acid doped

evaporation solution growth

colourless and transparent wi

studies reveal that GSA belogood crystalline nature of th

reflecting peaks. FTIR studies

functional groups present in t

from Vickers’s hardness analy

these materials are ideal can

evident that GSA has 0.613 ti

refractive index of the dopednight vision sensor devices.

absorption by the candidates

especially the self defocusing

and photonic devices.

Reference

1. D.S. Chemla and J.Z Crystals, Vol 1,2, Acad

2. H.S. Nalwa, Hand Bo

Devices, Vol.9, Acade

Kumararaman, Materia

3. Thaila T, Kumararam

Biomolecular Spectros


near refractive index, absorption coefficient

able 5. The negative value of nonlinear refra

he crystals and nonlinear absorption value t

s the materials which are opaque to a smalle

hen a large number of photons are incident

NLO single crystals GSA were successf

method at room temperature. The crysta

th well defined external appearance. Singl

gs to monoclinic system. Powder XRD ane samples and the planes responsible fo

are utilized to identify the modes of vibrat

e crystals. The crystals belong to the categ

sis. GSA is stable upto 273 oC. Hence belo

idates for device fabrication. From SHG

es SHG efficiency of KDP. The negative t

crystals makes them prominent materials fhe open aperture transmittance data con

. The promising third order NLO proper

ature suggest their suitability for applicatio

ss, Nonlinear Optical Properties of Orgemic press, Orlanto (1987)

ok of Advanced Electronic and Photonic

ic press, New York (2001). R. Valluvan,

ls Chemistry and Physics, 97 (2006) 81

an S. Spectrochimica Acta Part A:

opy, 82 (2011) 20

php; ISSN: 2454-5422

nd susceptibility for

ctive index indicates

ells that the crystals

r number of photons

on it.

lly grown by slow

ls are found to be

e crystal diffraction

alysis elucidates the the occurrence of

ion and the possible

ry of soft materials

these temperatures,

measurement, it is

hird order nonlinear

r protection optical irmed the saturable

ties of the crystals

s in optical limiting

nic Molecules and

Materials and

. Selvaraju, S.

olecular and



2016; IJ

4. Samson Yesuvadian,

Bhagavannarayana Go

Optik – Int. J. for Light

5. Lipson H, Steeple H,

edition, Macmillan, Ne

6. A.L. Smith, Applied In

7. P.R. Griffiths, J.A. De

Chichester (1986)

8. P.J. Haines, Thermal M

9. M.I. Pope, M.D. Judd,

10. www.wordftest.com/ m

11. http://www.gordonengl

12. S. Ishwar Bhat, P.

Characterization of ne

236 (2002) 318

13. C. Balarew, R. Dehlew ,

ligand co-ordination in

14. Sahadevan Suresh, Stu Lithium Potassium

Phy.(2013)8,0006

15. S.K. Bachav, N.S. Pati

of Cobalt doped Bariu

and App.,4,8,(2014),10

16. D. Jaishree, G. Kanc

thermal properties ofPhy.,(2014)

17. R. DeSalvo, N. Sheik-

refraction and absorpti


Anbarasu Selvaraj, Martina Mejeba Xavi

davarti, Vijayan Narayanasamy, Prem An

and Electron Optics, 126 (2015) 95

Interpretation of X-ray Powder Diffracti

w York, (1970)

rared Spectroscopy 2nd edition, Holden-Day

Hoseth, Fourier Transform Infrared Spectr

ethods of Analysis, Blackie, London (1995)

ifferential Thermal Analysis, Heyden, Phila

icrohardness test

and.co.uk/hardness/vickers.html.

ohan Rao, V. Upadyaya and H.S. Na

nonlinear optical mixed borate crystals, Jo

, Application of hard and soft acids and bas

double salt structures, Jour. Solid State Che

ies on growth, microhardness and dielectri

ulphate NLO single crystals, The A

l, M.S. Kale, D.S. Bhavsar, Crystal growth

Tartarate crystals by Silica Gel Method, I

8

ana, R. Kesavasamy, Investigations on

Sulphamic acid single crystals, Advances

Bahae et al, Z-scan measurements of the ani

on in crystals, Optics Letters,Vol.18,no.3,19

php; ISSN: 2454-5422

er Methodius,

nd Devarajan,

n Pattern, 5th

(1977)

scopy, Wiley,

delphia (1997)

araja, Growth and

ur. of Crys. Growth,

s concept to explain

m.,55,1(1984)1

characterization of

frican Review of

nd characterization

t. Jour. of Eng. Res.

rowth, optical and

in Conden. Matter

sotropy of nonlinear



2016; IJ

Volume: 2; Iss

Electrical conductivity me

M.P.Ra

1Department of Physics, Sarah Thuc

2P.G and Research Department of Ph

*Corresponding Author Email Id : tk

Crystals are the unacknowled

be no electronic industry, no p

is an interdisciplinary subje

engineering, metallurgy, cryst

growing interest on crystal gr

materials for technological ap

crystals have been grown by

characterization have been stusynthesize crystals which are

KH2PO4 (KDP) continues to

KDP is a representative of hyd

and nonlinear optical propert

interesting properties, we mad

in various concentrations (0.0

crystals were collected after 1electrical conductivity(resistan

different frequencies of pure a

to 1200Cusing simple two pro

electrical conductivity increase

doped KDP crystals were sligh

Keywords: KDP, NiSO4



surements of pure and nickel sulphate do

grown by gel medium

eela1, Vinu Bharathi2 and T. Asaithambi2*

er College For Women, Thirunelveli, India.

ysics, Alagappa Govt. Arts College, Karaikudi, India.

[email protected]

Abstract

ed pillars of modern technology. Without

hotonic industry, no fiber optic communicat

ct covering physics, chemistry, material

llography, mineralogy, etc. In past few deca

wth processes, particularly in view of the i

plications. Optically good quality pure an

icrobial free gel growth method at room t

ied. Gel method is a very simple method ahaving low solubility. Potassium dihydro

be an interesting material both academica

rogen bonded materials which possess very

ies in addition to interesting electrical pro

an attempt to grow pure and nickel sulphat

2, 0.004, 0.006, 0.008 and 0.010) using gel

5 days. We get crystals with good qualityce, capacitance and dielectric constant) val

d nickel sulphate added crystal with a tempe

be setup with Q band digital LCR meter pre

s with increase of temperature. The dielectri

tly decreased compared to pure KDP crystals

php; ISSN: 2454-5422

6. ISSN: 2454-5422

ed KDP crystals

rystals, there would

ions. Crystal growth

science, chemical

es, there has been a

creasing demand of

metal doped KDP

mperature and their

d can be utilized to gen orthophosphate

lly and industrially.

good electro – optic

perties. Due to this

doped kdp crystals

method. The grown

and shaped. The dc e were measured at

rature range of 400C

sent in our lab. The

c constants of metal

.



2016; IJ

Introduction

Potassium dihydrogen orthoph

both academically and industwhich possess very good electr

electrical properties. The dem

the application as frequency c

electric property of KDP cry

frequency stabilizers in electro

The excellent properties of K

resistance to damage by lacombination with reproducible

applications such as laser fusi

studies on the growth and pro

reported [3 - 4]. Potassium di

scientists due to its excellent

Microscopically, crystal growt

which are all related to the co

KDP, ADP and DKDP are the

to their exclusive properties.

electrical properties, optical tra


Pure and NiSO4 doped KDP si

analar grade KDP and NiSO4

dopant and sodium meta silica

room temperature figure (1).

damaging the cell surface .Wh

This induces nucleation and t

was carried out at room tempe

doped KDP crystals. Pure and


osphate (KDP) KH2PO4 continues to be an

rially. KDP is a representative of hydrogeo – optic and nonlinear optical properties in a

nd for high quality large single crystals of

nversion crystal in inertial confinement fus

stal makes it useful for the construction o

ic circuit’s .

DP include transparency in a wide region

ser radiation and relatively high non- ligrowth to large size. Therefore, it is comm

on, electro-optical modulation and frequenc

perties of KDP crystals in the presence of i

hydrogen phosphate (KDP) crystal draws p

quality and possibility of growing large- s

h includes crystal morphology, crystal defe

stituent growth units and their chemical bon

only nonlinear crystal currently used for th

he grown crystals were characterized usin

nsmittance, for pure and NiSO4 doped KDP

ngle crystals are grown in sodium meta silica

ith in concentrations of 0.002, 0.004, 0.006

te (1.08g/cm3 ). During the process pH was

thyl alcohol of equal volume is added ove

en the alcohol diffuses into the set gel, it re

e nuclei are grown into the single crystals.

rature. The growth period was about 20 days

KDP doped crystals are shown in the fig (2).

php; ISSN: 2454-5422

interesting material

n bonded materials dition to interesting

DP increase due to

ion [1-2]. The piezo

f crystal filters and

of optical spectrum,

near efficiency, in only used in several

y conversion. Many

mpurities have been

rsistent attention of

ize crystals [5 - 6].

ts, and growth rate,

ding process [7 - 8].

ese applications due

dielectric constant,

rystals.

te gel medium using

, 0.008 and 0.010 of

maintained at 5-6 at

the set gel without

duces the solubility.

The crystal growth

for pure and NiSO4



2016; IJ

Figure.1 Growth of pu


re KDP doped with NiSO4 with various co

php; ISSN: 2454-5422

ncentrations



2016; IJ

Fig. 2. Gel grown

Doping

Doping means adding impurity

amount of dopant solute is also

Table

Dopin

1 : 0

1 : 0

1 : 0

1 : 0

1 : 0


ure KDP and NiSO4 added KDP crystals

to the known pure crystal .To prepare a dop

mixed along with the pure solute.

1: Doping concentrations of impurities

g ratioMass of NiSO4 Adde

.002 0.06571

.004 0.13143

.006 0.19714

.008 0.26286

.010 0.32857

php; ISSN: 2454-5422

ed crystal a required

d in gm



2016; IJ

An impurity can suppress, enh

certain crystallographic faces

saturation, temperature and pH

Results and Discussions

Dielectric constant and electr

Dielectric properties are corre

when they are non- conductin

increases and the electrical

constant depends on the de

dielectric constant of materials

charge polarizations which d

polarization are active lower

reports are available about i

dielectric constant values ar

temperature dependence of die

Even though KDP has many r

perfection of crystals in our p

increasing frequency and lo

compared to the solution grow

for the enhancement of SHG

function of frequency at differ

are taking place in materials a

the pure and metal doped KD

crystals at room temperatureconstant of KDP and NiSO4 d

with increase in frequency. T

presence of all four polarizati

low values at higher frequenci

gradually. The nature of decr

crystals contain dipoles of cont


ance or stop the growth of crystal complete

. The effects depend on the impurity

of the solution.

ical conductivity studies

lated with electro- optic properties of the

g materials. Due to the incorporation of me

conductivity increases. (fig.5,6) The mag

ree of polarization, charge displacement

is due to the contribution of electronic, ioni

pends on the frequencies [5]. At low fr

frequencies and high temperatures [6], in

ts dielectric behavior and in our present

e in good agreement with the reported

lectric constant at frequency 100Hz to 1KHz

ports on dielectric loss, the study clearly en

resent case; it is observed that the dielectric

dielectric losses were observed for the

th. The lower value of dielectric constant is

signals. The measurement of dielectric co

ent temperatures give an idea about the ele

d these parameters were measured on the p

crystals. Frequency dependences of dielect

are observed from the figures and it is obsped KDP crystals are high at low frequencie

he very high value of ϵr at low frequencie

ns namely space charge, orientation, electro

es may be due to the loss of significance o

ase of ϵr frequency suggests that pure and

inuously varying relaxation times.

php; ISSN: 2454-5422

ly. It usually acts on

oncentration, super

crystals particularly

tal ions polarization

nitude of dielectric

in the crystal. The

c, dipolar and space

quencies, all these,

KDP crystals, many

work the measured

results [7-8]. The

is shown in fig. 4,5.

sures the crystalline

loss decreases with

gel method crystal

a suitable parameter

nstant and loss as a

trical processes that

lished (010) face of

ric constant of these

erved that dielectric s and they decreases

may be due to the

nic and ionic and its

f these polarizations

NiSO4 doped KDP



2016; IJ

Fig.3. Variation of dielectric

pure and NiSO4 doped KDP

Fig.4. Variation of dielectric


0

100

200

300

400

500

600

700

1 2 3

0

50

100

150

200

250

300

1 2 3


constant (εr) with temperature at frequen

rystals

constant (εr) with temperature at frequen

rystals

4 5 6 7 8

Series7

Series6

Series5

Series4

Series3

Series2

Series1

4 5 6 7 8

Series7

Series6

Series5

Series4

Series3

Series2

Series1

php; ISSN: 2454-5422

y of 100Hz for

y of 1KHz for



2016; IJ

Fig.5. Variation of electrical


Fig.6. Variation of electrical


0

20

40

60

80

100

120

140

160

1 2

0

20

40

60

80

100

120

140

160

1 2


onductivity (σ) with temperature at frequ

rystals

onductivity (σ) with temperature at frequ

rystals

3 4 5 6 7 8

Se

Se

Se

Se

Se

Se

Se

3 4 5 6 7 8

S

S

S

S

S

S

S

php; ISSN: 2454-5422

ency of 100Hz for

ency of 1KHz for

ries7

ries6

ries5

ries4

ries3

ries2

ries1

eries7

eries6

eries5

eries4

eries3

eries2

eries1



2016; IJ

Conclusion

Pure KDP crystals and metal d

the three dimensional structu

dielectric constant and electri

and NiSO4doped KDP crystal

crystals were slightly decrea

dielectric constant more is the

the pure KDP and NiSO4 do

temperature and frequencies.

References1. X.Sun, X, Xu, Z.Gao, Y.Fu,

2. N.Zaitseva, L.Carman, I.Sm

3. Bo Wang. Chang – shuiFang

guangXu, JianqinZhang,BingL

(2008) 5341-5346.

4. N.Pattanaboonmee, P.Rama

5. Dongli Xu, Dongfeng Xue.

6. Dogli Xu, Dongfeng Xue, J.

7. Dongli Xu, Dongfeng Xue.

8. S.Balamurugan, P.Ramasam


oped KDP crystals are grown by gel metho

res, the crystals are free from microbes.

al conductivity were measured at different

. The capacitance and dielectric constants

ed compared to pure KDP crystals. The

enhancement of SHG signals. The electrica

ped KDP crystals were found to be incre

S.Wahg, H.Zong, Y.Li, J.Cryst.Growth., 21

olsky, J.Cryst.Growth., 241 (2002) 363.

.Sheng – Iai Wang, Xun Sun, Quing-tianGu,

iu,with potassium carbonate as additives .J.C

amy, P.Manyumprocedia Engineering., 32 (

.Cryst. Growth., 310 (2008) 1385

Alloys Compd., 449 (2008) 353

.Cryst. Growth., 310 (2008) 1385

y, Spectrochimica Acta., Part A 71 (2009) 1

php; ISSN: 2454-5422

. In gel growth, due

he capacitance and

frequencies of pure

f metal doped KDP

lower the value of

l conductivity (σ) of

se with increase of

(2000) 404

i-ping Li, Xin-

ryst.Growth.,310,

012) 1019-1025.

79-1983



2016; IJ

Volume: 2; Iss

Systematical calculation of

gr

G. M.

1Rani Anna Government College for

2St. John’s College, Palayamkottai, I

*Corresponding Author Email Id: rc

The alpha decay is one of th

nuclei. Using Cubic Plus Yu

isotopes of Cm nuclei in the ra

nuclei in the range 246 ≤ A ≤

states of daughter nuclei have

(β4) deformations of parent an

half-lives are compared with

Hindrance factor and branchi

decay rate is also investigated.

Keywords: Alpha decay, Q - v

Introduction

Alpha decay can provide som

The alpha decay theory was

Condon on the basis of quant

by Salomon Rosenblum [2] in

nuclei from ground to ground

Yukawa Plus Exponential mo

the parent and daughter but tre

described in section 2. The res

are given in section 4.



Alpha decay half-lives of heavy nuclei fro

und and excited states of daughter

armel Vigila Bai 1 and R. Nithya Agnes 2*

women, Tirunelveli, India.

ndia.

[email protected]

Abstract

most important decay processes of the he

kawa Plus Exponential model, the alpha

nge 238 ≤ A ≤ 250, Cf nuclei in the range 24

56 from ground state to ground state and gr

een studied by including both quadrupole (β

daughter nuclei as well as the spin-parity e

vailable data and are found in good agreem

g ratio have been calculated. The centrifu

alue and fine structure

e reliable information on nuclear structure

formulated by Gamow[1] and independe

m tunnelling. The fine structure of alpha d

1929.In this paper we have studied the alph

and excited states of daughter nuclei using

el [3] by incorporating the ground state defo

ating the emitted cluster as a sphere. The det

lts and discussion are given in section 3. Fi

php; ISSN: 2454-5422

4. ISSN: 2454-5422

ground state to

vy and super heavy

decay of even-even

0 ≤ A ≤ 256 and Fm

und state to excited

2) and hexadecapole

fects. The computed

ent with each other.

al barrier effect on

nd nuclear reaction.

tly by Gurney and

cay was formulated

decay of even-even

(CYEM) Cubic Plus

rmation β2 and β4 of

ails of our model are

ally the conclusions



2016; IJ

Cubic plus Yukawa plus Exp

In this work, the spins and the

nucleus has a quadrupole defo

If the parent nuclei have defor

reaction is taken as the origin,

centre of mass distance 'r' of th

V(r) = Vc(r) + Vn(r)+ℓ(

Here Vc is the coulom

cluster. Vn is the nuclear inter

Vdf is the change in nucle

deformations in the daughterangular momentum, and ‘µ’ is

particle in a ground state to gr

odd-odd nuclei, it could not b

added with the Coulomb barri

from the usual nuclear spin an

Ji-J j≤ ℓ≤Ji+J j an

Where Ji,∏ i and J j,∏ j are the s

The effect of atomic electrons

The energy of alpha particle e

Where Qg.s→g.s is the Q- v

excitation energy of daughter

is given by

Qg.s→g.s = ΔMP-(ΔMd+

Where Mp, Md, Mα are the m

Audi et al [5].Where the ter

nucleus caused by the surrou

energy of the Z-electrons in t

nuclei of Z ≥ 60 and k2=13.

reported by Huang et al [6].


onential Model

parities of parent and daughter nuclei are in

mation only and the emitted cluster is consid

ations say quadruple and hexadecapole and

the potential for the post - scission region a

e fragment is given by

+1)ћ2 /2µr2 - Vdf (r) – Q

b potential between a spheroid daughter a

action energy due to finite range effects of

ar interaction energy due to quadruple

nuclei, ‘r’ is the distance between fragmenthe reduced mass . The angular momentum

und state transition of even-even nucleus is

equal to zero. In this case, the centrifugal

r. The values of natural angular momentum

parity conservation law,

πi / π j=(-1)ℓ

in and parity of parent and daughter nuclei r

on the energy of alpha particle should also b

itted from nucleus in alpha decay is

Qi=Qg.s→g.s-Ei*

lue for ground state to ground state trans

ucleus to the i ih state. The ground state to

Mα) + [ k1(ZPβ1-Zdβ1 ) - k2ZCβ2]

ass excess of parent, daughter and alpha nu

s in the brackets represent the effect of t

ding electrons. The quantity kZ β represe

e atom, where the values k1=8.7x10-6 M e

x10-6 Me V andβ2 =2.408 for Z < 60 ha

php; ISSN: 2454-5422

cluded; the daughter

ered to be spherical.

if the Q-value of the

s the function of the

(1)

d spherical emitted

Krappe et al[4]; and

and hexadecapole

centers , ‘ℓ’ is the carried by the alpha

ero . In odd-even or

barrier term must be

have been obtained

(2)

spectively.

taken into account.

(3)

ition and Ei* is the

round state Q-value

(4)

clei as tabulated by

he screening to the

ts the total binding

and β1 = 2.517 for

ve been found from



2016; IJ

For a prolate sp

direction, Pik - Pichak [7] obta

Vc(r) = ln

and for an oblate spher

Vc(r) = [ (1 +

For the overlapping reg

polynomial in (r) as suggested

Vc(r) = − [ ( ) +

ri ≤ r ≤ rt

Where rt = ae +

Here ae is the semi-maj

late (or) oblate shape of the em

the daughters and the emitted

If the nuclei have spher

axis of symmetry locating sharR () = Ro [1 + ∑∝

Here R0 is the radius of equival

If we consider spheroid defor

R() = 1 + 54

and if Nilsion hexadeca(6) becomes

R()=Ro 1 + 54

Expressing the energies

life time of the decay system w


heroid daughter nucleus with longer axis alo

ined

+

id daughter nucleus with shorter axis along t

) − ]

ion, we approximate the potential barrier by

by Nix[8]having the form

] −

Rd

or (or) minor axis of the spheroid cluster dep

itted cluster; and ri is the distance between th

article portions in the spheroid parent nucleu

oid shape, the radius vector R () making an

p surface of a deformed nuclei is given by re( )∝ ]

ent spherical nucleus.

ation 2 then

−12

pole deformation 4 is also included in the d

2 −1

2 + 94 (35

in MeV, lengths in fm and time in seconds

e use the formula,

php; ISSN: 2454-5422

g the fission

(5)

he fission direction

(6)

a third order

(7)

nding on the pro

e centers of mass of

s.

angle with the

f [3] (8)

(9)

formation then eqn

− 30 + 3)

(10)

or calculating the



2016; IJ

T = . × (1 + exp( ))

The action integral K is

Where KL = ∫ [2 ( )]

KR = ∫ [2 ( ) (

The limits of integratio

are found numerically.


We have made our calculatio

parent and daughter nuclei w

effects. We have calculated al

of Cm, Cf and Fm isotopes.

available data. The calculated

gives the Logarithmic half-liv

from ground state to ground st

Q values. Some of the nuclei

magicity of corresponding p

corresponding to daughter nuc

even-even isotopes of 244Cm, 25

All these transitions are taken

nuclei from ground state to ex

to the potential energy V(r). Fr

the half life value gets increas

gives alpha decay scheme forFig.3 showing the Histogram f

The standard deviation is estim

σ =


given by K = KL + KR

)]

ra and rb are the two appropriate zeros of th

ns by including quadrupole and hexadecap

ich are taken from the tables of Moller et

pha decay half lives for experimentally kno

he computed half-lives of alpha decay are

half-lives are in good agreement with the av

s for alpha decay of even-even isotopes of

ate transition. Figure 1 gives the plot of loga

re found to have long half-lives which indi

arent nuclei and lower half – lives value

lei. Table.2 gives the Logarithmic half-live2Cfand254Fm nuclei from ground state to ex

from Ref[11]. The angular momentum carri

ited state is not zero and hence the centrifu

om table 2, it is found that, with the inclusio

ed. Because it increases height of the pote

54Fm Parent nucleus to various levels of 250 r Branching ratio of 244Cm, 252Cf and 254F

ated using the following expression.

1(n − 1)

[log T . – log T .]

php; ISSN: 2454-5422

(11)

(12)

(13)

integrand which

ole deformations of

al[9]and spin-parity

n even-even nuclei

compared with the

ailable data. Table.1

some actinide nuclei

rithmic half lives vs.

ate the stability and

indicates the same

s for alpha decay of

ited state transition.

ed by the even-even

al potential is added

n of centrifugal term

tial barrier. Figure2

f daughter nucleus. nuclei.



2016; IJ

The estimated standard deviati

calculated by Ref [10] is 0.210

HF=

/.

/ .. The calculated HFof alpha decay to each state of

alpha decay width,

B

Where the sum n is going over

from the ground state of the pa

all ground to ground transition

Table1. Comparison of calculateactinide nuclei from ground state

Decay mode

96Cm →94Pu +2H96Cm →94Pu +2H96Cm →94Pu +2H96Cm →94Pu +2H96Cm →94Pu +2H96Cm →94Pu +2H98C f →96Cm +2H98C f →96Cm +2H98C f →96Cm +2H98C f →96Cm +2H98C f →96Cm +2H98C f →96Cm +2H98C f →96Cm +2H98C f →96Cm +2H

98C f →96Cm +2H1OOFm →98Cf +2

1OOFm →98Cf +2

1OOFm →98Cf +2

1OOFm →98Cf +2

1OOFm →98Cf +2

1OOFm →98Cf +2


on for the half lives by our model is 0.2395

08. The hindrance Factor (HF) is calculated

is close to unity which shows better result. Tthe daughter nucleus have been evaluated wi

Γ(Qi,ℓi)×100%/ ∑(Qn,ℓn)

all states, which can be populated during the

rent nucleus. The Branching ratio value is fo

and is going on decreased for all other trans

values of logarithm of half life time for oven-evto ground state transition.

Q(MeV) LogT(s)Expt Ref[10] CYE

6.668 5.51 5.26 5.466.440 6.52 6.29 6.486.258 7.28 6.86 7.385.945 8.87 8.57 8.97

5.518 11.26 11.10 11.475.204 13.16 13.14 13.51

e 7.760 2.03 1.75 1.90 e 7.560 2.41 2.52 2.61 e 7.374 3.18 2.88 3.30 e 6.907 5.21 5.19 5.29 e 6.406 7.56 7.19 7.68 e 6.174 8.69 8.45 8.86 e 6.262 8.01 8.08 8.46 e 5.972 9.31 9.99 10.05

e 5.600 10.87 12.22 12.25e 8.421 0.17 0.31 0.39e 8.048 1.66 1.55 1.68e 7.604 3.38 3.26 3.36e 7.198 5.04 4.97 5.01e 7.354 4.14 4.08 4.42e 7.073 5.14 5.27 5.65

php; ISSN: 2454-5422

hile the same

y the formula,

he branching ratios th the help of the

alpha transition

nd to be greater for

itions.

en isotopes of some

HF(cal.)

1.12201.09650.79430.7943

0.61660.6166

1.3489 0.6310 0.7586 0.8318 0.7586 0.6761 0.3548 0.1820

0.04170.60250.95491.04711.07150.52480.3090



2016; IJ

Table2. Comparison of calcul

of some actinide nuclei from g

Transiti

244Cm

0+→

0+→

0+→

0+→

0

+

→Cf →

0+→

0+→

0+→

0+→

0+→

Fm

0+→

0+→

0+→

0+→

Fig.1. Logarithmic half lives o

5.0 5.2 5.4 5.6 5.8 6.0 6.2 6.4 6.6 6.8

5

6

7

8

9

10

11

12

13

14 4He

2 from

238-248Cm

L o

g T ( s )

Q(MeV)

Expt.

Ref10 CYEM

. . . . . . . . .

0

1

2

3

4

5

6 -

L o g T ( s )

.


ted values of logarithm of half life time for o

round state to excited states of daughter nucl

on Q(MeV) LogT(s)(Calculated)

Bcal.

240Pu+

+

+

+

+

5.945

5.902

5.803

5.651

5.448

8.97

9.70

11.20

13.23

15.71

83.88

15.62

0.494

4.61e-3

1.53e-5Cm

+

+

+

+

+

6.262

6.219

6.118

5.964

5.757

8.46

9.26

10.89

13.10

15.70

86.04

13.64

0.320

1.97e-3

4.95e-6

Cf +

+

+

+

7.354

7.311

7.212

7.057

4.43

5.20

6.76

8.80

85.12

14.46

0.398

3.63e-3

f alpha decay Vs Q values including deforma

7.0 7.2 7.4 7.6 7.8 8.0 8.2 8.4 8.6

4He

2 from

246-256Fm

Q(MeV)

Expt.

Ref10

CYEM

5.8 6.0 6.2 6.4 6.6 6.8 7.0 7. .

2

3

4

5

6

7

8

9

10

114He

2 from

240-256Cf

L

o g T ( s )

Q(MeV)

.

php; ISSN: 2454-5422

ven-even isotopes

i

tion effects.

. . . . . . . 7 .2 7.4

xpt.

ef10

YEM



2016; IJ

Fig.2.Schematic representation

daughter nucleus.

Fig.3. Histogram for Branchin

Conclusions

We have calculated alpha de

computed half-lives are comp

each other. The calculated HF

Factor is between 1 and 4, th

height of the potential barrie

Branching ratio value is foun

transitions while the same dec

That means the alpha transmis

References

[1] G.Gamow, Z.Phys. 51,204

[2] Salomon Rosenblum, C.R.

0+ -> 0+ 0+ -> 2+ 0+ -> 4+ 0+ -> 6+ 0+ -> 8+

-20

0

20

40

60

80

252Cf

B c a l %

- - - - -

-

B c a l %


of alpha decay of 254Fm parent nucleus to v

ratio of 244Cm, 252Cf and 254Fm nuclei.

ay half – lives of even-even nuclei using

ared with available data and are found in g

is found to be unity which shows better res

e transition is called a ‘favoured transition’

r gets increased and it increases the half

d to be greater for all 0+→0+ transitions f

eases as we move from ground to other exc

ions to the remaining excited states are stron

(1928)

Acad. Sci.Paris 188 (1929) 1401

0+->0+ 0+->2+ 0+->4+ 0+->6+ 0+->8+

-20

0

20

40

60

80

244Cm

0+->0+ 0+->2+ 0+->4+ -

-20

0

20

40

60

80

254Fm

B c a l %

php; ISSN: 2454-5422

rious levels of 250Cf

CYEM model. The

ood agreement with

ult. If the Hindrance

. Due to this effect,

life value also. The

ollowed by 0+ →2+

ited state transitions.

gly hindered.

- - - 0+->6+

-

l



2016; IJ

[3] G.Shanmugam, G.M.Carm

[4] H.J.Krappe, J.R.Nix,andA.

[5] G. Audi, O.Bersillon, J.

nuclear and decay properties

[6] K.N.Huang, M.Aoyagi, M.

binding energies from relaxed

At.Data Nucl. Data Tables 18

[7] G.A. Pik – Pichak, Yad.Fiz

[8]J.R.Nix,Ann.Phys.(N.Y.)41

[9] P.Moller, J.R.Nix, W.D.

deformations At. Data Nucl. D

[10] V Yu Denisov and A A K

[11]http://www-nds.iaea.org/R


lVigilaBai and B.Kamalaharan, Phys. RevC

.Sierk,Phys.Rev.C20, 992 (1979)

lachot and A.H. Wapstra 2003 The NU

ucl. Phys. A7293.

H.Chen, B.Crasemaon and H.Mark 1976 N

-Orbital relativistic Hartree-Fock-Slater calc

43.

.44,1421(1986) Sovt. J. Nucl. Phys. 44,923 (

,52(1962)

Myers and W.J.Swiatecki Nuclear groun

ata Tables 59 185 – 381 (1995)..

hudenko, Phys. Rev.C80(2009)034603.

IPL-2/.

php; ISSN: 2454-5422

51, 2616 (1995)

ASE evaluation of

eutral-atom electron

ulations 2≤ Z ≤ 106

1986).

d-state masses and



2016; IJ

Volume: 2; Iss

Synthesized and Characte

R.

1Department of Physics, Sri.S.Ramas

Research Scholar, Bharathiyar Unive

1*Department of Physics, School of S

2Department of Physics, The MDT

In this work, nanoparticles o

using a microwave oven.

ammonium ceric nitrate. The

solution was adjusted to be at

the microwave oven at a tem

precipitates were thoroughly

as prepared powder. Conventiabout 2 hours. The synthesize

XRD, SEM, and FT-IR studie

Keywords: CeO2, nanoparticle

Introduction

Conventional materials like m

be converted into smart mate

inorganic to organic, crystall

aggregates, powders, nano

Nanomaterials have unique

materials [1]. Cerium oxide(

finds wide applications in ele

materials, in the field of cata

sensors and so on [2-6]. It h



ization of cerium dioxide (ceria) nanopar

microwave ovennitha1a, E.Kumar1* and D. Muthuraj2

amy Naidu Memorial College, Sattur, India.

rsity, Coimbatore, India.

cience, Tamil Nadu Open University, Chennai, India.

indu College, Tirunelveli, India.

Abstract

f cerium oxide (CeO2) were synthesized

he precursor used to prepare the nanopa

recursor was dissolved in de-ionized water

12 using sodium hydroxide . The prepared

erature of 70 oC for about 30 minutes. Th

ashed with de-ionized water, and dried at

nal thermal treatment of the as prepared pd CeO2 nanoparticles were subjected to var

s .

s,

tals, semiconductors, glass, ceramics, poly

rials in nano-scale dimensions. Nano

ine to amorphous, which can be found

ires, quantum dots, nanofilms, nan

nd interesting properties when compa

eO2), Ceria, is one of the most important

ctrolyte materials of solid oxide fuel cells ,

lysts, Chemical Mechanical Polishing (CM

as a fluorite – like cubic structure in which

php; ISSN: 2454-5422

9. ISSN: 2454-5422

icles by using a

by solution method

ticles of CeO2 was

and pH value of the

solution was kept in

en, the light yellow

5 oC for 8 h to form

wder at 200o

C for ious techniques like

ers, oxides etc can

aterials range from

as single particles,

ofibres, nanotubes.

ed to conventional

rare- earth oxides ,

ultraviolet blocking

P) and oxygen gas

each cerium site is



2016; IJ

surrounded by eight oxygen s

cerium site. Methods based on

method, microemulsion metho

many researchers [7-14]. But

CeO2 nanoparticles.

It is reported that nanopa

microwave oven [15]. This

nanosized inorganic material

heating has an advantage of hi

size distribution. This work

microwave-assisted solution

nitrate and sodium hydroxide.

Experimental

All chemicals were analytica

synthesis of CeO2 nanoparticl

was dissolved in deionized

hydroxide. A chemical reacti

formed. Then the prepared mi

minutes in air in a domestic m

coloured precipitate was form

yellow precipitate was filtered

8h to obtain as-prepared pow

2000C in air for 2 h resulted in

The powder XRD pattern

diffractometer (Model:Ritz-

mA). The particle size (d) of

full – width at half- maximum

) where λ is the X-ray wavel

synthesized nanopowder of c


ites in fcc arrangement and each oxygen si

wet chemical routes like co-precipitation, h

etc have been employed to synthesize of C

he above methods seem to be tedious and

ticles can be prepared in an easy manne

method has been successfully applied for

s [16-18]. Compared with conventional

gh efficiency and rapid formation of nanop

reports the studies of ceria nanopartic

ethod from an aqueous solution containi

l grade (AR) and used without further

es, the precursor ammonium Ce(IV) nitrat

water and pH value was adjusted to b

on took place in the solvent and a pale ye

ture solution was kept at a temperature of 7

icrowave oven (900 W, 2450 MHz., Onida,

d in the solution after the microwave heatin

and washed with de-ionized water and it w

der. Conventional thermal treatment of as-

the formation of CeO2 nanoparticles.

of the synthesized sample was taken usi

70 with Nickel filtered CuKα radiations (1

the sample can be estimated from XRD pat

(β) to the Debye-Scherrer’s relation d

ength and θ is the diffraction angle . The

ria was recorded using a Hitachi Scanning E

php; ISSN: 2454-5422

te has a tetrahedron

drothermal, sol- gel

O2 nanoparticles by

expensive to obtain

r using a domestic

the preparation of

heating, microwave

rticles with a nano-

les synthesized by

g ammonium ceric

purification. In the

e ((NH4)2Ce(NO3)6)

e 10 using sodium

llow precipitate was

00C for about for 30

India). Pale yellow-

g. Synthesized pale

as dried at 950C for

prepared powder at

g a powder X-ray

.54056 Å, 35KV,10

tern by applying the

(0.98 λ ) / (β cos θ

SEM image of the

lectron Microscope.



2016; IJ

Results and Dissusion

Figuue 1 shows the XRD pa

located at 2θ = 28.5, 33.1, 47.and (222) planes respectively

structure.

Fig.1: Powder XRD pattern o

For the various reflection pea

Debye-Scherrer’s relation and

around 12 nm. The Scannin

identify the morphology ofnanopaticles is displayed in t

agglomerated. Hence the shape

Fourier Transform Infrared (F

used to identify the functional

materials. When an infrared

intensity of the radiation wou

FITR spectra. The absorption

vibrations. Depending on the

certain frequencies. An FTIR

and wave number of IR radi

number range 400 cm-1 to 400

of the sample and hence the ch


ttern of the sample. From this figure, the

, 56.2 and 50.00

are corresponding to (111). These match well with the peaks of cub

ceria nanoparticls& Fig.2: SEM image of

s of the XRD pattern, the particle size was

the average size of nanoparticles of the sam

Electron Microscope(SEM) image of the

the nanoparticles. The SEM image of thhe figure 2. It is observed that that most

of a single nanoparticle is not clear from the

TIR) spectrometer is the sophisticated instr

groups of samples of nanomaterials, crystal

radiation is passed through a sample, c

ld be absorbed by the sample and that will

of IR radiation in the sample is due to str

aterial of the sample, absorption of IR ra

spectrum is recorded between percentages o

tion. By observing the absorption bands o

cm-1 of FTIR spectrum, one can ascertain t

emical formula and the sample can be identif

php; ISSN: 2454-5422

characteristic peaks

, (200), (220), (311) ic flouorite crystal

ceria nanoparticles

estimated using the

les was found to be

sample was used to

e synthesized ceria of the particles are

SEM image.

ment which can be

s and other types of

rtain percentage of

be indicated in the

tching and bending

iation will occur at

transmittance (%T)

peaks in the wave

he functional groups

ied.



2016; IJ

The FTIR pattern of cerium

absorption band located arou

residual water and hydroxyl gr

bending mode of associated w

cm-1 are due to unwanted resi

oxygen bond. The assignmen

the various absorption peaks o

Fig.3: FTIR pattern of c

Table 1 : Assignments for abs

B

Conclusion

Nanocrystalline CeO2 (ceria)

method using ammonium ceri

role in forming nanoparticles


dioxide nanoparticles is shown in the f

nd 3400 cm-1 corresponds to the O – H str

oups, while the absorption band at 1630 cm -1

ater. The complex bands observed at about

ues in the sample. The band at 848 cm-1 c

s for the bands/peaks of FTIR pattern were

the spectrum are provided in the table 1.

rium dioxide nanoparticles

rption bands of FTIR spectrum of cerium d

ands (cm-1) Assignments

3400 OH stretching

1630 OH bending

1518 CH2 bond

1350 CH2 bond

1053 -

848 Metal-O bond

articles have been synthesized by microwa

nitrate as the precursor. Sodium hydroxide

of ceria. The average size of nanoparticle

php; ISSN: 2454-5422

igure 3. The broad

tching vibration of

is due to the scissor

1518, 1350 , 1053

rresponds to metal –

the assignment for

ioxide nanoparticles

ve -assisted solution

played an important

of the sample was



2016; IJ

estimated by powder XRD stu

observing the absorption band

FTIR spectrum, one can ascer

formula and the sample can be

References

[1] E.PerryMurray, T.Tsai, S.

[2] R.X.Li, S.Yabe, M.Yamas(2002) 235

[3] M.G. Sanchez, J.L. Gazque

[4] M. Jiang, N.O. Wood. R. K

[5] N. Izu, W. Shin, N. Muray

[6] S. Yabe, T. sato, J. Solid st

[7] P.L. Chen, I.W. Chen, J.A

[8] B. Djuricic, S. Pickering, J

[9] X.D. Zhou, W. Huebner. H

[10] N. C. Wu, E. W. Shi, Y.

[11] M. Hirano, E. Kato, J. Ma

[12] L.P.Li, X.M.Lin, G.S.Li,

[13]T.Masui, K.Fujiwara, K.I.2197

[14] S.Komarneni,R.Rajha,Ma[15] M.Brightson, S.MeenaksConference on emerging adCollege of Engineering, Tamil

[16] X.H.Liao,J.J.Zhu,H.Y.Ch

[17] W.X.Tu,H.F.Liu,J.Mater.

[18] H.Wang,J.Z.Xu,J.J.Zhu,H


dies. SEM image revealed the morphology

s or peaks in the wave number range 400 c

tain the functional groups of the sample and

identified.

.Barnett, Nature 400 (1999) 649.

ita, S.Momose, S.Yoshida, S.Yin, T.Sato,

z, J. Catal. 104 (1987) 120

omanduri, Wear 220 (1998) 59

arna, S. Kanzaki, Sensor Actuat. B 87(2002)

te Chem 171(2003) 7

. Ceram. Soc. 76(1993)1577

.Euro. Ceram. Soc.19 (1999)1925

.U.Anderson. Appl.Phys.Lett. 80(2002)3814

. Zheng, W. J. Li, J. Am.Ceram. Soc.85(200

ter. Sci. Lett. 15(1996)1249

.Inomata, J.Mater.Res.16(2001)3207.

Machida, G.Y.Adachi, T.Sakata, H.Mori, C

ter.Chem.Phys.61(1999)50. i Sundar, T.H.Freeda, P.Selvarajan, Procee

aptive systems and technologies(EAST-2Nadu, 25th to 27th, October, 2007.

n,Mater.Sci.Eng.B85(2001)85.

hem.10(2000)2207.

.Y.Chen,J.Cryst.Growth244(2002)88.

php; ISSN: 2454-5422

of nanoparticles. By

m-1 to 4000 cm-1 of

hence the chemical

olidStateIonics. 151

95

2)2462.

hem.Mater. 9(1997)

ings of Second Int.

07), Noorul Islam



2016; IJCSR.

Volume: 2; Issu

Studies on molecular int

1Assistant Professor, Departm

2Associate Professor, Departm

*Coresponding AuthorE-mail:

Molecular interactions c

influence of local order

between permanent dip

correlation factor in dilu

The interactions between

modified form of the cor

interactions. The dielect308,313 and 318K. The

interactions was identifie

Keywords: Dielectric co

Introduction

Dielectric studies are of configurations, particula

ultrasonic and nuclear m

studying intermolecular

about molecular associati

Kirkwood correlation f

association among the as

is used as a solvent, as a

ethylating agent in orga

. 2(3): http://www.drbgrpublications.in/ijcsr.php;

e: 3 [Special Issue]; March-2016; pp 460-47

eractions of Bromoform and Ethyl bromi

at four different temperatures

K. Umamakeshvari1 and U. Sankar2*

nt of Physics, St. Johns College, Palayamkottai, India

ent of Physics, Sri KGS Arts College, Srivaikundam, I

[email protected].

Abstract

an be studied by dielectric measurements

and the overall dipole moment. The shor

les could readily be described by the

te solutions of bromoform and ethyl bromid

the solute species among themselves ma

relation factor gʹ by not taking into account

ic constants of the binary mixtures wereresults were interpreted in light of the the

in both the systems.

stant, Kirkwood correlation factor, H-bond,

great help in the assignment of the molely those of organic compounds. Altho

agnetic resonance (NMR) studies are the

H- bonds, dielectric studies provide very

on and intermolecular rotation. Determinati

actor (g) provides the information ab

sociating molecules (Purohit H D et al., 19

anesthetic in medicine, as a refrigerant, as

nic synthesis. It is possible to reconcile

ISSN: 2454-5422

1. ISSN: 2454-5422

e with Benzene

.

ndia.

by virtue of the

t range interaction

Kirkwood-Frolich

with inert solvent.

y be given by the

of solvent-solvent

measured at 303, ory. The nature of

Multimers

cular structures or gh infrared (IR),

powerful tools for

useful information

on of the modified

ut intermolecular

91). Ethyl bromide

a fumigant. It is a

the data obtained



2016; IJCSR.

from dipole moment stud

al., 2009). They have fou

hydrogen bonding betwe

of literature shows thatreviewed the various

Bromoform was used as

used as a laboratory reag

by density. Some work o

reported (S S Yadava et

benzene, to make other

synthetic fibers. In this co

composition and temper

acetate + benzene and et

acetic acid is due to sel

systems Bromoform in

on Kirkwood-Frohlich m


Ethyl Bromide (AR gra

commercially obtained fr

purification. Binary mixt

at 5 different concentrati

concentration was conve

dielectric constant was

The scale of the instr

tetrachloride, benzene, to

The temperature was mai

refractive indices were m

using a 10ml specific gra

measurement of dielectri

±0.0002 and ± 0.0001 gm

Theory

Attractive forces dipole-


ies of complexes of alcohols with ethyl br

nd that the enhancement of the dipole mom

en alcohol molecules and benzene with al

very little work on esters (L.Eberson ypes of hydrogen bonding in carboxylic

a solvent, sedative, and flame retardant, b

ent. Its high density makes it useful for sep

ultrasonic studies of bromopropane with be

al., 2004). Benzene is a colorless liquid wi

hemicals which are used to make plastics,

ntext, the variation of linear correlation fact

ature for the binary systems (acetic acid

hyl-methyl ketone+ benzene) carried out t

f-association (Krishnan et al., 1997). The

enzene (I), Ethyl bromide in benzene (II),

del.

e), Bromoform (AR grade) and Benzene

om S D Fine-chem. Limited (India) and us

res of Ethyl bromide, Bromoform and ben

ns by volume fraction. Assuming ideal mi

r ted into the molefraction (Prajapati et

measured at 1 KHz using a Systronix Digit

ument was calibrated using standard li

luene and chlorobenzene.

ntained at 298±1K using Sigma constant te

asured using Abbe’s refractometer. Densiti

vity bottle and a K-Roy microbalance. The

c constants, refractive indices and densiti

/cc respectively.

ipole interactions and other slowly varying

ISSN: 2454-5422

mide (T. Indira et

ent value confirms

cohol. The survey

et al., (1969) has acids and esters.

t now it is mainly

aration of minerals

nzene mixture was

th sweet odor. Use

resins, nylon and

r was studied with

benzene, methyl

e dimeric state of

following binary

ere studied based

(AR grade) were

ed without further

ene were prepared

xing behaviour the

al., 2010). The

al LCR meter 925.

uids like carbon

perature bath. The

s were determined

uncertainties in the

s were ± 0.0001,

interactions play a



2016; IJCSR.

role in the structure of the

intermolecular forces do

associated liquids it is al

continuum approach andmechanical approach of

measured dielectric cons

theory of dielectric polari

(Frohlich., 1958). The

correlations like hydrog

correlation parameter g’.

The interactions between

by a modification of th

interactions between the

correlation factor of

species, one can write (

= [ ( )– ( )](

( ) = ----

= ( )

-------

where ,n and represent

the solution respectively

constant, < > is the sq

weight fractions of the sol

and NA is the Avogadr

concentrations by measuri

solutions.


liquids. The modern theories of liquids sho

minate the structure of the denser liquid

most impossible to account for their dielect

one has to recourse to the theories base the dielectric constants. Theoretical inte

tants of associated liquids were enhanced

zation (Kirkwood., 1939) which was later m

Kirkwood-Frohlich treatment takes car

en bonding through the introduction of

the polar solute and the non-polar solvent

Kirkwood correlation factor, which take

solvent molecules among themselves. I

dielectric polarization between the solut

irkwood.,1939).

)-------------------------

-----------------------------------------------------------

-----------------------------------------------------------

the static dielectric constant, refractive index

and the suffix 1 indicates the solvent, k

ared dipole moment of the polar species,

vent and solute, M2 is the molecular weight

number. The value of g’ can be deter

ng the dielectric constant, refractive index

ISSN: 2454-5422

that the repulsive

s. In the case of

ric behavior in the

on the statistical rpretations of the

y the Kirkwood’s

odified by Frohlich

of short range

the dimensionless

may be considered

s into account the

g’ is the linear

and the solvent

---------- 1

--------------- 2

------------- 3

and the density of

is the Boltzmann

1 and w2 are the

of the polar solute

ined for different

and density of the



2016; IJCSR.


The variation of density,

correlation factor g’ with

system I and II are given

The variation of g’ with x

the dielectric constant val

with the increase of temp

clusters. On dilution, the

moment larger than the

clusters become very smal

with the volume fraction.

volume fraction (Kroeger

With the increase of tem

various concentrations de

molecules is disturbed.

temperature. Similar concl

to Bottcher et al., 1973).

concentrations. For all the

with increase of concentr

the molecular interaction

orientation of the dipole

orientation of the dipoles.

concentration of 0.2050

formation of -multimers

as proposed by Cole and

The rotation about the hy

dipoles in chain increase

dilution decreases, g de

decrease of dilution, mo

solute molecules. This


refractive index, dielectric constant and

concentration of the liquids at different te

in Table 1 and 2. The value of g’ is calcul

2 is graphically represented in Fig 1. From

e increases with concentration of the solute

erature. In pure liquids, the solute molecul

solute molecule exists as clustered species

as phase moment. As more and more sol

ler, until reaches a non-hydrogen bond. Th

Therefore the dielectric constant increases

t al., 1987).

erature the dielectric constant value of all

creases. Due to the thermal agitation, the

o the dielectric constant value decreases

usions were reported by many researchers (

The value of correlation factor g’ decrea

studied systems, for all temperatures, the

tions. The deviation of g’ value from unit

s. The value of g’ greater than unity i

. The value of g’ less than unity implie

In the system I, g’ greater than unity is

t 308K, this implies the parallel orientati

nd γ-multimers. The formation of linear mu

Dannhauser (Cole et al., 1955).

drogen bond is more restricted, the correl

s, leading for this type of molecules to high

creases. This may be explained as f

re solute molecules may be available for t

ay lead to the rupture of the H-bonds b

ISSN: 2454-5422

Kirkwood-Frohlich

mperatures for the

ted using Eqn (1).

he Tables 1 and 2,

and also decreases

es do not exist as

with a little dipole

vent is added, the

cluster sizes vary

ith the increase of

studied systems at

orientation of the

with the rise of

roeger et al., 1987

ses on increase of

g’ value decreases

is the measure of

plies the parallel

s the anti-parallel

obtained up to the

on of the dipoles,

ltimers is favoured

ation between the

er values of g’. As

ollows: with the

he interaction with

etween the solute



2016; IJCSR.

molecules and the solute

through a weak H-bond.

implies the anti-parallel or

dilution, the g’ value decrbonding (Bordewijk et al.,

At high dilution, as temp

due to hindrance of the s

interactions. Increase of t

molecules (linear multim

which may be the reasodeviation of g’ value fro

molecules. The strength

mixture is higher than the

303 and 308K for system I

318K g’ of system I va

association between solut

short-range interaction betmonomeric state. Small d

interaction (long-range) as

There may be a weak π-π

oxygen atom of the este

temperature. Deviation of

range interactions as wellII at 0.0519 concentratio

temperatures. For all othe

indicating antiparallel orie


molecules may tend to interact with the

Afterward the value of g’ less than unity

ientation of the dipoles, formation of β- mu

ases due to the self-association of solute m1973).

rature increases, solute-solute interaction m

lvent molecules. This results in favour of

mperature at very high dilutions may incre

ers) favouring parallel orientation of the

for the increase of g’ values with theunity indicates the strong self-association

f the solute-solute interactions in bromof

ethyl bromide-benzene mixture. Hence it m

, parallel orientation among solute molecules

ies about 10 to 17 percent. This indicate

e molecules through H-bonding. This sho

ween the solute molecules. The solute molviation of g’ values from unity may be d

well as π-π interaction between the solute a

interaction between the π electron clouds o

rs. g’ does not vary appreciably with x2

g’ value from unity up to 20% can be tak

as the π-π interactions (Thenappan., Sankarn g’ value is above 1 indicating parallel

r concentration and all temperatures g’ v

tation.

ISSN: 2454-5422

solvent molecules

are obtained. This

ltimers. Increase of

lecules through H-

y be less favoured

more solute-solute

ase the size of the

solute molecules,

emperature. Large among the solute

orm with benzene

ay be concluded at

exists. At 313 and

s there is no self

s the absence of

cules may exist in e to dipole-dipole

d solvent.

f benzene with the

as well as with

en as due to long-

., 2006). In system orientation at all

lue is less than 1



2016; IJCSR.

Fig.1- Variation o

System I-B

System II-


f g’ with concentration:

romoform in benzene

thyl bromide in benzene

ISSN: 2454-5422



p er a u re

(K) X2

0.0539

0.1050

3 03 0 .1550

0.2050

0.2595

0.0539

0.1050

3 08 0 .1550

0.2050

0.2595

0.0539

0.1050

3 13 0 .1550

0.2050

0.2595

0.0539

0.1050

3 18 0 .1550

0.2050

0.2595

Table 1 - Variation o

concentratio

binary mixt

Temd g m / c c

1.0491

n

1.5019

1

2.3576

1 .0 787 1 .5 045 2 .4 447

1 .1 785 1 .5 076 2 .5 215

1 .2 777 1 .5 132 2 .6 151

1 .3 911 1 .5 188 2 .7 000

1 .0 379 1 .4 942 2 .3 342

1 .0 675 1 .5 012 2 .4 113

1 .1 673 1 .5 062 2 .4 981

1 .2 665 1 .5 114 2 .5 817

1 .3 799 1 .5 164 2 .6 556

1 .0 283 1 .4 928 2 .3 108

1 .0 579 1 .4 972 2 .3 810

1 .1 578 1 .5 029 2 .4 607

1 .2 569 1 .5 068 2 .5 349

1 .3 704 1 .5 126 2 .6 151

1 .0 180 1 .4 902 2 .2 974

1 .0 478 1 .4 939 2 .3 576

1 .1 479 1 .4 983 2 .4 279

1 .2 472 1 .5 035 2 .4 981

1 .3 608 1 .5 090 2 .5 683

f density, refractive index, dielectric con

n at four different temperature of bromofo

res

g

1.4983

1.1904

1.1160

1.1051

1.0489

1.1922

1.0611

1.0564

1.0369

0.9753

0.9682

0.9571

0.9497

0.9445

0.9181

0.9174

0.8796

0.8796

0.8674

0.8372

stant and g’ with

m (X2) + Benzene



p er a u re

(K) X2

0.0519

0.1002

3 03 0 .151

0.1989

0.2461

0.0519

0.1002

3 08 0 .151

0.1989

0.2461

0.0519

0.1002

3 13 0 .151

0.1989

0.2461

0.0519

0.1002

3 18 0 .151

0.1989

0.2461

Table 2- Variation of d

concentration at four di

(X1)binary mixtures.

Temd g m / c c

0.8954

n

1.4912

1

2.6151

0 .9 208 1 .4 918 2 .8 492

0 .9 445 1 .4 882 3 .1 326

0 .9 694 1 .4 864 3 .2 705

0 .9 904 1 .4 814 3 .4 812

0 .8 842 1 .4 895 2 .5 917

0 .9 096 1 .4 889 2 .8 258

0 .9 333 1 .4 874 3 .0 896

0 .9 582 1 .4 832 3 .2 003

0 .9 792 1 .4 762 3 .3 641

0 .8 745 1 .4 872 2 .5 683

0 .9 1 .4 855 2 .8 024

0 .9 237 1 .4 832 2 .9 896

0 .9 486 1 .4 793 3 .1 003

0 .9 697 1 .4 738 3 .2 641

0 .8 643 1 .4 836 2 .5 449

0 .8 899 1 .4 819 2 .7 556

0 .9 138 1 .4 784 2 .8 96

0 .9 389 1 .4 762 2 .9 662

0 .9 601 1 .4 704 3 .0 833

nsity, refractive index, dielectric constant an

fferent temperatures of Ethyl bromide(X2)+

g

1.2236

0.9873

0.9379

0.808

0.7766

1.2008

0.9925

0.9249

0.7866

0.7399

1.1809

0.998

0.8602

0.7403

0.704

1.1714

0.9656

0.7991

0.6621

0.6167

d g¢ with

enzene



IJCSR; 2(

References

Ajay Chaudhari, Anita Das, G

Narain and Suresh Mehrotra, P

Ajay Chaudhari, Raju, G S., A

J Pure & Appl Phys, 39 (2001)

Bordewijk, P., Kunst, M, and

Bottcher, C J F.,Theory of DielEberson, L. Caeboxylic Acids

Frohlich H,Theory of dielectri

Indira, T., Parthipan, G., AswKirkwood J G, J Chem Phys, 7

Krishnan, S., KanagasabapathKroeger, M K., J Mol. Liquids,

Manda, H., Frood, D G., Habib

3145.

Prajapati A N, Vyas A D, Ran

Purohit H D & Sengwa R J, J

Sengwa, R J., & Purohit, H D.,Thenappan, T., Sankar, U., J

Vir Singh Rangra., & Sharma,Vyas, A D., & Vashisth, V M.,

Yadava, S S., Aniruddh Yadav

3); 2016 http://www.drbgrpublications.in/ijcsr.p

rigipati Raju, Harish Chaudhari, Prakash Kh

roc. Natl. Counc. Roc (A), 25 (2001) 205-21

nita Das., Harish Chaudhari, Narain and Sure

180.

ip, A., J Phys Chem,77 (1973) 548.

ectric Polarization, Vol I, Elsevier , Amsterdaand Ester.Patai, Interscience, 1969.

s, (Clarendon Press, Oxford), 1958.

thaman, H., Thenappan, T, J Mol. Liquids, 1 (1939) 911.

, K, Lett. Asian Chem, 1(1) (1997) 37. 36 (1987) 101-108.

ullah, M., Humeniuk, L., & Walker, S. J Che

V A & Bhatnagar S P, Journal of Mol Liqui

olym Mater ,8 (1991) 317.

Poym. Int ., 29 (1992) 25. ol Liquids.,126 (2006) 23-28.

D R., Indian J Pure & Appl Phys, 41 (2003) J Mol Liquids, 38 (1988) 11-22.

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p; ISSN: 2454-5422

irade, Navinkumar

0.

sh Mehrotra, Indian

m (1973),

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630-633.

340.




Z - Scan measurement and impedance analysis of L-alanine alaninium nitrate single

crystals (LAAN)

R. Jothi mani1*, P. Selvarajan2 and C.Parvathiraja1

1

Department of Physics, Sadakathullah Appa College, Tirunelveli, India.2Department of Physics, Aditanar College of Arts and Science, Tiruchendur, India.

*Corresponding Author E-mail: [email protected]

Abstract

L-alanine alaninium nitrate (LAAN) crystal is a semi-organic nonlinear optical material. XRD

analysis confirmed the monoclinic structure of LAAN crystal.SHG efficiency of the sample

show good value. Third order nonlinear optical studies using z-scan technique is done to find

open and closed aperture of LAAN crystal in order to estimate the nonlinear optical parameters.

The impedance analysis was also carried out for the sample to find out various electrical

properties as a function of frequency and temperature.

Keywords: Single crystal; XRD; Impedance; Third-order NLO; SHG

Introduction

Organic crystals with large second-order and third-order nonlinear susceptibilities are of greatinterest because of their potential use in optical parametric amplifier and oscillator in the

infrared region. Among the amino acids the L-alanine is a well-known organic nonlinear optical

material which has been examined by several researchers in the recent past on its crystal growth

and properties. The Z-scan technique is a popular method for the measurement of optical

nonlinearity of the material. It has the advantage of high sensitivity and simplicity and is used to

measure the third order nonlinear optical parameters. Impedance spectroscopy is a powerful

technique for the characterization of electrical behavior of optical material. This techniqueanalyzes the ac response of a system to a sinusoidal perturbation and subsequent calculation of



IJCSR;

the impedance as a function of

in a complex plane, appears i

phenomena due to bulk materi

Nucleation kinetics parametdielectric analysis, etching stu

single crystals grown by slow

Mani, et al. In this work imp

discussed for the first time.

Materials and Method

L-alanine and nitric acid was

amount of reactance was d

homogeneous solution. Crystal

(accuracy + 0.01 oC) by slo

transparent, colourless and it is

Figu

Results and Discussions

Second Harmonic Generatio

The generation of second har

green light of halved wavelen

( 1064 nm) of Nd:YAG la

of grown sample is 2.1 times t

Third Harmonic Generation

Third-order NLO studies were

determining the nonlinear ind

2(3); 2016 http://www.drbgrpublications.in/ijcsr.

frequency of the perturbation. The output re

n the form of a succession of semicircle re

l, grain boundary effect and interfacial phen

rs, solubility, growth, hardness parameties and nonlinear optical analysis of L-alani

ooling technique is already reported for the

edance analysis and Z scan measurements

taken in 2:1 molar ratio to synthesis LAAN

issolved in double distilled water and

lization was allowed to take place in a const

cooling method. It is observed that the

well formed with sharp edges (figure 1).

e 1: Harvested crystals of LAAN

analysis

onics was confirmed as the LAAN crystal

gth (532 nm) when it is irradiated by fund

ser. It is observed from this study that the rel

at of the reference KDP crystal.

analysis

carried out by Z-scan technique. It is a st

x of refraction (n2), nonlinear susceptibilit

php; ISSN: 2454-5422

ponse, when plotted

presenting electrical

omena.

rs, XRD analysis, ne alaninium nitrate

first time by R.Jothi

of LAAN sample is

sample. Calculated

stirred well to get

ant temperature bath

grown crystals are

is found to produce

amental wavelength

ative SHG efficiency

ndard technique for

y (χ (3))and nonlinear



IJCSR;

absorption coefficient (β). This

investigation along a focused

of the normalized transmitta

nonlinear absorption and nonli

This technique is also useful

nonlinear refractive index of t

valley, similarly the positive n

by transmittance peak.

Figure 2 : Op

The formulas for calculating n

The nonlinear absorption (β)

measured in open and close

nonlinear refractive index (n2

nonlinear absorption coeffici

saturation absorption process

10-6 (esu) is due to the π-electr

crystal. Z-scan data of LAAN

property and produces higher e

Impedance Analysis

Impedance spectroscopy is a

of NLO material. The comple

RC circuit with parallel combi

impedance (resistor and capac

-15 -10 -5 0 5

2

3

4

5

6

7

N o r m

a l i s e d

T r a n s m

i t t a n c e

( a r b

. u n i t s )

Z (mm)

O pen a


method depends on the position (Z) of the t

aussian laser beam. Measurements of open

ce is made in order to estimate the inte

near refraction process and the curves are sh

o find the sign of nonlinear refractive inde

he sample shows transmittance peak follow

nlinear refractive index shows the transmitt

en and closed aperture mode of LAAN sa

onlinear optical parameters are already expl

and nonlinear refractive index (n2) of t

d aperture curves respectively. The nega

= 6.476 x10-10 cm2 /W) reveals the self-de

nt (β = 10.60 x10-5 cm/W) value exhi

f sample. And third-order nonlinear suscept

on cloud movement from the donor to the a

shows that the sample has better third or

nergy for optical applications.

owerful technique for the characterization o

impedance of the sample demonstrated as t

nation. Figure: 3 shows the real (Z’) and i

itor behavior) and both are decrease with ri

10 15

LAAN

perture mode

-15 -10 -5 0 5

1

2

3

4

5

6

N o r m

a l i s e d

T r a n s m

i t t a n c e

( a r b

. u n i t s )

Z (mm)

LA

C losed ape

php; ISSN: 2454-5422

in sample under the

and closed aperture

sity dependence of

wn in figure:2

x (n2). The negative

ed by transmittance

nce valley followed

ple

ined in literature[8].

e crystal has been

tive sign values of

focusing nature, the

its the two-photon

ibility (χ (3) = 4.489 x

ceptor of the grown

er nonlinear optical

f electrical behavior

he sum of the single

aginary (Z”) part of

se in frequency and

10

AN

rture mode



IJCSR;

temperature and gives indicati

coincidence of the impedance

possible release of space char

different temperatures shows (

semicircular arcs and spikes h

due to the grain boundary (blo

bulk effect. This bulk effect a

LAAN material. The values

different temperatures have be

axis (table 1).

Figure 3: Variation of real

Figure 4: Nyquist plot an

0 1 2 3

-2

0

2

4

6

8

10

12

14

Z ' ( M Ω )

Log frequency

3

5

7

0 2 4 6 8

0

1

2

3

4

5

Z'(MΩ)

LAAN

- Z " ( M Ω

)

Nyquist Plot


n of increasing conduction with temperature

( Z ’) at higher frequencies at all the tem

ge. A Nyquist plot (complex impedance sp

figure: 4) the transport response function. C

ave been observed. The low frequency sem

cking core) whereas the higher frequency s

rises due to the parallel combination of bu

of bulk resistance ( Rb) and grain boundar

en obtained from the intercept of the semicir

nd imaginary part of impedance (Z’ and

variations of Dc conductivity with tempe

sample

4 5

0oC

0oC

0oC

LAAN

0 1 2 3

0

1

2

3

4

5

Log frequency

3

5

7

- Z " ( M Ω )

LAAN

10 12 14

30oC

50oC

70oC

30 40 50

20

40

60

80

100

120

140

D c c o n d u c t i v i t y x 1 0 - 7 Ω m - 1

Temperature (o

LAAN

php; ISSN: 2454-5422

and frequency. The

eratures indicates a

ctrum) of LAAN at

aracteristically, one

icircle is considered

micircle depicts the

lk resistance ( Rb) of

resistance ( Rgb) at

cular arc on the real

”) with frequency

ature for LAAN

4 5

0oC

0oC

0oC

60 70

)



IJCSR;

It is found that the values of Rb

negative temperature coefficie

Table: 1

Temperarure

305070

The dc conductivity values (

increase in conductivity with iin the material has been found

Conclusion

A nonlinear optical LAAN c

SCXRD analysis confirmed t

the sample. Nonlinear optical

measurements. Electrical pro

analyses shows that LAAN sa

Acknowledgement

The authors are grateful to the

India for the financial support

this work. Also the authors ar

Science, Tiruchendur for the

Engg college Tirunelveli, Cre

gratefully acknowledged for th

Reference

S.X. Dou, D. Josse, J. Zyss, J.

Lydia Carolin et al, Materials

Vimalan M., Ramanand A., Sa

Lucia Rose S.J., Selvarajan P.,


and Rgb decreases with rise in temperature.

t of resistivity (LAAN) behavior like that of

C Bulk resistance Rb

(ohm)Grain bound

resistance Rgb (5.54 x103.70 x10 6

1.17 x10 6

3.48 x101.91 x10 6

0.58 x10 6

igure: 4) found by the formula DC = d/A

creasing temperature. The electrical relaxatito be temperature dependent

ystal was grown by slow cooling techniqu

e monoclinic structure with non-centrosym

analysis was carried out by Kurtz powder t

erties were determined by Impedance ana

ple is promising NLO material for optoelect

Department of Science and Technology (D

(Major project approval No.SR/S2/LOP-001

e thankful to the management of Aditanar

ncouragement given to us to carry out the

sent Engg College Chennai, SAIF cochin

eir support.

Opt. Soc. Am. B 10, 1708 (1993).

hemistry and Physics 114 (2009) 490.

gayaraj P., Cryst. Res. Tech. 42 (2007) 1091.

Perumal S., Mater. Chem. Phys., 130 (2011)

php; ISSN: 2454-5422

his shows the

insulator.

ary ohm)

R (ohm m)-1 show

on process occurring

e for the first time.

etric space group of

chnique and Z-scan

lysis. All the above

ronic applications.

ST), Government of

8/2010) to carry out

College of Arts and

research work. PSN

nd VIT Vellore are

950.



IJCSR;

Sabari Girisun T.C, Dhanusko

Bharath D., Kalainathan S., Sp

Jothi Mani R., Selvarajan P. et

Jothi Mani R., Selvarajan P. et

Banarji Behera et al, J. Alloys

Arun K.J., Jayalekshmi S., J.


i S., Cryst. Res. Technol. 44 (2009) 1297.

ectrochimica Acta Part A: 120 (2014) 32.

all, Int. J. Adv. Sci. Tec.Res., 3 (2013) 2249.

all, Int.J. Sci. Engi. App. Special Issue, (201

and Compounds 436 (2007) 226.

inerals & Materials Charac.Engi. 8 (2009) 6

php; ISSN: 2454-5422

) 83.

35.




Studies on optical and mechanical properties of dl-malic acid doped ADP single crystals

I.Stella Jeya Christy1, A. Effie Cordelia1 and S. Perumal2

1Department of Physics, Sarah Tucker College (Autonomous), Tirunelveli, India.

2Physics Research Centre, S. T. Hindu College, Nagercoil, India.

Abstract

Nonlinear optical single crystals of DL malic acid doped Ammonium Dihydrogen Phosphate

were grown by slow evaporation solution growth method. The grown crystals were

characterized using X-ray diffraction studies. The possible functional groups present were

identified using Fourier Transform Infrared Spectroscopy. Optical parameters like

transmittance, absorbance, reflectance, optical absorption co-efficient, refractive index,extinction co-efficient, band gap energy, optical conductivity, electrical conductivity, electrical

susceptibility and real and imaginary parts of dielectric constant of the crystal were estimated

from UV-Vis-NIR spectrum. SHG efficiency was checked using Kurtz-Perry powder technique.

Third order nonlinear refractive index, nonlinear absorption co-efficient and third order

susceptibility had been calculated from Z-scan technique. Mechanical parameters such as work

hardening co-efficient, yield strength, elastic stiffness constant, fracture toughness and

brittleness index were obtained using Vicker’s microhardness studies.

Key Words: Solution growth, FTIR, UV-Vis-NIR spectrum, SHG, Z-scan technique, Vicker’s

micro hardness

Introduction

Ammonium Dihydrogen Phosphate, which is an important isomorph of Potassium Dihydrogen

Phosphate crystal, has been widely used for frequency conversion in laser systems, optical

switches and acousto optical devices. This hydrogen bonded compound also exhibits piezo

electric activity and low temperature order-disorder phase transition Below 148 5K ADP is



IJCSR;

ferroelectric and belongs to P

paraelectric having I4/2d sy

applications in the field of pho

optic modulation. DL-malic ac

Because of this attempt, the S

better advantage of using these

Experimental Work

The commercially available A

2mole% of DL-malic acid is

ADP. The solution is put in

mixture and filtered. After le

colourless transparent single

selected and characterized. Th

Figu


FTIR SPECTRAL ANALYSI

BRUKER IFS 66V FTIR Spe

crystal. The spectrum was give

table1.


212121 space symmetry group while above

metry [1]-[3]. This is also nonlinear opti

tonics for frequency mixing, parametric amp

id is an organic material which is chosen to

HG efficiency of ADP is found to increase

doped crystals in photonics and related field

R grade chemicals ADP and DL-malic acid

issolved in deionized water together with c

agnetic stirrer for about four hours to get

aving it in dust free undisturbed atmosphe

crystals had been harvested. Out of these

photograph of the grown crystal is given in

e 1.Photograph of the grown crystal

ctrometer was used to record the FTIR spe

n in fig.2 and the corresponding assignment

php; ISSN: 2454-5422

this temperature, it

cal material having

lification and electro

be doped with ADP.

so that we arrive at

s.

were purchased and

alculated amount of

highly homogenous

re for three weeks,

, fine crystals were

fig.1

ctrum of the grown

s [4],[5] are given in



IJCSR;

wavenumber

in cm-1

3242

O-H st

vibrati

2410 band d

2294 combin

1634 O-H be

1444 H-H be

1407 bendin1289 CH2 ro

1102 P-O-H

917 P-O-H

549 PO4 vi

414 PO4 vi


Fig. 2.FTIR Spectrum

Table 1-FTIR assignments

FTIR assignments

etching, P-O-H stretching , N-H

ns of ammonium

e to hydrogen bond

ation band

nding of water

nding of NH4

vibrations of ammoniumcking vibration

vibrations

vibrations

rations

rations

php; ISSN: 2454-5422



IJCSR;

UV-VIS-NIR SPECTRAL S

Optical transmission spectrumin the wavelength region 400-1

Fig.3.transmittance,

Good transmittance for a wide

fabrication and this is achieved

280 nm. and the band gap ener

the refractive index(n) of the

Fig.4.Optical absorptio

Fig.5.Variation of optical


UDIES

of the crystal was recorded using Lambda 35100nm and is shown in fig.3.

absorbance and reflectance as function of

region of wavelength is the required conditi

here. The cut off wavelength in the UV regi

gy from Tauc’s plot in fig.4 is 4.5 e V .[6],[7

rystal with wavelength is plotted in fig.5 .

coefficient and extinction coefficient vers

nd electrical conductivities and electrical s

photon energy

php; ISSN: 2454-5422

spectrophotometer

avelength

on for device

on is found to be

].The variation in

s wavelength

sceptibility with



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The calculated values of extinc

conductivity (Ϭel), electrical su

λ=700nm are estimated and ta

Tabl

Z- SCAN TECHNIQUE

When a third order material i

refraction changes causing fo

transmittance change through

able to determine the amplitud

without placing an aperture a

dependant absorption of the sa

He-Ne laser beam with wavel

of focal length 18.5 cm. The o

The input energy and energy

The normalized transmittance

was used to calculate the third

curves in both open and close

The calculated values of the th

Exti

effi

opti

elec

con

Ele

sus

R.P

con

I.P.

con


tion co-efficient (K), optical conductivity (Ϭ

sceptibility (χ c), real and imaginary parts of

ulated as below in table 2.

e 2 – Optical parameters of the crystal

s translated along a focused Gaussian lase

using or defocusing of the beam. By pro

a small aperture at the far field position (clo

e of the phase shift. By moving the sample t

t the detector (open aperture), one can det

ple.

ngth 632.8nm was used and it was focused

ptically polished 1mm thick crystal was tra

transmitted by the sample were measured u

or the positioned sample was measured at di

nonlinear optical property of the materials

d aperture modes are illustrated in fig.6 an

ird order parameters are,

nction co-

ient 2.241x10-5

cal conductivity 2.22x10 s-

trical

uctivity 82.74m2s-1

trical

eptibility 0.4247

.of dielectric

stant 5.338

f dielectric

stant 10.365x10-5

php; ISSN: 2454-5422

op), electrical

ielectric constant at

beam, its index of

erly monitoring the

sed aperture), one is

rough the focus and

ermine the intensity

using a convex lens

slated along Z-axis.

sing a power meter.

fferent positions and

[8],[9]. The Z- scan

d fig.7 respectively.



IJCSR;

nonlinear refractive index ( n2

nonlinear absorption co-efficie

the real and imaginary parts o

Im χ 3 = 5.193 x 10 -3esu.

Fig.6 . Z-scan – open aperture

3.4. VICKER’S MICROHAR

Mechanical strength of the m

Jianghong Gong el al, during

is converted to a strain energ

impression. The hardness of a

energy, De bye temperature, h

The Vicker’s hardness indenta

varied as 25g, 50g and 100g

was measured using Vicker’s

The indentation time was kept

using the relation

Hv = 1.8544 P/d 2 Kg/mm2

Where HV is Vicker’s microh

length of the indentation in m


) = 2.6245x10-11cm2 /W,

nt(β) = 7.512x10- 6cm/W,

f the third order susceptibility Re χ 3 = 3.601x

Fig.7. Z-scan- closed aperture

NESS TEST

aterial plays a key role in the device fabri

n indentation process, the external work ap

y component which is proportional to the

material is influenced by various paramete

at of formation and interatomic spacing.

tions were made on the cut and polished sa

nd the corresponding diagonal length of t

diamond indenter and attached to an incide

at 5s for all loads. The Vicker’s hardness nu

ardness number, P is the applied load in

. The variation of Hv with load P is shown i

php; ISSN: 2454-5422

10 -5esu ,

ation. According to

lied by the indenter

volume of resultant

s such as the lattice

mples and load was

he indentation mark

nt light microscope.

mber was calculated

g.,d is the diagonal

n fig.8.



IJCSR;

Fig.8. Dependance of H v wi

Fig.10 . Depend


th load Fig.9. Relation betwe

ence of various mechanical parameters wit

php; ISSN: 2454-5422

n log P and log d

load



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It is evident from the plot that

log P and log d is a straight lin

is found to be n= 3.75[10]. Fig.

The yield strength (Ϭy), elasticConstant (B) are calculated an

Table 3.

Load (P) g Yield str(σy)

25 1.9

50 2.47

100 3.36

SHG ANALYSIS

Nonlinear optical property of t

and its efficiency was compar

the randomly oriented micro c

tube after filtration of the incid

was confirmed by the emiss

wavelength is 532 nm. The re

crystals shows that the SHGcrystals.

Conclusion

DL-malic acid doped ADP si

solution growth method. The

using FTIR spectroscopy. Th

uniformity of refractive index


the hardness of the sample increases with lo

e and the slope of the line gives the work ha

.9.Hence this crystal belongs to the category

stiffness constant (C11), fracture toughness (given in table 3 as below.

echanical Parameters of the grown crystal

ength Pa

Elasticstiffness

constant (C11)1014 Pa

Fracturetoughness

coefficient (

105 kgm-3/2

7.675 7.502

5 12.193 15.003

6 20.892 30.006

he grown crystal was analyzed with Kurtz-P

d with KDP and urea. Second harmonic ra

rystals was focused by a lens and detected

ent radiation of wavelength 1064 nm. The d

ion of the green colour output radiation

lative measured output from the specimen

fficiency of the crystal is 1.032 times high

ngle crystals were successfully grown usi

functional groups present in the grown crys

wider bandgap of the material, significa

in the entire visible region make the candi

php; ISSN: 2454-5422

d. The plot between

rdening index which

of soft materials.

Kc) and brittleness

c)

Brittlenessindex (B)

m-1/2

43.588

28.394

19.313

erry powder method

iation generated by

by a photomultiplier

ubling of frequency

hose characteristic

ith respect to KDP

r than that of KDP

g slow evaporation

tals were elucidated

t transmittance and

ate ideal for device



IJCSR;

fabrication. Moreover, the crys

inferred from Z- scan techniq

withstand the processes involv

Acknowledgement

The authors are grateful to P

IISc, Bangalore for NLO-SH

studies.

Reference

1. M.E. Lines, A.M. Gl

materials, Clarendon P

2. N.G. Parsonage, L.A.K

3. L. Tenzer,B.C. Frazer,

H 2PO4 single crystals,

4. P. Rajesh, P. Ramas

characterization, Jour.

5. Briyan C.Smith, IR sp

New York6. Dhanaraj et al, Effect

properties of ADP crys

7. M. Senthil Pandian et a

and its analysis on

studies,Mat.Lett.62(20

8. R. DeSalvo, N. Sheik-

refraction and absorpti

9. M. Krishnakumar et a

properties of solution

monohydrate crystals,

10. E.M.Onitch, The prese

1950


tal has self focusing nature and two photon a

ue. The mechanical strength of the crystal

d in device fabrication.

of. Sastikumar, NIT, Trichy for Z-scan an

G studies and St.Joseph’s College, Trich

ss, Principles and applications of Ferroe

ress,Oxford,1977

. Stavely, Disorder in Crystals, Clarendon P

R. Pepinsky, A neutron structure analysi

cta Crys.11(1958)505

my, Growth of DL-malic acid doped A

rys,Grow.311,(2009)3491-3497

ectral interpretation, A systematic approac

of amino acid additives on crystal gro

tals,Mate.Chem.Phy,112,(2008)490

l, Growth of TGS single crystals by conventi

the basis of mechanical, thermal, o

8)3830

ahae et al, Z-scan measurements of the ani

on in crystals, Optics Letters,Vol.18,no.3,19 l, Studies on the structural and third ord

grown 4-hydroxy-3 methoxy-4’ - N’ -metyls

ptical materials,Vol.36,no.5,988-995,2014

t status of testing hardness of materials, Mi

php; ISSN: 2454-5422

bsorption process as

is also sufficient to

alysis, Dr.P.K.Dhas,

for microhardness

lectrics and related

ress,1978

of tetragonal NH 4

P crystals and its

-CRC Press (1999)

th parameters and

onal and SR method

tical and etching

sotropy of nonlinear

-196 r nonlinear optical

tilbazolium tosylate

croscope, 95, 12-14,




THERMAL AND DIELECTRIC PROPERTIES OF DL-MALIC ACID DOPED ADP

NLO SINGLE CRYSTALS

A.Roselin1, A. Sumathi1, A. Effie Cordelia1 and S. Perumal2

1Department of Physics, Sarah Tucker College, Tirunelveli, India

2Physics Research Centre, Nagercoil, Tamilnadu, India

Abstract

DL-malic acid doped ADP nonlinear optic single crystals were grown by solution method. The

thermal stability and the dielectric properties of the crystals were studied. Good thermal

stability and low dielectric loss of the crystals enable them as better candidates for opto

electronic device fabrication.

Keywords: Slow evoparation solution growth method, TG-DTA, AC conductivity, activation

energy

Introduction

Ammonium Dihydrogen Phosphate, which is an important isomorph of Potassium Dihydrogen

Phosphate crystal, has been widely used for frequency conversion in laser systems, optical

switches and acousto-optical devices. This hydrogen bonded compound also exhibits

piezoelectric activity and low temperature order-disorder phase transition. Below 148.5 K, ADP

is ferroelectric and belongs to P212121 space symmetry group while above this temperature, it is

paraelectric having I4/2d symmetry. This is also nonlinear optical material having applications

in the field of photonics for frequency mixing, parametric amplification and electro optic

modulation. DL-malic acid is a dicarboxylic acid which is chosen to be doped with ADP.

Because of this attempt, the SHG efficiency of ADP is found to increase so that we arrive at

better advantage of using these doped crystals ADPMA in photonics and related fields. These

l i l l f d d h i i ffi i



IJCSR;

than ADP. To avail the maxi

of these crystals were analyzed

paper.

Method of crystal growth

Analar Reagent (AR) grade

DL-malic acid were purchase

crystal ADPMA , 2 mole % o

dissolved in double distilled

three hours and filtered. Th

transparent colourless nonli

photographs of the crystals are


Single crystal X-ray diffractio

The unit cell parameters and c

using BRUKER- NONIUS M

table 1.

Table 1 Cel

Sample System

ADPMA Tetrago


um usage of these crystals, the thermal and

by the corresponding characterization tools

hemicals Ammonium Dihydrogen Orthoph

d commercially. To obtain DL-malic acid

f DL-malic acid along with the calculated a

ater The solution was stirred well using a

solution was kept undisturbed in dust

ear optical single crystals ADPMA w

shown in fig 1.

analysis

rystalline system of these three crystals AD

CH3 /CAD4 single crystal X-ray diffractom

l parameter values of ADPMA single crysta

a( ) b( ) c( )

nal 7.525 7.525 7.

Fig.1.Photograph of the grown crystal ADPMA

php; ISSN: 2454-5422

dielectric properties

and presented in this

osphate (ADP) and

doped ADP single

mount of ADP were

magnetic stirrer for

ree atmosphere till

re harvested. The

MA were found out

eter and tabulated in

s

V( )3

573 429



IJCSR;

In ADPMA, the system in whi

The lattice parameters vary a l

cell.

Powder X-ray diffraction anal

The harvested crystals ADP

diffractions were recorded u

diffractometer with CuK (=

80 o at the rate of 2 per minut

from the crystallographic para

From the patterns 2 values wcan be estimated. The d-spac

using Bragg’s law 2dsin = n

n is the order of diffraction a

using the procedures of Lips

crystals ADPMA are plotted i

FTIR spectral analysis

The Fourier Transform Infra

chemical bonding and it provi

compound. The spectrum was

range using KBr pellet techniq

bending, twisting, rotating and

Fig.2.


ch the material crystallizes remains the same

ittle and there is a small change noticed in th

ysis

MA were ground into fine powder and

ing X-ray diffractometer using BRUKER

1.5418 Å) radiation . The sample was scann

e. The crystalline phase structure of the sa

eters such as 2, d-spacing, relative intensit

re read directly and the relative intensity ofings corresponding to different peak positi

where d is the interplanar spacing, is the

d is the wavelength of X-rays used. The

on and Steeple. The powder X-ray diffrac

fig. 2 .

red spectral analysis has been carried ou

des useful information regarding the molec

recorded with Perkin Elmer FTIR spectrome

ue. Infrared absorption studies involve exam

vibrational modes of atoms in a molecule an

owder X-ray diffraction pattern of ADPMA

php; ISSN: 2454-5422

which is tetragonal.

e volume of the unit

the powder X-ray

AXS D8 advance

ed over the range 0-

ples was identified

y and hkl values.

the diffraction peaks ons were calculated

angle of diffraction,

peaks were indexed

tion spectra for the

t to understand the

ular structure of the

ter in 400-4000 cm-1

ination of stretching,

d hence to identified



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the functional groups of the

frequencies and thus it is easie

The FTIR Spectra of the crys

assignments are displayed in ta

Tab

Wave number cm-1

3243

2410

2294

1634

14441407

1289

1102

917

549

414

O-H st

band d

combi

O-H b

H-H bbendin

CH2 ro

P-O-H

P-O-H

PO4 vi

PO4 vi


samples. FTIR spectrum is interpreted

to characterize the substance.

tals ADPMA are given in fig.3 and the co

ble 2.

e 2 Spectral assignments for ADPMA

ADPMA

Assignments

retching, P-O-H stretching , N-H vibrations of ammo

ue to hydrogen bond

ation band

nding of water

nding of NH4

g vibrations of ammonium

cking vibration

vibrations

vibrations

brations

brations

Fig.3.FTIR spectrum of ADPMA

php; ISSN: 2454-5422

sing known group

rresponding spectral

nium



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Thermal analysis

Studies of thermogravimetric

check the thermal stability and

thermal curves of the grown cr

In ADPMA, the crystal is fou

196.88 oC. No other endother

TGA, there is weight loss of 5

C and 600 C, a weight loss o

Dielectric studies

The dielectric properties of t

Precision LCR meter. The expoC over a frequency range 100

at different temperatures is sh

different temperatures is sho

variation with temperature at

these crystals have similar beh

Fig.4.


and differential thermal analysis (TG-DTA)

to identify various endothermic and exothe

ystals ADPMA are given in fig.4.

d to be thermally stable upto 196.88 C an

ic and exothermic peak seen from DTA cu

1.3 % of the sample between 180 C and 23

f 33.3 % is observed.

he crystals ADPMA were determined usi

riment was conducted at various temperatur

Hz to 1 MHz The variation of dielectric con

own in fig. 5. The variation of dielectric lo

n in fig.6. Similarly these two dielectric

ifferent frequencies and these are plotted in

avior in which dielectric constant decreases

G-DTA thermogram for the crystal ADPMA

php; ISSN: 2454-5422

were carried out to

mic transitions. The

the crystal melts at

rve of the crystal. In

C. In between 280

g Agilent (4284A)

s from 40 oC to 140

stant with frequency

s with frequency at

arameters have the

fig. 7 and fig.8. All

with frequency and



IJCSR;

increases with temperature. As

found to posses enhanced opti

the NLO materials in the fields

It is observed that AC conduenergies are calculated at freq

table 5.

Fig.5.Dielectric constant v

Fig.6.Dielectric loss vers


the crystals have low dielectric loss at high

al quality with less defects. This is a require

of various applications.

tivity of the crystals increases with temperency 1 kHz for all the three crystals. The va

rsus frequency of the applied field at differ

us frequency of the applied field at differen

php; ISSN: 2454-5422

frequencies, they are

d vital parameter for

ature and activation lues are tabulated in

nt temperatures

t temperatures



IJCSR;

Fig.7.Dielectric c

Fig.8.Dielectri


onstant versus temperature at different freq

loss versus temperature at different freque

php; ISSN: 2454-5422

encies

ncies



IJCSR;

Table 3

Sample Frequency

Hz

40oC 60

ADPMA

102

103

104

105

10

6

7.68

6.83

6.46

6.23

5.97

8.

7.

6.

6.

6.

The values of AC co

frequencies and temperatures

9. Activation energy for the t

and shown in table 5.

Table 4 Variation of ac cond

Sample Frequency(Hz)

ADPMA

102

103

104

105

106


Dielectric parameters of ADPMA crystals

Dielectric Constant

εr

Die

C 80 oC 100oC 120oC 40oC 60oC

.16

.25

.66

.34

.06

9.79

7.68

6.95

6.47

6.11

10.53

7.91

7.36

6.77

6.35

11.98

8.62

7.84

6.99

6.51

0.09

0.048

0.034

0.021

0.02

0.13

0.06

0.045

0.027

0.024

ductivity of the crystals ADPMA were ca

nd listed in table 3. The corresponding curv

ree grown crystals at frequency 1 kHz is ca

ctivity of the crystals ADPMA with frequen

σac x

10-6(Ωm)

-1

40o C 60o C 80o C 1000

0.00384

0.0182

0.022

0.727

6.636

0.006

0.024

0.246

0.951

8.083

0.0125

0.03

0.0332

1.366

9.848

0.018

0.035

0.028

1.54

10.94

php; ISSN: 2454-5422

lectric Loss

tanδ

80oC 100oC 120oC

0.23

0.07

0.06

0.038

0.029

0.32

0.08

0.07

0.041

0.031

0.4

0.082

0.074

0.041

0.033

lculated at different

es are plotted in fig.

lculated using fig.10

cy and temperature

1200 C

7

2

6

1

0.027

0.0393

0.0422

1.593

11.94



IJCSR;

Fig. 9 Va

Fig.10 Graph d

Table 5 Activ


iation of AC conductivity with temperature

awn to calculate activation energy of the cr

ation energy of the crystals at frequency 1 k

Sample Eac eV

ADPMA 0.1032

php; ISSN: 2454-5422

ystals

Hz



IJCSR;

Conclusion

Novel NLO single crystal AD

growth method. The crystalli

crystal XRD analysis. Powdeplanes were indexed. The pos

from FTIR spectra. The hard

Thermal stability of the samp

were calculated and AC condu

dielectric studies.

Reference

1. M.E. Lines, A.M. Gl

materials, Clarendon P

2. N.G. Parsonage, L.A.K

3. L. Tenzer,B.C. Frazer,

H 2PO4 single crystals,

4. P. Rajesh, P. Ramas

characterization, Jour.

5. Briyan C. Smith, IR sp

New York

6. Dhanaraj et al, Effect

properties of ADP crys

7. M. Senthil Pandian et a

and its analysis on t

Mat.Lett. 62 (2008) 38

8. M. Krishnakumar et a

properties of solution

monohydrate crystals,


PMA were grown successfully using slow

ne nature and lattice parameters were fou

XRD pattern of the crystals were obtainesible functional groups present in the cryst

ness studies revealed the mechanical stren

le was checked using TG-DTA analysis.

ctivity and activation energy of the crystals

ss, Principles and applications of Ferroe

ress, Oxford, 1977

. Stavely, Disorder in Crystals, Clarendon P

R. Pepinsky, A neutron structure analysi

cta Crys.11 (1958) 505

my, Growth of DL-malic acid doped A

rys. Grow.311, (2009) 3491-3497

ectral interpretation, A systematic approach

of amino acid additives on crystal gro

tals, Mate.Chem.Phy .112, (2008) 490

l, Growth of TGS single crystals by conventi

e basis of mechanical, thermal, optical

0

l, Studies on the structural and third ord

grown 4-hydroxy-3 methoxy-4’ - N’ -metyls

ptical materials, .36(5), 988-995, 2014

php; ISSN: 2454-5422

vaporation solution

nd out using single

d and the reflecting als were determined

gth of the crystals.

ielectric parameters

were estimated from

lectrics and related

ess,1978

of tetragonal NH 4

P crystals and its

- CRC Press (1999)

th parameters and

onal and SR method

nd etching studies,

r nonlinear optical

tilbazolium tosylate



IJCSR;

Special Issue on INHIM’16

,

Volume: 2; Issue:

Solvothermal Synthesis and Ch

A.Suganthi*1, S.John Kennad

S.Karpagavalli5

*1&5Govindammal Adithanar College f

2&4 St. John’s College, Palayamkottai,

3 Principal,S.T.Hindu college,Nagercoil,

Manganese doped Copper oxid

thermal method using Copper ac

oxide nanoparticles. X-ray diff

sample is examined by Scannin

impurities present in the materi

doped copper oxide nanoparticle

Key words: Solvothermal, Nano

Introduction

In recent years, controlled sy

has attracted considerable intere

significant impact on their functi

P-type semiconductor oxide tha

applications. It has potentia

magnetic storage media and l

prepared by several methods r

state reaction to gas phase proc

powerful technique for generati

solvothermal technique provi

2(3); 2016 http://www.drbgrpublications.in/ijcsr.ph

arah Tucker College (Autonomous), Tirunelveli.

3 [Special Issue]; March-2016; pp 497-502. ISS

aracterization of Manganese Doped Copper

Like Nanostructures

y Vethanathan2, S.Perumal3, D.Priscilla

r Women, Tiruchendur, India.

ndia.

India.

Abstract

nanoparticles are synthesized by a microwa

etate as precursor. This gives a large scale pro

action pattern reveals cubic structure. The m

electron microscopy technique. The functiona

al are interpreted by FTIR. The optical prope

s are analyzed by UV-Visible spectroscopy.

particles

thesis of inorganic materials with well defi

st since the morphological diversity of inorgan

onal diversification and potential applications.

t is being widely studied due to its interestin

l applications in solar cells, Catalysis, el

ithium ion batteries. Copper oxide nanopar

nging from thermal reduction, sonochemial

ss. Among those, solvothermal process has be

ng novel materials with interesting propertie

es the alternative approach that allows

p; ISSN: 2454-5422

Page 497

N: 2454-5422

xide Flower

oilpillai4 and

ve assisted solvo

uction of Copper

orphology of the

l group and other

ty of manganese

ed morphologies

ic materials has a

opper oxide is a

g properties and

ctrode material,

icles have been

ethod and solid

en shown to be a

particularly the

the economical



IJCSR;


synthesis of fundamentally imp

The present work is focused

manganese doped copper oxid

method.


Copper (II) acetate monohydrat

hydrate are used as precursors.

dissolved in 100ml ethylene g

ethylene glycol. The solutions a

oven. Microwave irradiation i

completely. Colloidal precipita

distilled water and acetone to

atmospheric air.

Results

XRD analysis

The XRD pattern which is

nanoparticles is shown in fig.1.

Which was confirmed from the

(222) are corresponding to C

corresponding to Mn. No peaks

The average crystallite size was

D = k λ / βcos ,where K – Sch

and β–

Full width half maximum (FWH



rtant cell defined nanometer sized materials a

on the synthesis and characterization of n

e nanoparticle by a simple microwave assis

e, urea, ethylene glycol (solvent), Manganese

opper acetate and urea are taken in the molec

lycol as individually. Manganese acetate is

e mixed together. The solution is kept in a do

s carried out for 20 minutes till the solve

e is obtained. The precipitate is washed se

remove organic impurities. The prepared sa

btained in the present study for Mn dope

ll diffraction peaks can be indexed in the Cu2

CPDS 78-2076. The planes (110), (111), (200)

2O. The planes (002), (100), (101), (004

of impurities are found in XRD pattern.

estimated using Debye Scherrer’s equation ;

rrer constant, λ – Wavelength of the X-ray so

) of a diffraction peak

p; ISSN: 2454-5422

Page 498

mild conditions.

ano meter sized

ted solvothermal

(II) acetate tetra

ular ratio 1:3 and

lso dissolved in

estic microwave

nt is evaporated

veral times with

ple is dried in

d Copper oxide

cubic structure,

(220), (311) and

and (110) are

rce (1.5406 A0)



IJCSR;


I n

t e n

s i t y

( c o u

n t s )

* 0 0 2

* 0 0

2

* 0 0 2

* 0 0 2

T r a n s m

i t t a n c e

%

800

700

600

500

400

300

200

100

0

10

Fig 1FTIR analysis

The FTIR analysis is performed

3500 cm-1 and 1624cm-1 repr

attributed to C-H tensional .The

O) tremble respectively. The pe

cm-1 reveals the dopant Mn-O tr

150

Cu O: .2

Cu O: .2

100

50

0

4000

Fig 2: F



Cu2O: Mn (0.02)

CuO :Mn (0.06)2

*Mn

1 1 0

1 1 0

* 1 0 0

* 1 0 1

1 1 1

2 0 0

* 0 0

4

* 1 1 0

2 2 0

3 1 1 2 2

2

20 30 40 50 60 70 80

2 (degree)

: XRD spectrum of Mn doped Cu2O nanopa

by SHIMADZU MODEL-IRAFFINITY-1. T

sents (O-H) water tensional tremble. The pea

peak at 1458 cm-1 and 1384 cm-1 represen

ak at 986 cm-1 represents (O-C-O) tensional

emble respectively.

:Mn (0.02):Mn (0.06)

3500 3000 2500 2000 1500 1000 500

wavenumber(cm-1)

IRspectra of Mn doped Cu2O nanoparticles

p; ISSN: 2454-5422

Page 499

ticle

e peak at

at 2362 cm-1 is

ts (N-O) and (C-

tremble and 608

.

.



IJCSR;


SEM Analysis

In order to obtain insight inform

SEM analyses were performed.

Fig



ation about surface morphology and particle siz

ig.3. SEM image Cu2O: Mn (0.02g)

4 SEM image Cu2o: Mn (0.06g)

p; ISSN: 2454-5422

Page 500

e of the samples,



IJCSR;


283

294

A

b s o r b a n c e

SEM image reveals that Mn do

structure and the average size of t

UV – Visible analysis

UV-Visible absorption spectro

Mn doped copper oxide nanopa

is shown in Fig.5.It has been ob

around 294nm&283nm respectiv

1.0

0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

400

Fig.5.Abs

Discussion

Mn doped Cu2O nanoparti

method. The XRD result gives

average size of Mn (2 wt%&

33nm respectively. The aver

confirmation. FTIR spectrum a

VISIBLE absorbance spectrum

This shift towards lower wavel

nanoparticles.

Acknowledgement



CuO: Mn(0.022

CUO:Mn(0.02

ed Copper oxide nanoparticles exhibit rose fl

he image is found out using Image J software.

scopy has been used to investigate the op

ticles. The absorption spectra of Mn doped C

erved that the samples exhibit an absorption e

ely. The energy band gaps are 4.23ev&4.39ev.

600 800 1000 1200 1400 1600 1800

Wavelength(nm)

orbance spectra of Mn doped Cu2O nanoparticles

les are synthesized by microwave assi

a cubic structure with lattice parameters a=b=

wt %) doped Cu2O nanoparticles are found

ge crystallite size from XRD is very ag

alysis gives the brief investigation of functi

reveals blue shift in case of higher Mn dopi

ngth could be attributed to the quantum conf

p; ISSN: 2454-5422

Page 501

)

)

ower like

ical properties of

2O nanoparticles

ge

ted solvothermal

c=4.267 A0 .The

to be 39nm and

reed with SEM

nal groups. UV-

ng concentration.

inement effect of



IJCSR;


I state my deep sense of devotio

ideas, outstanding guidance an

thank my family members and fr

References

K. Sanfra, C.K. Sarkar, M.K.

Fernandes, R. Silva, A.A.W.

Mater. Chem. Phys. 115 (2009)

S.C. Ray, Sol. Energy Mater. S

Z. Zhong, V. Ng, J. Luo, S.P. T

M. Arumugam, N. Selvaraj, S.

51.

J.F. Deng, Q. Sun, Y.L. Zhang,

M. Frietsch, F. Zudock, J. Gosc

P. Poizot, S. Laruelle, S. Gruge

D.P. Singh and N. Ali, Sci. Adv

C. B. McAuley, Y. Du, G. G.

(2008)230.



n to my guide Dr.S.John Kennady Vethanatha

constant source of inspiration at every stag

iends who rendered direct and indirect help.

ukherjee, B. Cosh, Thin Solid Films 213 (

echenleitner, E. Radovanovic, M.A.C. Melo

10-115.

l. Cells 68(2001) 307.

h, J. Teo and A. Gedanken, Langmuir 23 (2007

umar, P. Selvam and A. Sambandam, Sci. Ad

S.Y. Chen and D. Wu, Appl. Catal. A 139 (199

nick and M. Bruns, Sensors Actuators B 65 (2

n, L. Supont and J.M. Taracon, Nature 407 (20

. Mater. 2 (2010) 295.

ildgoose and R.G. Compton, Sensors Actuat

p; ISSN: 2454-5422

Page 502

for his precious

of this work. I

1992) 226. D.M.

, E.A.G. Pineda,

) 5971.

. Mater.2 (2010)

) 75.

02) 379.

0) 496.

rs B 135



IJCSR;


Volume: 2; Is

OPTICAL AND STRUC

MANG

S. Karpagavalli*1, S .John Ken

*1Govindammal Adithanar College for

2&4 St. John’s College, Palayamkottai,

3Principal, S.T.Hindu College, Nagercoi

5Govindammal Adithanar College for

*Corresponding Author Email Id: karthi

ABSTRACT Cobalt doped

solvothermal route. The structu

particle size was calculated fro

Scanning electron microscope (S

spherical geometry. The optical

spectroscopy. UV-Vis spectra illu

blue shift from the bulk value

interpreted by Fourier transform i

have many applications in theproperties. Manganese oxide is e

performance, it is a good electrod

Keywords: Cobalt doped MnO2 n



ue: 3 [Special Issue]; March-2016; pp 503-509.

URAL CHARACTERIZATION OF COBA

ANESE OXIDE NANOPARTICLES

nady Vethanathan2, S.Perumal3, D. Priscilla K

and A. Suganthi5

omen, Tiruchendur, India.

ndia.

l, India.

omen, Tiruchendur, India.

[email protected]

anganese oxide nano particles have been

al properties were analyzed by X-ray diffra

XRD data by using Scherrer equation and

M) analysis. The SEM image shows that the n

roperties were analyzed by Ultraviolet – Visi

strates that Cobalt doped Manganese oxide nan

(2.5 eV). The functional groups present in

nfrared (FTIR) spectral analysis. Manganese o

near future by virtue of its magnetic propenvironmental friendly in nature. Due to good

material for super capacitors and batteries.

noparticles, Solvothermal route, XRD, SEM a

p; ISSN: 2454-5422

Page 503

ISSN: 2454-5422

T DOPED

ilpillai4

synthesized by

tion (XRD). The

is confirmed by

noclusters having

le (UV-Vis)

o particles acquire

he material were

ide nano particles

ties and catalytic lectro mechanical

d UV-Vis



IJCSR;


Introduction: A nano structured

one dimension in the nanomete

nanowires and nano rods are mad

for their mechanical, magnetic,

catalyst.Compared to bulk activ

higher capacities, larger surfac

relatively new and interesting tec

have been synthesized in rem

techniques eliminate the use of hi

for fast, reproducible synthesis of

In the present investigation we re

by microwave-assisted solvothe

morphology is examined by S

impurities present in the material

and the optical properties were an

Materials and Methods: AR gra

NH2CONH2 (catalyst) andCobalt

materials. The calculated amount

molecular ratio 1:3 and dissolv

hydrate(2wt% and 6wt %) were t

the completely dissolved solutio

carried out till solvent evaporate

with double distilled water and

samples were dried in atmospheri

Results:

X-Ray diffraction analysis:The

byBruker AXS D8 Advance mo

Cobalt doped MnO2nano syste

diffraction peaks are well indexed



material is defined as a solid material charac

range. The inorganic nano materials such a

e from metals, semiconductors or oxides are of

optical, chemical and other properties.It i

electrode materials, the corresponding nan

area, and lower current densities.Solvothe

nique for the synthesis of oxide materials. Vari

arkably short time under microwave irradi

gh temperature calcination for extended periods

crystalline metal oxide nano particles.

ort the synthesis of Cobalt doped Manganese o

rmal methodand characterized by powder

anning electron microscope, the functional

were interpreted by Fourier transform infrare

alyzed by ultraviolet - visible spectroscopy.

de Manganese II acetate tetra hydrate (CH3CO

II acetate tetra hydrate (CH3COO)2Co.4H2Owe

of Manganese II acetate tetra hydrate and ure

d in 100ml ethylene glycol separately.Coba

aken along with the precursors.The solution w

was kept in a microwave oven.The microwa

d completely.The prepared samples were was

then with acetone (to remove organic impu

air and were used for characterization studies.

crystal structure and phase purity of the sa

el diffractometer. Fig 1 shows the X-ray dif

with different dopant concentration (2%

to the orthorhombic structure with lattice const

p; ISSN: 2454-5422

Page 504

erized by at least

s quantunm dots,

particular interest

widely used as

materials possess

rmal synthesis is

ous nanomaterials

tion. Microwave

of time and allow

xide nanoparticles

-ray diffraction,

groups and other

spectral analysis

)2Mn.4H2O, Urea

re used as starting

were taken in the

lt II acetate tetra

s stirred well and

ve irradiation was

hed several times

ities) the washed

ples are analyzed

raction pattern of

and 6%).All the

ants of



IJCSR;


a = 9.3720A0, b=2.8508 A

0,c=4.4

The crystallite size was estimated

Where, K – Shape factor ≈0.9, λ

half maximum (FWHM) of adiffrtable1.

-200

0

200

400

600

800

1000

1200

1400

1600

1800

2000

I n t e n s i t y ( c o u n t s )

Fig1: XRD pattern of MnO2:Co n

Table1: Lattice parameters of Mn

Sample

MnO2:Co(0.02)

MnO2:Co(0.06)

Scanning electron microscope

examined by JEOL Model JSM

Cobalt doped MnO2nanosystem

Fig 2a and Fig 2b.



06 A0

and α = β = γ = 900.

using Debye Scherrer’s equation; D = kλ / βcos

Wavelength of the X-ray source (1.5406 A0)

actionpeak.The crystallite size and lattice para

10 20 30 40 50 60 70 80

0 0 2

0 0 2

0 0 1

0 0 1

0 0 1

* 1 1 0

* 1 1 0

* 1 0 2

* 1 0 2

* 0 0 2

* 0 0 2

* 1 0 0

* 1 0 0

2 1 2

2 1 2

2 1 1

2 1 1

1 1 1

1 1 1

2 0 1

2 0 1

1 0 1

1 0 1

2θ (degree)

MnO2: Co (0.02)

MnO2 : Co (0.06)

anosystem

O2: Co (0.02 & 0.06)nano particles

Crystallite size

(nm)

Lattice parameter (A0)

a b c

40.0007

9.3720 2.8508 4.470634.2709

analysis: The morphology of the as-prep

- 6390LV Scanning electron microscope. Th

ith different dopant concentrations (2% and

p; ISSN: 2454-5422

Page 505

θ(m)

nd β – Full width

eters are given in

ared sample was

SEM images of

6%) are shown in



IJCSR;


Fig: 2a SEM image MnO2: Co (0.

Fourier transforminfrared spec

in the material were interpreted

Cobalt doped MnO2nano system

4000

20

40

60

80

100

120

140

160

T r a n s m i t t a n c e ( a . u . )

Fig: 3 FTIR spectra of Cobalt dop

UV-Vis spectroscopy: The op

Ultraviolet – Visible spectrometer.

doped MnO2nano system with

Visible absorption shows peak at



02) Fig:2bSEM image MnO2:

tral analysis: The functional groups and other

y SHIMADZU MODEL – IR AFFINITY -1.

ith dopant concentration (2% and 6%) is prese

3500 3000 2500 2000 1500 1000 500

3 3 9 4

3 3 9 4

4 8 6 . 0

6

6 1 7 . 2

2

6 7 1 . 2

3

7 6 3 . 8

1

9 3 3 . 5

5

1 0 2 6 . 1

3

1 3 4 2 . 4

6

1 4 1 1 . 8

9

1 5 6 6 . 2 5

3 2 . 3

5

6 1 7 . 2

2

6 7 1 . 2

3

7 6 3 . 8

1 9 3 3 . 5

5

1 0 2 6 . 1

3

1 3

4 2 . 4

6

1 4 1 1 . 8 9

1 5 6 6 . 2

Wave number (cm-1)

MnO2:Co (0.02)

MnO2:Co (0.06)

ed MnO2nano particle

ical properties were analyzed by Model V

.Fig 4 shows theUltraviolet – Visible absorbanc

ifferent dopant concentration (2% and 6%).

273nm due to Cobalt doped MnO2nano particle

p; ISSN: 2454-5422

Page 506

: Co (0.06)

impurities present

TIR spectrum for

nted in Fig3.

arian, Cary 5000

spectra of Cobalt

he Ultraviolet –

.



IJCSR;


Fig: 4 UV-Vis spectrum of Cobal

Discussions:

The particle size reduces with in

(201), (111), (211), (212), (001)

and(100), (002), (102), (110) pl

30nm to 40nm is very agreed wi

shows that the nanoclusters havi

variety of pores due to the evolu

synthesis. Highly porous nature

adsorption characteristics. The

vibrations of hydrogen bonde

671.23cm-1, 617.22cm-1represent

located at 532.35 cm-1& 401.19c

spectra illustrates that Cobalt do

bulk of MnO2nano particles (ie)

to the effect of quantum confinem

Acknowledgement

I would like to express my

KennadyVethanathanwhogave m



400 600 800 1000 1200 1400 1600

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8 273

A b

s o r b a n c e ( a . u . )

Wavelength (nm)

MnO2:Co (0.02)

MnO2:Co (0.06)

doped MnO2nano particles

rease of dopant concentration. The Bragg refle

and (002) planes which corresponds to MnO

nes represents to Cobalt (JCPDS 05-0727). T

h the SEM by Image J software. The SEM im

ng spherical geometry. It consists of irregula

tion large amount of gases that are formed as

of cobalt doped manganese oxide nano parti

broad band at 3394.72 cm-1is associated w

surface water molecules and hydroxyl g

s MnO2 stretching, bending and wagging vib

-1 can be ascribed to the Co-O stretching and

ed Manganese oxide nano particles acquire b

.5 eV. Energy band gap increases with Cobalt

ent.

special thanks of gratitude to my g

the golden opportunity to do this wonderful w

p; ISSN: 2454-5422

Page 507

ctions from (101),

(JCPDS 44-0142)

he crystallite size

age confirmed the

r particles with a

by product during

cles enhances the

ith the stretching

roups.763.81cm-1,

rations. The band

wagging. UV-Vis

lue shift from the

concentration due

ide Dr.S John

rk on the topic



IJCSR;

Optical and Structural characteriz

helped me in doing a lot of resear

helped me a lot in finalizing this

References:

Toupin M, Brousse T, Belanger

electro chemical capacitor. Chem

Belanger D, Brousse T, Long J

chemical capacitors. Electro che

SONG Rui, WANG Hong-jun a

particles and Effect of Temperat

2012, 28(4), 577-580

Huachunzeng supplementary mat

BM Pradeepkumar, SriramKarik

BM N bh h “S h i


ation ofCobalt doped Manganese oxide nanop

h.I would also like to thank my family membe

aper within the limited time frame.

. charge storage mechanism of MnO2 electrod

Mater 2004, 16: 3184-3190

. Manganese oxides Battery materials make

Soc Interface 2008, Spring: 49-52

nd FENG Shou-hua “Solvothermal Preparatio

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