Growth, structural, thermal, optical, and electrical propertiesof potassium succinate–succinic acid crystal

A. Arunkumar • P. Ramasamy • K. Vishnu •

M. K. Jayaraj

Received: 8 June 2013 / Accepted: 1 November 2013

� Springer Science+Business Media New York 2014

Abstract Potassium succinate–succinic acid (KSSA),

semi-organic single crystals were grown by slow evapo-

ration growth technique using water solvent. Single crystal

X-ray diffraction study revealed that the KSSA crystal

belongs to monoclinic system. FT-IR and FT-Raman

spectral studies were performed to identify the vibrations

of functional groups. TGA/DTA analyses were carried out

to characterize the melting behavior and stability of the

title compound. The UV–Vis–NIR spectrum showed that

the grown crystal is transparent in the entire visible region.

Fluorescence studies were carried out in the range of

200–700 nm. The optical nonlinearity of KSSA was

investigated at 532 nm using 7 ns laser pulses, employing

the open aperture Z-scan technique. The photoconductivity

study was carried out to know the conducting nature of the

crystal. The laser damage threshold was measured using

Q-switched Nd:YAG laser (1064 nm). Electrical properties

of the crystal are studied using Hall Effect measurement.

Introduction

In recent years, there has been considerable interest on the

synthesis of semi-organic nonlinear optical materials with

excellent nonlinear optical and fluorescence properties

because of their potential applications such as, telecom-

munication, optical computing, optical data storage, light

emitting diodes, and optical information processing [1, 2].

Inorganic nonlinear optical single crystals have usually

high melting point, high mechanical strength, and high

degree of chemical inertness, but very poor second and

third harmonic generation efficiencies.

The nonlinearity of these materials is low compared to

organic NLO crystals [3, 4]. In contrast, organic crystals

exhibit higher nonlinear second and third order coeffi-

cients, but they have poor transparency, short optical band

gap, laser damage threshold, thermal, and mechanical

properties [5, 6]. To overcome such shortcomings of

organic materials, some new classes of optical crystals such

as metal organic or semi-organic crystals have been

developed. Ionic salt materials offer an important and

extremely flexible approach for the development of new

materials applicable over a very broad range of frequen-

cies. Organic materials are difficult to grow as large size

optical quality crystals for device applications [7]. Com-

bined organic and inorganic, named semi-organic, can be

grown easily by solution growth technique [8]. Semi-

organic materials gain importance over inorganic materials

because of their large polarizability, wide transmission, and

high laser damage threshold [9]. In this view, semi-organic

material, KSSA was synthesized and crystal was grown

and it yields the nonlinearity of a purely organic ion

combined with the favorable mechanical and thermal

properties of an inorganic counter ion [10, 11]. In this

present investigation, we report the synthesis, structure,

Electronic supplementary material The online version of thisarticle (doi:10.1007/s10853-013-7858-8) contains supplementarymaterial, which is available to authorized users.

A. Arunkumar � P. Ramasamy (&)

Centre for Crystal Growth, SSN College of Engineering,

Kalavakkam, Chennai 603 110, India

e-mail: proframasamy@hotmail.com; ramasamyp@ssn.edu.in

K. Vishnu � M. K. Jayaraj

Optoelectronic Devices Laboratory, Department of Physics,

Cochin University of Science and Technology,

Kochi 22, Kerala, India

123

J Mater Sci

DOI 10.1007/s10853-013-7858-8

crystal growth, and characterization of a semi-organic

material potassium succinate–succinic acid (KSSA) for the

first time in the literature.

Experiment

Solubility and crystal growth

The KSSA was obtained from an aqueous solution con-

taining potassium hydroxide and succinic acid in a 1:1

molar ratio. The reaction scheme and the chemical struc-

tures are illustrated in Fig. 1. The solubility of KSSA in

water was determined for different temperatures in the

range of 25–45 �C. The beaker containing the solution was

covered tightly. The solution was maintained at a constant

temperature and continuously stirred using a magnetic

stirrer. The required amount of KSSA to saturate the

solution at this temperature was estimated and this process

was repeated for different temperatures. This study was

carried out in a constant temperature bath with an accuracy

of ±0.01 K. A constant volume of 100 ml of the solution

was used. The solubility curve is presented in Fig. 2. In

accordance with the solubility studies, the growth solution

was prepared and stirred continuously for several hours at

room temperature. Then, the beaker was hermetically

sealed and placed in a dust-free atmosphere. Crystallization

was allowed to take place by slow evaporation technique

at room temperature. Single crystal with the dimen-

sions 15 9 8 9 5 mm3 was harvested after a typical period

of 25 days. Grown-single crystal of KSSA is shown in

Fig. 3

Characterization

Grown KSSA crystals have been subjected to various

characterization studies to analyze the structural, thermal,

optical, and mechanical properties.

Single crystal and powder XRD

Single crystal X-ray diffraction of KSSA was performed

with a specimen of dimension 0.35 9 0.25 9 0.2 mm3

which was carefully cut from the as grown crystal and is

mounted on a fiber tube. The data were collected using a

Bruker AXS Kappa APEX II single crystal CCD diffrac-

tometer equipped with graphite-monochromated MoKaradiation (k = 0.71073 A) at room temperature. Accurate

unit cell parameters were determined from the reflections

of 36 frames measured in three different crystallographic

zones. The data collection, data reduction and absorption

correction were performed by APEX2, SAINT-plus, and

SADABS program [12]. A total of 13424 reflections were

recorded with 2h range of 2.22�–25�, of which 2040

reflections are considered as unique reflections with I [ 2r(I). The structure was solved by direct methods procedure

and the non-hydrogen atoms were subjected to anisotropic

refinement by full-matrix least squares on F2 using

SHELXL-97 program. The positions of all the hydrogen

atoms were identified from difference electron den-

sity map, and they were constrained to ride on the

Fig. 1 Reaction scheme of KSSA

25 30 35 40 4512

14

16

18

20

22

24

26

28

So

lub

ility

(g

/100

ml i

n w

ater

)

Temperature ( oC)

Fig. 2 Solubility curve of KSSA

J Mater Sci

123

corresponding non-hydrogen atoms. The hydrogen atom

bound to carbon atoms was constrained to a distance

of C–H = 0.93–0.97 A and Uiso (H) = 1.2 Ueq(C) and

1.5 Ueq(C). The crystal structure was solved using the

SHELXS-97 program and refined by the SHELXS-97

program [13]. The final refinement converges to an R val-

ues of R1 = 0.0283 and WR2 = 0.0732. The ORTEP

drawing was performed with the ORTEP3 program [14].

The crystallographic data and the structure refinement

parameters of KSSA are presented in Table 1.

The crystal was ground to a fine powder and a small

amount of this powder was placed on a glass plate. Powder

X-ray diffraction analysis of KSSA crystals was carried out

using Rich-Seifert diffractometer with CuKa (k =

1.5405 A) radiation over the range 10�–70� at a scanning

rate 1� min-1.

FTIR and FT-Raman spectroscopy

The FTIR spectra of KSSA crystals were recorded in the

range 4000–400 cm-1 employing a JASCO FT-IR 410

spectrometer by the KBr pellet technique. The Raman

spectra were measured using a WiTec GmbH confocal

micro-Raman using the excitation wavelength of 532 nm.

Optical studies

Optical transmission study was carried out using a Perkin-

Elmer Lambda 35 UV–Vis spectrometer. The grown crystal

of 2 mm thickness without polishing or antireflection coat-

ing was used for the measurement in the region of

200–1100 nm.

Z-Scan

An intense laser beam of 532 nm and 7 ns pulse width is

split by means of a beam splitter, and a fraction of the beam

Fig. 3 Photograph of as grown

KSSA single crystals

Table 1 Crystal data and structure refinement for KSSA

Empirical formula C8 H11 K O8

Formula weight 274.27

Temperature 293(2) K

Wavelength 0.71073 A

Crystal system, space group Monoclinic, P21/c

Unit cell dimensions a = 7.451 (10) A, a = 90�b = 18.339(3) A, b = 109.52(2)�c = 9.033(2) A, c = 90�

Volume 1163.3(4) A3

Z, calculated density 4, 1.566 Mg m-3

Absorption coefficient 0.484 mm-1

F(000) 568

Crystal size 0.35 9 0.30 9 0.20 mm

Theta range for data collection 2.22�–25�Limiting indices -8 \= h \= 8, -21 \= k \=21,

-10 \= l \=10

Reflections collected/unique 9776/2040 [R(int) = 0.0220]

Completeness to theta = 25.00 99.5 %

Absorption correction Semi-empirical from equivalents

Max. and min. transmission 0.9093 and 0.8683

Refinement method Full-matrix least-squares on F2

Data/restraints/parameters 2040/3/167

Goodness-of-fit on F2 1.083

Final R indices [I [ 2sigma (I)] R1 = 0.0283, wR2 = 0.0732

R indices (all data) R1 = 0.0312, wR2 = 0.0759

Largest diff. peak and hole 0.237 and -0.226 e A-3

J Mater Sci

123

is sent to a reference photo detector where the beam under-

fills the active area of the diode. The remainder of the beam

sent through a ‘‘thin’’ sample is translated through the

beam waist using a motorized translation stage, after that

an aperture (iris) clips roughly half of the beam intensity.

After the aperture, an open photo detector detects the

remainder of the beam passing through the iris [15, 16].

The output of both photodiodes is sent to a dual channel

energy ratio meter interfaced to a PC. Figure 4 illustrates

the open aperture Z-scan experimental setup. The KSSA

crystal is highly cleavable in nature. A cleaved plate of

thickness \1 mm was used for the measurement.

Thermal analyses

A crystal sample weighing about 5 mg was taken in the

alumina crucible. Simultaneous thermogravimetric and

differential thermal analysis were carried out between

temperature range 30 and 400 �C in nitrogen atmosphere at

a heating rate of 10 �C min-1 using PerkinElmer Diamond

thermal analyzer.

Fluorescence study

Fluorescence of the KSSA crystal was studied in the

emission range of 200–700 nm using JASCO fluorimeter.

As grown crystal of 3 mm thickness was used for the

measurement.

Photoconductivity studies

Photoconductivity measurement is carried out using

Keithley—480 pico ammeter in the presence of dc electric

field. As grown crystal of dimension 10 9 6 9 3 mm3 was

attached into the microscopic slide. Electrical contacts are

made on the sample by silver-painted copper wire. The

sample is then connected in series to a dc power supply and

a pico ammeter (Keithely—480). After shielding the

sample from all radiations, the applied field is increased

from 0 to 100 V cm-1 and the corresponding dark current

(Id) in the pico ammeter is notified. The samples are then

illuminated with the radiation from a halogen lamp

(100 W) and the photocurrent (Ip) due to the generation of

carrier by photo excitation is recorded for the same range

of applied fields.

Laser damage threshold

Crystal of size 12 9 8 9 4 mm3 was cut and used for the

studies. The multiple shots of LDT measurement were

made on as grown surface using Q-switched Nd:YAG laser

operating at 1064 nm radiation (repetition rate—10 Hz;

pulse width—10 ns). For LDT measurement a lens with

focal length of 30 cm was used to focus the laser beam in a

spot of 1 mm diameter. The laser exposure time on the

sample was kept as 30 s for all energies and the energy of

the laser beam was measured by coherent energy/power

meter (Model No. EPM 200).

Hall Effect

The Hall measurements were carried out using the van der

Pauw method at room temperature (ECOPIA Hall Effect

measurement system). Crystal of size 10 9 6 9 1 mm3

was used for the measurement. For electrical contacts silver

paste was used.

Results and discussion

In the structure the potassium atom is coordinated by eight

oxygen atoms. In potassium succinate succinic acid, the

potassium adopts distorted cubic coordination. The oxygen

atoms 01, 03, 05 coordinated to the K? atom are at

Fig. 4 The open aperture

Z-scan experimental setup

J Mater Sci

123

position x, y, z. The oxygen atoms 01 (1 - x, -y, 1 - z),

03 (-x, -y, 1 - z), 06 (1 - x, -y, 2 - z) and 08 (x, y,

-1 ? z and -x, -y, z) constitutes the eightfold coordi-

nation of the cubic coordination geometry. The resultant

product contains KSSA in which the succinate anion and

potassium cation resulted from the proton transfer and

neutral succinic acid stands as a third partner. The potas-

sium is linked through the organic backbone of the succi-

nates and the rings to form a three-dimensional structure.

The observed lattice parameters values are a = 7.32(2) A,

b = 12.02(4) A, c = 19.96(6) A, a = 90�, b = 91.87�,

c = 90�, and volume of the unit cell is 1756(9) A3. The

crystal belongs to monoclinic system with space group

P21/c. The K? ion forms structural features as a conse-

quence of the large radius, adoption of different coordination

numbers and the possible occurrence of a stereo-chemically

active lone pair. Figure 5 illustrates the molecular structure

of KSSA. The unit cell projection along b-axis of KSSA is

shown in Fig. 6. The observed hydrogen bonds of KSSA are

summarized in Table 2. CCDC 876023 contains the sup-

plementary crystallographic data for this paper. These data

can be obtained free of charge via http://www.ccdc.cam.ac.

uk/data_request/cif or by emailing data_request@

ccdc.cam.ac.uk or by contacting The Cambridge Crystallo-

graphic Data Centre, 12 Union Road, CAMBRIDGE

CB21EZ, UK; Fax: ?44-01223-336033.

The obtained diffraction peaks were indexed using

‘‘TWO THETA’’ software package. The indexed powder

X-ray diffraction pattern is depicted in Fig. 7 and is well

compatible with the structure determination of the crystal

at room temperature. The well defined and sharp peaks

indicate that crystalline nature of the title compound is

good.

FTIR and FT-Raman spectral studies for KSSA were

carried out to analyze the chemical bonding and molecular

structure of the compound. The strong band at

1720 cm-1due to m(C=O) of carboxylic acid group [17, 18]

is absent in IR and Raman spectra of KSSA, which indi-

cates that succinic acid coordinates to the metal ion

through carboxylate (succinate) group [19], but the peaks at

1722 cm-1 from IR and 1736 cm-1 evidenced the pre-

sence of succinic acid as a third partner in this KSSA

complex. The asymmetric and symmetric stretching

vibrations of carboxylate were observed at 1548 and

1428 cm-1. The peak observed at 1722 cm-1 in IR and

1738 cm-1 in Raman spectra were assigned to C=O

stretching vibrations of succinic acid. The peaks observed

at 2934 cm-1 in IR and 2948 cm-1 in Raman spectra were

assigned to CH stretching vibrations of CH2 groups. The

bending modes of CH group occurred at 1428 (IR) and

1420 (Raman) cm-1. The asymmetric and symmetric

stretching vibrations of C–C group were observed at 1201,

957 cm-1 in IR and 1199 and 943 cm-1 in Raman spectra.

The C–O bending vibration was observed at 894 and

896 cm-1 in IR and Raman spectra, respectively. The

peaks at 741 cm-1 in IR and 738 cm-1 in Raman spectra

were assigned to C–H wagging vibration. The COO-

bending mode was observed at 636 and 635 cm-1 in IR

and Raman spectra, respectively. The rocking vibration of

COO- was observed at 536 and 534 cm-1 in IR and

Raman spectra, respectively. Figures 8 and 9 show the

FTIR and FT-Raman spectra of KSSA. The observed bands

for the title crystal with their tentative assignments are

tabulated in Table 3.

The UV–Vis spectrum occurs due to the electronic

transitions of the molecule. The KSSA crystal is active in

the UV–Vis region and the compound material could be

viable alternative for optical materials in that entire

region. It has sufficient transparency of about 52 % with

lower cut-off wavelength 240 nm as shown in Fig. 10.

The absorption coefficient (a) has been determined from

the transmission (T) spectrum based on the following

relation,

a ¼ 2:3026

tlog

1

T

� �ð1Þ

where T is transmittance, t is the thickness of the crystal. In

the high photon energy region, the energy dependence of

absorption coefficient suggests the occurrence of direct

band gap of the crystal obeying the following equation for

high photon energies (hm) [20],

ahtð Þ2 ¼ AðEg � htÞ ð2Þ

Fig. 5 Molecular structure of KSSA

J Mater Sci

123

where Eg is the optical band gap of the crystal and A is a

constant. The band gap of the crystal was evaluated by

plotting (ahm)2 versus hm [21] as shown in Fig. 11 and it

was found to be 4.8 eV.

The open-aperture Z-scan curve obtained for KSSA is

shown in Fig. 12. As the sample is translated through the

focal region of the beam, the open detector measures the

total transmitted intensity while the irradiance at the sam-

ple is changing as the sample is translated, any deviation in

the total transmitted intensity must be due to multi-photon

absorption. The observed two-photon type nonlinearity

originates from genuine two-photon as well as two-step

(excited state) absorptions, and hence the nonlinearity can

be considered as an ‘‘effective’’ two-photon absorption

process [22, 23]. For a two photon absorption process, the

Fig. 6 Crystal packing diagram

of KSSA

Table 2 Observed possible hydrogen bonds of KSSA

D–H…A d(D–H) d(H…A) d(D…A) \(DHA)

O(2)–H(2)…O(5)#8 0.849(17) 1.773(19) 2.5921(17) 161(3)

O(7)–H(7)…O(6)#8 0.869(16) 1.719(16) 2.5880(15) 178(2)

O(4)–H(4)…O(5) 0.852(17) 1.793(18) 2.639(2) 172(3)

10 20 30 40 50 60 70

0

500

1000

1500

2000

Inte

nsit

y (a

.u)

2θ (degree)

(011

)(0

30)

(111

)(0

12)

(022

)

(051

)(0

60)

(052

)

(16-

2)

(124

)

(441

)

Fig. 7 Indexed powder X-ray diffraction pattern

4000 3500 3000 2500 2000 1500 1000 500

0

20

40

60

80

100

Tra

nsm

itta

nce

(%

)

wavenumber (cm-1)

(293

4)

(253

3)

(197

2)(1

722)

(154

8)(1

428)

(134

2)(1

278)

(124

6)

(536

)(6

36) (5

90)

(741

)

(990

)

(840

)(8

96)

Fig. 8 FTIR spectrum of KSSA

J Mater Sci

123

transmitted open aperture Z-scan signal is given by the

equation

Tðz; S ¼ 1Þ ¼X1m¼0

½�q0ðz; 0Þ�m

ðmþ 1Þ3=2ð3Þ

q0ðz; tÞ ¼bI0ðtÞLeffz

20

z2 þ z20

;

where

Leff ¼½1� expð�aLÞ�

a

m is the integer, q0 is the parameter that can be obtained by

fitting the experimental result to Eq. (1), Z is the translated

length parallel to the beam propagation (4 cm), Z0 is the

Rayleigh range (Z0 = px02/k = 10.69 mm, x0 is beam

waist radius of laser beam = 42.5 lm), I0 is the intensity

of the incident beam at the focal point, B is the two photon

absorption coefficient, L is the sample thickness, Leff is the

effective thickness.

The value of the effective two-photon absorption coef-

ficient is calculated using best—fit curve for the Z-scan

data and is found to be 22.51 mm/GW. Imaginary part of

third order nonlinear optical susceptibility can be calcu-

lated by the following relation.

Imðvð3ÞÞ ¼ ke0n20cb

4pð4Þ

where n0 is the linear refractive index of the crystals, c is

the velocity of light in vacuum, k is the wavelength of laser

light (532 nm), b is the nonlinear absorption coefficient, e0

is the permittivity of free space (8.85187 9 10-12F m-1),

4000 3500 3000 2500 2000 1500 1000 500

0.00

0.05

0.10

0.15

0.20

0.25

0.30

Ram

an In

ten

sity

Wavenumber (cm-1)

(294

8)

(173

6) (169

4)

(142

0)(1

340)

(129

6)

(990

)(9

43)

(840

)(7

38)

(591

)Fig. 9 FT-Raman spectrum of KSSA

Table 3 The observed frequencies and corresponding assignments

FT-IR

(cm-1)

FT-Raman

(cm-1)

Assignments

1548 – COO– asymmetric stretching

of anion

1428 – COO- symmetric stretching

of anion

1722 1736 C=O stretching of succinic acid

2934 2948 C–H stretching

1428 1420 C–H bending

1201 1199 C–C asymmetric stretching

957 943 C–C symmetric stretching

894 896 C–O bending

741 738 C–H wagging

636 635 COO- bending

536 534 COO- rocking

Fig. 10 UV-Vis transmittance spectrum of KSSA crystal

1 2 3 4 5 6

20

40

60

80

100

120

140

160

optical band gap = 4.8 eV

(αh

ν )2

eV2 cm

-2

photon energy (eV)

Fig. 11 Plot of (ahm)2 versus photon energy

J Mater Sci

123

the estimated third order susceptibility (v(3)) value of

KSSA crystal is 6.20 9 10-9 (esu) and comparison with

the other crystals is presented in the Table 4.

Fluorescence generally occurs in molecules that are

aromatic compounds which contain multiple conjugated

double bonds with a high degree of resonance stability

[24]. The grown crystals were excited at the wavelength of

400 nm. The excitation and emission spectra of KSSA are

given in Fig. 13a, b. The sharp peak was observed at

590 nm which also reveals the crystalline nature. The full

width at half maximum (FWHM) of emission peak is

4.5 nm which confirms that the crystal quality is good. This

result indicates that the crystal emits red light and can be

used in the long pass optical filters [25].

Figure 14 shows the field dependent conductivity of

KSSA single crystal. The photocurrent is seen to be less

than the dark current for the same applied field, which is

termed as negative photoconductivity. The negative

photoconductivity exhibited by the sample may be due to

the reduction in the number of charge carriers or their

lifetime, in the presence of radiation [26].

The TGA and the corresponding DTA traces are

depicted in Fig. 15. In DTA curve, an endotherm at 168 �C

is assigned to the melting point of KSSA. The initial

Fig. 12 The open aperture Z-scan curve measured for KSSA crystal

Table 4 Third order susceptibility in some selected crystals

S.

no

Crystal name Third order

susceptibility

(v(3)) (esu)

Reference

1 Sodium acid

phthalate

hemihydrate

64.999 9 10-9 J Phys Chem A

2011, 115,

8216–8226

2 2-Furoic acid 2.547 9 10-7 Physica B 406

(2011)

2834–2839

3 4-Bromo-

40Nitrobenzylidene

aniline

5.95 9 10-9 pubs.rsc.org/doi:

10.1039/

C3CE26663J

4 Potassium succinate–

succinic acid

6.464 9 10-9 Present case

0

1

2

3

4

5

Inte

nsi

ty (

a.u

)

wavelength (nm)

590 nm (b)

450 500 550 600 650 700 750200 250 300 350 400 450 500

Inte

nsi

ty(a

.u)

wavelength (nm)

(a)Fig. 13 a Excitation and

b emission spectra of KSSA

crystal

0 20 40 60 80 1000

1

2

3

4

Voltage (V)

Cur

rent

(μA

)

Dark Current Photo Current

Fig. 14 Field-dependent conductivity of KSSA single crystal

J Mater Sci

123

weight loss started from 170 �C and the major weight loss

occurred at 240 �C. The absence of water of crystallization

in the molecular structure is indicated by the absence of

any weight loss up to 168 �C. Another important obser-

vation is that, there is no phase transition and color change

till the material melts and this enhances the temperature

range for the utility of the crystal for NLO applications.

The maximum output power can be obtained by

increasing the power density of the fundamental beam

which is proportional to the harmonic conversion effi-

ciency. However, a high power intensity beam can often

cause damage of the crystal. Hence, the damage studies

become important for newly discovered materials. The

laser damage threshold depends on a great number of laser

parameters such as wavelength, energy, pulse duration,

longitudinal and transverse mode structure, beam size,

location of beam, etc. The damage is controlled by the rate

of thermal conduction through the atomic lattice in the long

pulse regime (s[ 100 ps) and the optical breakdown and

various nonlinear ionization mechanisms become impor-

tant in the short pulse regime (s\ 100 ps) [27]. The laser

damage threshold of the grown crystals can be evaluated by

the following equation

Power density Pdð Þ ¼ E = s pr2;

where E is the energy (mJ), s is the pulse width (ns), and r

is the radius of the spot (mm).

The measured multiple shot (150 pulses per sec) laser

damage threshold value was found to be 10.6 GW cm-2

for 1064 nm wavelength of Nd:YAG laser radiation for

KSSA crystal.

The observed laser damage profile pattern is shown in

Fig. 16. The grown KSSA crystal is comparable with well-

known semi-organic L-arginine phosphate crystal and it

also indicates usefulness of KSSA single crystal for high

power laser applications.

The conduction properties of KSSA crystals were

studied using Hall Effect. It is found that the grown KSSA

crystals have negative hall coefficient, which confirms

n-type conductivity. The electrical parameters are tabulated

in Table 5.

Conclusion

Potassium succinate–succinic acid, a semi-organic com-

pound was synthesized and bulk crystals were successfully

grown by slow evaporation technique. The structure of

KSSA was reported for the first in the literature. The back

bone and side chain conformations were analyzed. The

three-dimensional hydrogen bond patterns were assigned to

different hydrogen bonding motifs. FT-IR and FT-Raman

spectral analyses confirmed the presence of functional

groups of the KSSA. Based on the results of thermal ana-

lysis it is observed that the material could be used for any

application below 168 �C. Linear optical study revealed

that the KSSA crystal is transparent in the wavelength

region 300–1100 nm. The two photon absorption

50 100 150 200 250 300 3500

20

40

60

80

100

Temperature ( oC)

wei

gh

t p

erce

nta

ge

(%)

-80

-70

-60

-50

-40

-30

-20

-10

0

TGA DTA

Hea

t fl

ow

(m

V)

Fig. 15 TGA and DTA curve of KSSA

Fig. 16 Laser damage profile of KSSA

Table 5 Hall measurements for KSSA single crystal

Parameters Bulk concentration (cm3) Mobility (cm2/Vs) Resistivity (X cm) Hall coefficient (cm3/C) Conductivity (1/X cm)

KSSA crystal -4.498E?08 2.965E?01 4.681E?08 -1.388E?10 2.136E-09

J Mater Sci

123

coefficient and third order nonlinear optical susceptibility

were calculated by Z-scan technique and affirm that KSSA

exhibits the nonlinear optical properties. The photocon-

ductivity studies reveal that KSSA crystal exhibits negative

photo conductivity. The emission peak is observed at

590 nm and it shows that the grown crystal is suitable for

red wavelength emission. The grown KSSA crystal has

comparable laser damage threshold value with well-known

semi-organic L-arginine phosphate crystal. It is found that

crystal has negative Hall coefficient which confirmed the

n-type conductivity.

Acknowledgements The authors thank Sophisticated Analytical

Instrumentation facility, IIT Madras Chennai for recording FTIR, FT-

Raman, and single crystal data collection. The authors also

acknowledge Prof. K. Ramamurthi, School of Physics, Bharathidasan

University, Tiruchirappalli-24, for extending the Hall measurement

facilities established under the DST grant (D.O. No. SR/S2/CMP-35/

2004).

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