Nanometrology in Brazil

Carlos Achete

-Introduction: Inmetro

-Materials m

etrology for

Outline

-Materials m

etrology for

today to

morrow

the future

Short historic

•Early 1900:NIST, PTB, NPL

•1973: Inmetro

Brazilian products reached quantity level

Brazilian products reached quantity level

for gaining the international market. Efforts

have to be made for guaranteeing quality.

•Materials Division –started 2006/2007

Campus, Xerém -RJ

Campus, Xerém -RJ

Mecanics and

Materials

Administration

Optics

Therm

ics

Chemstry

www.inmetro.gov.br

Materials

Electricity and

Telecomunications

Acustics and

Vibrations

DIMAT

Materials Metrology Division

Instrumentation

and

Theory for Nano-metrology

Instrumentation for electronics and computation

Computation cluster

Surface phenomena

Surface phenomena

Tribometer

Micro-tribometer

Friction sim

ulator

Ultra-high vacuum STM

AFM

XPS + AES + ISS + LEED

Microscopy

Microscopy

SEM + EDS + EBSD

Dual beam –

FIB+MEV

TEM with Cs correction

TEM

Organic Devices

Produção e caracterização de dispositivos orgânicos, metais e TCOs

Spectroscopy and

Spectroscopy and

Diffraction

Diffraction

X-ray diffraction

Micro-Raman spectroscopy

IR Espectrosc. (30-15800cm

-1)

UV-VIS Espectrosc. (175-3300nm)

Magnetism

Magnetism

Histeresim

eter

Magnetometer

Thermal analysis

Thermal analysis

Acoustosize

r

HFM

DSC-PCA

DSC

P-DSC

r

Microonda

MS

DMA

SDTA

NanoFlash

GHP

Autosorb -

BET

Metrology for today

Guarantee for quality and

consumer protection

consumer protection

-Emergencies

-National products

-International products

Accurate chemical analysis

X-ray fluorescence

Reference

material

material

1PPM de Pb

(“electronbackscatteringdiffraction”)

1. Acesita -(TSL)

2.UFSCAR, DEMA -(TSL)

3.USP Politécnica, São Paulo -(TSL)

4. IME -( JEOL / TSL)

Metallic texture by EBSD

Interlaboratorial

4. IME -( JEOL / TSL)

5. UFC -(Oxford)

6. UFSCAR, Quimica -(Oxford)

7. Usiminas–(Oxford / HKL)

8. IPT -( JEOL/ HKL)

9. LNLS ( JEOL/ HKL )

10. UFOP -( JEOL/HKL)

11. UFRGS -(JEOL/HKL)

Residual stress by X-ray analysis

()

ψτ

+ψ

σ+

ε=

εϕ

ϕψϕ

2si

nS

21si

nS

21hkl

2

2hkl

2

hkl

00

hkl

Tensor elástico

Polimorfism in drugs

Ex: Membendazol –form

s A, B e C

Ascaridiase in Brazil

(Ministério da Saúde)

Other exemples:

Mefenamic acid (ponstan)

Carbamazepine (anti-convulsionante)

Tibolone (fem. hormone)

Gestodene (anti-conceptional)

Metrology for tomorrow

Guarantee for quality, consumer

protection and exportation

Soja

Girassol

Canola

Canola

Soja

BIOFUEL S

oja

Girassol

Canola

Canola

Soja

Transesterification

Development of Certified

Reference Material

0

500

Fluxo de Calor (mW/g)Therm

al estability DSC

And purity

An

tes

Inte

raction w

ith c

arb

on s

teel

Com Diesel

0,10

0,11

0,12

0,13

0,14

BA

Friction coefficient

Lubricity

Mamona 24h, 250oC

Mamona novo

-100

0-500

Fluxo de Calor (mW/g)

Temperatura (°C)

-100

0-5000

500

Fluxo de Calor (mW/g)

Temperatura (°C)

Ap

ós

soja

Com Biodiesel

02468101214161820

0,07

0,08

0,09

0,10

0,11

0,12

0,13

0,14

B

A

Friction coefficient

Test time (x103s)

BD 200 N

02468101214161820

0,07

0,08

0,09

D 200 N

Test time (x103s)

Friction coefficient

Metrology for the future

Guarantee for quality, consumer

Guarantee for quality, consumer

protectionand exportation of

future goods –Nano

Mercado m

undial de Nanotecnologia

HardDisksDrives

(< 100 nm)

Market Size

HardDisksDrives

Electronics

International market

From Nanotechnology W

orld, 2005

SPMs

Carbon

Cond. Elétricos/ R

evestimento

Nanoproducts/ D

rugs

Large

GMR

OLED

OLED

1960

1980

2000

2020

Market Size

Small

Magnetic Fluids

GMR

OLED

OLED

NANOMETROLOGY

•Nanoparticles

•Nanocatalysis

•Nanocatalysis

•Organic semiconductors

•Carbon

•Lubricants

•Covering

•Pollution cleaning

Nanofluids:

nano-particles suspention in liquid m

edium

Stable

physically

•Pollution cleaning

•Drug delivery

•Functional tissue-cell interaction

•Pigments and colloring

•Heat Transfer

Stable

chemically

Small size particles

100 nm

ZnO, γ-Al 2O

3, CuO (Petrobrás)

56789

Razão de condutividade

termicas k/k0

K

Increase in Heat conductivity

Reported values:

4 %

vol A

l2O3

→ 8 %

k4 %

vol C

uO

→ 12 %

k10-4% vol T

hiol-Au→ 10 %

k0,5 %

vol Fe

→ 18 %

k

012345

0.5

11.5

22.5

% e

m v

olu

me d

e n

anopart

icula

s

Razão de condutividade

termicas k/k0

K HC

0,5 %

vol Fe

→ 18 %

k4 %

vol C

u→ 20 %

k0,1 %

vol SWCN

→150 %

k

Nano-particles

size

Scherrer Equation (1918)

Θ⋅

=co

sL

KB

λB–FWHM

L–crystallite “size”

Approximations:

1.

Cubic with same dim

ensions

2.

K arbitrary

“apparent” size

Experimental

Calculado

Modeling shape of

Nano-rutile (TiO

2)

200

300

400

500

600

700

800

900

1000

Intensity (arb. units)

Dedicated software based on several ( h k l ) and β βββ= (area/hight)

Nano-m

aterials

calibratedbyTEM

68

10

12

14

16

18

20

22

100

200

Intensity (arb. units)

2Θ (0) 50 nm

NanoRutile-TiO2size

from Raman spectroscopy

Frequency and width depends

on particle size

Uncertainty priciple

xq

xpx

∆∆

⇒∆⋅

∆1

~~h

r

0200

400

600

800

1000

5.8 nm

9.3 nm

9.8 nm

22.7 nm

Intensity (a.u.)

Raman shift (cm-1)

Bulk

[]

;)

2/(

)(

)(

)(

22

32

∫∫∫Γ

+−

∝BZ

q

qd

qC

Iω

ωω

r

NANOMETROLOGY

•Nanoparticles

•Nanocatalysis

•Nanocatalysis

•Organic semiconductors

•Carbon (see 11AM presentation)

Interface between surface science and catalisys

Building the thin film

oxide…

MoOx/Cu3Au (100)

Cleanning

O+(2x10-5mbar/ 650K,

5min

Metal deposition

O2at 773K

(165L)

(165L)

LEED e XPS

4 Å

Name Position Area % Area

Mo 5+ 3d5/2 230.99 1583.10 42.135

Mo 5+ 3d3/2 234.14 1345.60 35.770

Mo 6+ 3d3/2 325.81 381.90 10.145

Two film

s can be m

ade

70eV

LEED: sim

etry: retangular +

hexagonal

XPS, Mo(V) identified

240

235

230

225

220

Mo 6+ 3d3/2 325.81 381.90 10.145

Mo 6+ 3d5/2 232.66 449.30 11.950

CPS (u.a.)

Energia de Ligação (eV) Mo 5+ (3d5/2)

Mo 5+ (3d3/2)

Mo 6+ (3d 3/2)

Mo 6+ (3d 5/2)

(Mixture M

o0, Mo4+,Mo5+,M

o6+)

(predominance M

o5+)

83eV

15

20

25

Limpa

Coberta (V)

Vanadium in Silicon

STM –V = + 1.4 V

# eventos STM (80%)

Baixa-cobert.: 0.012 MC = 7.9x1014at/cm2

AB

CD

05

10

15

Estimativa experimental de massa:

~60% (eventos) do V depositado.

Energetics (eV):

“Bias” polarity effect:

HR-TEM

Inteface V

xO

y–Cu3Au

Nanofabrication and

lithography

Dual beam

–FIB+MEV

NANOMETROLOGY

•Nanoparticles

•Nanocatalysis

•Nanocatalysis

•Organic semiconductors

•Carbon (see 11AM presentation)

Market analysis

Al

N

OA

lO N

ON

ET

L

Alq

3

EL

Lum

ines

cent

Mat

eria

l

- +

OLED structure IT

O

Gla

ss

N

C HN

N

HT

L

MT

CD

LIG

HT

LIG

HT

Analyzing photo-degradation

N

O

H H

H

H

H

HH

N

Al

O

O

N

O

H

H

H

H

H

H

H

HH

H

H

N

O

H H

H

H

H

HH

Analyzing photo-degradation

N

Al

O

O

N

O

H

H

H

H

H

H

H

HH

H

H

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Absorbância (Intens. Normal.)

Alq3 - Irradiado

Alq3 - Não Irradiado

823/804/786

748

1113

1383/1330

1498/1466

1603/1576

1697

1279/1230

649

544

416

2000

1800

1600

1400

1200

1000

800

600

400

Número de Onda (cm-1)

Absorbância (Intens. Normal.)

Theoretical spectra for Alq

3

degradation

Alq

3

Equip

Equip