Recent Trends

in
Synthesis & Characterization
Of
Multifunctional Materials
(RTSCTMN-09)
22nd June 2009

Nano Materials
Characterization

Sulabha Kulkarni
Indian Institute of Science
Education & Research, Pune
Ref. Nanotechnology : Principles and Practices

By Sulabha K. Kulkarni

Capital Publishing Co.

7/28, Mahaveer Street, Ansari Road

Daryaganj, New Delhi -110002

Nano Materials,Characterization Techniques

Contents

Introduction to Quantum Mechanics

Structure and Bonding
Synthesis of Nanomaterials (Physical Methods)
Synthesis of Nanomaterials (Chemical Methods)
Synthesis of Nanomaterials (Biological Methods)
Analysis Techniques
Properties of Nanomaterials
Nanolithography
Some Special Nanomaterials
Applications
Practicals

Nano Materials,Characterization Techniques

Lecture I
• Which are the Nanomaterials are we looking for

• Methods of Synthesis

Lecture II
• What kind of analysis is needed

• Available and commonly required analysis techniques

• Principles of some analysis techniques with

Illustrative examples

Nano Materials, Characterization Techniques

 What kind of analysis is needed

Depends upon the Properties of Interest !

But

Sample Purity (Composition) ……. Essential

Size, Shape & Structure ……. Essential

Porosity, Surface Area etc.

Mechanical, Optical, Thermal, Electrical, Magnetic

Nano Materials,Characterization Techniques

 Size, Shape & Structure ……. Essential
Available Techniques
Microscopes
Confocal Microscope
Scanning Near Field Optical Microscope
Scanning Electron Microscope,
Transmission Electron Microscope
Scanning Tunneling Microscope
Atomic Force Microscope
Magnetic Force Microscope

X-ray Diffraction
Wide Angle X-ray Scattering
Small Angle X-ray scattering

Nano Materials,Characterization Techniques

Size, Shape and Distribution Analysis

Microscopes

Nano Materials,Characterization Techniques

Confocal Microscope

Scanned point Detector

Resolution

Objective lens Limited by Wavelength

Transparent specimen Of the Radiation used

Collector

Laser source

Nano Materials,Characterization Techniques

 Scanning Near Field Optical Microscope
Overcomes Diffraction Limit
Amplifier
Photomultiplie
r
Piezo
drive Computer
20 nm – 60 nm Laser
Beam Scaner
distance
Detector
control
Optical fiber
Sampl
e
Sourc Propagating Waves
e Metal
coating

Incident Rays
Sulabha Kulkarni,Nanotechnology
Principles and Practices
Evanescent Beam generated Nano Collector
by nano collector Evanescent Beam generated
by nanostructured object
Sample
surface

Nano Materials,Characterization Techniques

 Scanning Electron Microscope (SEM)
E ~ 5 –100 KeV
Resolution : ~ 50 –100 nm
Incident beam Back scattered
electrons Electron gun
Auger electrons
Characteristic X-rays
Secondary
Scanning
electrons Condenser lenses generator

CRT

Bottom of the sample

Scanning
coils

Specimen Amplifier

Sulabha Kulkarni,Nanotechnology
Principles and Practices

Nano Materials,Characterization Techniques

ZnO micro particles: different morphologies

Needles Flowers

Rods Tetrapods Belts

Kulkarni et al
 Growth of ZnO particles with central cavity

SEM
(a) (b)

(1) (2) (3)

(c)
1µm 1µm

(5) (4)

0.5
µm

(6)

communicated
 Aligned SnO2 Rods
Obtained by Sol-Gel route
On Glass Slide/Si

50 20 μm
µ m

Thin Solid Films 515 (2006) 1450

10
 Silica-Titania Core-Shell Particles

After first After Second

coating step coating step

Silica Particles Silica @ Titania core - shell Particles

328 nm
Intensity

Titania Particles

300 400
Silica@Titania
500 600
Particles
700 800

Silica Particles

Wavelength (nm)

Silica Particles of size ~

213 nm coated with 39 nm
thick shell of titania
Uncoated particles Thin coating Thick coating
 Titania-Silica Core-Shell Particles

Titania Particles Titania@Silica Particles

Intensity (arb units)

348 nm

325 nm

Titania@Silica Particles

300 400 500 600 700 800

Titania Particles

Wavelength (nm)

Titania Particles
Size ~ 350 nm

Titania@Silica Particle
Size ~520 nm

Pramana 65 (2005) 787

Mechanism for the binding antibody and antigene to
silica@silver particles.

Kulkarni et al, CPL 404 (2005) 136

 SEM Images
(a) (b)
Silica Particles Silver core shell particles

(c) (d)
Core shell particles With goat anti rabbit
with rabbit antibodies antibodies

Kulkarni et al, CPL 404 (2005) 136

 Nanoporous Materials….Aerogels

Aerogels are highly porous (~ 90 -98%porous) ,

low density materials (~ 0.8 - 0.05 gm/cc)

Aerogels of many materials and composites can be made

Thermally Insulating
Silica Aerogel
Transparent Silica Aerogel
SEM of an Aerogel

Department of Physics, University of Pune

 Transmission Electron Microscope
Electron source
CdS

Condensor
lens ~ 3 nm
Sample

Objective
lens
Direct Back focal plane
beam Diffracted of objective lens Resolution ~ 0.1 nm
beam Image
SiO2@CdS

Gold nanorods

J. Coll. Int. Sci. 278 (2004) 107

SiO2@ZnS
Surf. Engg. 20, no.4 (2004)

Nano Materials,Characterization Techniques

Fe2O3 particles

Fe2O3 particles
(TEM) (TEM )

Kulkarni et al
SiO2 particles (~ 250 nm)
prepared for
making core-shell particles
or
functional materials

Kulkarni et al
Silver Nanoshells (TEM)
CdSe Rods (TEM)

Kulkarni et al
Silica Tubes Coated with Silver Nanoparticles

0.3

398 nm
425 nm 0.2

0.1

0.0
300 400 500 600

300 400 500 600 700 800

) sti nu br a( yti s net nI

Wavelength (nm)

Kulkarni et al
Scanning Tunneling Microscope

Atoms on silicon surface

Nano Materials,Characterization Techniques

 Atomic Force Microscope

laser

metal tip

Nano Materials,Characterization Techniques

AFM Images of Candida bombicola cells immobilized on Al-Membrane

Height Friction
3D Images
SEM Images at Low and High magnification of Immobilized
Candida bombicola Cells on Al-Membrane

Candida bombicola Cells

Kulkarni et al
Size and Structure Analysis

Nano Materials,Characterization Techniques

 Determination of Size and Structure

Schematic of X-ray Diffractometer.

Monochromatic
x-ray beam detector

2θ

x-ray tube

sample

Nano Materials,Characterization Techniques

X-Ray Diffraction (XRD)

X-rays
gas I

0 θ
X-rays
liqui
d I
X-rays amorpho
us solid 0 θ

X-rays single I
crystal

0 θ

X-rays
nanocryst I
al
Sulabha Kulkarni,Nanotechnology
0 θ Principles and Practices

Nano Materials,Characterization Techniques

 Scherrer formula for average size determination

AC C′ A′
D D′
B θ B′ Imax
θ
1 θ
2
B

0.9λ
O d
T β
½*Ima
T =
Intensity
P
x

L M M′ L′ β cosθ B
S N′
N
2 2 2
θ 22 θ θ 1
θ B

Sulabha Kulkarni,Nanotechnology
Principles and Practices

Nano Materials,Characterization Techniques

 Analysis of ZnS (1.4 nm) Nanoparticles

Kulkarni et al

Nano Materials,Characterization Techniques

 5

4
◊ Gold (NPs)
22 nm Fited line
∆ 10% Au-PMMA
Small Angle X-ray Scattering
log I (a. u.)

38 nm
(SAXS)
3 □ 20% Au-PMMA
39 nm
○ 40% Au-PMMA
2 39 nm
Size and Shape Determination

1
Sizes ~ 100 – 5 nm

0.00 0.05 0.10

-1
0.15 0.20 Fractal Dimensions
S (nm )

Kulkarni et al Nanotechnology (2006)

Nano Materials,Characterization Techniques

 Composition Analysis
ESCA
hν = Ek + EB

hν

Sulabha Kulkarni,Nanotechnology
Principles and Practices

Nano Materials,Characterization Techniques

 XPS Ga3d As3d
hν=1486.6 eV

Using Al target

Ga3d As3d

Using Synchrotron
(55 eV)

Nano Materials,Characterization Techniques

 Some Characteristics of
Synchrotron Radiation
What is Synchrotron Radiation?

Petman,BESSY

Nano Materials,Characterization Techniques

Synchrotron Sources

SPRING-8 (8GeV )
ESRF(6GeV )
Photon Factory

ELETTRA BESSYII
INDUS-II
DARES BURY

INDUS-I
(400MeV )

Nano Materials,Characterization Techniques

 S 2p Spectra of CdS Nanoparticles
Photoemission Spectra Pho
toe
m issio
nS pectra
CdS Nanoparticles CdSN anopa
rticles
S 2p (d=7.0nm) (d
= 4
.0n
m ) (d
= 2
.7n
m )

hn =203 eV S 2p b
) hn =
203eV S2
p d
) hn =
203eV S2
p
Intensity (a. u.)

(b) (
E =41e
V) (E =41e
V)
k
in k
in
hn =203 eV
(E =41eV)
kin

I
I IV

Intensity (a. u.)

x2 I
II

2.7 nmS
II
III
ox.
II III
III a

Intensity (a. u.)

x3 b x2
x3

S
a
) hn = 5
00eV S2
p c) hn = 5
00eV S2
p

ox.
(E kin =
338
eV) (E kin =
338
eV)
(a)

4.0 nm
hn =500 eV
(E =338eV)
kin

IV I
I I
II

S
II III
ox. III
II III

7.0 nm x2
x2 x2

1
66 1
65 1
64 1
63 1
62 1
61 1
60 1
66 1
65 1
64 1
63 1
62 1
61 1
60
166 165 164 163 162 161 Bin
din
gEnerg
y(e
V )
Binding Energy (eV)

Binding Energy (eV) Binding Energy (eV)

Appl. Surf. Sci. 169-170(2003)438

CPL 306 (1999)95
Phys. Stat. Sol. 173 (1999)253

Nano Materials,Characterization Techniques

 Electronic Structure of CdS Nanoparticles
Valence Band and NEXAFS Measurements
Observation of Band Gap Variation with Size
Expts at BESSY
∆ EOptical 4.3 eV 3.5 eV 3.3 eV
CBM
1.5 eV 1.2 eV
1 eV
Ef
3.8 eV 2.7 eV
4.3 eV

VBM

163 eV 162.7 eV 162.5 eV

161.5 eV

S 2p
CdS-NP 1.1 nm 2.3 nm Bulk
1.8 nm

VBPES (hυ = 200 eV) BESSY Annual Report (2004) 97

 Concentration mapping
Of
a single semiconductor quantum dot

Ge / Si (111)

Kulkarni et al, Phys Rev Lett (2006)

Small (2006)
Analysis of Metal, Semiconductor Nanoparticles

Some Quick Methods

Nano Materials,Characterization Techniques

Optical (UV-Vis-NIR) Spectrometer
M
o
n
o

Sample Detector

Reference
Chopper
U
V

Sample
Detector
Absorption Spectra of Gold Nanoparticles
Sample Monochrom
Chamber ator

Nano Materials,Characterization Techniques

Effect of Size Variation on Energy Gap in Semiconducors

Eg Eg Eg

CdS Nanoparticles

Kulkarni et al
Appl. Surf. Sci. 169-170(2003)438
CPL 306 (1999)95
Phys. Stat. Sol. 173 (1999)253

Nano Materials,Characterization Techniques

Optical Properties of Metal Nanoparticles

Size Dependent Shifts (Au)

Surface Plasmon
Resonance

Kulkarni et al

Xia et al. Shape Dependent Shifts (Au)

MRS Bull 30 (2005)338

Haes et al. MRS Bull 30 (2005) 368

Nano Materials,Characterization Techniques

 Immunoassay for the detection of antibody
using silica silver core shell particles

0.50
453 nm
0.45

0.40

0.35

0.30
Intensity

0.25

0.20
431 nm
0.15

0.10

0.05 494 nm

0.00
300 400 457 nm 500 600 700

Wavelength
(nm)

Kulkarni et al, CPL 404 (2005) 136

Rapid Detection of E. Coli using Silver Nanoshells
A

0.50 0.5
No cell
8
µ m
10 cells
10
10 cells
0.45 3
10 cells
2
10 cells 1µ m
10 cells
5
0.40 10 cells
B

Intensity (Arb. Unit)

0.35

0.30
1µ
m
0.25 C

0.20

0.15 1µ m
300 400 500 600 700 800
Wavelength (nm) D

1µ m
Kulkarni et al. SMALL 2 (2005)335
 Specific, Sensitive and Rapid detection using
Silver Nanoshells
0.9 1.0

Intensity (A. U.)

0.85
Silver Nanoshells 2.0
443 nm 0.80 Silver Nanoshells
Silver Nanoshells
with Antibody Silver nanoshells
0.8 0.75
0.9 1.8 Mixed with E. coli
0.70 Silver Nanoshells
with Bacillus

Intensity / (Arb. Unit)

0.65
458 nm Silver Nanoshells 1.6
Intensity / (Arb.Unit)

0.7 0.60 0.8 with Pseudomonas

Intensity / (Arb. Unit)

0.55
1.4
0 300 600 900 1200
0.6 Amount of Antibody 0.7
(µg)
1.2

0.5 0.6
1.0

0.5 0.8
0.4
A 0.6
0.4
0.3
B 0.4
C 0.3
0.2
0.2
D
0.2
0.1 0.0
300 400 500 600 700 300 400 500 600 700
300 400 500 600 700
λ / nm λ / nm
λ / nm

Interaction of nanoshells
Detection is specific for Presence of Antibodies
with antibodies E. coli, presence of any is necessary for coupling
other microorganism than E. coli to the nanshells
E. coli could not be detected
Kulkarni et al. SMALL 2 (2005) 335
Detection of Toxic Ions Using Nanoshells
1.1 1.1
NoHgCl 2 NoZnCl 2
0.05ml 0.05ml
1.0 1.0
Intensity (Arb. Units)

Intensity (Arb. Units)

0.1ml 0.1ml
0.2ml 0.2ml
0.9 0.3ml 0.9 0.3ml
0.5ml 0.5ml
0.8 0.8 1ml
2ml
3ml
0.7 0.7
5ml

0.6 0.6

0.5
0.5
0.4
0.4
0.3
0.3
0.2
0.2
0.1
0.1
300 400 500 600 700 300 400 500 600 700
wavelength(nm) wavelength(nm)

Detection of Hg2+ and Zn2+ using silica core silver shell particles
Kulkarni et al
 Detection of Toxic Ions Using Nanoshells
1.0 2.0
NoCdAc NoPbCl 2
0.05ml 0.05ml
1.8

Intensity (Arb. Units)

Intensity (Arb. Units)

0.9 0.1ml 0.1ml

0.2ml
0.2ml
0.3ml
1.6 0.3ml
0.8 0.5ml
1ml 0.5ml
2ml 0.7ml
3ml 1.4
0.7 5ml
0.8ml
8ml
0.9ml
10ml 1.2 1ml
0.6
1.0
0.5
0.8
0.4
0.6
0.3
0.4
0.2
0.2
0.1
0.0
300 400 500 600 700 400 500 600 700
wavelength(nm ) Wavelength(nm)

Detection of Cd2+ and Pb2+ using silica core silver shell particles
Kulkarni et al
 Photoluminescence
Conduction Band (LUMO )
Radiationless
Band Edge Luminescence

decay
Defect
States
CdSe Nanoparticles (<10 nm)
Excitation

Dopants d- Optical absorption

States
40 Min

Orange emission
30Min

Blue
20 Min

10Min

emissio Dopants d-
0Min

400 500 600 700 800

UV light
Wavelength(nm)

Defect n States
States
Kulkarni et al

Valence Band (HOMO)

Nano Materials,Characterization Techniques

 Core-Shell Particles - ZnS:Mn@SiO2

TEM Photoluminescence Enhancement

SiO2 ZnS:Mn@SiO2 ESR of ZnS:Mn Nanoparticles

Variation of
Mn Concentration
250 nm
800 nm

APL67 (11995)2506
Phys. Rev.B60 (1999)8659
JCP 118 (2003) 8945
& also chosen by
Virtual J. Nano. Sci. & Nanotech. 7 (2003)
Photoluminescence
Entrapment of Dye Molecules inside Silica particles

J. Lumin.114 (2005) 15
 FTIR Spectrometer

Fixed Mirror

Sour
Beam Splitter
ce
Movable Mirror
Sample

Detect
or

Nano Materials,Characterization Techniques

 Synthesis of Core-Shell Particles
Silica Particles
TEOS (Tetraethylorthosilicate)
+ Ethanol+ Ammonium
Hydroxide+ Water
Surface modified Silica
Thioglycerol (TG) capped
Particles
ZnS / CdS nanoparticles
Use of 3-Aminopropyltriethoxysilane
Salts of Zn / Cd + TG + Na2S
(APS) to functionalize the surface
Size selective precipitation

Core shell particles

Attachment of TG capped
nanoparticles to functionalized
silica particles
 Analysis of SiO2@CdS Particles
OCH3
|
H−S−CH2−CH−CH2OH NH2−(CH2)3−Si−OCH3
| |
OH OCH3
Thiogycerol 3-
(TG) aminopropyltrimethoxysilane
(APS)

OCH3
|
CdS −S−CH2−CH−CH2OH SiO2
NH2−(CH2)3−Si−O−
| |
OH OCH3
TG capped CdS
3-
Nanoparticle
aminopropyltrimethoxysilane
(APS)
OCH3
| Kulkarni et al
CdS −S−CH2−CH−CH2−O−N−(CH2)3−Si−O− SiO2
| J. Coll. Int. Sci. 278 (2004) 107
OH
TG capped CdS Nanoparticle attached to APS
functionalised SiO2particle
 FTIR Spectra for E. Coli Investigations

E E. coli

CH
OH

C=O
C=C
C=N
C-O
C-C
C-N

NH
CH
D
E. coli with antibody-silver
Transmittance(%)

NH
nanoshells
C-O
C-C
C-N
C
CH

antibodies
C-O
C-C
C-N

C=O OH

B
C=C
C=N
NH
Antibodies – silver nanoshells
Si-OH

Si-O-Si

C-O

C-N
C-C

NH

A Silver nanoshells
Si-OH

Si-O-Si

OH

C=O
C=H
NO3

C=O,OH

450 900 1350 1800 2250

-1
Wave number (cm )
Kulkarni et al. SMALL (2005)335