Sulabha KulkarniIndian Institute of Science
Education & Research, Pune
Nano MaterialsCharacterization
Recent Trends in
Synthesis & Characterization Of
Multifunctional Materials(RTSCTMN-09)
22nd June 2009
Nano Materials,Characterization Techniques
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 MechanicsStructure and BondingSynthesis of Nanomaterials (Physical Methods)Synthesis of Nanomaterials (Chemical Methods)Synthesis of Nanomaterials (Biological Methods)Analysis TechniquesProperties of NanomaterialsNanolithographySome Special NanomaterialsApplicationsPracticals
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
Depends upon the Properties of Interest !
But
Sample Purity (Composition) ……. Essential
Size, Shape & Structure ……. EssentialPorosity, Surface Area etc.
Mechanical, Optical, Thermal, Electrical, Magnetic
What kind of analysis is needed
Nano Materials,Characterization Techniques
Size, Shape & Structure ……. Essential
Available Techniques
Microscopes Confocal MicroscopeScanning Near Field Optical MicroscopeScanning Electron Microscope, Transmission Electron MicroscopeScanning Tunneling MicroscopeAtomic Force MicroscopeMagnetic Force Microscope
X-ray Diffraction Wide Angle X-ray ScatteringSmall Angle X-ray scattering
Nano Materials,Characterization Techniques
Size, Shape and Distribution Analysis
Microscopes
Nano Materials,Characterization Techniques
Objective lens
Transparent specimen
Collector
Laser source
Scanned point Detector
Confocal Microscope
Resolution
Limited by Wavelength Of the Radiation used
Nano Materials,Characterization Techniques
Scanning Near Field Optical Microscope
Nano Collector
Source
Detector
Sample surface
Propagating Waves
Evanescent Beam generated by nano collector Evanescent Beam generated
by nanostructured object
Incident Rays
Amplifier
Piezo drive
Scaner distance control
Photomultiplier
Laser Beam
Metal coating
Optical fiberSample
Computer
Sulabha Kulkarni,NanotechnologyPrinciples and Practices
Overcomes Diffraction Limit
20 nm – 60 nm
Nano Materials,Characterization Techniques
Condenser lenses
Electron gun
Specimen
Scanning generator
Amplifier
CRT
Scanning coils
Scanning Electron Microscope (SEM)
Incident beam
Auger electrons
Secondary electrons
Back scattered electrons
Characteristic X-rays
Bottom of the sample
Resolution : ~ 50 –100 nm
Sulabha Kulkarni,NanotechnologyPrinciples and Practices
E ~ 5 –100 KeV
Needles Flowers
Rods Tetrapods
ZnO micro particles: different morphologies
BeltsKulkarni et al
1 m
0.5 m
1 m
(a) (b)
(c)
(1) (2) (3)
(4)(5)
(6)
Growth of ZnOparticles with central cavity
communicated
SEM
20 μm50 m
Aligned SnO2 Rods
10 m
Obtained by Sol-Gel routeOn Glass Slide/Si
Thin Solid Films 515 (2006) 1450
Silica-Titania Core-Shell Particles
After first coating step
After Second coating step
Silica Particles Silica @ Titania core - shell Particles
Thin coating Thick coating Uncoated particles
300 400 500 600 700 800
Wavelength (nm)
Inte
nsi
ty
Silica Particles
Titania Particles
328 nm
Silica@Titania Particles
Silica Particles of size ~ 213 nm coated with 39 nm thick shell of titania
Titania-Silica Core-Shell Particles
300 400 500 600 700 800
Wavelength (nm)
Inte
nsi
ty (
arb
un
its)
325 nm
348 nm
Titania Particles
Titania@Silica Particles
Titania Particles Titania@Silica Particles
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
(a) (b)
(c) (d)
SEM Images
Silica Particles Silver core shell particles
Core shell particles with rabbit antibodies
With goat anti rabbitantibodies
Kulkarni et al, CPL 404 (2005) 136
Department of Physics, University of Pune
Nanoporous Materials….Aerogels
Thermally InsulatingSilica Aerogel
Transparent Silica Aerogel
SEM of an Aerogel
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
Nano Materials,Characterization Techniques
Electron source
Condensor lensSample
Objective lens
Back focal plane of objective lens
Image
Diffracted beam
Direct beam
Transmission Electron Microscope
SiO2@CdS
J. Coll. Int. Sci. 278 (2004) 107
SiO2@ZnSSurf. Engg. 20, no.4 (2004)
CdS
Gold nanorods
~ 3 nm
Resolution ~ 0.1 nm
Fe2O3 particles (TEM )
Kulkarni et al
Fe2O3 particles
Kulkarni et al
(TEM)
SiO2 particles (~ 250 nm) prepared formaking core-shell particles orfunctional materials
Kulkarni et al
Silver Nanoshells (TEM)
CdSe Rods
(TEM)
Kulkarni et al
Silica Tubes Coated with Silver Nanoparticles
Wavelength (nm)
300 400 500 600 700 800
300 400 500 6000.0
0.1
0.2
0.3
Inte
nsi
ty (
arb
u
nit
s)
425 nm398 nm
Kulkarni et al
Nano Materials,Characterization Techniques
Scanning Tunneling Microscope
Atoms on silicon surface
Nano Materials,Characterization Techniques
laser
metal tip
Atomic Force Microscope
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
Nano Materials,Characterization Techniques
Size and Structure Analysis
Nano Materials,Characterization Techniques
2
Monochromatic x-ray beam
x-ray tube
sample
detector
Schematic of X-ray Diffractometer.
Determination of Size and Structure
Nano Materials,Characterization Techniques
X-Ray Diffraction (XRD)
I
0
I
0
I
0
I
0
X-rays
X-rays
X-rays
X-rays
X-rays
gas
liquid
amorphous solid
single crystal
nanocrystal Sulabha Kulkarni,Nanotechnology
Principles and Practices
Nano Materials,Characterization Techniques
T
S
2
Intensity
Imax
½*Ima
x
2B
21
22
B
2
1
d
N
MLN′
M′ L′
DA C A′
B′D′
C′
B
O
P
B
T
cos
9.0
Scherrer formula for average size determination
Sulabha Kulkarni,NanotechnologyPrinciples and Practices
Nano Materials,Characterization Techniques
Kulkarni et al
Analysis of ZnS (1.4 nm) Nanoparticles
Nano Materials,Characterization Techniques
0.00 0.05 0.10 0.15 0.20
1
2
3
4
5
Fited line
S (nm-1)
log
I (a
. u.)
◊ Gold (NPs) 22 nm∆ 10% Au-PMMA 38 nm□ 20% Au-PMMA 39 nm○ 40% Au-PMMA 39 nm
Small Angle X-ray Scattering (SAXS)
Size and Shape Determination
Sizes ~ 100 – 5 nm
Fractal Dimensions
Kulkarni et al Nanotechnology (2006)
Nano Materials,Characterization Techniques
h
h = Ek + EB
Composition AnalysisESCA
Sulabha Kulkarni,NanotechnologyPrinciples and Practices
Nano Materials,Characterization Techniques
Ga3d As3d
h=1486.6 eV
As3dGa3d
Using Al target
Using Synchrotron(55 eV)
XPS
Nano Materials,Characterization Techniques
Some Characteristics of Synchrotron Radiation
Petman,BESSY
What is Synchrotron Radiation?
Nano Materials,Characterization Techniques
INDUS-I(400 MeV )
SPRING-8 (8 GeV )
Photon Factory
ESRF(6 GeV )
DARES BURY
Synchrotron Sources
ELETTRA BESSYIIINDUS-II
Nano Materials,Characterization Techniques
166 165 164 163 162 161 160
Photoemission Spectra
CdS Nanoparticles
S 2p
x2
x2
(d=2.7nm)
x2
x3
(d=4.0nm)
a) hn =500 eV
(Ekin
=338eV)
b) hn =203 eV
(Ekin
=41eV)
S 2p
IIIII
I
Inte
nsity (a. u.)
Binding Energy (eV)166 165 164 163 162 161 160
S 2p
IV
III
II
I
b
a
S 2p
c) hn =500 eV
(Ekin
=338eV)
d) hn =203 eV
(Ekin
=41eV)
I
IIIII
IV
IIIII
I
166 165 164 163 162 161
x2
x3
x2
(d=7.0nm)
S 2p
IIIII
I
(a) hn =500 eV (E
kin=338eV)
(b) hn =203 eV (E
kin=41eV)
Inte
nsit
y (a
. u.)
Binding Energy (eV)
Photoemission Spectra CdS Nanoparticles
I
II
III
Binding Energy (eV)
S 2p Spectra of CdS Nanoparticles
S 2p
Sox.
Sox.
Sox.
7.0 nm
4.0 nm
2.7 nm
hn =203 eV
Binding Energy (eV)
Inte
nsit
y (
a.
u.)
Appl. Surf. Sci. 169-170(2003)438CPL 306 (1999)95Phys. Stat. Sol. 173 (1999)253
Electronic Structure of CdS Nanoparticles Valence Band and
NEXAFS MeasurementsObservation of Band Gap Variation with Size
Expts at BESSY
VBPES (h = 200 eV) BESSY Annual Report (2004) 97
161.5 eV
1.5 eV
EOptical 4.3 eV
4.3 eV
163 eV
CdS-NP
VBM
CBM
Ef
3.5 eV
162.7 eV
3.8 eV
1.2 eV
3.3 eV
162.5 eV
1 eV
2.7 eV
2.3 nm1.8 nm1.1 nm
S 2pBulk
Concentration mapping Of
a single semiconductor quantum dot
Ge / Si (111)
Kulkarni et al, Phys Rev Lett (2006) Small (2006)
Nano Materials,Characterization Techniques
Analysis of Metal, Semiconductor Nanoparticles
Some Quick Methods
Nano Materials,Characterization Techniques
M o n o
Sample Detector
U V
Sample Chamber
Monochromator
Detector
Reference
Sample
Chopper
Optical (UV-Vis-NIR) Spectrometer
Absorption Spectra of Gold Nanoparticles
Nano Materials,Characterization Techniques
EgEgEg
Effect of Size Variation on Energy Gap in Semiconducors
Kulkarni et alAppl. Surf. Sci. 169-170(2003)438CPL 306 (1999)95Phys. Stat. Sol. 173 (1999)253
CdS Nanoparticles
Nano Materials,Characterization Techniques
Surface Plasmon Resonance
Xia et al. MRS Bull 30 (2005)338
Optical Properties of Metal Nanoparticles
Haes et al. MRS Bull 30 (2005) 368
Size Dependent Shifts (Au)
Shape Dependent Shifts (Au)
Kulkarni et al
Kulkarni et al, CPL 404 (2005) 136
Immunoassay for the detection of antibody using silica silver core shell
particles
300 400 500 600 7000.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
453 nm
431 nm
494 nm
457 nm
Wavelength (nm)
Inte
nsit
y
A
1m
B
1m
C
1m
D
1m
0.5 m
300 400 500 600 700 800
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
No cell
105 cells10 cells102 cells103 cells1010 cells108 cells
Inte
ns
ity
(Arb
. Un
it)
Wavelength (nm)
Kulkarni et al. SMALL 2 (2005)335
Rapid Detection of E. Coli using Silver Nanoshells
300 400 500 600 7000.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0 300 600 900 1200
0.55
0.60
0.65
0.70
0.75
0.80
0.85
458 nm
443 nm
Inte
nsi
ty /
(Arb
.Un
it)
/ nm
D
CB
A
Inte
nsi
ty (
A. U
.)
(g)Amount of Antibody
300 400 500 600 700
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
with Pseudomonas
with Antibody
Inte
nsi
ty /
(Arb
. Un
it)
/ nm
Silver NanoshellsSilver Nanoshells
Silver Nanoshellswith BacillusSilver Nanoshells
300 400 500 600 7000.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
Mixed with E. coli
Silver Nanoshells Silver nanoshells
Inte
nsi
ty /
(Arb
. Un
it)
/ nm
Specific, Sensitive and Rapid detection using Silver Nanoshells
Interaction of nanoshells with antibodies
Detection is specific forE. coli, presence of anyother microorganism thanE. coli could not be detected
Presence of Antibodies is necessary for couplingE. coli to the nanshells
Kulkarni et al. SMALL 2 (2005) 335
Detection of Toxic Ions Using Nanoshells
Detection of Hg2+ and Zn2+ using silica core silver shell particles
300 400 500 600 7000.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
Inte
nsit
y (
Arb
. U
nit
s)
wavelength (nm)
No HgCl2
0.05 ml 0.1 ml 0.2 ml 0.3 ml 0.5 ml
300 400 500 600 700
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
Inte
nsit
y (
Arb
. U
nit
s)
wavelength (nm)
No ZnCl2
0.05 ml 0.1 ml 0.2 ml 0.3 ml 0.5 ml 1 ml 2 ml 3 ml 5 ml
Kulkarni et al
Detection of Toxic Ions Using Nanoshells
Detection of Cd2+ and Pb2+ using silica core silver shell particles
300 400 500 600 700
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Inte
nsit
y (
Arb
. U
nit
s)
wavelength (nm)
No CdAc 0.05 ml 0.1 ml 0.2 ml 0.3 ml 0.5 ml 1 ml 2 ml 3 ml 5 ml 8 ml 10 ml
400 500 600 7000.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
Inte
nsit
y (
Arb
. U
nit
s)
Wavelength (nm)
No PbCl2
0.05 ml 0.1 ml 0.2 ml 0.3 ml 0.5 ml 0.7 ml 0.8 ml 0.9 ml 1 ml
Kulkarni et al
Nano Materials,Characterization Techniques
UV light
CdSe Nanoparticles (<10 nm)
400 500 600 700 800
40 Min
30 Min
0 Min
10 Min
20 Min
Wavelength (nm)
Optical absorption
Kulkarni et al
Photoluminescence
Defect States
Defect States
Dopants d-States
Dopants d-States
Orange emission
Blueemission
Radiationless decay
Excit
ati
on
Valence Band (HOMO)
Conduction Band (LUMO)B
an
d E
dg
e L
um
inescen
ce
Core-Shell Particles - ZnS:Mn@SiO2
TEMSiO2
ZnS:Mn@SiO2
Photoluminescence
800 nm250 nm
Photoluminescence EnhancementESR of ZnS:Mn Nanoparticles
APL67 (11995)2506Phys. Rev.B60 (1999)8659
JCP 118 (2003) 8945 & also chosen by
Virtual J. Nano. Sci. & Nanotech. 7 (2003)
Variation of Mn Concentration
J. Lumin.114 (2005) 15
Entrapment of Dye Molecules inside Silica particles
Nano Materials,Characterization Techniques
Fixed Mirror
Source
Sample
Detector
Beam Splitter
Movable Mirror
FTIR Spectrometer
Surface modified Silica Particles
Use of 3-Aminopropyltriethoxysilane (APS) to functionalize the surface
Synthesis of Core-Shell Particles
Silica ParticlesTEOS (Tetraethylorthosilicate)
+ Ethanol+ Ammonium Hydroxide+ Water
Thioglycerol (TG) cappedZnS / CdS nanoparticlesSalts of Zn / Cd + TG + Na2S
Size selective precipitation
Core shell particlesAttachment of TG capped
nanoparticles to functionalized silica particles
Kulkarni et alJ. Coll. Int. Sci. 278 (2004) 107
HSCH2CHCH2OH | OH
Thiogycerol(TG)
OCH3
|NH2(CH2)3SiOCH3
| OCH3
3-aminopropyltrimethoxysilane
(APS)
OCH3
|SCH2CHCH2ON(CH2)3SiO | OH
TG capped CdS Nanoparticle attached to APS functionalised SiO2particle
CdS SiO2
SCH2CHCH2OH | OH
TG capped CdS Nanoparticle
CdS SiO2
OCH3
|NH2(CH2)3SiO | OCH3
3-aminopropyltrimethoxysilane
(APS)
Analysis of SiO2@CdS Particles
450 900 1350 1800 2250
C-O
C-C
C-NS
i-O
HS
i-O
H
Si-
O-S
iS
i-O
-Si
C=O,OH
C
B
Tra
nsm
itta
nc
e(%
)
Wave number (cm-1)
A
NH
NHC
H
C-O
C-C
C-N
NH
NO
3
C=
H
C=
O
C-O
C-C
C-N
CH
NH
OH
C=
OC
=C
C=
N
E
OH
CH
OH
C=
OC
=C
C=
N
C-O
C-C
C-N
D
Silver nanoshells
Antibodies – silver nanoshells
antibodies
E. coli with antibody-silvernanoshells
E. coli
FTIR Spectra for E. Coli Investigations
Kulkarni et al. SMALL (2005)335
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