Download - Dr Sulbha Kulkarni-1
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Sulabha KulkarniIndian Institute of Science
Education & Research, Pune
Nano MaterialsSynthesis
Recent Trends in
Synthesis & Characterization Of
Multifunctional Materials(RTSCTMN-09)
22nd June 2009
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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
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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
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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
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Nano Materials,Synthesis & Characterization Techniques
Materials with Size Dependent Properties
Properties of all materials are size dependent below ~ 100 nm!
(M. Faraday1857)!
CdS
CdSe
Ag
Au
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Smith & Nie, Analyst 129 (2004) 672
Imaging using Quantum Dots of CdSe
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Shape Dependence
Aspect ratio > 1
400 600 800 1000
0.25 ml AgNO3 720
0.3 ml AgNO3
780
BDAC/CTAB = 0.15M/0.2M
0.5 ml AgNO3
857
Inte
nsi
ty
Wavelength (nm)Photograph of gold nanospheres (left) and gold nanorods of increasing aspect ratio.
Photograph of gold nanospheres (left) and gold nanorods of increasing aspect ratio.
a 50 nm
300 400 500 600 700 8000.0
0.1
0.2
0.3
0.4
0.5
Ex
tin
cti
on
(ar
b.u
nit
s)
Wavelength (nm)
527 nm
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Photonic Band Gap Materials
Kulkarni et al
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Wonderful Carbon
Graphite Diamond
Fullerenes Carbon Naotubes
Latest is Graphene!
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Look at the Nature Carefully
Micro + Nano StructureWaxy surface
Superhydrophobic !
Inspiration from the Nature
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Understanding the behaviour of a water drop on a surface
water
hydrophobic surface
water
superhydrophobic
water
hydrophilic surface
Water loving-Water spreads almost completelye.g.glass
waterSuperhydrophilic surface
water
Water hating – A water bead is formede.g. teflon pan, lotus leaf
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Wenzel Cassie-Baxter Both
Different Models to explain observed wettability
Roach et al. Soft Matter, 2008, 4, 224–240
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Roach et al.
Soft Matter, 2008, 4, 224–240
Lithographyically Created Hydrophobic Surfaces (Si & SU8)
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Hydrophobicity Tuning (S. K. Kulkarni)
Hydrophobic-Hydrophilic Transitions (TiO2)
X400 50mX400 50m
X400 50mX400 50m
0.5m
0.5m
5m
5m
5m
5m
5m
Thickness : 112 nm, 250 nm, 369 nm, 500 nm
RMS Roughness : 106 nm, 138 nm, 142 nm, 193 nm
Magnetron Sputter Deposited Thin Films
Super-hydrophobicity, CA ~ 176o
Anatase
5m5m
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UV Induced Hydrophobicity to Hydrophilicity Transitionin TiO2 Thin Films
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Feet of Lizard (Geko Effect)
Reminds you of Ghorpad used by Tanaji?
Novel Robos, stick tapes etc by mimicking a lizard
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CdSe
TiO2
OTE
h
e
e h
h
h
CdSe
TiO2
OTE
h
e
e h
h
h
PtGlass
ITO
Aluminum
Redox or Hole Transport Layer
Met
al
SemiconductorNanocrystals
(a)
Glass
ITOPEDO
T
Aluminum
Active Polymer/Semiconductor Layer
(b) (c)
CdSe
TiO2
OTE
h
e
e h
h
h
CdSe
TiO2
OTE
h
e
e h
h
h
Pt
CdSe
TiO2
OTE
h
e
e h
h
h
CdSe
TiO2
OTE
h
e
e h
h
h
PtGlass
ITO
Aluminum
Redox or Hole Transport Layer
Met
al
SemiconductorNanocrystals
Glass
ITO
Aluminum
Redox or Hole Transport Layer
Met
al
SemiconductorNanocrystals
(a)
Glass
ITOPEDO
T
Aluminum
Active Polymer/Semiconductor Layer
(b)
Glass
ITOPEDO
T
Aluminum
Active Polymer/Semiconductor Layer
(b) (c)CdSe
TiO2
OTE
h
e
e h
h
h
CdSe
TiO2
OTE
h
e
e h
h
h
PtGlass
ITO
Aluminum
Redox or Hole Transport Layer
Met
al
SemiconductorNanocrystals
(a)
Glass
ITOPEDO
T
Aluminum
Active Polymer/Semiconductor Layer
(b) (c)
CdSe
TiO2
OTE
h
e
e h
h
h
CdSe
TiO2
OTE
h
e
e h
h
h
Pt
CdSe
TiO2
OTE
h
e
e h
h
h
CdSe
TiO2
OTE
h
e
e h
h
h
PtGlass
ITO
Aluminum
Redox or Hole Transport Layer
Met
al
SemiconductorNanocrystals
Glass
ITO
Aluminum
Redox or Hole Transport Layer
Met
al
SemiconductorNanocrystals
(a)
Glass
ITOPEDO
T
Aluminum
Active Polymer/Semiconductor Layer
(b)
Glass
ITOPEDO
T
Aluminum
Active Polymer/Semiconductor Layer
(b) (c)
CdSe
TiO2
OTE
h
e
e h
h
h
CdSe
TiO2
OTE
h
e
e h
h
h
PtElectrolyte
Polymer Polymer Solar CellSolar CellPolymer Polymer Solar CellSolar Cell
Quantum Dot Quantum Dot Sensitized Solar CellSensitized Solar CellQuantum Dot Quantum Dot Sensitized Solar CellSensitized Solar Cell
Metal Metal Junction Junction Solar CellSolar Cell
Metal Metal Junction Junction Solar CellSolar Cell
Solar Cells using Nanomaterials
By P. V. Kamat
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Electronics
Spintronics
Photonics
Space Vehicles
Medical/Diagnostics
Sports/Toys
Energy
Display Panels
Food/Agriculture
Consumer Goods
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Nano Materials,Characterization Techniques
Size Dependent Physico-Chemical Propertiesrange of materials with change of properties,
without changing chemical composition
Large Surface to Bulk Atoms Ratio ideal for composites, reacting systems, drug delievery,
energy storage etc
Assemblyorganization in biological systems occurs at nanoscale,
in nanoscience non-bio materials also assembled at nanoscle
Which are the Nanomaterials are we looking for
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Bulk, Quantum Well, Quantum Wire and Quantum Dot
Jacak, Hawrylak, Wojs, Quantum Dots (1998)
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Band Gap Engineering CdS, ZnS, CdSe, ZnSe, PbS, ZnO, MnSb, SnO2 etc
Fluorescent Particles ZnS (CdS):Mn, Cu, Pb, Pure Semiconductors
Pigments Fe2O3, CoAl2O4, ZnCo2O4, etc
Core-shell Particles SiO2@CdS, ZnS etc or Au,CdS,ZnS @SiO2 or PS
Fullerenes C60 , C70
Porous Materials Aerogels (SiO2, RF etc), Porous Silicon, MCM-41
Spintronics Diluted Magnetic Semiconductors &Multilayers
Self Assembly Ge/Si (111) 7x7, In/Si (111) 7x7
Q - Well Spectroscopy Al / Si (111) 7x7
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Gallery of Engineered Materials (nm to m)
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Nano Materials, Synthesis Techniques
Materials can be in the form of
Single particles (powder)
Colloids, in liquids
Thin Films, Multilayers, Nanowires, Nanorods, Nanotubes, Quantum Dots, etc etc
Bulk Materials can be Metals, Semiconductors, Insulators
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Top Down Nanotechnology Approaches
Bottom Up
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Needles Flowers
Rods Tetrapods Belts
Fe2O3 particles
SiO2@Ag/Au
ZnOCdSe
SnO2
CdS
Aerogel
Some Nano-Materials Synthesized in our Laboratory
AAO
Au
BiFeO3
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Synthesis of Nanomaterials
Physical -MBE,Sputter,Laser,lithography
Chemical-Sol-gel, coprecipitation
Biological
Hybrid-CVD,MOCVD etc
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Synthesis of Nanomaterials
Complicated Simple
Choice depends upon money and expertise available
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Nano Materials,Synthesis Techniques
Synthesis
Physical Chemiclal Biological Hybrid
Colloids, sol-gel, L-B films, Inverse micelles
Using biomembranes, DNA, enzymes and micro organisms
Electrochemical,Chemical vapour deposition, Particle arresting in glass or zeolites or polymers,Micro emulsion-zeolite
Vapour depositionMechanical
Physical vapour deposition, Laser ablation, Sputter deposition, electric arc deposition, ion implantation
High enrgy ball milling, melt mixing
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Nano Materials,Synthesis Techniques
Different milling machines
Fritsch planetary miller Medium -high energy
research miller (<250g)
What we have!
Tumbler mill Energy depends on diameter and speed of
drum Primarily used for large -scale industrial
applications
SPEX miller: High energy,
research -scale
~10cm 3
Attrition mill High energy
small -industry scale (<100kg)
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Nano Materials,Synthesis Techniques
Vacuum pump
Laser beam
Target
Plume
Substrate
Time
Laser Ablation
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Lithography
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Eelectron Beam
Lithography
Electron Microscope for
Lithography
EBL for making
Devices
Bragg-Fresnel lens in silicon using EBL
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Scanning Tunneling Microscope
Atoms on silicon surface
Ultra High Vacuum STM
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Lithography using STM/AFM Probe
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Atom Corrals
Eigler et al
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Dip Pen Lithography
Mirkin et al
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Techniques of Soft Lithography
Micromolding in Capillaries (MIMIC)
Micro Contact Printing (μCP)
Annu.Rev.Mater.Sci.28 1998) 153
J.Am.Chem.Soc. 118 (1996)5722
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Patterning of Silica Particles Using Micro Contact Printing
Kulkarni et al
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Advantages of Chemical MethodSimple
Inexpensive (less instrumentation)
Control of Concentrations, Doping etc
Low temperature Synthesis
Large Quantities
Charge Carriers and Spins,Independently Controlled
Variety of Sizes (nano to micro) & Shapes Control
Liquids, Powders or Thin Films
Self Assembly/Patterning Possible
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Chemical Synthesis of Nanoparticles
Bawendi et al
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substrate
Subphase
(1)
(2)
(3)
(4)
Compressed layer
(5)Re-compressed layer
Langmuir-Blodgett Deposition
head
tail
water
Hydrophobic
bic end
Hydrophilic end
H
C HH
C
C HH
C HH
C
O O
H
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(b) inverse micelle
W/O emulsion
oil
water droplet
micelle(a)
O/W emulsion
water
oil droplet
Micellar emulsion
oil droplet
Water
micelle
Micelles / Inverse Micelles
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Sol
Supercritical extraction
Aerogel
Sol fiberspowders
Xerogel film
heat
Gel
Evaporation of solvent
Xerogel
Ceramic Film
Dense glass/Ceramic
Dry, heat
Sol-Gel
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Nano Materials,Synthesis Techniques
Bio-Nano
Use of micro-organisms like fungi, yeast, bacteria
Use of plant extracts or enzymes
Use of templates like DNA, membranes, viruses etc
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Nano Materials,Synthesis Techniques
Self assembly of nanoparticles
CdS nanoparticles
(a)
COO-
COO-
COO-
COO-
COO-
AlOxide Layer
Adsorption of silver colloidal particles
COO
Al
COO
S
COO
S
COO
S
COO
S S
(c)
COO
Al
COO
S
COO
S
COO
S
COO
S S
(b)
S
S
MetalS
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
MetalS
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
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Nano Materials, SynthesisTechniques
(d)
(c)(e)
(a)
(b)
S-layer
Gold NP Substrate
Lipid
Use of S-Layers in Nanoparticles Synthesis
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Nano Materials, Synthesis Techniques
Metal ion
Channel
Cavity
Protein shell6 nm 12 nm
Monomer subunit
(a) (b)
Ferritin for the Synthesis of Nanoparticles