By : Noha Mohamed

Abd El Twab
Cairo University
Faculty Of Engineer
Post Graduated
Mechanical Design And Production
PART I
FUNDAMENTALS OF NANOMATERIALS
SCIENCE
CHAPTER 1
Quantum Mechanics and Atomic Structure
PHOTOELECTRIC EFFECT

cathode illuminated by light, ammeter record current I



Below threshold frequency ( Vo ) no current depend on material
of cathode metal.

current directly proportional to intensity of light.

K.E of electrons, not related to intensity but frequency of light.

Increasing intensity of light increase the saturation current.









3
EINSTEINS EXPLANATION
This contradict Maxwell wave theory

Assumed light is particles he called light quanta photons.

energy of photon expressed as

photoelectric is interaction between incident photons and
electrons inside metals.

Work function m energy required to emit a bond electron is
property to cathode metal



K.E of electron = -e x Stopping
voltage(Vo) =
Energy of light - Metal work function
=hv hvo
4
Duality of Light
Light has both characteristic of wave and particle

DUALITY OF ELECTRONS
Broglie :all matter had wave/particle duality.
relation between momentum (particle), and
wavelength, (wave).

Youngs double-slit exper.
electron beam show
interference and diffraction




5
TIME INDEPENDENT SCHRODINGER EQU.
Proposed equation analogous to harmonic wave
1-D
=h/2
m:electron mass
V electron potential energy
wave format of electron.

Born proposed probability finding electron at location x
and time t as.
Based on assumption obey following rules:
1. has to be continuous and smooth in the space.
2. the probability, so it has to be a real number.








6
ELECTRONS IN POTENTIAL WELL
1D infinite potential V (x )
Out potential probability finding
electron zero.
In potential well electron like free
electron

Using boundary conditions.





7
electron energy in potential well be at finite
discrete levels

difference between 2 adjacent energy levels
be

If a is large enough energy level not consider
discrete but continuous

Quantum mechanics produces the same
results as classical mechanics.

8
THE HYDROGEN ATOM
wave function expressed in

quantum numbers:
principle quantum number n
orbital angular momentum quantum number l
magnetic quantum number ml

in hydrogen n, l, and ml related to each other






9
Level energy, function of n for hydrogen atoms


for the ground state, n = 1, l = 0, and ml = 0,


next energy level,several available states:
- n = 2, l = 0, ml = 0 -n = 2, l = 1, ml = 0
-n = 2, l = 1, ml = 1 - n = 2, l = 1, ml = 1



10
THE PERIODIC TABLE
l = 0,1, 2, 3, they called s (sharp), p (principle), d (diffuse),
and f (fundamental).
Energy level of 1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < . . . .




11
periodic table built based on three principles:

lowest energy rule: electrons fill up from bottom (lowest
energy) to top.

Pauli exclusion principle: Electrons cant share the same
exact quantum states.
Any combination of n, l, ml hold pair of electrons, one spin up
and one spin down.

Hunds rule: electrons in same n and l orbitals would
prefer their spins to be parallel





12
CHAPTER 2
Bonding and Band Structure

CLASSIC ATOMIC BONDING
bonding seeks to balance
Coulomb force proportional to 1/r
@ro repultion force=attraction force stable
bond length
Eo bond strength


LCAO THEORY
when atoms form molecule, electrons from
atoms occupying molecular orbitals expressed
as
linear combination of atomic orbitals

14
:wave function of atom i in n-atom molecule
Ci : atomic contribution to molecular orbitals
Get contribution of each atom Huckel assumed:
1. coulomb integrals equal (ionization energy)
2. Bonding only between neighbor atoms. Resonance integral nonzero

3. wave functions of atoms orthogonal, overlap integrals zero



Molecular orbital wave function

HMO (Huckel molecular
orbitals).

15
EXAMPLE: TWO-ATOM MOLECULE H2
coulomb integral H atom=ionization energy= 13.6 eV
overlap integral 2 adjacent H =bonding energy 1 eV
2 molecular orbitals:

1. bonding molecular orbital
2. antibonding molecular orbital




16
bonding molecular orbital has lower energy. So electrons
occupy this state


The bonding energy : difference before and after the
molecule is formed, in this case

Need to provide amount of additional energy to either
ionize the atom or break bond in molecule



17
Ring

Bonding formed between
atoms 12 ,23 and 31








ring structure energy
favorable for a three-atom
molecule

THREE-ATOM MOLECULE

Chain

Bonding formed between
atoms 12 and23












18
MANY-ATOM MOLECULE

# molecular orbital energy levels is = # atoms in the
molecule.
energy levels systematically distributed below and above
All valence electrons occupy energy states below
when # energy levels gap between adjacent energy
levels becomes consider continuous energy spectrum


19
ATOMIC BONDING IN CRYSTALLINE SOLIDS: BAND
THEORY

Energy Band in Solids
N atoms in solid provide N orbitals between
&

N large, energy levels no longer discrete

energy level overlap to energy bands Between
bands forbidden gap no energy level exists.

highest energy band occupied by electrons called
valence band (VB)

If VB fully occupied,next energy band called conduction
band (CB).



20
PARTIALLY FILLED ENERGY BAND FOR METALS

Li fully 1s orbital and partially 2s orbital
Solid lattice 2s level electron split to N level
N levels between & consider
continuous band
N orbitals can contain up to 2N electrons
Li provide N electrons so half-filled 2s band
formed




Left V0 Apply electron energy on left raised of eV0 .
band partially filled empty orbitals available electrons on
left have higher energy electrons move from left to right to
pass a current.
This is why Li is conductive

21
ENERGY BAND FOR INSULATORS AND
SEMICONDUCTORS
IVA group has 4 valence electrons in outer shell
carbon and silicon belong to IVA
For a C
2s & 2p close energy over lap






4 orbitals distributed, it forms a tetrahedral structure with
all four neighboring called diamond structureby covalent
bond bonding and anti bonding form .



22
BONDING AND BAND STRUCTURES IN NANOCRYSTAL
MATERIALS

Macroscopic crystalline solid 10exp(23)atoms
Nanocrystal 100 to 10,000 atom
Molecules 2 to 10 atoms

2 Method to study

1. Button up method: Expand single molecule calculation (LCAO)
to nanocrystal ,Need high computing power (useful up to 1000
atoms)
2. Top-down method: adds size-dependent unique properties on
top of the standard band structure of macroscopic crystalline
materials.
This method is very useful for quantum well and other thin-film
structures.


23
TOP-DOWN METHOD FOR QUANTUM WELLS
AND DOTS
Quantum wells & quantum dots examples for method.
Quantum wells : potential wells confine electron motion to
2D planar instead 3D in free electron
semiconductor layer of small energy gap between 2
semiconductor layer with larger energy gaps
Thickness 10A to 100A comparable to de Broglie
wavelength so levels inside well discrete.
Example:
quantum well layer band gap 2.5 eV, To Calculate the
ground state in quantum well of 10A




24
QUANTUM DOT
Nanocrystal embedded in wide bandgap insulator.
Ground state energy 3times that of quantum well
quantumization of energy is more significant has
narrower spectrum .
Quantum dots used for light emitting diodes (LEDs),
lasers, solar cells, optical devices, and displays.



25
BOTTOM-UP METHOD FOR CARBON-BASED
NANOCRYSTALS
Used on nanocrystal structures, as CNTs and the
fullerene ball


DIAMOND: 3D CARBON-BASED STRUCTURE
form sp3 hybrid orbitals and covalent bonding with
its 4 neighbors in a tetrahedral structure.
strong covalent bonding, diamond is hard
and not easily deformed
because of large bandgap it is electric insulator but
& crystal clear (no visible light absorbed)


26
GRAPHITE: 2D CARBON-BASED STRUCTURE

sp2 hybridize carbon atom form plane covalent
bond with 3 neighbors (120) and hexagonal
network
Reminder electron form pi bond
band electron touch each other
no energy gab
graphite is conductor in direction perpendicular to
plane
Pi is weak bond ,graphite has anisotropic mechanical
properties
27
CARBON NANOTUBE
rolled-up form of 1-atomic-layerthick graphite, called 2D
graphene sheet.

CNT classify by chiral vector (n, m)

Ch impact out-of-plane bonding and band structure.
if metallic n-m multiple of 3.
m = 0 zigzag,
n = m armchair. Conductor

Band structure also function
of raduis
As radius dec it be metallic

28
C60 FULLERENE BALL
consists of 20 hexagons and 12 pentagons.
2 kinds of bonding, between pentagons and
hexagons and between two hexagons
CC single bonds and C=C double bonds


29
CHAPTER 3
Surface Science for Nanomaterials
CRYSTAL STRUCTURE AND CRYSTALLOGRAPHY
CRYSTAL STRUCTURES
crystalline materials considered repeating pattern of
points in called a lattice.
Classified into7 crystal systems&14 brave lattice 3 most
common in pure metal FCC , BCC,& HCP





a or c called lattice constant
Crystallography : systematic method for specify planes
and directions in crystal structure

31
COORDINATE SYSTEM.
Directions 3 noncoplanar axes along edges (a, b, c) with
origin at corner
Unit cell edges not same length and not so coordinate
not Cartesian unless in cubic (FCC,BCC)
[uvw] integers indicate steps from origin
<uvw> family of directions identical due to symmetry


plane // or intercept one of 3 axes.
Reciprocal of interceptions on 3axes(hkl)Miller index
index orientation of plane.
plane // to axes interception infinite reciprocal is 0
{hkl } to index a family of crystal planes

32
CLOSE-PACKED DIRECTIONS, PLANES, AND
STRUCTURES

assume atoms are solid balls with the same radius r
BCC Structures
Diagonal or <111> close-packed direction all atoms touch
other
relationship between r and a
close-packed plane {110}
volume packing density (atomic packing factor or APF)
BCC have 8 atoms @ corner shared by 8 neighbor cubes and
1 atom @ center.



33
CLOSE-PACKED STRUCTURES
It can be proven mathematically that max. packing
density is 12 atoms

APF and packing density of HCP equal of FCC

Both HCP and FCC are closed packed structure but
with different stacking sequence.
34
SURFACE ENERGY
Atoms in surface has fewer neighbors compared with
bulk atom
It has unsaturated bonds that added extra energy
Total surface energy 1/R
of 1 micro sphere =1000 of 1nm
v.significant at nano scale
surface energy / uint area
Total surface energy E= x S ;s:surface area
Nature aim to decrease extra energy by 2 ways :
Min surface energy / unite surface by :
Use surface plane that have low surface energy
Altering local surface atomic geometry (reconfigration )
Reduce S
35
CRYSTALLOGRAPHICALLY PREFERRED SURFACE
Closed packed plane highest neighbors fewest unsaturated bond
BUT it may not have min. since has more atoms per unit area


WULFF CONSTRUCTIONS AND EQUILIBRIUM SHAPE FOR
NANOPARTICLES

inc as inc.
Edge atom has 2 broken bonds
particle size dec. edge atoms be v. significant

WULFF CONSTRUCTIONS polar
representation of used to predict
equilibrium shape of single-crystal
particles, especially nanoparticles.


36
SURFACE RECONFIGURATIONS
1-HOMGENOUS RELAXATION AND RECONSTRUCTIONS

Surface atoms assume different positions to bulk to relax surface
energy.
Surface relaxation
atoms in surface shift relative to layer underneath, while their position
within surface layer unchanged




This difference in
interatomic distance
diminish in 3
rd
or 5
th
layer
Surface reconstructions
Lead to Change in surface structure and symmetry



2 Si atoms reunite with 2
dangling bonds. #of dangling
bonds dec.by 2,lower surface
energy. 2 1 symmetry

symmetry
of 2 2

37
2-HETROGENEOUS ADSORPTION
Take place when 2
nd
medium exist air vapor .. Etc
adsorption layers have own unit cell & symmetry

ADSORPTION SITES
1-ON-TOP
SINGLE BOND WITH BELOW ATOM
2-BRIDGING SITE
BOND WITH 2 ATOMS
3-HOLLOW SITE
FORM MORE BONDS
PHYSICAL AND CHEMICAL ADSORPTION
Depending on bond nature, adsorption divided into physical (van der
Waals bonding) and chemical adsorption(covalent bonding).


Chemical adsorption Physical adsorbtion
Temp. of process
molecules type condensation point of gas
Adsorption enthalpy
ch. Bond strength (40/80KJ) molecule mass &polarity (5/40KJ)
Saturation
Limited monolayer Multilayer
38
SURFACE AREA&SURFACE THERMODYNAMICS
Min. surface energy throuh exposing less surface
area
Surface area in nanomaterial
in CNT unpaired electron form pi bond inside tube to
minimize surface energy
Half buckeye ball (C60) on tip of tube
Thermo dynamic equilibrium state
Nanosphere of radius r thermodynamically
equilibrium if
r > r*
Gets from overall Gibbs free energy change

To push critical size r* smaller, dec. for nanoparticle ( ) or inc. Gibbs
free energy per unit volume (Gv ).


39
WETTING
phenomenon use in nanomaterial fabrications
combine of dec. surface area and to min. overall energy
YOUNGS EQUATION AND CONTACT ANGLES
Liquid drop on solid surface
wetting angle characteristic value to evaluate how well
the liquid spreads on substrate surface in vapor environment.




COMPLETE AND PARTIAL WETTING


2nd phase spread on substrate complete wetting

>
Have 2 interfaces (S-L , L-V) to min surface energy ,ideal case for
painting, coating, and depositing films in nanomaterial fabrications

40
CHAPTER 4
Nanomaterials Characterization

X-RAY DIFFRACTION AND LAUE LAW
Add 2wave of same amplitude and frequancy
In phase constructive diffraction
180 phase diff. destructive diffraction
LAUE Method
if wave length of X-ray similar to lattice parameters it
possible to diffract X-ray through crystal lattice.


Braggs Law
beam 2 has to travel extra distance
MO2 + MO2 = 2d sin

To be in phase 2d sin =n

n = 1,2,3.. d = lattice parameter

Knowing & get d 42
ELECTRON MICROSCOPY FOR NANOMATERIAL
Electron accelerate under high voltage to get small to
provide high resolution at nanoscale

Interaction Between Electron Beams and Solids
According to the properties and directions signals transmitted can be divided
into the categories

1-Transmitted Electrons
Scattered elastically or not ch. Properties determine
by energy loss
2-backscattered electron
Electrons adsorbed & scattered and then escaped
determine crystal orientation
3-secondary electrons when electron
surface excite electrons use to determine ch. Comp.
4-x-rays
Electron in inner shell also excited , electron in outer
fill inner shell delta energy is x-ray characteristic ch.
Composition
5-Auger electrons
X-rays excite other electrons use to determine ch.
Comp. of lower layers



43
TRANSMISSION ELECTRON MICROSCOPE (TEM)
Consist of electron gun, magnetic lens chamber
and screen
Revealing phase/crystallographic orientation
using diffraction and ch. Comp. use energy
spectrum
Resolution up to 0.5A
Example :SWCNTs
Diffraction pattern can determine diameter and
chiral angle
Energy spectrum give inf. About ch. Comp. bond
and dielectric properties
Situ TEM can record process as phase
transformation deformation or film growth
Example :
heat sample then cool directly &recored phase
deformation
Run tesile test or indentation
44
SCANNING ELECTRON MICROSCOPE (SEM)
Scan electron beam across sample
surface & collect scattered electron for
imaging

Image formed use back scattered signals
beam energy not need to be high
sample not need to be transparent
only need to be conductive
resolution up to 1 to 5 nm
Reveal inf. About surface topography
Backscattered electrons related to atomic
nu. (z)
45
SCANNING PROBE MICROSCOPE (SPM)
probe of fine tip scan surface
Atomic level
Two types Depending on signals collected:
1. atomic force microscope (AFM) atomic force recorded
cantilever and piezo material
2. scanning tunneling microscope (STM), record tunneling
current between probe tip and surface to reconstruct
surface information


46
SURFACE ANALYSIS METHODS
To descover ch. Comp. bonding&band structure
1-Auger electron spectroscopy AES
Plot electron bean intensity vs K.E of electron
if beam kicks electron K shell, then electron L
shell falls in K shell emitted EK EL .release
Auger electrons EA. So K.E detector record E =
EK EL EA
3 energies element specific use for surface ch.
Comp. analysis.
2- X-Ray Photoelectron Spectroscope (XPS)
Related to binding energy
If x-ray energy = Ei & K.E of electron Ep
binding energy Eb= Ei-Ep
obtain binding energy inf. and subsequent
bonding/ electronic band

47
PART II
NANOMATERIALS FABRICATION
CHAPTER 5
Thin-Film Deposition: Top-Down Approach

THIN-FILM DEPOSITION
Fabricate 2 to 3 larger in 1 or 2 dimens. than desired then nano-
patterning technique to get small feature
HOMOGENEOUS FILM GROWTH MECHANISMS
System stable equilibrium between thermodynamics and kinetics to 2
mechanisms takes place
1-STEP PROPAGATION
Terrace island 4side extra surface
Steps 2 side extra surface
Kinks no extra surface, less overall surface, stable
Steps and kinks probability small, need high temp.& fast
diffusion
2-ISLAND GROWTH
Terrace forming cluster to min. surface energy
Cluster less mobile ,stable &attract more atoms
takes place @low Temp. low surface diffusion
&deposition rate
49
HETEROGENEOUS FILM GROWTH MECHANISMS
Deposited on substrate of differ materials& structures
Total energy include surface energy & elastic energy due to lattice
mismatch
Classify into 3 category
1-Frankvan der Merwe Model
If Lattice parameter film match substrate elastic energy negligible
To form continuous film wet criteria must satisfy

Surface energy of substrate >surface energy of film +interface energy
2- VolmerWeber Model
Wetting doesnt satisfy ;it grown into 2D island but assume perffect lattice
match
3- StranskiKrastanov Model
There mismatch
Model based on competition between surface energy &elastic strain
energy



50
THIN-FILM DEPOSITION METHODS
PHYSICAL VAPOR DEPOSITION (PVD)
Substrate heated or biased film (source of energy)vapor
condensation on substrate
Process happen in high vacuum
PVD sub divide according source of energy
THERMAL EVAPORATION
Equipment sample ,High deposition rate large substrate size but limited
material (need low evaporation Temp.)
SPUTTERING
Moment transfer high energy ions bombard
target surface transfer K.E > chemical bond energy
Material sputter &deposit on substrate


51
CHEMICAL VAPOR DEPOSITION (CVD)
Involve chemical reaction
1-mass transportation of reactants gas/liquid
2-adsorption of reactants
3- chemical reaction on substrate surface
4- desorption of by-products of chemical reaction
5- pumping away by-products and unreacted reactant.

52
53
CHAPTER 6
Nanolithography: Top-Down Approach

NANOLITHOGRAPHY
Divide based on patterning strategy into
1-parallel replication 2-serial writing
Parallel replication useful for patterns predefined by serial
writing
PHOTOLITHOGRAPHY
use light shining through masked area on photoresist coated
substrate

substrate then etched in plasma or
solvent ,remove certain areas and
make patterns on substrate
Limitation
size of pattern must up to the
wavelength of t light(37 nm)
process done only on flat surface

55
NANOIMPRINT LITHOGRAPHY (NIL)
high-throughput, high-resolution
replicate by mechanical contact & 3D material
displacement
NIL Process
resist can be thermal plastic or
UV curable polymer (UV-NIL)
or other deformable material

Air Cushion Press






RIE reactive
ion etching
to reduce mold damage and prolong its lifetime, avoid
high-pressure, relative rotation and lateral shifting
between the mold and substrate

air cushion press (ACP) developed utilizes a gas (or fluid) to press the
mold and substrate against each other in a chamber
56
SERIAL WRITING
AFM LITHOGRAPHY

writing using sharp probe tips with an atomic force
microscope (AFM).
Advantages: simple, fine size (10nmlevel),high resolution
accuracy and speed

SCRATCHING AND NANOINDENTATION
AFM use for nanoscale material removal
Mechanical: direct tip scratch ,plowing
Chemical :tip-induced electrochemical etching.
Limitation :tip forces cant be large to possible damage





57
NANOGRAFTING
a nanoscale patch of a thiol-on-gold SAM is exchanged
with a different thiol by the action of an AFM tip operated in
contact mode at high load
58
TEMPLATED SELF-ASSEMBLY OF BLOCK
COPOLYMERS
combining bottom-up self-assembly with top-down patterned templates,
templated self-assembly (TSA) can provide
TSA are not required to be crystalline materials
topography or chemical pattern of top templates guide organization of
component materials.
LS ranges from the characteristic length scale, Lo much larger than Lo



59
CHAPTER 7
Synthesis of Nanoparticles and Their
Self-Assembly: Bottom-Up Approach

NANOPARTICLES NPS
Less than 10nm at least 1D
Unique properties ,large surface area ,quantum effect and surface
plasmon resonance
SYNTHESIS OF NANOPARTICLES
1-CO PRECIPITATION
NPs made by precipitation of solids from aqueous sol. Then thermal
decomposition of those precipitates
Steps : nucleation, growth, coarsening and agglomeration

Complex, particle morphology sensitive to conditions but
environmentally friendly

NiO, ZnO precipitated from metal chloride gives amorphous product;
subsequent annealing to give NPs crystalline

reaction rate plays a key role
slow growth :NPs follow Oswald ripening process
rapid growth: irregular morphology and scattered size distribute




61
Oswald ripening process
Small particles vanish while large particles grow in size.
Surface Molecules less stable than well ordered and packed in the interior.
Large particle has lower surface-to- volume ratio
system lower its energy, surface molecules of small particle diffuse and add
to surface of larger
Nonaqueous
use of an organic solvent
Can Create inorganic semiconductor NPs (metal oxide) with control
morphologies and size distributions
Not sensitive for condition but toxic and require long time (days)
Example :CdSe NPs shapes explained on basis of model and selective
adsorption of surfactants on different crystallographic faces









62
2-SOL-GEL PROCESS
hydrolysis and condensation of liquid precursor to solid

63
Finding suitable precursor and
solvent is the key

Aqueous and Nonaqueous
solvent is used

Hydrolysis controlled by water
amount in nonaqueous and PH
in aqueous

Surfactants and coordinating
solvent use as satbilizing to
resist agglomeration

TiO2 nanorods produced by
this method


3-MICROEMULSIONS
1943, Hoar and Schulman reported
combinations of water, oil, surfactant & alcohol or
produce clear and homogeneous solutions
surfactant(hydrophilic head & hydrophobic tail) in
mixture of water & oil form spherical aggregates ,
which polar ends of surfactant molecules orient
toward the center
self-assemble nanostructure can
form spherical and cylindrical
Types :
Direct (oil in water)
Reverse (water in oil)


64
4-HYDROTHERMAL/SOLVOTHERMAL METHODS

In sealed vessel, brought solvent above boiling point.
Where Chemical reactions taking
Above critical point solvothermal be supercritical process
where happen change in density

Supercritical fluid (SCFs) has
characteristics of both liquid and gas

Ch. Compounds easily desolve in SCFs
Low surface tension low viscosity and high diffusivity
nanoscale materials demonstrated in supercritical water
(SCW).
metal nitrates used as precursors to prepare a wide variety
of metal oxides

65
5-TEMPLATED SYNTHESIS
Mesoporous materials of uniform pore size use as template for
synthesizing nanoparticles ,use as nanoreactors
2 methods to load semiconductor NPs into pores of a
mesoporous material:
1-in situ:mix NPs precursors with micelles before formation of
mesopores
2- post-treatment: grafting NPs onto pore surfaces of an as-prepared
mesoporous material
6- NPS OF ORGANIC SEMICONDUCTORS
organic NPs easy to synthesize and mechanically flexible
Reprecipitation method: dilute solution of starting material in
water soluble media injected stirred water causes the solutes
to be precipitated in the form of nanocrystals
Organic semiconducting NPs of monomers (single molecules),
oligomers (monomers linked to form a short chain), and
polymers (monomers linked with a long chain) are all revealed.








66
SELF-ASSEMBLY OF NANOPARTICLES
for creating functional devices for nanoelectronics and
sensors
noncovalent interactions dictate self-assembly include
hydrogen bonding
dipoledipole
Electrostatic
van der Waals
hydrophobic interactions
1- HYDROGEN BONDING-BASED ASSEMBLY
surfactants coat NPs surface
provide hindrance between neighboring NPs
make NPs able to form hydrogen bonds between terminal
NPs consider bricks& ligands are mortar
example of surfactant is dendrimer.





67
2-ELECTROSTATIC ASSEMBLY
Electrostatic interaction simple way to create organize layer-by-
layer (LbL) assembly of nanostructures
based on the alternating adsorption of oppositely charged
materials
Potential applications in areas as:
surface modification
electrochemical devices
chemical sensors
nanomechanical sensor
Lead to freestanding structures not full contact with a solid
substrate to sustain their shapes
Prepare:
LbL microcapsules
microtubules,
Microcubes
Microcantilevers
Fabricate NPNP composite nanostructure array


68
3-SHAPE-SELECTIVE ASSEMBLY
NPs prepared as tetrahedral
octahedral and cubic
Due to polarity difference between
faces of particles dipole moments
generated within NPs
Nanocubes
with <100> dipoles form wires
with <110> dipoles form sheets
4-HYDROPHOBIC ASSEMBLY
hydrophobic effect driven to
assemble into larger structures
assemble silver nanocubes into
highly ordered superlattices, through
selective face with hydrophobic
ligands



69
5-TEMPLATE-ASSISTED ASSEMBLY
templates provide platform to organize particles
through covalent and noncovalent interactions
NPs can assemble at interior or exterior of
template
ice use as template to prepare NP fibre








70
COLLECTIVE PROPERTIES OF SELF-
ASSEMBLED NANOPARTICLES

These self-assembled NPs display collective properties
different from the isolated particles and bulk phases

NPs organized in 2D superlattices has collective optical
and magnetic properties can be observed as a result of
the dipolar interactions

For example:optical properties of self-organized NPs
give rise to several plasmon resonance modes

Np organized 3D superlattices a new generation of
materials.

71
PART III
NANOMATERIALS PROPERTIES AND
APPLICATIONS
CHAPTER 8
Nanoelectronic Materials

NANOELECTRONIC MATERIALS
today, we are able to pack more than 1.9 billion
transistors into one chip compared with 60
transistors in the same area 40 years ago
SINGLE-ELECTRON TRANSISTORS (SETS)
device control the motion of a single electron with
quantum dots and a tunnel junction
it is based on nanomaterials science and the
quantum effect

to understand the fundamental principles of SETs, we
need to start with a single-electron capacitor (SEC),
which is the simplest known single-electron device.
Also called a single-electron box




73
SINGLE-ELECTRON CAPACITOR
consists of a quantum dot located between 2
electrodes
Closer source tunnel junction
other electrode control gate capacitor

apply voltage electron injected
into or from quantum dots depend on sign

because of size of quantum dots every
injected electron into quantum dots need
excessive energy due to Coulomb blockade
effect
This unique property enables to control motion of
single electron through tunnel junctions




74
SINGLE-ELECTRON CAPACITOR
voltage zero no electron tunnel quantum dot charge zero
voltage increase electron attract to quantum dot
Take anther excessive energy > Coulomb blockade energy
new electron emit
Plot relation between net charge in quantum dot and gate
voltage is step function


75
OPERATING PRINCIPLES FOR SETS
SET 3-terminal device source , drain & gate electrode
with quantum dot in middle of source and drain

Source grounded and voltage apply on
gate (Vg) & drain electrode (Vd)

Vg=0 no electron emit
Vg>=Vt (threshold voltage) electron
tunnel through source & eject into drain
forming current
76
CARBON NANOTUBE-BASED NANOELECTRONIC DEVIC
INTRODUCTION TO CNTS
Carbon has 4 electron in outer shell Can form sp3 hybridization
as in diamond or sp2 hybridization as graphite and graphene
BAND STRUCTURE OF GRAPHENE AND GRAPHITE
Relation between energy state E and wave vector Ky & Kx
&* touching each other in 6 Corner
Other location separated
by band gabs
@ specific Temp. band gap become
zero and graphene called gapless
semiconductor
A set of planes stacked electronelectron
interaction Then graphite is metallic and conductive

77
BAND STRUCTURE OF CNT
axial direction along tube axis considered infinite
Radius direction has periodicity defined by chiral vectors
Ch
periodic boundary condition of CNTs determine that only
discrete set of the (kx , ky ) state is allowed
The armchair CNT is gapless semiconductor
But due to small dim.
Electron interact with
each other and be
Conducting
For general; CNTs are
Semiconductor because of exist band gabes




78
FABRICATION OF CNTS
PVD METHODS
physical vapor deposition where momentum transfer sputters
off target
First PVD methods called electric-arc discharge
2 graphite electrodes placed close to each other inside
chamber full of inert gas
voltage applied across two electrodes
electric arc discharge occurs between electrodes
heating the electrode locally up to thousands of degrees
evaporating the carbon atoms from electrode
carbon atoms recrystallize at the end of the negative electrode
forming a multiwall CNT (MWCNT)
Easy ,cheap but difficult to control
Radius from 4 to 40 nm
Transition metal use as catalyst to produce SWCNT

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CVD METHODS
vaporliquidsolid (VLS) root growth
Hydrocarbon disassociate at metal surface into H and C
dissolve into transition metals
carbon supersaturated inside metal
precipitate out in form of a curved-up graphene sheet
leads to a fullerene cup.
more hydrocarbons disassociate at surface and precipitates
forming elongated carbon nanotubes



provide better control on CNT growth
transition metal as Co or Ni needed
Use hydrocarbon CnHm as methane

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CHAPTER 9
Nano Biomaterials

NANO BIOMATERIALS
Biology adds sophisticated nanomachines operating by
entirely classical molecular mechanisms
Nature source of inspiration to the fabrication biological
components with structures having incredible functions
DNA illustrates features of self-assembly predictable
structure develop systems simulate behavior





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CHAPTER 10
Nanostructural Materials

NANOGRAIN-SIZED STRUCTURAL MATERIALS
thermal and thermal mechanical processing use to refine
grain size down to nanograin-sized structural materials
Why Grain Refinement?
materials strength and toughness have inverse relation
Grain refinement useful for both
Hall-Petch equation
y:yield strength d:grain size
i:internal friction Ky:Hall Petch slop
fracture strength f derived from dislocation &Griffith
theory for brittle crack


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i proportional to Temp
f slightly change with temp. resulting ductile-brittle
transition
At y= f at temp. equal Tc (Transition Temp.)



C,B, constant
grain refinement only mean to
yield strength inc.
apparent fracture strength inc.
transition temperature lowered

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NANOGRAIN-SIZED STRUCTURAL MATERIALS
GENERAL APPROACHES FOR GRAIN REFINEMENT
ferritic steel cleaves along the {100} planes.
effective grain size
defined as coherent length on crystallographic cleavage planes,
Or mean free path of crack propagation along the {100} planes in
BCC ferritic steel
plastic deformation is dislocations glide along {110} planes
Example :lath martensitic steel
grains subdivide into packets of thin
close martensitic laths
structure within packet V.fine 100nm
laths within packet close crystallographic order and
lath boundaries only low-angle boundaries
Packet size define effective grain size





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Fracture cleavage follow {100} plan

2 ways accomplish grain refinement:
Thermal mechanical
Thermal processing
THERMAL MECHANICAL PROCESSING
combination of mechanical work to obtain large amount of
plastic deformation and thermal exposure to induce
recrystallization
Disadvantage:
difficult achieve large amount of uniform plastic deformation
to produce ultrafine grain size through thickness of plate steel
espical in high strength , high alloy thick plate



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THERMAL PROCESSING
applicable to high-strength thick plates, bars
cyclic thermal treatment change properties of martensitic
transformation and produce ultrafine grain size in lath
martensitic steel
Ex:During diffusionless martensitic transformation steel Show
coherent crystallographic relationship with parent phase
under certain thermal process conditions
Crystallographically cleavage planes {001} show large angle
misorientation
Where dislocation slip planes {011} small angle orientation
between adjacent martensitic laths
effective grain size for cleavage fracture refined to around 100
of nm whereas effective grain size for plastic deformation still
at micron level
Can improve toughness without impact strength




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NANOINDENTATION
It is hard to prepare indenter but the impacted volumes from test
proportional to indenter size
Principles of Nanoindentation
Test consist of constant load P indenter of size A
Hardness H =P/A
The Harder material the smaller A
difficult to measure the indentation
size Instead record load vs depth
to determine indentation size
Can proposed mechanical properties from curve as elastic modulus,
stress/strain behavior, yield strength, and work hardening rate
TEM direct observe of indentation

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CdS Nanoparticles
hollow CdS nanoparticle test using nanoindentation under
observation of TEM








contact pressure 1 GPa and shell still capable of
withstanding without any failure
elastic deformation reach up to 20% before nanoparticle
breaks
possible to achieve high strength and high ductility in the
single nanoparticle during deformation






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MECHANICAL INSTABILITY OF NANOSTRUCTURES

Instability or buckling affect reliability of nanodevices
WRINKLING OF THIN FILMS
thin metal film deposited atop
elastic substrate cooling introduced
mismatch of shrinking between two
materials
Wrinkles under capillary force
exerted by a drop of water placed on
Surface

stress induced by surface tension about 100 times stress
developed due to weight drop
Spontaneous buckling of thin films on substrates can
achieve order patterns due to mismatched deformation,
which can be manipulated in different ways



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BUCKLING OF SPHEROIDAL CORE/SHELL STRUCTURES
buckling behavior on closed surface differ from on surface
with free boundaries
triangular patterns self-assemble on surface of SiO2 shell
on spherical Ag core structure by cooling

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BUCKLING OF NANOBEAMS
Periodic nanostructures atop an elastic material, PDMS
show surface features
Euler Low
Assume :ideal column straight,
homogeneous, and free from initial stress.
Assume linear strain deformations
Boundary condition free upper end


critical load


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TIMOSHENKO ENERGY METHOD


buckling of bar under distributed axial loads
critical value of the uniform load for the beam



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