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WEEK 4: CLASSIFICATION OF NANOMATERIALS:

CLASSIFICATION OF NANOMATERIALS
0D 1D 2D 3D
1 dimension of the
Nano-dimensions in 2 dimensions are All dimensions are
nanostructure will be
all the three outside the outside the Nano
outside the
directions nanometer range meter range
nanometer range
Nano films such as
Quantam dots Nanowires and
coatings and Nano Bulk materials
nanotubes.
sheets
Long (micrometer in large (several square
Spherical in size, length), but with micrometer),but the Blocks which are in
Diameter of these
particles (1-50 nm) diameter of only a thickness is always the nanometer scale
few nanometer. in Nano scale range
0D NANOMATERIALS : QUANTUM DOTS
Quantum dots are small devices that contain a tiny droplet of free electrons.
Typical dimensions are between nanometers to a few microns.
A quantum dot can have anything from a single electron to a collection of several thousands.
The size ,shape and number of electrons can be precisely controlled
Just as in an atom, the energy levels are quantized due to the confinement of electrons.
The 3D spatial confinement is observed in the quantum dots.
In quantum dots even if one electron leaves the structure there is a significant change in the properties.
Unlike atoms however, quantum dots can be easily connected to electrodes and are therefore excellent tools to study atomic-like properties.
The potential of nearby metal gate is changed.
The atomic structure might behave as a lead one minute and gold next minute
The fanciful idea of designer materials might be realized
0D Dendrimers 0D Fullerenes
Dendrimers are spherical polymeric In the mid-1980s carbon 60 (C60) was
molecules, formed through a nanoscale discovered. C60 is spherical molecules about
hierarchical self-assembly process. There are 1nm in diameter, comprising 60 carbon
atoms arranged as 20 hexagons and 12
many types of dendrimer; the smallest is
pentagons: the configuration of a football.
several nanometres in size. Dendrimers are The C60 species was named
used in conventional applications such as Buckminsterfullerene. In 1990, a technique
coatings and inks, but they also have a range to produce larger quantities of C60 was
of interesting properties which could lead to developed by resistively heating graphite
useful applications. For example, dendrimers rods in a helium atmosphere. Several
can act as nanoscale carrier molecules and as applications are envisaged for fullerenes,
such as miniature ball bearings to lubricate
such could be used in drug delivery.
surfaces, drug delivery vehicles and in
Environmental clean-up could be assisted by electronic circuits.
dendrimers as they can trap metal ions,
which could then be filtered out of water
with ultra-filtration techniques.
1D NANOMATERIALS: CARBON NANOTUBES
Carbon nanotubes (CNTs) were first observed by Sumio Iijima in 1991. CNTs are extended tubes of rolled graphene sheets. There are two types of CNT: single-walled (one tube) or multi-walled (several
concentric tubes) Both of these are typically a few nanometres in diameter and several micrometres (10-6m) to centimetres long. CNTs have assumed an important role in the context of nanomaterials,
because of their novel chemical and physical properties. They are mechanically very strong (their Youngs modulus is over 1 terapascal, making CNTs as stiff as diamond), flexible (about their axis), and
can conduct electricity extremely well (the helicity of the graphene sheet determines whether the CNT is a semiconductor or metallic). All of these remarkable properties give CNTs a range of potential
applications: for example, in reinforced composites, sensors, nanoelectronics and display devices.
1D NANOMATERIALS: NANOWIRES
Nanowires are ultrafine wires or linear arrays of dots, formed by self-assembly. They can be made from a wide range of materials. Semiconductor nanowires made of silicon, gallium nitride and indium
phosphide has demonstrated remarkable optical, electronic and magnetic characteristics. Nanowires have potential applications in high-density data storage; either as magnetic read heads or as patterned
storage media, and electronic and opto-electronic nanodevices, for metallic interconnects of quantum devices and nanodevices. The preparation of these nanowires relies on sophisticated growth
techniques, which include self-assembly processes, where atoms arrange themselves naturally on stepped surfaces, chemical vapour deposition (CVD) onto patterned substrates, electroplating or
molecular beam epitaxy (MBE).
One-dimensional structure Exhibits crystal structure Many different materials
Diameter: 1-100 nanometers Unlike quantum dots (0- Metals, semiconductors,
(10-9 m) dimensional) oxides
Length: microns (10-6 m)

2D THIN FILM, LAYERS AND SURFACES


Two-dimensional nanomaterials, such as thin films and engineered surfaces, have been developed and used for decades in fields such as electronic device manufacture, chemistry and engineering. In the
silicon integrated-circuit industry, for example, many devices rely on thin films for their operation, and control of film thicknesses approaching the atomic level is routine. Monolayers (layers that are one
atom or molecule deep) are also routinely made and used in chemistry. The formation and properties of these layers are reasonably well understood from the atomic level upwards, even in quite complex
layers (such as lubricants). Advances are being made in the control of the composition and smoothness of surfaces, and the growth of films.
4B: GRAPHENE
WHAT IS GRAPHENE?
Graphene is a one-atom-thick planar sheet of sp2-bonded carbon atoms that are densely packed in a honeycomb crystal lattice.
APPLICATIONS BASED ON GRAPHITIC CARBON
Steel company: Coke
Rubber/plastic: Carbon black
Pencil: graphite + clay
Graphite refractory
Graphite electrode
GRAPHITIC COMPOSITION MATERIALS: CARBON FIBER
Weigh ~ of aluminium
Strength ~ 10 times of steel
Electrical conductor
Thermal conductor
HOW THICK IS IT?
A million times thinner than paper
HOW STRONG IS IT?
Stronger than diamond.
HOW CONDUCTIVE IS IT?
Better than copper.
PROPERTIES OF GRAPHENE
electronic properties,
thermal properties,
mechanical properties,
optical properties,
relativistic charge carriers
anomalous quantum hall effect
ELECTRONIC PROPERTIES
High electron mobility (at room temperature ~ 200.000 cm2/ (Vs), carbon nanotube: ~ 100.000 cm2/(Vs), organic semiconductors (polymer, oligomer): <10 cm2/(Vs).
Resistivity of the graphene sheet ~106 cm, less than the resistivity of silver (Ag), the lowest resistivity substance known at room temperature (electrical resistivity is also as the inverse of the
conductivity (sigma), of the material.
Silver is the best electrical conductor of any known metal
Copper is commonly used in electrical wire applications due to very good conductivity and price compared to silver
Gold is commonly used in electrical contacts because it does not easily corrode.
Graphene is a semiconductor with zero gap or a gapless semiconductor. Scientists are developing methods to make useful devices out of grapheme
ELECTRONIC PROPERTIES OF GRAPHENE

GRAPHENE HAS UNUSUAL ENERGY BANDS


The pz electrons (2 in each hexagon) completely fill the lower band. The upper band is empty. One can introduce (or take away) electrons into the upper (lower) band by various methods.
GRAPHENE: EXTREMELY GOOD SEMICONDCUTOR
Electrons move without much resistance on the plane of graphene. High mobility materials have been under intensive research as an alternative to silicon for high performance.
MECHANICAL PROPERTIES
High Youngs modulus (~1,100 Gpa),
High fracture strength (125 Gpa).
Graphene is as the strongest material ever measured, some 200 times stronger than structural steel.
OPTICAL PROPERTIES: ALMOST TRANSPARENT
One atom thick membrane nearly transparent (useful in devices).
CHEMICAL PROPERTY: IMPERMEABLE MEMBRANE
Not permeable even for proton. Graphene is ideal one atomic thick impermeable membrane.
WEEK 4C: THE DEVELOPMENT, AND APPLICATIONS OF FULLERENES
BUCKYBALL DISCOVERY
1985: British chemist Harry Kroto studied molecules with exactly sixty carbon atoms found near red giant stars. Kroto collaborated with Richard Smalley and Robert Curl to recreate the conditions in the
laboratory and form C60 molecules by laser vaporization of graphite.The scientists hypothesized that the molecules were made of hexagonal carbon rings blasted apart from the graphite structure, and
that the molecule must be spheroid to satisfy valence requirements
DETERMINING THE C60 STRUCTURE
After considerable work, Kroto, Smalley, and Curl determined that the structure of the C60 buckyball was a combination of 12 pentagonal and 20 hexagonal rings, forming a spheroid shape with 60
vertices for the 60 carbons. The pentagonal rings sit at the vertices of an icosahedron such that no 2 pentagonal rings are next to each other. Curl, Kroto, and Smalley received the Nobel Prize in 1996 for
their work. The architect R. Buckminster Fuller designed a geodesic dome for the 1967 Montreal World Exhibition with the same structure; the scientists thus named the new molecule
Buckminsterfullerene, which was shortened to fullerene when referring to the family of molecules.
HAYMETS PREDICTION
Independently, near the same time, Tony Haymet of the University of California at Berkeley published a paper predicting the existence of a compound of this kind, which he called footballene. The
molecule corannulene, with a similar nonplanar assembly of carbons in pentagonal and hexagonal rings, led Haymet to predict the existence of a similar spheroid molecule, with sixty carbons in twelve
pentagons and twenty hexagons.
BOND STRUCTURE AND REACTIVITY
The bonding pattern of the C60 fullerene is shown here, with yellow bonds representing double bonds and red bonds representing single bonds. The pentagonal rings contain only single bonds; double
bonds have a shorter bond length and lead to instability in the pentagonal ring. The limitations on double bond locations lead to poor delocalization of electrons, increasing the molecules reactivity.
FULLERENE REACTIONS
Possible reactions C60 and C70 (to a lesser extent) may undergo:
Additions, Polymerization, Substitutions also possible (doping with boron)
CONVENTIONAL SYNTHESIS
Kroto, Smalley, and Curl used laser vaporization of graphite to produce the carbon soot from which the fullerenes could be isolated in microscopic quantities
Krtschmer and colleagues developed a contact arc discharge method for macroscopic production, known as the Krtschmer-Huffman method.
Graphite electrodes kept in gentle contact are arc passing alternating current through them in an atmosphere of helium
The evaporated graphite takes the form of soot, which is dissolved in a nonpolar solvent. The solvent is dried away and the C60 and C70 fullerenes can be separated from the residue.
Optimizing current and helium pressure and flow rate leads to yields of up to 15% with this method.
SELECTIVE-SIZE SYNTHESIS
There is a desire to control the size of the fullerenes for various applications.
o Example: to increase the size of molecules to encage in fullerenes creates the need for a larger cage
o Currently the mechanism by which fullerenes form is unknown
o In conventional fullerene formation only C60 and C70 are produced due to their stability
Two groups (Rubin and Tobe) independently investigated cyclic polyynes as precursors to fullerenes.
o Neither group were able to produce C60 by flash vacuum pyrolysis (FVP) of the cyclic polyyne
o They still believe this synthesis will work
PROPOSED MECHANISM
Cyclic polyyne folds onto itself so tightly the new carbon bonds can form (dotted lines)

FULLERENE ENGINEERING
Exohedral Fullerenes Endohedral Fullerenes Nanopeapods
Atoms, molecules, and Molecules are enclosed Fullerene molecules
complexes are attached to within the cage contained in carbon
the exterior of the cage nanotubes
EXOHEDRAL FULLERENES--APPLICATION FOR HYDROGEN STORAGE
Hydrogen storage for fuel-cell powered vehicles; USDOE says need 9 wt% hydrogen storage density
Organometallic molecules based upon C60 and boron-doped C48B12
Complexes of transition metals with hydrogen on pentadiene rings can store up to six dihydrogen species
o May polymerize when the hydrogen is removed, rendering the process irreversible.
Arranging the complexes on buckyballs, such as C60[ScH2]12 and C48B12[ScH]12, leads to stable species which can reversibly absorb additional hydrogen.
HYDROGEN STORAGE
Nearly 9 wt% can be retrieved reversibly and room temperature and near ambient pressure.
Doping with boron
Reduces the fullerene weight
Enhances the complexs stability by increasing the binding energy
Allows the binding of an additional H2 molecule per Sc, increasing the amount of retrievable H2
ENDOHEDRAL FULLERENES
Fullerene cages with encapsulated molecule have many potential applications. For example scientists believe they will be able to encage a radioactive tracer and inject that safely into the human body.
Currently various molecules can be encaged in the fullerene cage.
Metal (La@C82), noble gas (He@C60), multimetallofullerene (Sc2@C66)
Product yields are less than 2% in all cases
Endohedral fullerenes have presented a lot of new information to researchers.
For metallofullerenes there is a charge transfer between the cage and enclosed metal, Sc2@C66 stabilizing what may not be a stable cage alone.

TNT SYNTHESIS
Improved synthesis of endohedral formation came in 1999 by introducing nitrogen to conventional Krtschmer-Huffman generator
Sc3N@C80 trimetal nitride fullerene
Increased yields to ~5%
This new process was named trimetal nitride template (TNT) and applied to form a variety of products.
M3N@C80 where M=Sc, Y, Tb, Ho, and Er
Dunsch and co-workers enhanced the synthesis by using NH3 as the reactive gas in the generator. Endohedral fullerenes were formed as the major product for the first time.
C80 and Sc3N are not stable individually.
Very restricting, it can only apply to trimetal nitrides.
NANOPEAPODS
Single-walled carbon nanotubes (SWNTs) encapsulating C60
Conventional synthesis of nanopeapods had a lot of challenges. Reactions had to be run under very difficult conditions and were very restricting.
Vaporization of thermally stable fullerene molecules
At least 350C in high vacuum
Theoretical studies showed the activation barrier for this reaction to be only ~0.37eV.
The reaction should proceed at room temperature
VARIOUS NANOPEAPOD SYNTHESES
Khlobystov and group attempted numerous synthesis methods at or near room temperature (30-50C) with a yield <1%
Mechanical mixing
Adding SWNTs to concentrated solution of fullerenes
Adding fullerenes to SWNTs solution
Supercritical fluids, most important scCO2, was the next used in the process
SWNTs and fullerenes mixed in solvent, evaporated solvent, put in supercritical CO2 under high pressure for 10 days
Produced yields ~30%
scCO2 PROPERTIES

Investigating why scCO2 increases


product yield compared to other
solvents
The interaction with carbon 60 can
vary between favorable and
repulsive by changing the molar
density of CO2, a function of temp
and pressure
Carbon dioxide has the smallest
critical diameter

MECHANISM FOR NANOPEAPOD FORMATION


scCO2 can carry the fullerene into the SWNT because of the attraction between the molecules
Varying temperature and pressure can create a repulsive interaction encouraging the solvent molecule to diffuse out of the SWNT
WEEK 4D: CARBON NANOTUBES
CNT is allotropes of carbon with a cylindrical structure. It can be capped on the ends with buckyballs or open ended composed entirely of sp 2 bonds.
GRAPHITE
Hexagonal graphite:
i. Graphite has a structure containing layers of atoms arranged at the corners of contiguous hexagons.
ii. (not to be confused with hexagonal close packed).
iii. The ease with which layers slide against each other is consistent with the much larger distance between carbon atoms in different layers (335 pm) than between carbon atoms in the same layer (142 pm).
iv. The lattice constant a = 246.6 pm
v. C=669 pm

WHAT IS TUBE ROLLED OUT OF ?


An ideal nanotube can be thought of as a hexagonal network of carbon atoms that has been rolled up to make a cylinder.
width: nanometer: "capped" with half of a fullerene molecule.
Length: microns
WHAT IS A CARBON NANOTUBE?
CNT is a tubular form of carbon with diameter as small as 1nm.
Length: few nm to microns. CNT is configurationally equivalent to a two dimensional graphene sheet rolled into a tube. A CNT is characterized by its Chiral Vector: Ch = n 1 + m 2, Chiral Angle
with respect to the zigzag axis.

WHY DO CARBON NANOTUBES FORM?


Carbon:
Graphite (Ambient Diamond (High temperature Nanotube/Fullerene (certain
conditions) and pressure) growth conditions)
sp2 hybridization: planar sp3 hybridization: cubiC sp2 + sp3 character:
cylindrical
Finite size of graphene layer has dangling bonds. These dangling bonds correspond to high energy states.

TYPES OF CNTS
Single Wall CNT (SWCNT)
Multiple Wall CNT (MWCNT)
Can be metallic or semiconducting depending on their geometry.
HOW TO ROLL THE NANOTUBE ?
1. A carbon nanotube is based on a two-dimensional graphene sheet.
2. The chiral vector is defined on the hexagonal lattice as Ch = n1 + m2
3. Chiral angle
4. Role/cap off
WHAT ARE THE MAIN PROPERTIES?
1. Diameter of nanotube 2. Chiral angle
Both depend on n and m. Diameter=length of chiral vector divided by 4 (has to do with the capping)
WHY SHOULD WE CARE?
Unique properties Material of the future seemingly infinite applications
Possible health issues
PROPERTIES
132,000,000:1 Length-To-Diameter Ratio Lengths in the millimeter range
Diameter of 3 to 9 nm Efficient electrical conductors
Can act as both thermal conductors and thermal insulators
CNT PROPERTIES
The strongest and most flexible molecular material because of C-C covalent bonding and seamless hexagonal network architecture.
Youngs Modulus of over 1 TPa vs 70 GPa for Aluminium , 700 GPa for C-fiber.
o Strength to weight ratio 500 time > for Al; similar improvements over steel and titanium; one order of magnitude improvement over graphite/epoxy
Maximum strain ~10% much higher than any material
Thermal conductivity ~3000 W/mK in the axial direction with small values in the radial direction.
Electrical conductivity six order OF MAGNITUDE HIGHER THAN COPPER
Can be metallic or semiconducting depending on chirality.
o Tunable band gap
o Electronic properties can be tailored through application of external magnetic field, application of mechanical deformation.
Very high current carrying capacity
Excellent field emitter; high aspect ratio and small tip radius of curvature are ideal for field emission.
Can be functionalized.
STRENGTH
SWNT compared to some common materials

*Values = (Carbon Nanotube Property) / (Material Property)


REACTIVITY
Flourination Diazonium salt addition Possible catalyst
TOXICITY
Research is still in the early stages
In rodents, carbon nanotubes have been found to cause several lung issues
The needle-like shape of the fibers is similar to that of asbestos
Single-Wall Nanotube (SWNT) Multi-Walled Nanotubes (MWNT)
Armchair Zig-Zag Multiple rolled layers of graphene sheets
More resistant to chemical changes than
SWNTs

CHAPTER 5 :SYNTHESIS AND PROCESSING


There are two general approaches to the synthesis of nanomaterials and the fabrication of nanostructures:
Top down Bottom up
(Start with the bulk material and cut (Building what you want by assembling it from
away material to make the size you building blocks (atoms or molecules) Atom-by-
wanted) atom, molecule-by-molecule, or cluster-by-
These approach use larger (macroscopic) cluster)
initial structure Structure is assembled from well-defined
Can be applied for variety of materials chemically or physically synthesized building
Limited by lithography resolution, blocks
selectivity of etching etc Self assembly, selective growth
Typical examples are Lithography, Require accurate control and tunable chemical
etching, ball milling composition, structure, size and microbiology
building blocks
In principle limited only by atomic dimensions
TOP-DOWN VS. BOTTOM-UP
Top-down methods begin with a pattern generated on a larger scale, then reduced to nanoscale. By nature, arent cheap and quick to manufacture. Lastly, Slow and not suitable for large scale production.
Bottom-up methods start with atoms or molecules and build up to nanostructures. Lastly, Fabrication is much less expensive.
Top down approach physical process
1. Mechanical grinding : Structural decomposition simple, inexpensive, wide classes of materials
Disadvantages: Contamination from milling media, atmosphere powder consolidation
2. High energy methods : discharge plasma method
Top down approach chemical process
1. Wet chemical Synthesis: Single crystals are etched in an aqueous solution produce nanomaterials
2. Anodizing : insulating porous oxide layer is created on a conductive metal anode in electrolytic solution.
Synthesis process for TOP DOWN
1. Inert gas condensation process
2. Laser ablation process
3. Lithography
TOP DOWN: LITHOGRAPHY
At the moment, the most used top-down approach is photolithography. It has been used for a while to manufacture computer chips and produce structures smaller than 100 nm. Typically, an oxidized
silicon (Si) wafer is coated with a 1m thick photoresist layer. After exposure to ultraviolet (UV) light, the photoresist undergoes a photochemical reaction, which breaks down the polymer by rupturing
the polymer chains. Subsequently, when the wafer is rinsed in a developing solution, the exposed areas are removed.
Problems in lithography
The actual implementation is very complex and expensive.
This is because
nanostructures significantly smaller than 100 nm are difficult to produce due to diffraction effects,
masks need to be perfectly aligned with the pattern on the wafer,
the density of defects needs to be carefully controlled, and
Photolithographic tools are very costly, ranging in price from tens to hundreds of millions of dollars.
Electron-beam lithography
Electron-beam lithography and X-ray lithography techniques have been developed as alternatives to photolithography. In the case of electron beam lithography, the pattern is written in a polymer film
with a beam of electrons.
Since diffraction effects are largely reduced due to the wavelength of electrons, there is no blurring of features, and thus the resolution is greatly improved.
However, the electron beam technique is very expensive and very slow. In the case of X-ray lithography, diffraction effects are also minimized due to the short wavelength of X-rays, but conventional
lenses are not capable of focusing X-rays and the radiation damages most of the materials used for masks and lenses.
The most recent lithography methods
Printing, stamping, and molding use mechanical processes instead of photons or electrons. These methods are normally called soft lithography methods because they involve the use of polymers.
Micro-contact printing method (under lithography method)
A chemical precursor to polydimethylfiloxane (PDMS) is poured over and cured into the rubbery solid PDMS stamp that reproduces the original pattern. The stamp can then be used in various
inexpensive ways to make nanostructures. The stamp is inked with a solution consisting of organic molecules and then pressed into a thin film of gold on a silicon plate. The organic molecules form a
self-assembled monolayer on the solid surface that reproduces the pattern with a precision of approximately 50 nm.
Advantages of lithography
Once the master template has been made, no special equipment is required. Soft lithographic methods are capable of producing nanostructures in a wide range of materials and can print or mold on curved
as well as planar surfaces.
FOCUSED ION-BEAM (FIB) MACHINING (UNDER LITHOGRAPHY METHOD)
FIB machining offers the greatest resolution, with the ability to make features as small as 20 nm, but it is very slow. In FIB a beam of gallium ions from a liquid metal ion source is accelerated, filtered,
and focused with electromagnetic lenses to give a spot size of 58 nm. The beam is tracked across the surface, contained in a chamber under high vacuum. The high-energy ions blast atoms from the
surface, allowing simple cutting of slots and channels or the creation of more elaborate 3-D shapes. Secondary electrons are emitted when the gallium ions displace the surface atoms. These can be used
to image the surface, allowing observation and control of the process as it takes place. Dual-beam FIBs have an additional electron gun.
Synthesis process for BOTTOM UP
1 AFM
2 Molecular self-assembly
Nature uses self-assembly in infinitely subtler ways; indeed, the whole of the natural world is self-assembled.
Spontaneous organization of molecules into stable, structurally well-defined aggregates (nanometer length scale).
Molecules can be transported to surfaces through liquids to form self-assembled monolayers (SAMs).
3 Atomic layer deposition

METHODS FOR MAKING 0-D NANOMATERIALS


Nanoparticle condensation in inert gas
An inorganic material is vaporized inside a vacuum chamber into which an inert gas (typically argon or helium) is periodically admitted. Once the atoms boil off, they quickly lose their energy by
colliding with the inert gas. The vapor cools rapidly and supersaturates to form nanoparticles with sizes in the range 2100 nm that collect on a finger cooled by liquid nitrogen.
A material, often a metal, is evaporated from a heated metallic source into a chamber which has been previously evacuated to about 107 torr and backfilled with inert gas to a low-pressure. The metal
vapor cools through a collisions with the inert gas atoms, becomes supersaturated and then nucleates homogeneously; the particle size is usually in the range 1100 nm and can be controlled by
varying the inert gas pressure. Ultimately, the particles are collected and may be compacted to produce a dense nanomaterial.
Example of nanoparticles obtained by IGC.
Decahedral gold nanoparticle generated from an inert gas aggregation source using helium and deposited on amorphous carbon film
Plasma based synthesis (vacuum arc ejector)
Vacuum arc deposition is well-established process for producing of thin films and nanoparticles. This technique involves the initiation of an arc by contacting a cathode made of a target material. An
igniter is attached to an anode in order to generate a low-voltage, high-current self-sustaining arc. The arc ejects ions and material droplets from a small area on the cathode. Further, the ions are
accelerated towards a substrate while any large droplets are filtered out before deposition.
Vapor condensation
One of the outstanding strides in plasma processing for nanoparticles synthesis is the developed process of the vapor condensation. The precursor material is put into the working chamber with a stable
arc.The chamber is filled by reactive gas that becomes ionized; then molecular clusters are formed and cooled to produce nanoparticles.
SYNTHESIS METHODS FOR CARBON NANOSTRUCTURES
1. CVD
1.1 Thermal Chemical Vapor Deposition
1.2 Plasma Enhanced Chemical Vapor Deposition
2. VAPOR PHASE GROWTH
3. ARC DISCHARGE
4. LASER ABLATION
METHODS FOR MAKING 1-D AND 2-D NANOMATERIALS
The production route for 1-D rod-like nanomaterials by liquid- phase methods is similar to that for the production of nanoparticles. CVD methods have been adapted to make 1-D nanotubes and
nanowires. Catalyst nanoparticles are used to promote nucleation. Nanowires of other materials suZch as silicon (Si) or germanium (Ge) are grown by vapor-liquid-solid (VLS) methods.
1. Molecular Beam Epitaxy (MBE)
In solid-source MBE, ultra-pure elements such as gallium and arsenic are heated in separate quasi-Knudsen effusion cells until they begin to slowly evaporate.The evaporated elements then condense on
the wafer, where they may react with each other. In the example of gallium and arsenic, single- crystal gallium arsenide is formed. The term beam simply means that evaporated atoms do not interact
with each other or any other vacuum chamber gases until they reach the wafer, due to the long mean free paths of the beams. The substrate is rotated to ensure even growth over its surface.By operating
mechanical shutters in front of the cells, it is possible to control which semiconductor or metal is deposited.
2. Metal-organic Chemical Vapor Deposition (MOCVD)
3. Electrodeposition*
Electrodeposition is a long-established way to deposit metal layers on a conducting substrate. Ions in solution are deposited onto the negatively charged cathode, carrying charge at a rate that is
measured as a current in the external circuit. The process is relatively cheap and fast and allows complex shapes. The layer thickness simply depends on the current density and the time for which the
current flows. The deposit can be detached if the substrate is chosen to be soluble by dissolving it away.

CHAPTER 5A :TECHNIQUES FOR SYNTHESIS OF NANOMATERIALS (II)


Liquid phase synthesis
Precipitating nanoparticles from a solution of chemical compounds can be classified into five major categories:
(1) colloidal methods;
(2) sol gel processing;
(3) water oil microemulsions method;
(4) hydrothermal synthesis; and
(5) Polyol method
Colloidal methods
Colloidal methods are simple and well established wet chemistry precipitation processes in which solutions of the different ions are mixed under controlled temperature and pressure to form insoluble
precipitates.

Sol gel techniques


Sol-gel process consists in the chemical transformation of a liquid (the sol) into a gel state and with subsequent post-treatment and transition into solid oxide material. The main benefits of solgel
processing are the high purity and uniform nanostructure achievable at low temperatures. The application of Sol Gel method are Optical and photonic functions (solar cell, laser element, light
amplification), electronic functions (capacitor, transparent semiconductor, solid electrolyte), thermal function (aerogels, refractory ceramics)

Sol gel process

Sol gel for coating


In the dip coating process the substrate is immersed into a sol and then withdrawn with a well-defined speed under controlled temperature and atmospheric conditions. The sol left on substrate forms a
film with thickness mainly defined by the withdrawal speed, the solid content and the viscosity of the liquid. Next stage is a gelation (densification) of the layer by solvent evaporation and finally
annealing to obtain the oxide coating
In an angle-dependent dip coating process the coating thickness is dependant also on the angle between the substrate and the liquid surface, so different layer thickness can be obtained on the top and
bottom side of the substrate.
Spin coating is used for making a thin coating on relatively flat substrates . The material to be made into coating is dissolved or dispersed into a solvent, and then deposited onto the surface and spun off
to leave a uniform layer for subsequent processing stages and ultimate use.
In the flow coating process the liquid coating system is poured over the substrate to be coated. The coating thickness depends on the angle of inclination of the substrate, the liquid viscosity and the
solvent evaporation rate. The advantage of the flow- coating process is that non- planar large substrates can be coated rather easily.
High-energy milling (advantages)
Deformation localization in shear bands containing a high dislocation density
Annihilation/recombination/rearrangement of dislocation to form cell/sub-grain structure with finer dimension
Random orientation of grains
Severe plastic deformation (SPD)
Severe plastic deformation (SPD) processing in which materials are subjected to the imposition of very large strains without the introduction of concomitant changes in cross-sectional dimensions of the
samples, is one of the most successful top-down approaches. Materials produced by SPD techniques have grain sizes in the range of 501000 nm. However, they have sub-grain structures, which are often
much smaller than 100 nm.Now there are several SPD processing available: equal-channel angular pressing (ECAP), high-pressure torsion, accumulative roll-bonding, repetitive corrugation.

ECAP
During ECA pressing a billet of material is multiple pressed through a special die. The angle of two channels intersection is usually 90 0, however, in the case of a hard-to- deform material, the angle may be
changed. Moreover, for processing of hardly deformed materials, ECA pressing can be conducted at elevated temperatures.
During ECAP the direction and number of billet passes through the channels are very important parameter for microstructure development.
TORSION
A method of torsion straining under high pressure can be used for fabrication of disk type samples. An ingot is held between anvils and strained in torsion under the applied pressure of several GPa. A lower
holder rotates and surface friction forces deform the

Sintering of nanoparticles
Thermodynamically, nanopowders are highly unstable. The sintering process is driven by the tendency to reduce the excessively large surface area per unit volume
Sintering process starts when powder is packed together and heated to high temperatures, typically about 2T melt/3. At this stage, diffusion becomes significant. The densification process consists of solid
particle bonding or neck formation followed by continuous closing of pores from a largely open porosity to a pore-free body.
Special methods of sintering
Microwave sintering has a rapid processing time, two to fifty times faster than conventional heating . There is also an acceleration of sintering and diffusion in the material because of high
electrical fields; thus densification can occur at lower temperatures.
field assisted sintering (FAS). Electric FAS is an emerging technology for the fabrication of metals, ceramics and their composites starting from powders. FAS often referred as spark plasma
sintering (SPS) or pulsed electric current sintering (PECS). All these methods are essentially identical in the application of a pulsed discharge and subsequent or simultaneous resistance sintering.
The consolidation process consists of two stages: an initial activation through the application of a pulsed voltage, and the subsequent heating and densification by using DC current.
Spark plasma sintering : The spark plasma, generated by spark discharge appears in the gap between the particles of a material, increases a local high temperature state of several to ten thousand
. This causes vaporization and the melting of the surfaces of the powder particles during the SPS process; constricted shapes or necks are formed around the contact area between the
particles. Since only the surface temperature of the particles rises rapidly by self-heating, particle growth of the starting powder materials is controlled. Therefore, a precision sintered compact is
manufactured in a shorter time

Methods for making nanoparticles, nanoclusters and nanolayers


Inert gas condensation, vapour phase expansion, sol gel deposition, beating, CVD, PVD
Methods for making bulk nanostructures
Melt spinning, powder milling, micro machining, pressure sintering
WEEK 5B
HOW TO GET GRAPHENE?
Mechanical Exfoliation (Pencil drawing & Scotch tape method)
Advantage Disadvantage
- simple and easy - Low efficient & Laborious
- High quality, good for fundamental physical study
PREPARATION AND CHARACTERIZATION GRAPHENE
Top-down approach (From graphite)
- Micromechanical exfoliation of graphite (Scotch tape or peel-off method)
- Creation of colloidal suspensions from graphite oxide or graphite intercalation compounds (GICs)
Bottom up approach (from carbon precursors)
- By chemical vapour deposition (CVD) of hydrocarbon
- By epitaxial growth on electrically insulating surfaces such as SiC- Total Organic Synthesis
Advantages Disadvantages
Mechanica -Low-cost & easy -Serendipitious
l -No special equipment -Uneven films
exfoliation needed -Labor intensive (not
-SiO2 thickness is tuned for suitable for large-
better contrast scale production
Epitaxial -Most even films (of any -Difficult control of
Growth method) morphology &
-large scale area adsorption energy
-High temperature
process
Graphene -Straightforward up-scaling -fragile stability of
Oxide -versatile handling of the the colloidal
suspension dispersion
-rapid process -reduction to
graphene is only
partial
CHARACTERIZATION METHODS
- Scanning Probe Microscopy (SPM)
- Raman Spectroscopy
- Transmission electron Microscopy (TEM)
- X-ray diffraction (XRD)
- Atomic force microscopes (AFMs)
- Scanning tunneling microscopy (STM)
PREPARATION METHODS AND DISCUSSIONS (TOP-DOWN APPROACH ;FROM GRAPHITE)
Direct exfoliation of Graphite
Graphite intercalation compound
Graphite oxide method
TOP-DOWN GRAPHENE
On the other hand, graphite or its derivatives obtained from the top-down methods offers significant economic advantages over the bottom-up methods. Processing for Expanded graphite - Alkali metal-
or acid-intercalated graphite can be expanded upon heat treatment to produce a thicker (100 nm) form of 2-D carbon known as expanded graphite (EG), which is commonly used as a filler for
polymer composites. Recently, a thinner form (10 nm) of EG known as graphite nanoplatelets (GNP) was produced by either thermal expansion of fluorinated graphite intercalation compounds or
microwave radiation of acid-intercalated graphite followed by pulverization using ball milling or ultrasonication.
BOTTOM-UP GRAPHENE
In bottom-up processes, graphene can be synthesized by chemical vapor deposition (CVD), arc discharge, epitaxial growth on SiC, chemical conversion, reduction of CO, unzipping carbon nanotubes[9-
17], and self assembly of surfactants. CVD and epitaxial growth often produce tiny amounts of large-size, defect-free graphene sheets. However, graphene obtained from the aforementioned method is not
suitable for polymer nanocomposites because fabrication of nanocomposites requires a large amount of graphene sheets preferably with modified surface structure.
CHEMICAL VAPOR DEPOSITION
Chamber:12-in chamber quartz reactor
Heater: graphite electrodes placed at the top and
bottom with a separating distance of 10 cm
IR detector: temp. measurement
Substrate: A cupper foil was placed on the bottom
heater
Annealing: by H2 and Ar (increase Cu grains)
Deposition: using CH4 and H2 as precursor
Cooling: rapidly cooling under Ar

Mechanisms:
1.Adoption of Cu:(a) low solubility of carbon in Cu,
(b) surface diffusion of carbon atoms on Cu;
2.Absorption and de-absorption of hydrocarbon
molecules on Cu;
3.Decomposition of hydrocarbon to form carbon
atoms;
4.Aggregation of carbon atoms on Cu surface to form
graphene nucleation centers;
5.Diffusion and attachment of carbon atoms to
nucleation centers to form graphene film
Analysis (I): Hydrocarbon precursor and substrate
1. .Methane is a relatively stable hydrocarbon compound due to strong C-H bond, as a result, decomposition occurs at elevated temperature (>1200C)
2. Other hydrocarbon compounds such as ethane and acetylene are not suggested due to rapid decomposition at high temperature;
3. Other transition metal such as Fe, Co, and Ni are not preferred for mono or bilayer graphene growth due to their higher-than-desirable capacity to decompose hydrocarbons.
4. The low decomposition rate of methane on Cu allows the possibility of controlling the number of graphene layers.
Analysis (II): Decomposition of hydrocarbon
1. Cu foil: Cu foil is usually not single crystal possessing grain boundaries and steps;
2. The sites have much higher chemical activation energy than those of the flat regions of Cu; as a result, hydrocarbons prefer to decompose on the sites to form nucleation centers;
3. Cu foil with smooth surface is preferred: pre-polish and in-situ polish.
EPITAXIAL GROWTH

Production of EG on diced (3 mm by 4 mm)


commercial SiC wafers.

Steps:
hydrogen etching to produce atomically
flat surfaces;
(2) vacuum graphitization to produce an ultrathin
epitaxial graphite layer;
(3) application of metal contacts (Pd, Au),
(4) electron-beam patterning and
development;
(5) oxygen plasma etch to define graphite
structures;
(6) wire bonding.
When SiC substrates are
annealed at high temp., Si
atoms selectively desorb from
the surface and the C atoms
left behind naturally form FLG
(few-layer graphene)
Advantage: Patterned graphene structure
Drawback: Ultra-high vacuum, high cost
Based on the theoretical analysis, stability of the C
atoms on SiC substrate was investigated. At a C
coverage of 8/3 MLs, corresponding to 8 C atoms
on three SiC unit cells, C atoms form a graphene-
like two-dimensional sheet and are strongly
stabilized.@1
When more C atoms are added, they become highly
unstable on the buffer layer and prefer to reside
between the buffer layer and SiC substrate.
At a C coverage of 16/3 MLs, a new buffer layer is
formed at the interface and the original buffer layer
loses bonds with the substrate.

GRAPHENE NANORIBBONS (FROM CARBON NANOTUBE)

Figure 3(a)-(d) Figure 3(e)


Electrons have wave-like properties, and their kinetic energy determines the wavelength, as shown in Fif. 3(a). Electrons reflected from the graphene surface and graphene/SiC interface can interfere,
which causes the electron reflectivity to change periodically as a function of the electron energy and FLG thickness.
The LEEM image intensity corresponds to the electron reflectivity. From LEEM images sequentially obtained while the electron beam energy was changed, we obtained the energy dependence of the
electron reflectivity from regions 1 to 8, as shown in Fig. 3(e).**

Growth processes
After annealing at 1060C, preferential nucleation of the buffer layer occurred at the atomic steps on the SiC surface, where 1/3 of the ML of Si adatoms(@1) was periodically arranged (Fig. 4(a)). After
annealing at a higher temperature (Fig. 4(b)), the whole surface was covered with the buffer layer and the surface steps eandered widely(@2).

At the initial stage of graphene growth, ML graphene preferentially formed near the substrate steps (Fig. 4(c)). When the annealing temperature was further increased, bilayer (BL) graphene appeared
before the buffer layer completely disappeared (Fig. 4(d)). This means that uniform ML graphene is difficult to grow in UHV.

1. The nanogap probe contains two Pt electrodes with a gap of 30 nm fabricated at the tip of the cantilever of an atomic force microscopy (AFM) apparatus.
2. An electrical conductivity map of BL graphene is shown in Fig. 5(c). Linear contrasts, which correspond to the substrate steps, reveal that the substrate steps modify the electrical conductivity.
3. The TEM image (Fig. 5a) depicted that FLG covered the substrate steps like a carpet. FLG was locally bent near the steps, and this bending could affect the carrier transport.

Fig. 1. Graphene films.


(A)Photograph (in normal white light) of a large multi-layer graphene flake on top of an oxidized Si wafer.
(B) AFM image of 2 m by 2 m area of this flake near its edge. Colors: dark brown, SiO2 surface; orange, 3 nm height above the SiO2 surface. (C) AFM image of single-layer graphene.
Materials: HOPG
Preparation:
1. prepared 5 mm-deep mesas on top of the platelets (mesas were squares of various sizes from 20 mm to 2 mm).
2. Pressed the structured surface on a 1-mm-thick layer of a fresh wet photoresist spun over a glass substrate. After baking, the mesas became attached to the photoresist layer, which allowed us to cleave
them off the rest of the HOPG sample. Then, using scotch tape to repeatedly peel flakes of graphite off the mesas
3. Thin flakes left in the photoresist were released in acetone.
4. Dipping a Si wafer was in the solution and then washed in plenty of water and propanol, some flakes became captured on the wafers surface (chose thick SiO2 with t =300 nm).
5. Used ultrasound cleaning in propanol to remove mostly thick flakes. Thin flakes (d < 10 nm) were found to attach strongly to SiO2, presumably due to van der Waals and/or capillary forces.
(Left) Optical photograph in white light of a large Hall bar made from multilayer graphene (d 5nm). The central wire is 50mm long.
(Right) A short (200 nm) wire made from few-layer graphene.
Advantages : Production of single layer graphene is feasible
Drawbacks : Limited quantity

Chemical synthesis through oxidation of graphite


The most promising methods for large scale production of graphene are based on the exfoliation and reduction of GO. The commonly adopted method for producing GO is the Hummers method in which
graphite is oxidized using strong oxidants such as KMnO4, KClO3, and NaNO2 in the presence of nitric acid or its mixture with sulfuric acid.
GO is composed of graphene oxide sheets stacked with an interlayer spacing between 6 and 10 A depending on the water content.
The model describes GO as built of pristine aromatic islands separated from each other by aliphatic regions containing epoxide and hydroxyl groups and double bonds
GO contains ketones, 6-membered lactol rings, and tertiary alcohol in addition to epoxide and hydroxyl groups. GO has an approximate C/O/H atomic ratio of 2/1/0.8.
Although GO can be readily dispersed in water and in organic solvents after chemical modification, graphene oxide is electrically insulating and thermally unstable. Therefore, at least partial reduction of
graphene oxide is necessary to restore electrical conductivity. A number of different methods currently exist for the exfoliation and reduction of GO to produce chemically modified graphene.
Stable colloids of graphene oxide can be obtained using solvents such as water, alcohol, and other protic solvents combined with either sonication or long stirring. Alternatively, GO can be exfoliated in
polar aprotic solvents by reacting with organic compounds.
Colloidal graphene oxide or the organically treated version can be chemically reduced producing chemically reduced graphene (CRG) using hydrazine.
Potential application of graphene
- Single molecule gas detection, Graphene transistors, Integrated circuits
- Transparent conducting electrodes for the replacement of ITO, Ultracapacitors, Graphene biodevices
-Reinforcement for polymer nanocomposites:
Electrical, thermally conductive nanocomposites, antistatic coating, transparent conductive composites..ect

WEEK 5D: (CARBON NANOTUBE)


WAYS TO SYNTHESIS CNT:
Arc Discharge
Laser Ablation
Chemical Vapor Deposition (CVD)
Ball Milling
ARC DISCHARGE:
A direct current creates a high temperature discharge between two electrodes
Atmosphere is composed of inert gas at a low pressure
Originally used to make C60 fullerenes
Cobalt is a popular catalyst
Typical yield is 30-90%
Advantages Disadvantages
Simple procedure Requires further purification
High quality product Tubes tend to be short with random sizes
Inexpensive
LASER ABLATION:
Vaporizes graphite at 1200 C
Helium or argon gas
A hot vapor plume forms and expands and cools rapidly
Carbon molecules condense to form large clusters
Similar to arc discharge
Yield of up to 70%
Types of laser ablation:
Pulsed -Much higher light intensity (100 kW/cm2)
Continuous-Much lower light intensity (12 kW/cm2)
Advantages Disadvantages
Good diameter control Costly technique, because it requires
Few defects expensive lasers and high power
Pure product requirement
CHEMICAL VAPOR SEPOSITION (CVD)
Carbon is in the gas phase
Energy source transfers energy to carbon molecule
Common Carbon Gases (Methane, Carbon monoxide, Acetylene)
After energy transfer, the carbon molecule binds to the substrate
Temperature between 650 900 C
Yield is usually about 30%
One of the most common methods of carbon nanotube synthesis
Advantages Disadvantages
Easy to increase scale to industrial Defects are common
production
Large length
Simple to perform
Pure product
BALL MILLING
Powder graphite is placed in a stainless steel container
Argon gas is used
Process occurs at room temperature
Powder is then annealed
Combining Ball Milling and Vapor Deposition
Arkema France developed the process
Process generates the highest carbon purity
Products have improved dispersion
GROWTH MECHANISM
Electronic and Mechanical Properties are closely related to the atomic structure of the tube.
Essential to understand what controls the size, number of shells, helicity & structure during synthesis.
Mechanism should account for the experimental facts: metal catalyst necessary for SWNT growth, size dependent on the composition of catalyst, growth temperature etc.
MWNT Growth Mechanism:
- Open or close ended? - Lip Lip Interaction Models
SWNT Growth Mechanism
Is uncatalyzed growth possible?
Simulations & Observations No!
Spontaneous closure at experimental temperatures of 2000K to 3000K.
Closure reduces reactivity.
Catalytic Growth Mechanism
Transition metal surface decorated fullerene nucleates SWNT growth around periphery.
Catalyst atom chemisorbed onto the open edge. Catalyst keeps the tube open by scooting around the open edge, ensuring and pentagons and heptagons do not form.
APPLICATION
1. Electrical: Field Emission Display ( FED)
- Uses electron beam to produce color images (FED)
- Traditionally cathode ray tubes are used but recently more focus on using carbon nanotubes
- NASA is researching this technology to use in space exploration
2. Energy Storage: a) Lithium Battery
- Nanotubes have the highest reversible capacity of any carbon material for use in Lithium ion batteries
- Nanotubes have intrinsic characteristics desired in material used as electrodes in batteries and capacitors
- Nanotubes are outstanding materials for super capacitor electrodes
- They also have a number of properties including high surface area and thermal conductivity that make them useful as electrode catalyst supports in Polymer Electrolyte Membrane (PEM) fuel cells
2 b) Hydrogen Storage
- Single-walled carbon Nanotubes can store hydrogen
- Nano tube technology will meet the challenge of storing hydrogen and releasing them adequately in hydrogen fuel car in future
- Physisorption and chemisorption e mechanisms used for hydrogen storage in carbon nanotubes
3. Biological. a) Sensors
- Many spherical Nano-particles have been fabricated for biological applications.
- Nanotubes offer some advantages relative to Nano-particles by the following aspects:
a) Larger inner volumes can be filled with chemical or biological species.
b) Open mouths of Nano tubes make the inner surface accessible.
c) Distinct inner and outer surface can be modified separately.
3b) AFM tips
Carbon nanotubes as AFM probe tips: Small diameter maximum resolution
3c) DNA sequencing
- Nanotubes fit into the grove of the DNA strand
- Apply voltage across CNT, different DNA base-pairs give rise to different current signals
- With multiple CNT, it is possible to do parallel fast DNA sequencing
4. Paper Battery
- Could easily be mistaken for a sheet of black paper
- Functions as both a lithium-ion battery and a supercapacitor
- Lightweight, thin, flexible
- Can function at a wide range of temperatures
5. Nanotube speaker
- Thin carbon nanotube films can act as speakers
- New generation of cheap, flat speakers
- Transparent, flexible, stretchable, and magnet free
6. Artificial Muscles
- Aerogels made from carbon nanotubes (CNTs) can serve as electrically powered artificial muscles
- Sheet becomes 220% wider and thicker when voltage is applied
- Flexes about 3 orders of magnitude faster and generates more than 30 times the force than human muscles of the same size
7. Nanotube Thermocell
- uses multiwalled carbon nanotubes as electrodes
- 3 times efficient than conventional
- Converts waste heat from industrial plants, pipelines into electricity
8. Nanotube Catalyst
- Carbon nanotubes doped with Nitrogen
- Reduce oxygen more effectively than platinum catalysts
- Not susceptible to carbon monoxide poisoning, known to deactive platinum catalysts
WEEK 6: CHARACTERIZATION AND DISADVANTAGES OF NANO MATERIALS
WHAT IS CHARACTERIZATION?
Characterization refers to study of materials features such as its composition, structure, and various properties like physical, electrical, magnetic, etc.
WHY IS CHARACTERIZATION OF NANOPARTICLES IMPORTANT?
- Nanoparticle properties vary significantly with size and shape
- Accurate measurement of nanoparticles size and shape is, therefore, critical to its applications
SCANNING PROBE MICROSCOPE
Atomic Force Microscope
Scanning Tunneling Microscope
Atomic force microscope:
Operation: see figure
Modes of operation:
i. Contact mode ii. Non-contact mode
iii. Tipping mode

Limitations Advantages
Probe tip radius, high resolution microscope, capable of producing 3d images,
image processing speed, pre-treatment of samples is not necessary, vacuum chamber not
small image size required for some mode of operation
i. Contact mode
Used for scanning hard samples and resolution > 50 nanometres are required. The cantilever may be constructed from silicon or silicon nitride. Resonant frequencies of contact cantilevers around 50 KHz
and the force constant are below 1N/m.
ii. Non-contact mode
The cantilever is oscillated slightly above its resonant frequency; oscillation <10nm; tip doest not touch the sample. Instead, it oscillates above the adsorbed fluid layer. Constant oscillation amplitude is
maintained. The resonant frequency of the cantilever is decreased by the van der Waals forces which extend from 1-10 nm above the adsorbed fluid layer. This in turn changes the amplitude of oscillation.
iii. Tapping mode
A cantilever with attached tip is oscillated at its resonant frequency and scanned across the sample surface. Constant oscillation amplitude is maintained during scanning. Typical amplitudes are 20-
100nm. Forces can be 200 pN or less. The amplitude of the oscillations changes when the tip scans over bumps or depression on a surface.
In contact mode, the tip is usually In non-contact mode, the bottom-most point
maintained at constant force by moving the of each probe cycle is in the attractive
cantilever up and down as it scans region of the force-distance curve.
In non-contact mode or tapping mode, the In tapping and contact mode the bottom-
tip is driven up and down by an oscillator. most point is in the repulsive region.
Especially soft materials may be imaged by Variations in the measured oscillation
a magnetically-driven cantilever (MAC amplitude and phase in relation to the
ModeTM) driver frequency are indicators of the
surface-probe interaction.

Advantage of the main modes of AFM


Contact mode Tapping mode
- High scan speed - High lateral resolution on most samples (1
- The only mode that can obtain atomic to 5nm)
resolution images - Lower forces and less damage to soft
- Rough samples with extreme changes in sample imaged in air
topography can be scanned more easily - Lateral forces are virtually eliminated so
there is no scraping
Disdvantage of the main modes of AFM
Contact mode
- Lateral (shear) forces can distort features in the image
- The forces normal to the tip-sample interaction can be high in air due to capillary forces from
the adsorbed fluid layer on sample surface
- The combination on lateral and high normal forces can results in reduced spatial resolution
and may damage soft samples (i.e biological samples, polymers, silicon)
Tapping mode
- Slightly lower scan speed than contact mode AFM
Scanning tunnelling microscope
Operation: based on tunnelling current, which is explained in quantum physics
Modes of operation:
i. constant-current ii. Constant-distance
Advantages: very high image resolution (capable of seeing and manipulating atoms), wide temperature range and capable of operating in ultra-high vacuum and other gas environments
Limitation: again, radius of curvature of tip, extremely sensitive to ambient vibrations.
TRANSMISSION ELECTRON MICROSCOPE
Transmission Electron Microscope
Selected Area Electron Diffraction
High Resolution Transmission Electron Microscope
Transmission electron microscope
Operation: image is generated based on the interaction pattern of electrons that transmit through the specimen
Variation: scanning transmission electron microsope
Advantage: additional analysis technique like x-ray spectrometry are possible with the STEM, high- resolution, 3-D image construction possible but aberrant
Limitations: need very high-vacuum chamber, sample preparation necessary, mostly used for 2-D images
SCANNING ELECTRON MICROSCOPE
Operation: generates image by scanning the surface of the sample in a raster pattern, using an electron beam
Modes of operation:
i. Secondary ii. Black-scattered electrons (BSE) iii. X-rays
electrons
Advantages: Bulk-samples
can be observed and larger
sample area can be viewed,
generates photo-like
images, very high-
resolution image are
possible
Disadvantages: samples must
have surface electrical
conductivity; non-
conductive samples need to
be coated with a
conductive layer.

RAMAN SPECTROSCOPY
When electromagnetic radiation passes through matter, most of the radiation continues in its original direction but a small fraction is scattered in other directions. Light that is scattered at the same
wavelength as the incoming light is called Rayleigh scattering. Light that is scattered in transparent solid due to vibrations (phnons) is called Brillouin scattering. It is typical shifted by 0.1 to 1 cm -1
from the incident light. Light that is scattered due to vibrations in molecules or optical phonons in solid is called Raman scattering. Its light is shifted by as much as 4000 cm-1 from the incident light.
Raman scattering is the measurement of the wavelength and intensity of in elastically scattered light from molecules. The Raman scattered occurs at wavelengths that are shifted from the incident light
by the energies of molecular vibrations. The mechanism of Raman scattering is different from that of infrared absorption, and Raman and IR spectra provide complementary information. Typical
applications are in structure determination, multicomponent qualitative analysis, and quantitative analysis.
Raman spectroscopy - Basic
Raman spectroscopy is a spectroscopic technique used in condensed matter physics and chemistry to study vibrational, rotational and other low-frequency modes in a system. It relies on inelastic
scattering of monochromic light, usually from a laser in the visible, near infrared, or near ultraviolet range.

Basic of RS
The Raman Effect occurs when light impinges upon a molecule and interacts with the electron cloud of the bonds of that molecule. The incident photon excites one of the electrons into a virtual state. For
the spontaneous Raman Effect, the molecule will be excited from the ground state to a virtual energy state, and relax into a vibrational excited state, which generates Stokes Raman scattering. If the
molecule was already in an elevated vibrational energy state, the Raman scattering is then called anti-Stokes Raman scattering. A molecular polarizability change or amount of deformation of the
electron cloud, with respect to the vibrational coordinate is required for the molecule to exhibit the Raman effect. The amount of polarizability change will determine the Raman scattering intensity,
whereas the Raman shift is equal to the vibrational level that is involved.
X-RAY DIFFRACTION
X-ray diffraction associated to calculations is a powerful tool to study the:
Structure
Crystallinity
Particle size and size distribution
Particle shape
Homogeneity of the whole sample
ELECTRON ENERGY LOSS SPECTROSCOPY (EELS)
Inelastic scattering of an electron of the incident beam and atomic electron of the solid.
Transition from an inner-shell (K,L M) to an unoccupied energy level ( i.e. above Fermi level)
Transition of a valence electron across the energy gap ( insulator, semiconductor) or excitation of plasma resonance (mostly in metals).

CONCLUSIONS
TEM permits the structural characterization of a collection or isolated nanoparticles
Electron Diffraction structure of single or many particles
HRTEM structure, orientation, crystallinity, defaults
Image processing: fundamental tool for structural studies in electron microscopy
Spectroscopy: EELS,EDX local structure, band structure,composition
Do not permit to study properties of the whole sample Necessity to compare the results with other technique
CHALLENGES
Accurate characterization of nanoparticles is very critical to study their properties. Image analysis is very tedious and current methods are not robust, which reduces their compatibility. Faster, robust and
more accurate methods need to be developed.
GENERAL CONCERNS OF NANOSCALE VERSUS MICROSCALE MATERIALS
Higher exposure per unit mass
- Small size, large surface area, may result in increased ability to generate reactive oxygen species (ROS)
Routes of exposure may differ due to smaller size
Different distribution to tissue by virtue of their different size of surface coating/chemistry.(E.g ability to move within the body)
Novel property of nanoscale material may translate into a new mode of action.

POTENTIAL ENVIRONMENTAL EFFECTS


Nanoparticles have higher surface areas than the bulk materials which can cause more damage to the human body and environment compared to the bulk particles. Therefore, concern for the potential risk
to the society due to nanoparticles has attracted national and international attentions.
Nanoparticles are not only beneficial to tailor the properties of polymeric composite materials and environment in air pollution monitoring, but also to help reduce material consumption and remediation.
For example, carbon nanotube and graphene based coatings have been developed to reduce the weathering effects on composites used for wind turbines and aircraft. Graphene has been chosen to be a
better nanoscale inclusion to reduce the degradation of UV exposure and salt. By using nanotechnology to apply a nanoscale coating on existing materials, the material will last longer and retain the initial
strength longer in the presence of salt and UV exposure. Carbon nanotubes have been used to increase the performance of data information system. However, there are few considerations of potential
risks need to be considered using nanoparticles:
The major problem of nanomaterials is the nanoparticle analysis method. As nanotechnology improves, new and novel nanomaterials are gradually developed. However, the materials vary by shape and
size which are important factors in determining the toxicity. Lack of information and methods of characterizing nanomaterials make existing technology extremely difficult to detect the nanoparticles
in air for environmental protection.
Also, information of the chemical structure is a critical factor to determine how toxic a nanomaterial is, and minor changes of chemical function group could drastically change its properties.
Full risk assessment of the safety on human health and environmental impact need to be evaluated at all stages of nanotechnology. The risk assessment should include the exposure risk and its probability
of exposure, toxicological analysis, transport risk, persistence risk, transformation risk and ability to recycle.
Life cycle risk assessment is another factor that can be used to predict the environmental impacts.
Good experimental design in advance of manufacturing a nanotechnology based product can reduce the material waste.
As current nanoscale materials are becoming smaller, it is more difficult to detect toxic nanoparticles from waste which may contaminate the environment. Nanoparticles may interact with environment in
many ways: it may be attached to a carrier and transported in underground water by bio-uptake, contaminants, or organic compounds. Possible aggregation will allow for conventional transportation to
sensitive environments where the nanoparticles can break up into colloidal nanoparticles.
we are concerned not only with where nanoparticles may be transported, but what they take with them.
There are four ways that nanoparticles or nanomaterials can become toxic and harm the surrounding environment
Hydrophobic and hydrophilic nanoparticles: Nanocoating researchers are currently working on TiO2 powder as a coating inclusion that will reduce the weathering effects, such as salt rain degradation on
composite materials. However, the concern is that the effect of TiO2 nanoparticles to be assessed when leaked into the environment.
Mobility of contaminants: There are two general methods that nanoparticle can be emitted into atmosphere. Nanoparticles are emitted into air directly from the source called primary emission, and are the
main source of the total emissions. However, secondary particles are emitted naturally, such as homogeneous nucleation with ammonia and sulfuric acid presents. Nanoparticles can easily be attached
to contaminations and transported to a more sensitive environment such as aqueous environments. For example, nuclear waste travelled almost 1 mile from a nuclear test site in 30 years. Only after
40 years of the incident the first flow mechanism model is being developed to describe the methods of nanoparticle based waste travels.
Solubility: Nanoparticles are invented and developed in advance of the toxic assessment by scientists. Many of the nanoparticles are soluble in water, and are hard to separate from waste if inappropriately
handled.
Disposal: Any waste product, including nanomaterials, can cause environmental concerns/problems if disposed inappropriately.
LECTURE 6A: EXAMPLES APPLICATION OF NANOMATERIALS
FUEL CELLS
A fuel cell is a device that generates electricity by a chemical reaction. Every fuel cell has two electrodes, one positive and one negative, the anode and cathode. The reactions that produce electricity take
place at the electrodes. Every fuel cell also has an electrolyte, which carries electrically charged particles from one electrode to the other, and a catalyst, which speeds the reactions at the electrodes
WORKING PRINCIPLE
Electrochemical energy conversion

DIFFERENT TYPES
Fuel: hydrocarbons (also alcohols), hydrogen, etc
Oxidant: chlorine, chlorine dioxides, oxygen, etc..
Electrolyte: aqueous alkaline solution, polymer membrane, molten carbonate, ceramic solid oxide, etc..
Operational temperature: 50C - 1100C
ADVANTAGES AND APPLICATIONS
High efficieny energy conversion (Theoretically 83% at 25C) /High power density/ Reliable/ Compact/ Lightweight
WHY HYDROGEN FUEL CELLS?
Also called Proton Exhange Membrane/ Polymer Electrolyte Membrane fuel cell (PEMFC)
Durable, compact/ Low temperature (50C -100C)/ fast start-up
Hydrogen fuel economy- Especially transportation applications
IMPORTANT COMPONENTS OF PEMFC
1. Proton Exchange Membrane (PEM)
2. Electrodes (Catalysts)
Proton Exchange Membrane (PEM)
Conduct H+, but no e-
Ionomer-Polymer with ionic properties
Nafion-Teflon backbone with sulfonic groups
Transport through Membrane
Thin film (~20-100 m)
Hydrated (depends on temperature)
Water channel model (Inverted-micelle cylinders, Ionic groups line up in water channel, Protons hop from one acid site to another and Crystallites provide strength)
Challenges
Thermal balance: want to operate at higher temperature
Better cooling possible
Better heat recovery
Reduce CO poisoning (H2 reforming)
Problem: Water Management
Add Pt nanoparticles
Not sustain water, but generate it: self-humidifying
Pt-PDDA/ PTFE (Teflon)/ Nafion composite membrane
Pt particles ~3 nm
Permeating H2 and O2 generates water
Improving Conductivity
Add acidic nanoparticles (SiO2, TiO2, Zr(HPO4)2)
Increased water content/improved proton conductivity/ Operate at higher temperatures
Electrodes
Consist of Carbon, with Platinum catalyst
Anode (H2): fast oxidationm
Cathode (O2): slower reduction, critical component
Disadvantages:Cost& CO poisoning (H2 reforming)
Reduce cost: increase Pt utilization
Nanoparticles:
High-surface area: Carbon powder or Carbon nanotubes
Reduction of Pt-salt in solution
Nanoparticles attached to C backbone
Pt Nanowires- 1-D nanowires/ Lower surface area, but increased activity
Replace noble metals- Replace electrode with Nitrogen-doped carbon nanotube arrays
Vertically aligned nitrogen-doped carbon nanotubes (VA-NCNTs)
Prepared by pyrolysis of iron (II) phthalocyanine plus NH3 vapour
Self-assembly on quartz substrate
N2 induces increased O2 chemisorption
Increased performance
Increased catalysis (Air-saturated 0.1 M KOH)
Pt: 1.1 mAcm-2 at -0.29 V
VA-NCNTs: 4.1 mAcm-2 at -0.22 V
No CO poisoning
High-surface area, good electrical, mechanical and thermal properties
SUMMARY
Add nanoparticles to membrane
Improved performance, operational temperature
Increased cost
Nanostructured Pt electrodes, N2 doped CNTs
improved catalysis
Decreased cost
CONCLUSIONS
Interesting and growing field of research
Nanotechnology essential for future developments
Problems: Infrastructure (storage) and Sustainable H2 source
WHAT IS A NANOSENSOR?
Biological, chemical, or physical sensory points used to convey information about nanoparticles to the macroscopic world
WHY NANOSENSORS?
Smaller, require less power to run, greater sensitivity, better specificity
METHODS OF PRODUCTION
Top-down lithography - Starting out with larger blocks and carving out the desired form
Bottom up assembly - Starting with components such as molecules and atoms and placing them one-by-one into position to create the desired form
Molecular Self-Assembly (2 Methods)
Method 1:Using a piece of previously created or naturally formed nanostructure and immersing it in free atoms of its own kind, making it more prone to attract more molecules and captures free atoms
and continue creating more of itself, thus larger components of nanosensors.
Method 2: Starts with a complete set of components that would automatically assemble themselves into a finished product.
BLUE CRABS NANOSENSORS
A substance found in the shell, called chitosan, is a key component used in a nanosensor, a system on a chip at the nanoscale - developed at the University of Maryland
Detects minute quantities of explosives, bioagents, chemicals, and other dangerous materials in air and water. This could lead to security and safety developments for airports, hospitals, etc.
What is Chitosan?
A biological compound that readily binds to negatively charged surfaces
It can interact with a wide variety of substances and works well in complex, sensitive devices, such as nanosensors. Commonly used in weight loss supplements.
How the Blue Crab Sensor Works?
Multiple mini vibrating cantilevers, which resemble diving boards, are coated with the chitosan
Optical sensing technology is used to see when the cantilevers vibrations change
(Different cantilevers detect different substances and concentrations)
When the targeted substance enters the device from the air/water, the chitosan on a specific cantilever interacts with the substance and causes that cantilevers vibration to change (The optical sensing
system sees the vibration change and indicates that the substance has been detected)
TYPES OF SENSOR
Electrometer: Consists of a torsional mechanical resonator, a detection electrode, and a gate electrode used to couple charge to the mechanical element.
Chemical Sensor: Incorporates capacitive readout cantilevers and electronics for signal analysissensitive enough to detect single chemical and biological molecules.
APPLICATIONS OF NANOSENSORS
Transportation, Communications, Integrated Circuits, Building and Facilities, Medicine, Safety, National Security and Aerospace.
Biosensor
Nanowire sensors can detect chemicals and biologics
Biologics are defined as any therapeutic serum, toxin, antitoxin, vaccine, virus, blood, blood component or derivative, allergenic product, or analogous product, or derivatives applicable to the prevention,
treatment, or cure of injuries or diseases of man.
Researchers are developing intra-cellular devices to sense pre-malignant cancerous changes in living cells
The devices are created from synthetic polymers, called dendrimers that are made layer-by-layer into spheres with diameters of less than 5nm
Nanosensor to detect asthma attacks up to 3 weeks in advance
DNA and other biomaterials can be sensed using encoded antibodies on Nanobarcode particles.
DNA molecules attach to the ends of vertical carbon nanotubes that are grown on a silicon chip. These detect specific types of DNA in an analyte.
Military / National Security
The SnifferSTAR is a nano-enabled chemical sensor that is integrated into a micro unmanned aerial vehicle.
A lightweight, portable chemical detection system combines a nanomaterial for sample collection and concentration with a MEM based chemical lab-on-a-chip detector.
Most likely to be used in defense and homeland security
Aerospace
Nanosensors can pass through membranes and into white blood cells, called lymphocytes, to detect early radiation damage or infection in astronauts
May be able to eventually be administered through the skin every few weeks, avoiding injections or IVs during space missions
This eliminates the need to draw and test blood
The Future
Could lead to tiny, low power, smart sensors manufactured cheaply in large quantities
Service areas could include:Situ sensing of structural materials, Sensor redundancy in systems, Size and weight constrained structures and Satellites and space platforms
Challenges
Reducing the cost of materials and devices
Improving reliability
Packaging the devices into useful products
Mass-producing (Methods are typically incompatible with those used in making electronics that amplify and process the signals the nanowires generate)
NANOTECHNOLOGY IN BUILDING AND CONSTRUCTION
Nanostructured Materials
Gaining control of materials at the nanoscale brings different laws of physics into play.
Traditional materials show radically enhanced properties when engineered at the nanoscale.
Material Needs in Building and Construction
Deterioration of the nations infrastructure:
Cost of repairs is estimated to exceed $2 trillion (NRC, ASCE).Housing is plagued with poor material quality and excessive fire losses that have led to premature failure and annual repair costs exceeding
$60 billion.
Nanotechnology offers tremendous potential for improving building materials.
Nanomaterials in Construction
Strong industry interest in use of nanostructured materials to improve service life and flammability performance of building materials
Lack of measurement science capability to predict service life and flammability performance of nanostructured materials.
Measurement science research is critical to enable U.S. construction industry to innovate and respond to global competition and new environmental regulations
Cement and Concrete
Nano silica and clinker used to increase densification and hence mechanical properties and durability of cementitious materials.
Service life can be doubled through the use of nano-additive viscosity enhancers which reduce diffusion of harmful agents in concrete (patent pending).
Photocatalytic TiO2 added to concrete to reduce carbon monoxide and NOx emissions on roadways.
Carbon Nanotubes
Heralded as one of the Top ten advances in materials science over the last 50 years, Materials Today, 2008.
Sales of carbon nanotubes projected to exceed $2B, >103 metric tons annually in the next 4-7 years.
Major use electronics and composites.(Enhanced strength, stiffness and toughness without added weight, Improved durability, increased functionality and reduced flammability)
Probes for microscopy and chemical ranging
Coatings Organic
Projected to make up 73 % of nanocomposites market by 2010.
Thin film, clear nanocomposites for improved scratch and mark properties.
Antimicrobial, self-cleaning surfaces.
Smart coatings: Sense pressure, impact, damage, chemicals, heat, light, etc.
Coatings Inorganic
Self-cleaning glass Nano-TiO2 coated
Photovoltaics
Predominant photovoltaic material is silicon, but an emerging technology involves the use of dye-sensitized nano-TiO2.
Large surface area of nano TiO2 greatly increases photovoltaic efficiency.
Also has potential for lower material and processing costs relative to conventional solar cells.
Nanoadditive Fire Retardants
Use of nanoadditive fire retardants prompted by bans on halogenated flame retardants enacted in many states.
Polymer nanocomposites filled with clay, CNTs, etc., possess improved flammability resistance while maintaining or improving mechanical properties.
Reduces heat release rate during fire event by formation of surface char which insulates underlying material.
Challenges
Techniques for dispersing nanofillers AND measuring degree of dispersion.
Measurement of adhesion and interfacial properties.
Chemical and mechanical measurements at the nanoscale.
Prediction of nanocomposite properties and service life over a wide range of length scales.
Unknown health and environmental effects virgin, released material.
OTHER APPLICATIONS
Liposome
Liposomes are currently investigated for a variety of additional therapeutic agents; anticancer drugs such as paclitaxel, camptothecin, cisplatin; antibiotic such as amikacin, vancomysin, ciprofloxacin;
biologics such as antisense oligonucleotides, DNA.
Pharmacy on A Chip
The drug released from the implanted microchip demonstrated similar measures of safety and therapeutic levels in blood to what is observed from standard, recommended multiple subcutaneous
injections.
Process of Drug Delivery
The first drug delivery microchip. Microchip-based implant wirelessly programmed to release drugs inside the body.
1. Reservoirs are filled with drugs. - Prior to implanting. Drugs are stored in an array of sealed microreservoirs.
2. Device is implanted. - Device with microchip is implanted under skin.
3. Device is activated.- When electrical current is applied, the membrane sealing the microreservoir melts.
4. Drug is released.- Releasing drug from reservoir.
5. Ongoing drug administration.- When drug reservoir is empty, the next dose can be delivered from another reservoir.
Ceramic in Bonds
The European Commission reports that ceramic nanocomposites developed in BIOKER could solve the problem of fracture failures in artificial joint implants. This would extend patient mobility and
eliminate the high cost of reparative surgery.
Point of Care Testing (POCT)
POCT can augment the capabilities of disaster medical assistance teams, and provide minimally-invasive monitoring in critical and emergency care environments.
ENERGY
Sun is natural energy.
Energy Source
Nanotechnologies provide essential improvement potentials for the development of both conventional energy sources (fossil and nuclear fuels) and renewable energy sources like geothermal energy,
sun, wind, water, tides or biomass.
Energy Distribution
Researchers at Rice University are working to develop wires containing carbon nanotubes that would have significantly lower resistance than the wires currently used in the electric transmission grid. The
so-called armchair quantum wire would be composed of carbon nanotubes woven into a cable.
Energy Storage
adding Li to H2 increase storage
If we add small amounts of lithium to hydrogen and if we keep the pressure at about one-fourth of a pressure (on which hydrogen turns into a metal) hydrogen transforms into a metal with
superconductivity properties.
NANOBIOTECHNOLOGY
Genetic Engineering
Enzyme/Cell Engineering
Nanotechnology
Bioinformatics
Nanobots
Nanobots swims in blood it is provided with microcamera,capacitor,payload and swimming tail. It reaches the targeted area and finds the unwanted growth or any tumor cell and ruputes the particular
diseased area.

Gene Therapy (Viral Vector)


Viral vectors are a tool commonly used by molecular biologists to deliver genetic material into cells.

Genetherapy (By Non Viral Vector)


Synthetic or non-viral gene delivery vectors typically consist of DNA (usually plasmid DNA produced in bacteria) or RNA which may be delivered to the target cell.

Gene Delivery (By Direct Injection)


In the direct injection method a blood sample is taken from patient , cell isolation and expansion is done it is placed on matrix. As a result new tissue is created and it is implanted into the patients body.

ANTIMICROBIAL ACTIVITY
Panel A Panel B
1. Concentrations of Ag+ ions built up 1. Ag+ ions from the silver nanoparticle
by elution from the silver nanoparticle coating did not result in Ag +concentrations
coating were high enough to kill bacteria. high enough to activate blood platelets.
2 and 3: Possible killing of bacteria by 2 and 3. Activation of blood platelets by
contact-dependent transfer of Ag+ ions contact-dependent transfer of Ag+ ions
following collision with the silver following collision with the silver
nanoparticle-containing surface. nanoparticle-containing surface

ENVIRONMENT
Global Warming
Polymers like thermosets, thermoplastics and elastomers reinforced with colloidal silica, nanoclay and nanotubes are promising candidate materials. Employing nano composites can lead to reduced
energy consumption in cars, with the impact of their use being likely to be even more dramatic in the aerospace sector. Hence the global warming can be reduced.
Percentage of Global Warming Caused by Various Sector
Transporation (Diesel Truck, Jet Airplane, Petrol Car) 28%
Industrial (Cement Plant, Chemical Factory) 20%
Residential and Commercial 11%
Electrio Power 34%
Agriculture 7%
Pollution (Water)
Nanoparticles is used to clean industrial water pollutants in ground water through chemical reactions that render them harmless, at much lower cost than methods that require pumping the water out of the
ground for treatment.
Researchers have developed a nanofabric "paper towel," woven from tiny wires of potassium manganese oxide, that can absorb 20 times its weight in oil for cleanup applications.
Cleaning Up Organic Polluting Ground Water
Iron nanoparticles can be effective in cleaning up organic solvents that are polluting groundwater. The iron nanoparticles disperse throughout the body of water and decompose the organic solvent in
place. This method can be more effective and cost significantly less than treatment methods that require the water to be pumped out of the ground.
Food and Agriculture (Food Contaminant Detection)
In 2008, thousands of people, especially children, got sick as a result of melamine contamination in dairy products from China.
A quick and easy way to detect melamine in milk using gold nanoparticles. In the presence of melamine, the mixture changes from pink to blue.
Agriculture
Use of new biopesticides, sensor to monitor soil condition and agrichemical delivery the agriculture productivity can be increased.

INFORMATION AND COMMUNICATION


Memory Storage
Memory storage before the advent of nanotechnology relied on transistors, but now reconfigurable arrays are formed for storing large amount of data in small space. For example, we can expect to see the
introduction of magnetic RAMs and resonant tunnel elements in logical circuits in the near future. Every single nanobit of a memory storage device is used for storing information. Molecular electronics
based on carbon nanotubes or organic macromolecules will be used.
Semiconductors
Nano amplification and chip embedding is used for building semiconductor devices which can even maintain and neutralize the electric flow.