INTRODUCTION TO NANO MATERIALS AND

TECHNOLOGY

INTRODUCTION

 What are Nanomaterials?

 Nanomaterials are the materials which have at least one of the dimensions in the range of
1-100 nm.
 Nanotechnology is the technology of dealing with nanomaterials (1-100 nm)
 Nanomaterials have very high surface area to volume ratio.
 These materials have different mechanical, thermal, optical, and magnetic properties
than those of their bulk materials. Thus within the same material one can get a range
of properties.
INTRODUCTION…

 Nano stems from the Greek word “nanos” which means the dwarf.
 Nano has been assigned to indicate the number 10-9.

 1 nanometer (nm) = 10-9 m

 1 nm is approximately the length equivalent to 10 hydrogen or 5 silicon atoms aligned in a line

Source: britannica.com
 JUST HOW SMALL IS NANO?

Size Abbrev. Sci. Representative objects

scale Unit
Metre m 1 Height of an about 7 year old child
Deci- dm 10-1 Size of our palm
Centi- cm 10-2 Length of a bee
Milli- mm 10-3 Thickness of ordinary paperclip
Micro μm 10-6 Size of typical dust particles
Nano nm 10-9 Diameter of a C60 molecule is about 1nm
Pico pm 10-12 Radius of a Hydrogen atom (in ground state) is about 50 pm
Femto fm 10-15 Size of a typical nucleus of an atom is 10 fm
Atto am 10-18 Estimated maximal size of an electron

NANOMATERIALS

Classification of nanomaterials according

to the dimension of the Nanostructure

Zero-dimensional One-dimensional Two-dimensional Three-dimensional

Nanostructures Nanostructures Nanostructures Nanostructures
 NANOMATERIALS

Classification of nanomaterials according

to the dimension of the Nanostructure

Zero-dimensional One-dimensional Two-dimensional Three-dimensional

Nanostructures Nanostructures Nanostructures Nanostructures

Source: Khurram Shehzad et. al. Chem. Soc. Rev., 2016,45, 5541-5588

NANOMATERIALS

Types of nanomaterials
according to their composition

Carbon based Metal based

Composites Dendrimers
nanomaterials nanomaterials
• cover a vast range of • nanosized polymers
• fullerene, carbon • gold, silver, ceramic, metallic and built from branched
nanotubes, metal oxides ceramometallic units.
graphene, etc. etc. materials in the form • A direct application
of bulk materials and of the dendrimers is
thin films. for drug delivery.
TYPES OF NANOCOMPOSITES

 (a) Composite consisting of zero-dimensional

particles in a matrix, ideally, the individual particles do
not touch each other
 (b) One-dimensional nanocomposites consisting of
nanotubes or nanorods distributed in a second matrix
 (c) Two-dimensional nanocomposites built from stacks
of thin films made of two or more different materials

NANOMATERIALS
Classification of the nanomaterials based on
the origin

Natural Artificial

CNTs Graphene

Dendrimer
ZERO-DIMENSIONAL NANOMATERIALS

 No dimensions.
 the most common representation of zero-dimensional nanomaterials are nanoparticles.
 Nanoparticles can:
 be amorphous or crystalline
 be single crystalline or polycrystalline
 be composed of single or multi-chemical elements
 exhibit various shapes and forms
 exist individually or incorporated in a matrix
 be metallic, ceramic, or polymeric

Silver Nanoparticles
Source: Techinstro

ONE-DIMENSIONAL NANOMATERIALS

 One dimension that is outside the nanoscale

 this leads to needle like-shaped nanomaterials
 1-D materials include nanotubes, nanorods, and nanowires.
 1-D nanomaterials can be:
 Amorphous or crystalline
 single crystalline or polycrystalline
 Chemically pure or impure
 Stand alone materials or embedded in within another medium
 Metallic, ceramic, or polymeric
TWO-DIMENSIONAL NANOMATERIALS

 Two of the dimensions are not confined to the nanoscale

 2-D nanomaterials exhibit plate-like shapes
 Two-dimensional nanomaterials include nanofilms, nanosheets, and nanocaotings
 2D nanomaterials can be:
 Amorphous or crystalline
 made up of various chemical compositions
 used as a single layer or as multilayer structures
 deposited on a substrate
 metallic, ceramic, or polymeric

THREE-DIMENSIONAL NANOMATERIALS

 Bulk nanomaterials are materials that are not confined to the nanoscale in any dimensions. These materials are
thus characterized by having three arbitrary dimensions above 100 nm.
 Materials posses a nanocrystalline structure or involve the presence of features at the nanoscale
 In terms of nanocrystalline structure, bulk nanomaterials can be composed of a multiple arrangement of nanosize
crystals, most typically in different orientations.
 3D nanomaterials can contain dispersions of the nanoparticles, bundles of nanowires, and naotubes as well as
multinanolayers.
 PROPERTIES OF NANO MATERIALS

Melting at nano scale occurs over

a broad range of temperature
unlike the bulk materials where
melting occurs at a particular
temperature.
Stark et al., Chem. Soc. Rev.,
2015,44, 5793-5805

PROPERTIES OF NANO MATERIALS

As particle size decreases,

electromagnetic radiation interacts
with free electrons to absorb, reflect,
or transmit different colors of light

Stark et al., Chem. Soc. Rev.,

2015,44, 5793-5805
 PROPERTIES OF NANO MATERIALS

• As particle size decreases, energy

band gap increases
• As particle size decreases,
conductivity decreases

Stark et al., Chem. Soc. Rev.,

2015,44, 5793-5805

PROPERTIES OF NANO MATERIALS

 For semiconductors such as ZnO, CdS, and Si, the bandgap changes with size
 Bandgap is the energy needed to promote an electron from the valence band to the conduction
band
 When the bandgaps lie in the visible spectrum, changing bandgap with size means a change in color

 For magnetic materials such as Fe, Co, Ni, Fe3O4, etc., magnetic properties are size
dependent
 The coercive force is size dependent
 the strength of a particle's internal magnetic field can be size dependent

Source: G. Herzer, Physica Scripta, T49, 307-314, 1993.

NANOTECHNOLOGY IN NATURE – I

 Lotus leaf
 leaf that doesn’t get wet
 lotus leaf has a nanoscale roughness that causes it to
be superhydrophobic surface
 water droplets hardly touching the surface of the leaf
and roll of the leaf.
 This effect is known as the lotus effect
 principle use to develop self-cleaning surface

Source: https://www.nnci.net/nature-helps-nanotechnology

NANOTECHNOLOGY IN NATURE – II

 Walls of the Nepenthes Pitcher Plants

 Walls are so slick that insects slide down and digested by juices at the
bottom of the bloom.
 Walls are wetable due to its hydrophilic surface chemistry and surface
roughness.
 these features cause to slip down the insects.
NANOTECHNOLOGY IN NATURE – III

 Gecko Foot
 Gecko have hairs on the bottom of their feet that you can’t
see unless you look through a high-powered microscope.
 First there is a layer of micron-sized hairs and attached to
each of these hairs is a series of nano-sized hairs.
 The presence of all these nano-sized hairs increases the
surface area of the feet by a great amount, which
significantly increases the adhesion forces and the contact
area between the feet and the wall, and this is what enables
gecko to scale walls.
Source: How gecko toes stick. American Scientist
94, 124-132

NANOTECHNOLOGY IN NATURE – IV

 Structural Coloration in Bird Feathers

 What if I told you a peacock is brown?
 Peacocks are known for their bright colors, but
when their feathers are wet they appear brown.
 This indicates that the bright colors aren’t a
result of pigmentation.
 A peacock’s bright teal and brilliant blue features
are not result of pigments but rather nanoscale
networks that reflect specific wavelengths of light.

Images courtesy of WikiCommons

NANOTECHNOLOGY IN NATURE – V

Source: Jenny Orbeck, inspired by

Source: Zi et al. 2003
“How Birds Make Colorful Feathers”

EMERGENCE OF NANOTECHNOLOGY

 The Chinese are known to use Au nanoparticles as an inorganic dye to introduce red color into their
ceramic porcelains more than thousand years ago.
 Medical applications of colloidal gold present another example.
 Colloidal gold is still used for treatment of arthritis
 no. of diseases were diagnosed by the interaction of colloidal gold
 Swarna (gold) bhasma has been used as a therapeutic agent in the traditional Indian Ayurvedic
medicine such as
 bronchial asthma, rheumatoid arthritis, diabetes mellitus, and nervous system
 Roman glass artifacts contained metal nanoparticles, which provided beautiful colors.
EMERGENCE OF NANOTECHNOLOGY
(a) Padmapani painting (Ajanta caves), (b)
Brihadeshwara Temple wall paintings,
Tanjore
Source: Mapin Publishing and British
Museum Press
Cathedral windows
Source: nano—tech.blogspot.com/p/history.html
Lycurgus Cup
Source: en.Wikipedia.org/wiki/lycurgus Cup
• The Lycurgus cup is made of a dichroic glass.
• Dichroic glass: glass containing multiple micro-layers of
metals or oxides which give the glass dichroic optical
properties.
• It has a particular transmitted color and a completely
different reflected color.
WHAT IS REALLY NEW ABOUT NANOTECHNOLOGY?

 ability to image, engineer and manipulate systems in the

nanometer scale
 and understanding of atomic scale interactions
 eg. Discovery of STM, SPM, AFM, TEM techniques

MOORE’S LAW

 Moore’s law predicted in

1965
 trend line illustrates the
transistor size has decreased
by a factor of 2 every
months since 1950
 FABRICATION APPROACH FOR SYNTHESIS OF NANOMATERIALS

Bottom Up Approach Top Down Approach

• Atomic/Molecular
Condensation
• Vapor Deposition
• Sol-gel Process
• Spray Pyrolysis, etc.
• Sputtering
• Chemical etching
• Thermal/Laser ablation
• Mechanical/Ball milling
• Explosion Process Source: https://doi.org/10.1007/978-3-319-56979-6_2

TOP-DOWN APPROACH

 Top-down means starting from large pieces of material and producing the intended structure by mechanical or
chemical methods
BOTTOM-UP APPROACH

PROBLEMS WITH TOP-DOWN APPROACH

 Imperfection of the surface structure

 For example, nanowires made by lithography are not smooth and may contain a lot of impurities and
structural defects on its surface.
 Significant impact on physical properties and surface chemistry of nanostructures and nanomaterials
 Example: reduced conductivity due to inelastic scattering which in turn would lead to the generation of
excessive heat
SYNTHESIS OF NANOPARTICLES

INTRODUCTION

 Requirement for fabrication of nanoparticles:

 identical size of all particles (also called monosized or with uniform size distribution)
 identical shape or morphology
 identical chemical composition and crystal structure that are desired among the different particles and within individual
particles
 No agglomeration. If agglomeration does occur, nanoparticles should be readily redispersible.
INTRODUCTION

 Four major steps for the formation of particles:

 Nucleation: a nucleus is the smallest stable unit and usually
consists of two or, in most cases, three atoms or molecules.
 The nucleus acts as core for further condensation of atoms or
molecules. Therefore, the nucleus grows and forms clusters, and
later a particle.
 Cluster reached a certain size that further coagulation of particles
is impossible.
 Now, the process of agglomeration starts. Agglomerates consist of
two or more individual particles.
 The size distribution of the particles follows a Poisson distribution.

INERT GAS CONDENSATION PROCESS

 Oldest process for synthesizing nanoparticles

 For example: production of gold Nanoparticles
 gold is evaporated in a “boat” that is heated to a sufficiently high
temperature.
 atoms of the gold vapor that emanate from the boat collide with
atoms of the inert gas, losing energy with each collision, and the gold
vapor is increasingly thermalized.
 thermalized gold atoms are now able to collide with other atoms of
the same type, leading to nucleation and subsequently to particle
formation.
 Particles formed in the gas phase drift by thermophoresis (=thermal
diffusion) to a liquid nitrogen-cooled finger, where they are collected
from the surface.
INERT GAS CONDENSATION PROCESS – II

 Limitations
 introduction of elements that limit particle size growth
 Possible measure to control the particle size and particle size distribution
 a reduction of the residence time of the particles in the reaction zone
 rapid cooling of the particles after they have left the reaction zone
 But, both measures is not possible in this process.

PHYSICAL AND CHEMICAL VAPOR SYNTHESIS PROCESS – I

Physical vapor synthesis process

 Utilize an electric arc as a source of energy to
evaporate the metallic precursor.
 This is a quite difficult process to control as
the extremely high temperature of the arc
may lead to high evaporation rates.
 A high concentration of the evaporated
precursor in the carrier gas usually results in
the large particles
 Although until now metal rods or powders
have been used as precursors, this approach is
not in all cases either economic or efficient.
PHYSICAL AND CHEMICAL VAPOR SYNTHESIS PROCESS – II

Chemical Vapor synthesis

 use chemical compounds with a relatively high vapor pressure as the
precursor
 utilizes a tubular furnace with temperature up to 1500 K as a source of
heat
 a carrier gas (Ar or Nitrogen) transports the evaporated precursor
through the heated reaction zone. Source:
https://sites.google.com/site/nanomodern/Home/CNT/syncnt/cvd
 Precursor:
In most cases, this reaction requires a
 carbonyls temperature in the range 1200-1500
 metal organic compounds K, but adding water to the system
leads to significant reduction in the
 to obtain the metal oxide, a typical reaction might be
temperature
→ 2 −
2 2 2 2
→

PHYSICAL AND CHEMICAL VAPOR SYNTHESIS PROCESS – III

 The advantage of a reduced reaction temperature is outweighed by the disadvantage of having highly corrosive
hydrochloric acid as a byproduct in the system.
 Use of a carbonyl is recommended in the synthesis of magnetite
13
2 → 10
2
 This reaction occur successfully in most cases at temperature below 600 or 700 K.
 Handling is difficult because most carbonyls are highly toxic and have limited stability in open air.
 However, by selecting appropriate temperatures, the use of carbonyls will provide much more freedom in terms
of the morphology of the intended powder.
 Low temperatures lead to extremely fine and amorphous powders, whereas the products tend to be more
crystalline when using a higher reaction temperature
PHYSICAL AND CHEMICAL VAPOR SYNTHESIS PROCESS – IV

 In addition to oxides, chemical vapor synthesis also allows the synthesis of carbides and nitrides.

→ 3 an inappropriate selection of the

reaction temperature may lead to
→ 2 the formation of elemental silicon
particles and carbon (as soot)

 In order to synthesis nitrides, nitrogen is used as the reaction and carrier gas.

→
2 2

to shift the equilibrium towards nitride

and hydrochloric acid formation

LASER ABLATION PROCESS – I

 Source of energy: a pulsed laser beam

 Advantage
 metal as well as oxides can be used as a precursors
 Plume (a supersonic jet of evaporated material) is ejected
perpendicular to the target surface and expands into the
gas space above the target
 The carrier gas may also contain reactive gas components
 oxygen to obtain the oxides
 methane (CH4) for carbides
 ammonia (NH3) for nitrides
LASER ABLATION PROCESS – II

 Issue with Laser Ablation Process:

 a high concentration of evaporated material gathers in the
plume.This may lead to the formation of the agglomeration
or web like structure. And individual particles are not
visible.

Web like structure of silicon nanoparticles with a

primary particle size of 10 nm.

Source: S. Li and M.S. El-Shall, Appl. Surf. Sci., 127-129, 330-33, 1998.

RADIO AND MICROWAVE PLASMA PROCESSES

 plasma is ignited at the intersection of the reaction tube, this is the zone
where the reaction occurs.
 evaporated precursor is introduced into the system via a stream of
mixed carrier and reaction gases.
 particles originated in the plasma zone carry electric charge.
 gas pressure is in the range from 500 to 10 4 Pa and temperature is
adjusted from 400 to 800 K.
 frequency is 2.45 GHz.
 Benefits of plasma process
 high production rates of unagglomerated particles
 narrow particle size distribution
 chemical reactions are the same as in a conventional furnace , albeit at a
lower temperature.
FLAME AEROSOL PROCESS

 Used for the mass production in the kiloton range

 Since prehistoric times, in China, carbon black (as a
pigment for inks) has been produced by flame aerosol
processes, and today this same technology- or one of
its many variants - is still used to produce thousand
of metric tons of carbon black, fumed silica, and titania
pigments.
 Here, methane was used as the fuel and hexamethyl
disiloxane as a precursor to produce silica.

SYNTHESIS OF COATED PARTICLES

 The process used for particle coating must

fulfill a series of requirements.
 particles remain individualized and are not
agglomerated
 this requires either extremely low
particle concentrations in the gas
atmosphere or particles that carry
electrical charges of equal sign
 temperature in the coating step must be
sufficiently low

Setup for synthesis of ceramic-coated ceramic nanoparticles in a microwave plasma

SYNTHESIS OF ONE-DIMENSIONAL
NANOSTRUCTURES

INTRODUCTION

 One-dimensional nanostructures have been called by a variety of names including: whiskers, fibers, nanowires and
nanorods.
 Nanotubes and nanocables are also considered one-dimensional structures.
 Many techniques have been developed in the synthesis and formation of one-dimensional nanostructured
materials.
 These techniques can be generally grouped into four categories.
TECHNIQUES FOR SYNTHESIS OF ONE-DIMENSIONAL
NANOSTRUCTURES

Techniques of 1D Nanostructures
Synthesis

Template-based Electrospinning Lithography

Spontaneous growth
synthesis

Evaporation (or dissolution) - Electroplating and

condensation electrophoretic deposition

Vapor (or solution)-liquid-solid Colloid dispersion, melt, or

(VLS or SLS) growth solution filling

Stress-induced recrystallization Conversion with chemical

reaction

EVAPORATION (OR DISSOLUTION)-CONDENSATION PROCESS – I

 Nanowires and naorods grown by evaporation (or dissolution)-condensation is due to the anisotropic growth.
 Several mechanisms are known to result in anisotropic growth
1. different facets in a crystal have different growth rate.
 in silicon with a diamond structure, the growth rate of {111} facets is smaller than that of {110}
2. Presence of imperfections in specific crystal directions such as screw dislocation, micro twins, stacking faults
3. Preferential accumulation of or poisoning by impurities on specific facets
EVAPORATION (OR DISSOLUTION)-CONDENSATION PROCESS – II

Schematic illustrating six steps in crystal growth, which can be generally

considered as a heterogeneous reaction
Source: Cao, Nanostructures and nanomaterials synthesis, properties and applications (2004, Imperial
College Press)

EVAPORATION-CONDENSATION PROCESS – I

 Sears was the first to explain the growth of mercury whiskers (or nanowires,
with a diameter of ~200 nm and a length of 1-2 mm)
 The mercury whiskers or nanowires were grown by a simple evaporation-
condensation method
 condensation temperature of - 50 °C under vacuum,
 Wang et al. reported growth of single crystal nanobelts of various
semiconducting oxides by
 evaporating the desired metal oxides at high temperature under a
vacuum of 300 torr
 condensing on an alumina substrate, placed inside the same alumina
tube furnace, at relatively lower temperature
 Oxides are: zinc oxide (ZnO), tin oxide (SnO2) indium oxide, cadmium
oxide

Source: Raúl J. Martín-Palma, Akhlesh Lakhtakia,

Engineered Biomimicry, 383-398, 2013
EVAPORATION-CONDENSATION PROCESS – II

• typical thickness and width-to-thickness ratios of the

ZnO nanobelts are in the range of 10 to 30 nm and 5 to
10 respectively.
• two growth directions were observed: [0001] and
[0110]
• a single stacking fault parallel to the growth axis in the
nanobelts grown along [0110] direction

SEM and TEM pictures of ZnO nanobelts

Source: Z. W. Pan, Z. R. Dai, Z. L. Wang, Science, 291, 1947, 2001

DISSOLUTION-CONDENSATION GROWTH – I

 Dissolution-condensation process differs from evaporation-condensation in growth media.

 In dissolution-condensation process, the growth species first dissolve into a solvent or a solution, and then diffuse

through the solvent or solution and deposit onto the surface resulting in the growth of nanorods or nanowires.

 The nanowires in this method can have a mean length of < 500 nm and a mean diameter of 60 nm.
DISSOLUTION-CONDENSATION GROWTH – II

 Single nanowires of selenium

• spherical colloidal particles of amorphous selenium with size of ~ 300 nm
in aqueous solution is produced
• by reduction of selenious acid with excess hydrazine at 100 °C.
Step First • when solution is cooled to room temperature, nanocrystalline selenium
with trigonal structure is precipitated

• solution aged at room temperature in dark, amorphous selenium colloid

particles dissolved into the solution, whereas the selenium crystallites grew
• In this solid-solution-solid transformation, the morphology of the
crystalline selenium product is determined by the anisotropic growth,
Second step which is attributed to one dimensional characteristics (helical chains of
selenium in trigonal structure).

VAPOR (OR SOLUTION) – LIQUID – SOLID (VLS OR SLS) GROWTH

 In VLS growth
 a second phase material (either impurity or
catalyst) is introduced to direct and confine the
crystal growth on to a specific orientation and
within the confined area
 a catalyst forms a liquid droplet by itself or by
alloying with growth material during the growth
which act as a trap of growth species.
 enriched growth species in the catalyst droplets
subsequently precipitates at the growth surface
resulting in one-direction growth

Source: Choi HJ. (2012) Vapor–Liquid–Solid Growth of Semiconductor Nanowires. In: Yi GC. (eds) Semiconductor Nanostructures for
Optoelectronic Devices. NanoScience and Technology. Springer, Berlin, Heidelberg.
 GROWTH OF SILICON NANOWIRE BY VLS GROWTH

 Gold as a catalyst
 Steps for growth of Si nanowire
synthesis
1. A thin layer of gold is sputtered on Si-
substrate
2. Annealed at an elevated temperature
(above the eutectic point of 385 °C of
silicon-gold system)
3. during the annealing, silicon and gold
react and form a mixture
4. silicon species is evaporated from the
source and preferentially condensed at
the surface of liquid droplet
5. liquid droplet supersaturated with
silicon and precipitate at the solid-liquid
interface resulting in growth of silicon Source: Wei Lu and Charles M Lieber, J. Phys. D:
Appl. Phys.39(2006) R387–R406

VAPOR (OR SOLUTION) – LIQUID – SOLID (VLS OR SLS) GROWTH –

I

 Control of the size of nanowires

 size of nanowires is determined by the size of the liquid catalyst droplets.
 size of the liquid catalyst droplets can be controlled by the thickness of the catalyst film on the
substrate.
 for example: 10 nm Au film yield single crystal germanium nanowires of 150 nm in a diameter
 while 5 nm Au film results in the growth of 80 nm sized germanium nanowires.
 further reduction of diameters of nanowires could be achieved by dispersing monosized catalyst
colloids on the substrate surface, instead of thin film of catalyst
 SOLUTION – LIQUID – SOLID (SLS) GROWTH – I

 SLS mechanism is analogous to vapor-liquid-solid (VLS) mechanism

 SLS growth is conducted with a solution phase (normally employing organic solvents), typically at temperatures of
200 -350 °C, in which low-melting metallic nanoparticles (in the molten, liquid form under the reaction
conditions) catalyze the decomposition of metalloorganic precursors at the solution-liquid interface and dissolve
the semiconductor components so obtained.
 limited solubility of a semiconductor component in the liquid metallic catalyst droplet results in supersaturation,
inducing crystallization of the semiconductor phase from the catalyst droplet.
 the growing semiconductor phase naturally acquires a pseudo-one-dimensional morphology.

SOLUTION – LIQUID – SOLID (SLS) GROWTH – II

Silica nanorods arrays on the substrate

Source: Wang et al., Chem. Rev. 2016, 116, 10888−10933
Source: Fang et al., Adv. Sci.2020, 7, 2000310
STRESS-INDUCED RECRYSTALLIZATION

 Application of pressure on solids at elevated temperatures is known to result in the growth of whiskers or
nanowires with diameters as small as 50 nm,
 Growth rate of tin whiskers increased proportionally with applied pressure.
 Growth of such nanowires or whiskers is based on a dislocation at the base of whisker and growth proceeds
from the base not from the tip.

TEMPLATE-BASED SYNTHESIS – I

 Template-based synthesis of nanostructured materials is a very general method and can be used in fabrication of
nanorods, nanowires and nanotubules of polymer, metals, semiconductors and oxides.
 Commonly used templates are
 anodized alumina membrane
 radiation track-etched polymer membranes
 nanochannel array glass
 radiation track-etched mica
 mesoporous materials
 porous silicon by electrochemical etching
of silicon wafer, zeolites and carbon nanotubes

Porous alumina template

Source: Asoh et al., Journal of The Electrochemical
Society,148, B152-B156 (2001)
TEMPLATE-BASED SYNTHESIS – II

Requirements of template based synthesis

 template materials must be compatible with the processing conditions.
 for example: an electrical insulator is required for a template to be used in electrochemical deposition
 Depositing materials or solution must wet the internal pore walls.
 Synthesis of nanorods or nanowires, the deposition should start from the bottom or one end of the template
channels and proceed from one side to another, while for the growth of nanotubules, the deposition should start
from the pore wall and proceed inwardly.
 Easiness of release of nanowires or nanorods from the templates and of handling during the experiments

TEMPLATE-BASED SYNTHESIS – III

 Deposition techniques for template-based synthesis

 Electrodeposition (or electrochemical deposition)
 electrophoretic deposition
 Template filling
1. colloidal dispersion filling
2. Melt and solution filling
3. chemical vapor deposition
4. Deposition by centrifugation

Mz+ is the metal ions

Electrodeposition
TEMPLATE-BASED SYNTHESIS – IV

 Electrodeposition
 this method is only applicable to electrically conductive
materials such as metals, alloys, semiconductors, and
electrically conductive polymers
 An external electric field is applied between two
dissimilar electrodes, charged species flow from one
electrode to the other, and electrochemical reactions
occur at both electrodes
 electrode connected to the positive side of the power
supply, termed as anode, where oxidation reaction
takes place
 electrode connected to the negative side, is termed as
cathode and a reduction reaction occurs

Source: Shang H., Cao G. (2007) Template-Based Synthesis of Nanorod or Nanowire Arrays. In: Bhushan B. (eds)
Springer Handbook of Nanotechnology. Springer Handbooks. Springer, Berlin, Heidelberg

TEMPLATE-BASED SYNTHESIS – V

 In template-based electrodeposition technique, before starting the electrodposition process in template, the
template is pre-processed.
 A thin layer of the conductive layer is sputtered on the bottom side of the template
 this conductive layer makes a bridge over the pores and pores remain open
 After that, the template is soaked in the deionized water for a certain period by ultrasonication.
 After ultrasonication of the template, electrodeposition is performed on it.

A schematic diagram of the formation of

gold nanotubes from hollow morphology
to the solid morphology

Source: IntechOpen
TEMPLATE-BASED SYNTHESIS – VI

 Electrophoretic deposition
 is a special colloidal processing technique that uses
the electrophoresis mechamism for the movement of
charged particles suspended in a solution under a
electric field
 In the first step, particles having acquired an electric
charged in the liquid in which they are suspended, are
forced to move towards one of the electrodes by
applying electric field to the suspension
 In a second step, the particles or 1D nanostructures
collect at one of the electrodes. The deposit takes the
shape imposed by their electrode.

Source: Thandapani et al., Woodhead Publishing Series in

Biomaterials, 2018, Pages 79-110

TEMPLATE-BASED SYNTHESIS – VII

Types of Electrophoretic Deposition

Cathodic electrophoretic Anodic electrophoretic

deposition deposition

• Particles are positively charged • Particles are negatively charged

• deposition happens on the cathode • deposition happens on the anode

• By suitable modification of the surface charge on the particles, any of the two mode of deposition is possible.

Source: Besra et al., Progress in Materials Science 52 (2007) 1–61

TEMPLATE-BASED SYNTHESIS – VIII

 Charged development on the particles

 when particles dispersed in a polar solvent or an electrolytic solution, the surface of a nanoparticles
develops an electric charge via one or more of the following mechanisms:
1. preferential dissolution
2. deposition of charges or charged species
3. preferential reduction or oxidation
4. physical adsorption of charged species such as polymers

TEMPLATE-BASED SYNTHESIS – VIII

 Example: electrophoretic deposition to form nanorods of ZnO from colloidal sols

 ZnO colloidal sol was prepared by hydrolyzing an alcoholic solution of zinc acetate with NaOH, with a small amount of Zinc
nitrate added to act as a binder.
 this solution was then deposited into the pores of anodic alumina template at voltage in the range of 10-400 V.
 At lower voltage led to dense , solid nanorods
 At higher voltages causes the formation of hollow tubules.
 Example: electrophoretic deposition to form nanorods of TiO2 from colloidal sols
 TiO2 electrolyte solution was prepared using Ti powder dissolve into a H2O2 and NH4OH aqueous solution
 TiO2+ ionic clusters formed
 an external electric field applied , TiO 2+ ionic clusters diffused to cathode and results nanorods of amorphous
TiO2 gel.
 After heat treatment at 240 °C for 24 hours in air, nanowires of single crystal TiO2 were synthesized
TEMPLATE-BASED SYNTHESIS – VIII

 Example: electrophoretic deposition to form nanorods of ZnO from colloidal sols

 ZnO colloidal sol was prepared by hydrolyzing an alcoholic solution of zinc acetate with NaOH, with a small amount of Zinc
nitrate added to act as a binder.
 this solution was then deposited into the pores of anodic alumina template at voltage in the range of 10-400 V.
 At lower voltage led to dense , solid nanorods
 At higher voltages causes the formation of hollow tubules.
 Example: electrophoretic deposition to form nanorods of TiO2 from colloidal sols
 TiO2 electrolyte solution was prepared using Ti powder dissolve into a H2O2 and NH4OH aqueous solution
 TiO2+ ionic clusters formed
 an external electric field applied , TiO2+ ionic clusters diffused to cathode and results nanorods of amorphous
TiO2 gel.
 After heat treatment at 240 °C for 24 hours in air, nanowires of single crystal TiO2 were synthesized

Source: Cao, Nanostrucutres and nanomaterials: synthesis, properties and application (2004, Imperial College Press)

TEMPLATE-BASED SYNTHESIS – IX

 Template Filling
 a liquid precursor or precursor mixture is used to fill the pores.
 Requirement for filling a template
1. wettability of the pore wall should be good enough to permit the penetration and complete filling of
the liquid precursor or precursor mixture
2. template materials should be chemically inert
3. control of shrinkage during solidification is required
 if adhesion between the pore walls and the filling material is weak, solidification start one end of the
pore, or a solid nanorids are most likely form
 if the adhesion is very strong, solidification starts at the interfaces and form a hollow nanotubes
TEMPLATE-BASED SYNTHESIS – X

 Colloidal dispersion filling

 colloidal dispersions are prepared using appropriate sol-gel processing
 a template is placed in a stable sol for various periods of time
 due to capillary force , sol fills the pores
 after that, template withdrawn from the sol and dried prior to firing at elevated temperature
 firing at elevated temperatures serves two purposes
 removal of template so that free standing nanorods obtain
 densification of green nanorods

TEMPLATE-BASED SYNTHESIS – XI

 Drawbacks of Colloidal dispersion filling

1. difficult to ensure the complete filling of the template pores
2. nanorods are commonly polycrystalline or amorphous
TEMPLATE-BASED SYNTHESIS – XII

 Melt and solution filling

 metallic nanowires synthesize by filling a template with molten metals
 Example: 1
 preparation of bismuth nanowires by pressure injection of molten bismuth into the nanochannels of anodic
alumina template.
 alumina template is degassed and immersed in the liquid bismuth at 325 °C and then high pressure Ar gas of ~
300 bar is applied to inject liquid Bi into nanochannels of template for 5 hr.
 Bi nanowires with diameters of 13-110 nm will be obtained.
 Example: 2
 Polymeric fibers have been made by filling a monomer solution (desired monomer + polymerization reagent) into
the template pores and then polymerizing the monomer solution.

TEMPLATE-BASED SYNTHESIS

 Chmical vapor deposition

 Ge nanowires were grown by Leon et al. by diffusing Ge 2H6 gas into mesoporous silica and heating. The
precursor reacted with residual surface hydroxyl groups in the template, forming Ge and H2.
 Lee et al. used a platinum organometallic compound to fill the pores of mesoporous silica templates, followed
by pyrolysis under H2/N2 flow to yield Pt nanowires.
TEMPLATE-BASED SYNTHESIS

 Deposition by centrifugation
 template filling by the action of centrifugation force
 Example: lead zirconate titanate (PZT) nanorod array
 arrays grown in polycarbonate membrane from PZT sol by centrifugation at 1500 rpm for 60 min.
 samples are attached to silica glass and fired at 650 °C in air for 60 min.

ELECTROSPINNING
 also known as electrostatic fiber processing
 this technique has been originally developed for
generating ultrathin polymer fibers
 electrospinning uses electrical forces to
produce polymer fibers with nanometer-scale
diameters
 Morphology of the fibers depends on the
process parameters
 solution concentration
 applied electric field strength
 feeding rate of the precursor solution

Source: nanoscience.com/techniques/electrospin/
ELECTROSPINNING

ELECTROSPINNING

 Synthesis of TiO2/PVP composite nanofibers

 Precursor solution: ethanol solution containing both
poly vinyal pyrrolidone (PVP) = 0.03 g/mL and
titanium tetraisopropoxide = 0.1 g/mL
 applying a strong electric field, results in the TEM image of TiO2/PVP composite nanofibers
formation of amorphous TiO2/PVP composite
nanofibers
 upon pyrolysis of PVP at 500 °C in air, porous TiO2
fibers with diameter ranging from 20 to 200 nm.

TEM image of TiO2 nanofibers

Source: Cao, Nanostrucutres and nanomaterials: synthesis, properties and application (2004, Imperial College Press)
LITHOGRAPHY (OR PATTERNING) – I

 Lithography is the process of transferring geometrical patterns (shapes) from a mask to a thin layer of radiation-
sensitive material (called resist) covering the surface of a semiconductor wafer.
 Many techniques of lithography have been developed in the last half a century with various lens system and
exposure radiation sources including photons, X-rays, electron, ions and neutral atoms.
 Lithography is the most widely used technique in microelectronic fabrication, particularly for mass production of
integrated circuits.

LITHOGRAPHY (OR PATTERNING) – II

 Photolithography
 Overview of photolithography

Source: www7b.biglobe.ne.jp/~kcy05t/lithography.html
PHOTOLITHOGRAPHY

 Steps used in photolithography

1. Wafer and mask cleaning
 Dust particles or other impurities settling on
semiconductor wafers and masks can cause defects
in devices.
 Wafer and mask are chemically cleaned to remove
organic, ionic, and metallic impurities.

Source: cityu.edu.hk

PHOTOLITHOGRAPHY
 Steps used in photolithography
2. Photoresist application on wafer by spin coating technique
 wafer is placed on a vacuum chuck
 a vacuum holds the wafer on the chuck
 resist is applied
 Chuck accelerates for desired resist thickness
 chuck continues to spin to dry film
 Chemicals commonly use as photoresist are:
 Poly methyl methacrylate (PMMA)
 Poly methyl glutarimide (PMGI)
 Phenol formaldehyde resin (DNQ/Novolac)

spin coating technique

Source: nanoscale.unl.edu/
PHOTOLITHOGRAPHY

 Steps used in photolithography

2. Photoresist application on wafer by spin coating technique
 wafer is placed on a vacuum chuck
 a vacuum holds the wafer on the chuck
 resist is applied
 Chuck accelerates for desired resist thickness
 chuck continues to spin to dry film

spin coating technique

Source: nanoscale.unl.edu/

PHOTOLITHOGRAPHY

 Steps used in photolithography

3. Softbake
 after the photoresist is applied to the desired
thickness, a softbake is used to remove the residual
solvents of the photoresist
 after the softbake, the wafer is cooled to room
temperature.
 photoresist become photosensitive after prebaking.

Source: nanoscale.unl.edu/
PHOTOLITHOGRAPHY

 Steps used in photolithography

4. Expose
 The wafer is exposed by UV (ultraviolet) from a
light source traveling through the mask to the resist
 A chemical reaction occurs between the resist and
the light
 Only those areas not protected by the mask
undergo a chemical reaction.

Source: nanoscale.unl.edu/

PHOTOLITHOGRAPHY

 Steps used in photolithography

4. Exposure
 photoresist is a mixture of organic compounds in a
solvent solution.
 Two types of resist:
1. Positive resist: exposed regions become more
soluble. A positive mask is left after develop.
2. Negative resist: exposed materials harden. A
negative mask is left after develop.

Source: nanoscale.unl.edu/
PHOTOLITHOGRAPHY

 Steps used in photolithography

5. Develop
 portion of the photoresist are dissolved by a
chemical developer
 with positive resist, the exposed resist is dissolved
while the unexposed resist remains on the wafer.
 With negative resist, the unexposed resist is
dissolved while the exposed resist remains.

Source: nanoscale.unl.edu/

PHOTOLITHOGRAPHY

 Steps used in photolithography

5. Hard Baking
 hard bake is used to harden the final resist image at the
temperature (120 to 150 °C), so that it will hold out
the harsh environments of etching.
6. Etching
 etching is performed either using wet chemicals such
as acids, or more commonly in a dry etching (by
exposing the material to a bombardment of ions).
 the photoresist will resist the etching and protects the
material covered by the resist.
 When the etching is complete, the resist is stripped
leaving the desired pattern.

Source: nanoscale.unl.edu/
 TYPES OF LITHOGRAPHY

Lithography

Photolithography (optical
Electron lithography X-ray lithography Ion lithography
lithography)

ELECTRON LITHOGRAPHY – I

 Electron beam lithography is a specialized technique for creating extremely fine patterns.
 Advantages of electron lithography
 Print complex patterns directly on wafers
 High resolution up to 20 nm (photolithography ~ 50 nm)
 Flexible technique
 Disadvantage of electron lithography
 low throughput (approximately 5 wafers/hour at less than 0.1 μm resolution)
 Expensive and complicated
ELECTRON LITHOGRAPHY – II

 Electron resists are polymers.

 For a positive electron resist, the polymer-electron
interaction causes chain scission, that, is broken chemical
bonds
 The irradiated areas can be dissolved in a developer
solution
 Common positive electron resists are
 poly methyl methacrylate (PMMA)
 poly butane-1 sulfone (PBS)
 Positive electron resists typically have resolution of 0.1
μm or better

ELECTRON LITHOGRAPHY – II

 When electrons impact a negative electron resist, polymer

linking is induced.
 Common negative resist
 poly glycidyl methacrylate-co-ethyl-acrylate
 resolution is limited to about 1 μm.
X-RAY LITHOGRAPHY – I

 X-rays (0.04 nm to 0.5 nm) is another radiation source for high resolution design reproduction into polymeric
resist materials
 X-ray lithography can be extended optical resolution of 15 nm.
 Essential elements in X-ray lithography
 a mask consisting of a pattern made with an X-ray absorbing material on a thin X-ray transparent membrane
 X-ray source of sufficient brightness
 X-ray sensitive resist material
 X-ray lithography has a higher throughput when compared to e-beam lithography

X-RAY LITHOGRAPHY – II

 Electron beam resists can be used in X-ray lithography because when an X-ray photon impinges on the specimen,
electron emission results
 Dichloropropyl acrylate (DCOPA) and glycidyl methacrylate-co-ethyl acrylate are most attractive X-ray resist
 Advantages
 Faster than EBL
 Uniform pattern
 High resolution
 Disadvantage
 Masks are expensive to produce
ION LITHOGRAPHY

 Ion lithography can achieve higher resolution than optical, X-ray, or electron beam lithography techniques because
ions undergo no diffraction and scatter much less than electrons
 Resists are more sensitive to ions than to electrons
 Commonly used Ion beams are Ga and Au-Si-Be alloys source due to their long lifetime and high stability
 Ion beam lithography is capable of producing electronic devices with sub micrometer dimensions
 Disadvantage
 lower throughput and extensive substrate damage

SYNTHESIS OF TWO-DIMENSIONAL
NANOSTRUCTURES