Synthesis of nanomaterials

Nanostructure materials have attracted a great deal of attention because their physical,
chemical, electronic and magnetic properties show dramatic change from higher dimensional
counterparts and depends on their shape and size.
 Many techniques have been developed to synthesize and fabricate nanostructure
materials with controlled shape, size, dimensionality and structure.
 The performance of materials depends on their properties. The properties in tern depend
on the atomic structure, composition, microstructure, defects and interfaces which are
controlled by thermodynamics and kinetics of the synthesis.
Classification of Techniques for synthesis of Nanomaterials
There are two general approaches for the synthesis of nanomaterials as shown in Figure 2:
a) Top- down approach
b) Bottom–up approach.
a) Top-down approach
 Top-down approach involves the breaking down of the bulk material into nanosized
structures or particles.
 Top-down synthesis techniques are extension of those that have been used for
producing micron sized particles.
 Top-down approaches are inherently simpler and depend either on removal or
division of bulk material or on miniaturization of bulk fabrication processes to
produce the desired structure with appropriate properties.
 The biggest problem with the top-down approach is the imperfection of surface
structure.
For example, nanowires made by lithography are not smooth and may contain a lot of
impurities and structural defects on its surface. Examples of such techniques are high-
energy wet ball milling, electron beam lithography, atomic force manipulation, gas-phase
condensation, aerosol spray, etc.
Schematic representation of ‘top-down’ and 'bottom-up’ approaches for synthesis of
nanoscale materials.
b) Bottom-up approach
 The alternative approach, which has the potential of creating less waste and hence
the more economical, is the ‘bottom- up’.
 Bottom-up approach refers to the build-up of a material from the bottom: atom-by-
atom, molecule-by-molecule, or cluster-by cluster.
 Many of these techniques are still under development or are just beginning to be
used for commercial production of nano powders.
  Oraganometallic chemical route, revere-micelle route, sol-gel synthesis, colloidal
precipitation, hydrothermal synthesis, template assisted sol-gel, electro deposition
etc, are some of the well- known bottom–up techniques reported for the preparation
of luminescent nanoparticals.
Methods used in the synthesis approaches

a) Top down approach

 Sol-Gel method
b) Bottom down approach
 Chemical vapour deposition (CVD)
 Physical vapour deposition (PVD)

SOL-GEL METHOD
Sol-Gel Process: “Formation of an oxide network through polycondensation reactions of a
molecular precursor in a liquid”.
The sol-gel process, involves the evolution of inorganic networks through the formation of a
colloidal suspension (sol) and gelation of the sol to form a network in a continuous liquid
phase (gel). The precursors for synthesizing these colloids consist usually of a metal or
metalloid element surrounded by various reactive ligands. The starting material is processed
to form a dispersible oxide and forms a sol in contact with water or dilute acid. Removal of
the liquid from the sol yields the gel, and the sol/gel transition controls the particle size and
shape. Calcination of the gel produces the oxide.
Precursors
The precursor used in sol-gel process for the synthesis of nanoporous materials are metal
alkoxides M(OR) . They readily react with water to form gels.
Sol-gel processing refers to the hydrolysis and condensation of alkoxide-based precursors
such as Si(OEt) 4 (tetraethyl orthosilicate, or TEOS). The reactions involved in the sol-gel
chemistry based on the hydrolysis and condensation of metal alkoxides M(OR)z can be
described as follows:
Examples
 Tetra methoxy silane [Si(O3CH4)]
 Tetra ethoxy silane [Si(O2C5H4)]
 Tetra butoxy titanate [Ti(O4C9 H4)]
Process (Synthesis of silica aerogel):
This process consists of four main steps.
1. Hydrolysis of precursors
2. Condensation followed by polycondensation
3. Gelation
4. Supercritical drying

1. Hydrolysis
It occurs by the addition of water to any one of the precursor material to form silanol
(SiOH) particles.

2. Condensation
The self condensation of silanol groups produces siloxane linkages filled with by
products of water and alcohol.

3. Polycondensation
The condensation process continues to form poly condensed silica gel with Si-O-Si
linkages.
 4. Drying
The gels are subjected to super critical drying in an autoclave. The critical pressure
and critical temperature used are 78 bar and 294oC respectively in order to remove liquid
from silica gel to form the network structure of silica aerogel.

The interest in this synthesis method arises due to the possibility of synthesizing
nonmetallic inorganic materials like glasses, glass ceramics or ceramic materials at very low
temperatures compared to the high temperature process required by melting glass or firing
ceramics.
The major difficulties to overcome in developing a successful bottom-up approach is
controlling the growth of the particles and then stopping the newly formed particles from
agglomerating. Other technical issues are ensuring the reactions are complete so that no
unwanted reactant is left on the product and completely removing any growth aids that may
have been used in the process. Also production rates of nano powders are very low by this
process. The main advantage is one can get monosized nano particles by any bottom up
approach.

Advantages of Sol-gel process

  It produces thin bond-coating to provide excellent adhesion between the metallic
substrate and the top coat.
 It produces thick coating to provide corrosion protection performance.
 It easily shapes materials into complex geometries in a gel state.
 It has low temperature sintering capability, usually 200-600°C.
 It provides a simple, economic and effective method to produce high quality coatings.
Disdvantages of Sol-gel process
 Controlling the growth of the particles is difficult.
 Stopping the newly formed particles from agglomeration is also difficult
Applications of Sol-gel process
 It can be used in ceramics manufacturing processes as an investment casting material
or as a means of producing very thin films of metal oxides for various purposes.
 Sol-gel derived materials have diverse applications in optics, electronics, energy,
space, (bio) sensors, medicine (e.g. controlled drug release) and separation (e.g.
chromatography) technology.
 One of the more important applications of sol-gel processing is to carry out zeolite
synthesis.
CHEMICAL VAPOUR DEPOSITION (CVD)
Chemical vapour deposition (CVD) is a vacuum deposition method used to produce high
quality, high-performance, solid materials. The process is often used in the semiconductor
industry to produce thin films.

Principle

Chemical vapour deposition (CVD) method involves a transport of reactant gases towards the
substrate kept at some temperature where reactants crack into different products which
diffuse on the surface and undergo certain chemical reactions at appropriate site nucleate and
grow to form desired films, coatings, wires and tubes.

Chemical vapour deposition may be defined as the deposition of a solid on a heated surface
from a chemical reaction in the vapour phase. It belongs to the class of vapour-transfer
processes which is atomistic in nature, that is the deposition species are atoms or molecules
or a combination of these.

In this method nanoparticles are deposited from gas phase. Material is heated to form a gas
and then allowed to deposit on a solid surface, usually under high vacuum. In deposition, by
chemical reaction new product is formed. Nano powders of oxides and carbides of metals can
be formed if vapours of carbon or oxygen are present with the metal.

It involves pyrolysis of vapours of metal organic precursors in a reduced pressure

atmosphere. In the simplest form, a metal organic precursor is introduced into the hot zone of
the reactor using mass flow controller. The precursor is vapourised either by resistive or
inductive chamber. The hot atoms collide with cold atoms and undergo condensation through
nucleation and form small clusters. In side reaction chamber other reactants are added to
control the reaction rate. Then these clusters are allowed to condensate on a moving belt
arrangement with scrapper to collect the nanoparticles. The particle size could be controlled
by rate of evaporation (energy input), rate of cluster formation (energy removal rate) and rate
of condensation (cluster removal from the reaction chamber).

Sequence of events during deposition

1) Diffusion in of reactants through boundary layer

2) Adsorption of reactants on substrate
3) Chemical reaction takes place
4) Desorption of absorbed species
5) Diffusion out of by-products.
Precursors
The common precursors used in CVD reactions are

 Metal hydrides – SiH4 ,GeH4

 Metal halides-TiCl4 , TaCl5 , WF6
 Metal organics- AlMe3 , AlBu3 , Fe(CO)5 , Ni(CO)4

CVD Reactions

(i) Thermal Decomposition (Pyrolysis): Silicon deposition from SiH4 at 650ºC

SiH4 (g) → Si (s) + 2H2 (g)
(ii) (ii) Reduction: W-deposition at 300ºC
WF6 (g) + 3H2 → W (s) + 6HF (g)
(iii) (iii) Oxidation: SiO2 deposition at 450ºC
SiH4 (g) + O2 → SiO2 (s) + 2H2 (g)

Types of CVD

In CVD, the temperature of 300-1200oC is usually used. The heat input can be in the form of
thermal, light, plasma and so on. This give rise to number of CVD techniques.
Mechanism
The system follows a five step mechanism for any type of CVD.
Transport of precursors into the reactors
Absorption and diffusion of precursors on the substrate
Chemical reactions at the substrate
Deposition and growth of film
Transport of unreacted precursors and by-products

Advantages
 Versatile- CVD can deposit any element or compound.
 CVD produces high dense films.
 Economical in production since many products can be coated at a time.
 Used for coatings or freestanding structures
 Fabricates net or near-net complex shapes
 Self-cleaning—extremely high purity deposits (>99.995% purity)
 Conforms homogeneously to contours of substrate surface
 Controllable thickness and morphology
 Forms alloys
 Coats internal passages with high length-to-diameter ratios
 Simultaneously coat multiple components
 Coats powders
Disadvantages
 high temperatures
 complex processes
 toxic and corrosive gasses
Applications
 CVD can be used for the synthesis of nanotubes and nanowires.
 CVD can be used for hard coatings and metal films which are used in
microelectronics.
 CVD can also be used for preparing semiconducting devices, dielectrics, energy
conversion devices etc.
 CVD processes are used on a surprisingly wide range of industrial components from
aircraft and land gas turbine blades, timing chain pins for the automotive industry,
radiant grills for gas cookers and items of chemical plant to resist various attacks by
carbon, oxygen and sulphur.
 Surface modification to prevent or promote adhesion.
 Photoresist adhesion for semiconductor wafers Silane/substrate adhesion for
microarrays (DNA, gene, protein, antibody, tissue).
 BioMEMS and biosensor coating to reduce "drift" in device performance.
 Promote biocompatibility between natural and synthetic materials Copper capping
Anticorrosive coating
 PHYSICAL VAPOUR DEPOSITION (PVD)
Nanomaterials in the form of thin films, multilayer films, nanoparticles and nanotubes can
beproduced by physical vapour deposition methods.
Definition
Physical vapour deposition (PVD) is a technique by which a metal, ceramic or a compound
canbe converted into gaseous form and then deposited on the surface of a substrate.
In general, PVD methods are subdivided into:
1. Evaporation
2. Sputtering
3. Pulsed Laser Deposition or Laser Ablation
EVAPORATION
The source materials used in this process are generally refractory metals such as W, Ta, Mo
etc. In evaporation technique, both substrate and source materials (to be deposited) are placed
inside the vacuum chamber (10-6 to 10-7 torr). The vacuum is required to allow the molecules
to evaporate and to move freely in the chamber. An electron gun (e-gun) is used to produce
electron beam of 10 keV. This beam is directed at the source material in order to develop
sufficient vapour so as to produce deposits on wafer or substrates. Figure. shows the
schematic diagram of evaporation equipment.

SPUTTERING
The source materials used in this process are generally an alloy, ceramic or a compound.
Insputtering technique, a high energy atom in ionized form usually Ar+ is used to hit the
surface atoms of the targeted source material. Then the knocked out atoms in vapour form are
deposited on the surface of the substrate to produce a uniform coatings.
Pulsed Laser Deposition or Laser Ablation
Pulsed Laser Deposition (PLD) is a thin film deposition technique that is used to deposit
materials on substrates. A base system consists of a target, substrate carrier which is mounted
in a vacuum chamber. An excimer laser is used to energize the surface of a target to produce
a deposition plume. The plume is typically directed towards the substrate where a thin-film is
deposited. Since each shot of the laser is directly related to the amount of material ablated,
the deposition rate can be calibrated and controlled very precisely. Figure.1.9 shows the
schematic diagram of pulsed laser deposition.

Advantages
 Ultrapure films or particles can be produced by PVD since it uses a vacuum
environment.
 PVD can provide good structural control by careful monitoring of the processing
conditions.
 Materials can be deposited with improved properties compared to the substrate
material.
  Almost any type of inorganic material can be used as well as some kinds of organic
materials.
 The process is more environmentally friendly than processes such as electroplating.
Disadvantages
 Since PVD operates in a low pressure range, it increases the complexity of deposition
and cost of production.
 It is a line of sight technique meaning that it is extremely difficult to coat undercuts
and similar surface features.
 High capital cost.
 Some processes operate at high vacuums and temperatures requiring skilled operators.
 Processes requiring large amounts of heat require appropriate cooling systems.
 The rate of coating deposition is usually quite slow.
Applications
 PVD is used to produce the deposit of various metals, alloys or compounds in the
form of coatings or films for: Optics (Ex: Antireflection coatings) Electronics (Ex:
Metal contacts) Mechanics (Ex: hard coatings on tools) etc.
 PVD coatings are generally used to improve hardness, wear resistance and oxidation
resistance.
 PVD coatings use in a wide range of applications such as:
Aerospace
Automotive
Surgical/Medical
Dies and moulds for all manner of material processing
Cutting tools
Fire arms 3030
Atomic Force Microscope

Atomic force microscopy (AFM) or scanning force microscopy (SFM) is a very-high-

resolution type of scanning probe microscopy (SPM), with demonstrated resolution on the order
of fractions of a nanometer, more than 1000 times better than the optical diffraction-limit.

Atomic Force Microscopy (AFM) is a new and relatively cheap method of imaging objects from the
nano- to micron-scale. Surfaces can be scanned in 3D with an AFM, which provides a quick and easy
way to measure dimensions, roughness, and many other material characteristics in scientific fields
across the board.

An atomic force microscope images objects on the scale of angstroms to microns through physical
scanning, rather than optical methods (like conventional microscopes). The basic mechanism of the
AFM is shown in Figure 7. A tip attached to a cantilever interacts with a surface. Light from a laser is
bounced off from the cantilever into a photodetector. From this signal, one measures the deflection
of the cantilever. A sample is placed on a special stage underneath the tip. The stage contains a
piezoelectric driver that is controlled by software. In particular, it may be made to wiggle around in a
raster scan pattern, as well as engage in feedback with the cantilever (constant-force mode).
Variations in the height of the sample cause deflections of the cantilever, which are then picked up
by the photodetector. Through this lab, you should gain a good understanding of how an AFM
works, the types of data you can get from it, how you can use this data to make meaningful
conclusions, and the limitations of the system.

Why AFM over other microscopy techniques?

• Take images in all environments (air, liquid, vacuum). • Interaction with the surface allows for
measurements of physical properties of a surface. • The sample needs not be conductive (compare
to STM). • Examples of surface features that may be imaged include: atomic terraces, carbon
nanotubes, colloidal particles, viruses, DVD textures up to micro lens textures, fractured surfaces,
and complex multi-phase polymers. • AFM can deliver 3D topographic info from the angstrom level
to the micron scale. • Very high vertical resolution (AFM have imaged individual atoms). • Can
manipulate surface features (nanolithography), given a magnetic or specially hardened tip (ours is
not equipped for this).

What is the advantage on an AFM over other microscopes?

Ans: There are several advantages of using an atomic force microscope. Some are:
• It is non destructive (unlike TEM)

• True Vertical height measurement is possible, with a sub nm resolution.

• Material property characterization, such as topography, adhesion, hardness, friction etc., can be
done

• It is not necessary for the surface to be conducting, which is mandatory for STM (scanning
tunneling microscope)

• Dip pen nano lithography and tip induced oxidation enables creation of surface patterns with very
low lateral resolution (few nm).