SPRAY PYROLYSIS

Spray pyrolysis method is based on forming an aerosol from various precursor solutions, which
could be a solution of metallic salts or a colloidal solution. The generated solution droplets
(aerosol) are then very rapidly heated in a furnace at given temperature, thus passing through
several stages: (1) evaporation of the solvent from the surface of the droplets, (2) drying the
droplets containing the precipitated solute, (3) the annealing of the precipitate at high
temperatures (thermolysis), (4) formation of microporous particles of defined phase composition,
(5) formation of solid particles, and (6) sintering of solid particles.

spray pyrolysis technique is a cost-effective method, and, likewise, it does not require the use of
high-quality reagents and the compositions. Furthermore, the morphology and size of particles can
be efficiently controlled by varying the preparative conditions, nature of additives, flow rate, and
concentration of reactants in the precursor solution.

WET CHEMICAL SYNTHESIS

Wet-chemical synthesis routes deal with chemical reactions in the solution phase using precursors
at proper experimental conditions.

THERMAL DECOMPOSITION

A chemical process in which metal precursor when heated above its decomposition temperature
in high boiling solvent is known as thermal decomposition. Metal oxide nanoparticles obtained by
thermal decomposition do not need post-synthesis thermal treatment and these nanoparticles are
highly monocrystalline. Along with monocrystalline nature, particles are monodisperse in size and
shape.

MICROWAVE ASSISTED SYNTHESIS

Rapid heating in the reaction system can be achieved using microwave radiation which enhances

reaction rates and reduces reaction time. Hence, microwave radiation has been used to reduce
reaction time by enhancing reaction kinetics. Microwave radiation can be absorbed by the solvents
having high dielectric constant and produces heat during irradiation and causes uniform heating in
a reaction mixture through dipole-dipole interaction with the alternating electric field generated
by microwave. This property makes microwave energy more efficient for selective heating. This
method requires less energy and time to obtain nanoparticles compared to conventional heating
method. Microwave heating induces homogeneous heating that leads to uniform nucleation and
growth kinetics in entire solution and gives the better quality product, preferably under efficient
mixing.

SOLVOTHERMAL SYNTHESIS

Chemical process performed in closed vessels at above ambient pressure and temperature is
known as solvothermal process. During solvothermal method, reaction vessels or autoclaves are
operated in temperature range of 100 to 1000˚C and pressure range of 1 to 10000 bar. Due to high
pressure and temperature, interactions between reactants are facilitated that gives single
crystalline product. Products obtained with this method are highly selective and reproducible in
terms of purity, crystallinity and morphologies.

Variety of sizes and shapes of metal oxide nanopowders can be obtained by adjusting reaction
parameters (ligand to metalprecursor ratio, temperature, pressure, reaction time, etc.).

SELF ASSEMBLY

Self-assembly synthesis occurs when a disordered system of pre-existing components form a well-
organized structure or pattern as a result of interaction between species [81]. This technique is
most suitable for the synthesis of 2D nanostructured metal oxides, like nanosheets, with precise
molecular self-assembly [82,83]. The self-assembly process can be classified as static or dynamic.
In a static process there is an absence of external influences and the self-assembly of structures is
driven by energy minimization. In a dynamic process, external influences are present and the self-
assembling system will adjust to the surrounding environment [81].

This approach, however, requires a high degree of control to guide the aggre-gation or
organization of the constituent units during the solution preparation and synthesis processes

In the self-assembly system, surfactants have a direct effect on the growth environments of
the“target”materials and help to achieve the controllable fabrication of their nano-structures.

SOL-GEL SYNTHESIS

The sol–gel processing method has been in use for many years for producing metal oxide and
ceramic powders with high purity and high homogeneity. The sol–gel route offers a degree of
control of composition and structure at the molecular level. The process involves the generation of
a colloidal suspension (‘sol’), which is subsequently converted to viscous gel and solid material. In
the process, reactive metal precursors were initially hydrolysed, followed by condensation and
polymerization reactions. The factors that influence the hydrolysis reaction are:

• Nature of the alkyl group

• Nature of the solvent
• Concentration of each species in the solvent
• Temperature
• Water to alkoxide molar ratio
• Presence of acid or base catalysts

Removal of the solvents and appropriate drying are important steps to achieve gel densification.
When a solvent is evaporated from the gel under atmospheric conditions, capillary pressure due
to the interfacial tension of the solvent places a high stress on the gel network. This leads to
considerable shrinkage and fracture of the gel during drying. The resultant hard, glassy and porous
product is called a xerogel. When the liquid within the gel is removed above its critical
temperature and pressure (hypercritical) in an autoclave, the capillary pressure can be eliminated.
The product thus obtained is referred to as an aerogel. An aerogel is generally amorphous and
exhibits several unique properties such as high surface areas and porosities, and low densities and
conductivities.
These include the formation of high purity powders as a result of homogeneous mixing of the raw
materials on the molecular level, and the largescale industrial production of nanopowders. The
disadvantage of the process is the high cost of alkoxide precursors.

PHYSICAL VAPOR DEPOSITION

Physical vapor deposition (PVD) is a vaporization coating technique that involves the transfer of
material at the atomic level. The process can be described according to the following sequence of
steps. (1) The material to be deposited is converted into a vapor by physical means (high-
temperature vacuum or gaseous plasma), (2) the vapor is transported to a region of low pressure
from its source to the substrate, and (3) the vapor undergoes condensation on the substrate to
form a thin film. Typically, PVD processes are used to deposit films with thicknesses in the range of
a few nanometers to thousands of nanometers. However, they can also be used to form multilayer
coatings, graded composition deposits, very thick deposits, and freestanding structures. In general,
this process can be divided into two groups: evaporation and sputtering. Evaporation refers to thin
films being deposited by thermal means, whereas in the sputtering mode the atoms or molecules
are dislodged from the solid target through the impact of gaseous ions (plasma). Both methods
have been further developed into several specific techniques.

Thermal evaporation has a limitation in multicomponent materials since one of the metallic
elements typically evaporates before the other, due to the differences in boiling point and vapour
pressure of the evaporating species. On the contrary, sputtering is capable of depositing high
melting point materials such as refractory metals and ceramics, which are difficult to convert to
nanomaterials by evaporation. Sputtering can result in better stoichiometric control of the film
compared to evaporation techniques.

INERT GAS CONDENSATION

(IGC) combined with thermal evaporation is commonly used to synthesise metallic and metal
oxide nanopowders with a well-defined and narrow size distribution. In this process, a metal is
evaporated inside an ultra-high vacuum (UHV) chamber filled with inert gas, typically helium (Fig.
3.1). The vapourised species then loses energy via collisions with helium molecules. As collisions
limit the mean free path, supersaturation can be achieved above the vapour source. At high
supersaturation, the vapours rapidly form large numbers of clusters that grow via coalescence and
agglomeration. The clusters in the condensing gas are transported by convective flow to a vertical
cold finger surface filled with liquid nitrogen. The removal of particles from the cold finger is
carried out by a scraper assembly. They are collected via a funnel and transported to an in situ
compaction device or coated with a surfactant agent that prevents them from agglomeration. The
scraping and consolidation of particles are carried out under UHV conditions to prevent oxidation
of the metallic nanoparticles. The size, morphology and yield of the clusters in gas condensation
are dependent on three fundamental parameters:

• Rate of supply of atoms to the region of supersaturation where condensation occurs

• Rate of energy removal from the hot atoms via the condensing gas medium
• Rate of removal of clusters once nucleated from the supersaturated region

LASER ABLATION

In this technique, an intense pulsed laser beam irradiates the target of interest, thereby vaporising
atoms and clusters from the target. The total mass ablated from the target per laser pulse is
usually referred to as the ablation rate. Laser ablation in combination with IGC is an attractive
route to synthesize larger amounts of the multicomponent nanocrystalline materials. A typical
laser ablation set up is shown in Fig. 3.3. In the process, atoms ablated by laser pulse tend to
collide with helium gas, losing their kinetic energy rapidly. They eventually condense to form a
cloud consisting of fine nanocrystalline clusters. The production rate of nanoparticles in this
technique varies with helium gas pressure and laser pulse energy. When the laser pulse is
absorbed by the target, energy is first converted to electronic excitation and then into thermal,
chemical and mechanical energy, resulting in evaporation, ablation, plasma formation and even
exfoliation. The ejected species expand into the surrounding vacuum in the form of a plume
containing many energetic species including atoms, molecules, electrons, ions, clusters,
particulates and molten globules, before depositing on the typically hot substrate

ELECTRON BEAM DEPOSITION

Electron beam physical vapor deposition, or EBPVD, is a form of physical vapor deposition in which
a target anode is bombarded with an electron beam given off by a charged tungsten filament
under high vacuum. The electron beam causes atoms from the target to transform into the
gaseous phase. These atoms then precipitate into a solid form, coating everything in the vacuum
chamber (within line of sight) with a thin layer of the anode material [16].
Concisely, high kinetic energized electrons strike the target material, heating it at a spot and
making it melt and sublimate, which is then used for further deposition. The advantage of this
method is the high deposition rate, in addition to the possibility of depositing materials which
range from conducting to insulating states.

SPUTTERING DEPOSITION

Sputtering is a vacuum-based PVD method, which involves the ejection of electrons from a target
or by striking the target with high-speed ions. The principle of sputtering is the transfer of
momentum by which the atoms of the target are ejected by ion bombardment. The atomic weight
of the gas used for sputtering may be close to the atomic weight of the target material, which is
the most significant criterion. For example, the synthesis of oxide materials through sputtering,
where only oxygen should be used as the reactive gas.

The sputtering deposition of materials takes place in the following steps:

1.Mostly Ar-like neutral gases are used to generate plasma that is in-between the two electrodes
due to the collision of electrons with gaseous molecules.

2. While applying the potential among the two electrodes, the ions are accelerated toward the
target material.

3.The ions that have suitable energy may strike the target species that leads to ejection of the
material easily.
4.Finally, the ejected material is easily transported and deposited onto the desired substrate.

Sputter deposition has some advantages; elements, alloys and compounds can all be sputtered
and deposited. Also, the sputtering target provides a stable, long-lived vaporization source.

CHEMICAL VAPOR DEPOSITION

Chemical vapour deposition (CVD) is a process where one or more gaseous adsorption species

react or decompose on a hot surface to form stable solid products. The main steps that occur

in the CVD process can be summarized as follows: 1. Transport of reacting gaseous species to the
surface 2. Adsorption of the species on the surface 3. Heterogeneous surface reaction catalysed by
the surface 4. Surface diffusion of the species to growth sites 5. Nucleation and growth of the film
6. Desorption of gaseous reaction products and transportation of reaction products away from the
surface

Generally, CVD processes consist of chemically reacting a volatile compound of the material to be
deposited with other gases to produce a nonvolatile solid that deposits at atomic level on a
suitable substrate. The versatile chemical nature of CVD processes is demonstrated by the wide
range of reactants and precursor that can be used to deposit a given film. In CVD, as in PVD, vapor
supersaturation affects the nucleation rate of the film, whereas substrate temperature influences
the rate of film growth. These two factors together influence the extent of epitaxy, grain size, grain
shape and texture. Low gas supersaturation and high substrate temperatures promote the growth
of single crystal films on substrates. High gas supersaturation and low substrate temperatures
result in the growth of polycrystalline, nanocrystalline, or even amorphous films.

NANOLITOGRAPHY

Micro- and nanolithography is the technology that is used to create patterns with a feature size
ranging from a few nanometers up to tens of millimeters.

Lithography techniques are divided into two types by the use of masks or templates: masked
lithography and maskless lithography. Masked lithography makes use of masks or molds to
transfer patterns over a large area simultaneously, thus, enabling a high-throughput fabrication
up to several tens of wafers/hr.

On the other hand, maskless lithography, such as electron beam lithography [22-29], focused
ion beam lithography [30-33], and scanning probe lithography [34-44], fabricates arbitrary
patterns by a serial writing without the use of masks. These techniques create patterns in a
serial manner which allows an ultrahigh-resolution patterning of arbitrary shapes with a
minimum feature size as small as a few nanometers.

AFM based

Direct contacting, writing or scratching is referred to as a mechanical action of the AFM tip that is
used as a sharply pointed tool in order to produce fine grooves on sample surfaces. Although
direct scratching creates grooves with high precision, low quality results are often obtained due to
tip wear during the process.
DIP-PEN

In dip-pen nanolithography (DPN), the tip of an AFM operated in air is ‘inked’ with a chemical of
interest and brought into contact with a surface. The ink molecules flow from the tip onto the
surface similar to a fountain pen. The water meniscus that naturally forms between the tip and the
surface enables the diffusion and transport of the molecules. Inking can be done by dipping the tip
in a solution containing a small concentration of the molecules, followed by a drying step (e.g.,
blowing dry with compressed difluoroethane).