Thin films

A thin film in general, refers to films with thickness ranging from 0.1 µm to about 300
µm. Coatings such as paint or varnish are typically much thicker. Thin film coatings have
unique properties and hence make them desirable for a variety of reasons including materials
conservation and design flexibility. A large number of materials which are used for coatings
today range from the naturally occurring oxide layer (which protects the surfaces of many
metals such as aluminum, titanium, and stainless steel), to those with very deliberate and
controlled alloying additions to the surface to produce specific properties as follows;

 Chemically stable in the environment where it is used 

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 Adhere well to the substrate 
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 Uniform thickness 
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 Chemically pure or of controlled chemical composition 
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 The low density of imperfections 
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 Optical or magnetic properties, insulator or semiconductor as required for 

particular applications

As the film is inherently fragile, the bonding between the thin film and substrate provides
the structural support. The bonding forces may be primary chemical in nature. Eg. The oxide
lattices of the metal oxide and the glass blend at the interface forming a thin zone of intermediate
composition. The bonding energies are in the range of 250 - 400 kJ/mol. In some cases, the bonds
are based on intermolecular van der Waals and electrostatic forces. The energies are in the range
of 50-100 kJ/mol. Eg. Deposition of polymer film on a metal surface

Uses of thin films

They are used as conductors, resistors and capacitors. They are widely used as optical
coatings on lenses to reduce reflection and to protect the softer glass against scratching. Thin
metallic films have been used as protective coatings on metals. Eg. Silver plating, chrome plating.
Metal tool surfaces are coated with ceramic thin films to increase their hardness. The top of the
drill bit is normally coated with a thin film of tungsten carbide to impart hardness and wear
resistance. The films are applied to the glass to reduce scratching and abrasion and to increase
lubricity.
Formation of thin films

The process of applying a thin film to a surface is known as thin-film deposition or

fabrication. It is the technique for depositing a thin film of material onto a substrate or onto
previously deposited layers. Thin films are formed by different techniques such as physical vapor
deposition (PVD) or chemical vapor deposition (CVD). In PVD there is no change in the chemical
nature of the source and coated material whereas in CVD due to chemical reactions occurring, the
chemical identity of the source and the coated thin film materials are different.

Physical vapor deposition

PVD processes are atomistic deposition processes in which material is vaporized to form a solid
or liquid source in the form of atoms or molecules, transported as vapor through a vacuum or low
pressure gaseous (or plasma) environment to the substrate where it condenses. The material to be
deposited is placed in an energetic, entropic environment so that particles of material escape its
surface. Facing this source is a cooler surface which draws energy from these particles as they
arrive, allowing them to form a solid layer. The whole system is kept in a vacuum deposition
chamber, to allow the particles to travel as freely as possible. Since particles tend to follow a
straight path, films deposited by physical means are commonly directional, rather than conformal.

Typically, PVD processes are used to deposit films with thicknesses in the range of a few
nanometers to thousands of nanometers. The substrates can range in size from very small to very
large, in shape from flat to complex geometries. The source-substrate geometry influences the
ultimate film uniformity. Two principal methods for optimizing film uniformity over large areas
involve varying the geometric location of the source and interposing static as well as rotating
shutters between evaporation sources and substrates. The chemical purity of evaporated films
depends on the nature and level of impurities that (1) are initially present in the source, (2)
contaminate the source from the heater, crucible, or support materials, and (3) originate from the
residual gases present in the vacuum system. Typical PVD deposition rates are 10-100 Å/s.

Fig. PVD: Process flow diagram

Vacuum evaporation is one of the important methods for depositing thin films using PVD
technique.

Vacuum deposition: This method is used to form thin films of substances that can be vaporized
without destroying their chemical identities. Eg. Optical lenses are coated with inorganic materials
such as MgF2, Al2O3 and SiO2. During evaporation, a target consisting of the material to be
deposited is bombarded by a high energy source such as a beam of electrons or ions in a high
vacuum chamber with a pressure of 10-5 torr or less. This dislodges atoms from the surface of the
target, ‘vaporizing’ them. Vaporized atoms from the target move in a straight path to the substrate
to be coated. Finally, the metal atoms get deposited on the substrate surface mounted at an
appreciable distance away from the evaporation source. Uniformity is obtained by rotating the
substrate to be coated.

Fig. Schematic diagram of vacuum deposition

The vacuum environment may serve the following purposes by providing low pressure plasma
environment, a means for controlling gas and vapor composition and a means for mass flow
control into the processing chamber. And reducing the particle density of undesirable atoms and
molecules (contaminants) so that the mean free path for collision is long

Advantages:

 PVD coatings are harder and more corrosion resistant than coatings applied by the
electroplating process.
 Most coatings have high temperature and good impact strength, excellent abrasion
resistance
 • More environmentally friendly than traditional coating processes such as electroplating
and painting.

 It is possible to change the target material without disturbing the system so that multilayer
films can be formed.

Disadvantages:

 It is extremely difficult to coat undercuts and similar surface features 

 High capital cost 
 Some processes operate at high vacuums and temperatures, require skilled operators 
 Processes involving a large amount of heat requires appropriate cooling systems 
 The rate of coating deposition is usually quite slow 

Chemical Vapor Deposition (CVD)

In this method, the surface is coated with a volatile, stable chemical compound at a
temperature below the melting point of the surface. It involves the dissociation and /or chemical
reactions of gaseous reactants in an activated (heat, light, plasma) environment, followed by the
formation of a stable solid product. The deposition involves homogenous gas phase reactions,
which occur in the gas phase, and/or heterogeneous chemical reactions which occur on/near the
vicinity of a heated substrate leading to the formation of powders or films, respectively. It has
been used to produce ultrafine powders and thin films.

In general, the CVD equipment consists of three main components:

(a) Chemical vapor precursor supply system: to generate vapor and deliver to the reactor.

(b) CVD reactor component: consists of a reaction chamber equipped with a load-lock for the
transport and placement of the substrate into the chamber, a substrate holder, and a heating
system with temperature control. The main function is to heat the substrate to the
deposition temperature.

(c) Effluent gas handling system: This component consists of a neutralizing part for the
downstream gases, and /or a vacuum system to provide the required reduced pressure for the
CVD process.

Process principles and deposition mechanism: CVD process involves the following key steps:

1. Generation of active gaseous reactant species

 2. Transport of these gaseous species into the reaction chamber.

3. Gaseous reactants undergo gas phase reactions forming intermediate species.

(a) At a high temperature above the decomposition temperatures of intermediate species

inside the reactor, homogeneous gas phase reaction can occur where the intermediate
species undergo subsequent decomposition and/or chemical reaction.

(b) At temperatures below the dissociation of the intermediate phase,

diffusion/convection of the intermediate species across the heated substrate surface
occur. These intermediate species subsequently undergo steps (4-7)

4. Adsorption of gaseous reactants on to the heated substrate and the heterogeneous reaction
occurs at the gas-solid interface (i.e. heated substrate) which produces the deposit and by-
product species.

5. The deposits will diffuse along the heated substrate surface forming the crystallization
center and growth of the film takes place.

6. Gaseous by-products are removed from the boundary layer through diffusion or
convection.

7. The unreacted gaseous precursors and by-products will be transported away from the
deposition chamber.

Examples: Titanium tetrabromide is evaporated and the gaseous TiBr4 is mixed with hydrogen. The
mixture is then passed over a substrate heated to about 1300 °C, such as silica or alumina. The metal
halide undergoes reaction with hydrogen to form a thin film of titanium metal
TiBr4(g) + 2H2(g) Ti(s) + 4HBr(g)

Films of silicon are formed by decomposing SiCl4 in the presence of H2 at 1200 °C.

SiCl4(g) + 2H2(g) Si(s) + 4HCl(g)

 Fig. Schematic diagram of simplified CVD reactor

Advantages

 Capable of producing highly dense and pure materials without carbon or oxygen
impurities. 
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 Produces uniform films with good reproducibility and adhesion at reasonably high
deposition rates. 
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 Has good throwing power and hence can be used to uniformly coat complex shaped
components and deposit films. 
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 Able to control crystal structure, surface morphology and orientation of the products by
controlling the process parameters. 

 Deposition rate can be adjusted readily. The low deposition rate is favored for the growth
of epitaxial thin films for microelectronic applications. The deposition of thick protective
coatings is favored by a high deposition rate. 
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 Reasonable processing cost using the CVD technique. 
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 The flexibility of using a wide range of chemical precursors such as nitrides, borides,
organometallics which enable the deposition of a large spectrum of materials including
metal carbides, nitrides, oxides and sulfides. 

Drawbacks
 Chemical and safety hazards caused by the use of toxic, corrosive, flammable and/or
 explosive precursor gases. 

 Difficult to deposit multicomponent materials with well-controlled stoichiometry using
multisource precursors because different precursors have different vaporization rates. 

 The use of more sophisticated reactor and /or vacuum system by CVD variants such as
low pressure or ultrahigh vacuum CVD, plasma-assisted CVD and photo-assisted CVD
tends to increase the cost of fabrication. 

Applications:

 Production of high-quality optical fibers suitable for long distance applications. 


 Diamond thin films: They are used as heat sinks for microelectronics and optoelectronics,
sensors, microwave devices, coatings for IR windows in nuclear detectors, UV imaging,
cold cathodes. The potential applications of diamond films involve speaker diaphragms
which are coated with thin films of diamond to provide improved acoustic properties. 

Comparison between PVD & CVD

Features PVD CVD

Mechanism of Thermal energy Chemical reaction

deposition

Deposition rate High Moderate

Deposited species Atoms & ions Precursor molecules

dissociate into atoms

Energy of deposited Low (0.1-0.5 eV) Low; can be high with

species plasma-assisted CVD

Throwing power Poor Good

Nano-materials

Nanoscience and nanotechnology deal with objects that have dimensions in the range from 1
 nm to about 100 nm. Nano-materials are materials which have at least one of their dimension
in the nanometer (1 nm= 10−9 m) range. The physical and chemical properties of nano-materials
differ significantly from those of their bulk counterparts. The new properties are the result of
an increase in the ratio of surface area to volume. This will change the surface effects such as
those that give rise to catalysis, adsorption, adhesion and photonic effects. The reason for this
is that the electrons in nanomaterials are confined within such a small volume that quantum
effects now dominate optical and electronic behavior. Nano-fibers, nano-wires, nano-scale
particles, Nano-channels and nano-tubes are some of the important nanostructures. The nano-
science field is progressing so rapidly that it is probably hard to find any technical areas that
are not useful.

The most important aspects of this field are connected with four issues;

i) The way in which nanoparticles interact with their neighbors in solid arrays or
with the second phase in composite materials.

ii) Miniaturization of electronic circuits below the micro-scale to pack an

increasing number of features into an integrated array.

iii) Development of methods to produce nano-fibers that are of interest in

geological tissue engineering, advanced textiles and filtration technology.

iv) Use of micelles with diameters in the nano range for controlled drug delivery.

Classification

(a) Based on origin

(i) Natural nanomaterials (ii) Artificial nanomaterials

Natural nanomaterials are those which are obtained naturally. Examples:- Carbon-nanotubes
and fibers. Artificial nanomaterials are those which are synthesized artificially Examples:-
Au/Ag nanoparticles, Polymeric nano-composites.

(b) Based on dimension

This classification is based on the number of dimensions which are not confined to the nanoscale
range (<100nm). They may be amorphous or crystalline, single crystalline or polycrystalline,
made up of one or more elements, metallic, ceramics or polymers.
(i) Zero-dimensional: Materials wherein all the dimensions are within the nanoscale range are
called zero-dimensional nanomaterial. Eg: quantum dots.

(ii) 1 dimensional: Here two dimensions are at the nanoscale range, another dimension is not.
This leads to needle-like nanomaterials. Eg: nanotubes, nanorods, nanowires.

(iii) 2 dimensional: Here one dimension is at the nanoscale range, the other two dimensions
are not. They exhibit plate-like shapes. Eg: nanocoatings, nanofilms

(iv) 3 dimensional: These materials are not confined to the nanoscale in any dimension. These are
characterized by having three arbitrarily dimensions above 100 nm. They are also known as bulk
nanomaterials. 3-D nanomaterials can contain dispersions of nanoparticles, bundles of nano wires/
nanotubes as well as multilayers. Eg: Nanocrystalline materials, nanospheres.

There are other types of classifications based on their field of application, shapes, properties,
structures, manufacturing process and morphologies.

Preparation of nanomaterials:

Nanomaterials can be synthesized by two different approaches. They are “Bottom-up” and “Top-
down methods”. Top-down methods start with micro – or macro scale materials, which are then
broken down chemically or physically to nanoparticles. Methods that are used include ball milling,
chemical etching, electrospinning and the vaporization of metals using plasmas. They are slow, not
cheap, and not suitable for large-scale production. Bottom-up methods involve the assembly of very
small units (atoms, molecules or small nanoparticles) to create larger nanomaterials and systems. The
fabrication is much less expensive.

“Bottom-up” Approach:

Sol-gel method

The sol-gel process is a wet-chemical technique used primarily for the fabrication of materials
starting from a chemical solution which acts as the precursor for the preparation of gel by either
discrete particles or network polymers. The process usually consists of five steps:

1. Preparation of a precursor solution: The desired colloidal particles are dispersed in a

liquid to form a sol. Typical precursors are metal alkoxides, which undergo various forms
of hydrolysis and polycondensation reactions. The formation of a metal oxide involves
connecting the metal centers with oxo (M-O-M) or hydroxo (M-OH-M) bridges, therefore
generating metal-oxo or metal-hydroxo polymers in solution.
 2. Deposition of the sol onto a substrate: The sol solution is coated on a substrate by
spraying, dipping or spinning.

3. Formation of gel: The particles in the solid state are polymerized through the removal of
the stabilizing components. This can be done either by heating the sol at a low temperature
or allowing it to stand for a certain duration. This results in the formation of a gel.

4. Drying process: Removal of the remaining liquid (solvent) phase requires a drying
process, which is typically accompanied by a significant amount of shrinkage and
densification.

5. Heat Treatment: After drying, a thermal treatment, or firing process, is often necessary to
favor further poly-condensation reaction and enhance mechanical properties, structural
stability of the gel.

The sol-gel approach is a cheap and low-temperature technique that allows for the fine control of
the product’s chemical composition. Even small quantities of dopants, such as organic dyes and
rare earth elements, can be introduced in the sol and end up uniformly dispersed in the final
product. It can use used as a means of producing very thin films of metal oxides for various
purposes. Examples include Gallium based nano-materials, Dye-doped gel Glasses, Glass
dispersed liquid crystals, Synthesis of glass-metal nano-composite, Metal-silica and Metal oxide-
silica nanocomposites.

“Top Down” Approach:

Ball Milling

In this process, small balls are allowed to rotate around the inside of a drum and drop with gravity
force on to a solid enclosed in the drum. The significant advantage of this method is that it can
be readily implemented commercially. The grinding of ceramics can reduce them to a fine powder
with each individual particle having nanoscale dimensions. It is difficult to avoid contamination
of the nanoparticles by the materials used in the abrasion process and the particle sizes are not
uniform. Polymers cannot be reduced to nanoparticles by grinding because of their molecular
structure and their impact resistance. Ball milling can be used to make a variety of new carbon
types, including carbon nanotubes. It is useful for preparing other types of nanotubes, such as
boron nitride nanotubes and a wide range of elemental and oxide powders. For example, iron
with grain sizes of 13-30 nm can be formed. Ball milling is the preferred method for preparing
metal oxides.

To successfully prepare metal oxides, it is important to keep the crystallites from reacting and to
have an understanding of the kinetic energy transferred during crushing. However, a by-product
can sometimes be useful. In the production of nanocrystalline Zirconia (ZrO2), zirconium chloride
is treated with magnesium oxide during milling to form zirconia and magnesium chloride:
ZrCl4 + 2MgO ZrO2 + 2MgCl2

The by-product, magnesium chloride, acts to prevent the individual nanocrystallites of zirconia
agglomerating. It is washed out at the end of the process.