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Thin Film Deposition Techniques PDF
Thin Film Deposition Techniques PDF
Part-A
Part-B
Characterization Techniques
2. B.1. Introduction 77
2. B.1.1. Cyclic Voltammetery (CV) and Linear 77
Sweep Techniques (LSV)
2. B.1.2. Thickness Measurements 82
2. B.1.3.Optical Absorption 82
2. B.1.4. X-Ray Diffraction Technique (XRD) 85
2. B.1.5. Raman Spectral Study 86
2.B.1.6 Scanning Electron Microscopy (SEM). 92
2. B.1.7. Energy Dispersive Analysis by x- Rays 95
measurement (EDS)
2. B.1.8.Transport Properties 95
2. B.1.9. Atomic Force Microscopy (AFM) 100
References 102
45
Chapter-II
Part-A
The field of material science and engineering community’s ability to conceive the novel
materials with extraordinary combination of chemical, physical and mechanical,
properties has changed the modern society. There is a increasing technological
progress. Modern technology requires thin films for different applications [1]. Thin film
technology is the basic of astounding development in solid state electronics. The
usefulness of the optical properties of metal films, and scientific curiosity about the
behavior of two-dimensional solids has been responsible for the immense interest in the
study science and technology of the thin films. Thin film studies have directly or
indirectly advanced many new areas of research in solid state physics and chemistry
which are based on phenomena uniquely characteristic of the thickness, geometry, and
structure of the film [1].
When we consider a very thin film of some substance, we have a situation in which the
two surfaces are so close to each other that they can have a decisive influence on the
internal physical properties and processes of the substance, which differ, therefore, in a
profound way from those of a bulk material. The decrease in distance between the
surfaces and their mutual interaction can result in the rise of completely new
phenomena. Here the one dimension of the material is reduced to an order of several
atomic layers which creates an intermediate system between macro systems and
molecular systems, thus it provides us a method of investigation of the microphysical
nature of various processes. Thin films are especially appropriate for applications in
microelectronics and integrated optics. However the physical properties of the films like
electrical resistivity do not substantially differ from the properties of the bulk material.
For a thin film the limit of thickness is considered between tenths of nanometer and
several micrometers.
46
Thin film materials are the key elements of continued technological advances
made in the fields of optoelectronic, photonic, and magnetic devices. The processing of
materials into thin films allows easy integration into various types of devices. The
properties of material significantly differ when analysed in the form of thin films. Most of
the functional materials are rather applied in thin film form due to their specific electrical,
magnetic, optical properties or wear resistance. Thin film technologies make use of the
fact that the properties can particularly be controlled by the thickness parameter. Thin
films are formed mostly by deposition, either physical or chemical methods. Thin films,
both crystalline and amorphous, have immense importance in the age of high
technology. Few of them are: microelectronic devices, magnetic thin films in recording
devices, magnetic sensors, gas sensor, A. R. coating, photoconductors, IR detectors,
interference filters, solar cells, polarizer’s, temperature controller in satellite,
superconducting films, anticorrosive and decorative coatings.
Although the study of thin film phenomena dates back well over a century, it is
really only over the last four decades that they have been used to a significant extent in
practical situations. The requirement of micro miniaturization made the use of thin and
thick films virtually imperative. The development of computer technology led to a
requirement for very high density storage techniques and it is this which has stimulated
most of the research on the magnetic properties of thin films. Many thin film devices
have been developed which have found themselves looking for an application or,
perhaps more importantly market. In general these devices have resulted from research
into the physical properties of thin films.
Thirdly, much of the finance for early thin film research originated from space and
defence programmes to which the device cost is less important than its lightweight and
other advantages, the major applications of thin film technology are not now exclusively
in these areas but rather often lie in the domestic sector in which low cost is essential
[1,2].
Thin film materials have already been used in semiconductor devices, wireless
communications, telecommunications, integrated circuits, rectifiers, transistors, solar
cells, light-emitting diodes, photoconductors, light crystal displays, magneto-optic
memories, audio and video systems, compact discs, electro-optic coatings, memories,
multilayer capacitors, flat-panel displays, smart windows, computer chips, magneto-
optic discs, lithography, micro electromechanical systems (MEMS), and multifunctional
emerging coatings, as well as other emerging cutting technologies.
i) Optical Coatings:
ii) Photovoltaic:
In the familiar rigid solar panel, the energy of incoming photons is converted to
electricity in cells containing two thin layers of crystalline silicon. What makes roll-to-roll
production of flexible film solar products possible is replacement of the crystalline silicon
with amorphous silicon, supplied in high-solids slurries that can be deposited onto
substrates by web-converting processes like slot die coating. Microlayer film, EDI can
48
outfit its Contour cast film dies with a new system, based on technology licensed from
‘The Dow Chemical Company’, which makes it possible to produce film of standard
thickness, yet with dozens of exceedingly thin ‘micro-layers’. The multiple layer-to-layer
interfaces create a torturous path for gas molecules and thus substantially increase the
barrier properties of the film. This is critical for photovoltaic applications, which require
barrier layers to prevent performance losses caused by infiltration of oxygen or moisture
vapour.
"Though as yet little known in the solar industry, the continuous-web production
methods familiar to EDI and its converter customers are a key to developing high-
volume, low-cost production of solar electric systems," said Miller. "In working with solar
product manufacturers, EDI draws on extensive experience in other applications that
require thin-gauge, optically clear, close-tolerance films and coatings with critical
functionalities, including films and coatings for flat panel displays and flexible batteries
particularly relevant, since solar cells are a kind of battery. In comparison with
conventional coating methods, such as spray, roll, and spin coating, slot dies provide
greater control over coating weight and distribution because they are closed systems
into which coating material is pumped at closely pre-determined rates; in turn this
greater control makes possible thinner coatings,"
Many in the solar power industry and the investment community, believe the
arrival of grid parity, the point when cost of electricity generated by a rooftop
photovoltaic (PV) cell system is equivalent to that purchased from an electrical utility will
mark a major inflection point for the market that will deliver a huge increase in growth.
However, even when true grid parity arrives, it’s unlikely to generate an abrupt rise in
solar system installations due to the high upfront costs and the long-term return of
investing in a rooftop photovoltaic system, according to iSuppli Corp. In fact, growth is
set to moderate during the years when grid parity arrives for various regions of the world
as the industry enters a more mature phase.
49
iii) Semiconductor:
v) Optoelectronic:
Since first patents were in the 1950, the idea of storing charge in the electric
double layer that founds at the interface between a solid and an electrolyte has
presented itself as an attractive notation while was considerable development was
carried out by the slander oil company, Cleveland, Ohio (SOHIO) in the 1960 a lack of
sales lead them to license the technology to Nippon electric company. The first high
power double layer capacitor were developed for military applications by the pinnacle
research institute in 1982.
Gas sensors generally operate different principles and various gas sensing
elements have been developed have been past years, out of which resistive metal oxide
sensors comprise a significant part. However these sensing elements typically operate
at an elevated temperature for maximum performance. This makes higher power
consumption which is not suitable for the inflation. Over the last decayed carbon
nanotube has attracted considerable attention, and great efforts have been made to
exploit their unusual electronic and mechanical properties. These properties make them
potential candidates for building blocks of active materials in nanoelectronics, field
emission devices, gas storage and gas sensors. Among these the room temperature
gas sensing property is very attractive for many applications.
The vast varieties of thin film materials, their deposition processing and
fabrication techniques, spectroscopic characterization and optical characterization
probes that are used to produce the devices. It is possible to classify these techniques
in two ways [1, 2].
Physical Process
Chemical Process.
Physical method covers the deposition techniques which depends on the
evaporation or ejection of the material from a source, i.e. evaporation or sputtering,
whereas chemical methods depend on physical properties.Structure-property
relationships are the key features of such devices and basis of thin film technologies.
Underlying the performance and economics of thin film components are the
manufacturing techniques on a specific chemical reaction [3]. Thus chemical reactions
may depend on thermal effects, as in vapour phase deposition and thermal growth.
However, in all these cases a definite chemical reaction is required to obtain the final
film.
When one seeks to classify deposition of films by chemical methods, one finds
that they can be classified into two classes. The first of these classes is concerned with
the chemical formation of the film from medium, and typical methods involved are
54
electroplating, chemical reduction plating and vapour phase deposition. A second class
is that of formation of this film from the precursor ingredients e.g. iodization, gaseous
iodization, thermal growth, sputtering ion beam implantation, CVD, MOCVD and
vacuum evaporation.
The methods summarized in table 2.1 are often capable of producing films
defined as thin films, i.e. 1 µm or less and films defined as thick films, i.e. 1 µm or more.
However, there are certain techniques which are only capable of producing thick films
and these include screen printing, glazing, electrophoretic deposition, flame spraying
and painting.
55
PHYSICAL CHEMICAL
2.A.3.1.2 Evaporation:
Evaporation or sublimation techniques are widely used for the preparation of thin
layers. A very large number of materials can be evaporated and, if the evaporation is
undertaken in vacuum system, the evaporation temperature will be very considerably
reduced, the amount of impurities in the growing layer will be minimised.
2.A.3.1.3 Sputtering:
The advantages of physical methods are laid in dry processing, high purity and
cleanliness, compatibility with semiconductor integrated circuit processing and epitaxial
film growth. However, there are certain disadvantages such as slow deposition rates,
difficult stoichiometry control, high temperature post deposition annealing often required
for crystallization and high capital expenditure[6].
Among chemical and electrochemical methods the most important are chemical vapour
deposition, cathode electrolytic deposition, anodic oxidation and Chemical Bath
Deposition
the control of the usual deposition process variables, the reactions of the reactants must
be well understood. Various types of chemical reactions are utilised in CVD for the
formation of solids are pyrolysis, reduction, oxidation, hydrolysis, synthetic chemical
transport reaction etc.
Thin films can be deposited by number of physical and chemical techniques and
can be classified as shown in Table 2.1. Among the methods mentioned in the Table
2.1, the chemical methods are economical and easier than that of the physical methods.
Physical methods are expensive but give relatively more reliable and more reproducible
results. Most of the chemical methods are cost effective, but their full potential for
obtaining devise quality films has not been fully explored [2]. But there is no ideal
method to prepare thin films, which will satisfy all possible requirements. Among the
chemical methods, the electrodeposition technique (ED) is the most popular technique
today because large number of conducting and semiconducting thin films can be
prepared by this technique.
Among the chemical methods of thin film depositions, Chemical Bath Deposition
(CBD) is probably the most simplest method available for this purpose and it is also
known as Chemical Solution Deposition (CSD) or Chemical Deposition (CD). It is not a
new technique as early as in 1835 Liebig reported the first deposition of silver, the silver
mirror deposition using a chemical solution technique. The deposition technique was
first described in 1869. The only requirements of these methods are a vessel to contain
the solution (usually an aqueous solution of common chemicals) and the substrate on
which deposition is to be carried out. In addition to this various complications such as
some mechanism for stirring and a thermostated bath to maintain a specific and
constant temperature are options that may be useful. The first general review on this
topic was published by Chopra et al. in 1982[7]. Next review was published by
Lokhande [8]. Then a comprehensive and general review was published by Lincoln et
al. in 1998[9].
59
This rate control can be accomplished by generating the sulphide slowly in the
deposition solution. The rate of generation of sulphide, and therefore reaction, can be
controlled through a number of parameters, in particular the concentration of sulphide
forming precursor, solution temperature, and pH. Although CBD can be carried out both
acidic and alkaline solutions, most of the CBD reactions have been carried out in
alkaline solutions.
In spite of the fact that CBD has been in use for a long time and that the
reactions involved appear to be quite simple, the mechanism of the CBD process is
often ambiguous There are several different mechanisms of CBD. These can be divided
into four fundamentally different types. Deposition of Cdmium Sulphide is taken as an
example.
2+ 2+ 2+
[Cd(NH3)4] Cd + 4NH3 (dissociation of complex to free Cd ions) ------ (2.1)
- 2-
(NH2)2CS + 2OH S + CN2H2 + 2H2O (formation of sulphide ions) --(2.2)
2+ 2-
Cd + S CdS (CdS fromation by ionic reaction) -------------- (2.3)
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2+
nCd + 2nOH [Cd(OH)2]n (formation of a Cd(OH)2 cluster) ------------ (2.4)
2-
[Cd(OH)2]n + nS nCdS + 2nOH (exchange reaction) ------------- (2.5)
2+ 2+
(NH2)2CS + Cd [(NH2)2CS-Cd] --------------- (2.6)
2+ -
[(NH2)2CS-Cd] + 2OH CdS + CN2H2 + 2H2O -------------- (2.7)
------------ (2.9)
The last reaction continues until conversion of all the Cd(OH)2 to CdS.
The first two mechanisms involved free sulphide ions (or other anions). While the
last two are based on breaking of a carbon-chalcogen bond and do not involve
formation of free chalcogenide [10].
Chemical reaction either takes place on the surface of the dipped substrate or in
the solution itself, where a mixing of components on the surface to be coated is
required. Most of the coatings are formed in a two step fashion;
i) “Sensitizing” the surface for the nucleation reaction of the adhering coating
layer.
ii) Deposition of coating by selected reactions.
The most widely used deposition methods are listed below
The chemical bath deposition method for the preparation of thin films has
recently been shown to be an attractive technique because of its simplicity,
convenience, low cost and low temperature, and it has been successfully used for
depositing ternary metal chalcogenide thin films [11]. Understanding of the chemistry
and physics of the various process involved in a deposition processes has now made
possible to obtain undoped/doped, multicomponent semiconductor thin films of
usual/unusual and metastable structure.
No single technique is ideally suited for preparation of large area thin films with
all the desired properties. Hence choice and selection of deposition process plays a vital
role in the formation of good quality thin films, and while selecting a particular technique
it should be tested satisfactorily for the following aspects:
Cost effectiveness.
It should be able to deposit desired material.
Film microstructure and deposition rate should be controlled.
Stoichiometry should be maintained as that of the starting materials.
Operation at reduced temperature.
62
It is ideally suited for large area thin film depositions; substrate surfaces of
both accessible and non-accessible nature could easily be deposited.
It is simple, inexpensive and does not require sophisticated instrumentation.
The deposition is usually at low temperature and avoids oxidation or corrosion
of the metallic substrates.
Stoichiometry of the deposits can be maintained since the basic building
blocks are ions rather than atoms.
Slow film formation process facilitates better orientation of the crystallites with
improved grain structures over the substrate surface.
Doped and mixed films could be obtained by merely adding the mixant /
dopant solution directly into the reaction bath.
Electrical conductivity of the substrate material is not an important criterion.
63
This is a standard method of electroplating. Two metal electrodes are dipped into
an electrolyte solution and on application of an external field across the electrodes;
metal ions from the solution are deposited on cathode as a film. Deposition of the films
is mainly controlled by the electrical parameters such as, electrode potential and current
density.The mass of the substance deposited is proportional to the amount of electrical
charge. The proportionality constant is the electrochemical equivalent of the given
substance, which is for example, is 2.04 x 10-3 g./C, for Au and 0.09 x 10-3 g/C for Al.
By this method it is possible to deposit films only on conducting substrates.
The electrodeposition is the simplest of the chemical methods, and it has many
advantages [2] like
2. In most of the cases the deposition can be carried out at room temperature enabling
to form the semiconductor junctions without interdiffusion.
4. Toxic gaseous precursors need not to be used (unlike gas phase methods).
5. The deposition process can be controlled more accurately and easily
Electrodeposition of metallic films has long been known and used for preparing
metallic mirrors and corrosion resistant surfaces, etc. During last two decades,
electrodeposition has become a tool of materials technology for obtaining films of wide
variety of materials including binary-ternary semiconductors, high Tc superconductors,
polymer films etc.
b) Mechanism of Electrodeposition:
1. Electrolyte
2. Cathode and anode
3. Source of electricity.
65
When direct current is passed through cathode and anode, immersed in electrolyte
containing the metal(s) ions, the metal ions get attracted towards the cathode,
neutralized electrically by receiving electrons and get deposited on cathode. The
deposition is controlled by monitoring the amount and the rate of charge passing
through the electrolyte. Thus the electrical energy is used to cause chemical change.
On the other hand, if the electrolyte contains more than one ionic species that can be
simultaneously deposited then the electrodeposition process for, say two types of ionic
species can be written as
N+ + e- N ------ (2.12)
Or
66
Q=ct ……….(2.14)
W c t or W=zct ……….(2.15)
An important implication of the Faraday’s second law is that the ratio of the mass
of electrodeposit to its gramequivalent weight is a constant equivalent to 1 Faraday or
96,500 Coulombs (c) or 26.3 ampere-hour (Ah).
67
d) Electrode-Electrolyte Interface:
1. A compact double layer, known as Helmholtz double layer adjacent to the electrode,
and
2. A diffuse layer known as Gouy-Chapman layer.
The Helmholtz Layer:
The Helmholtz double layer is a dense layer of ions stuck to the electrode. In this
region the potential varies linearly with distance as shown in fig. 2.2(b). This dense layer
is divided into inner and outer Helmholtz planes. The inner Helmholtz Plane (IHP) is
adjacent to the electrode surface and consists of completely oriented solvent dipoles
and specifically adsorbed (or contact-adsorbed) ions. The orientation of solvent dipoles
depends on the specific interaction with the electrode surface as well as the electric
field. Large ions with negative free energy of contact adsorption are expected to be
contact adsorbed. In aqueous system, the cations react rather strongly with the water
molecule, and their inner hydration sphere is retained. This limits their closest distance
68
of approach to the electrode. They are thus separated from the electrode by
approximately one or two electrolyte molecules. On the other hand, anions interact
weakly with electrolyte; hence hydration sheath is not covered on them. Thus the
closest distance of approach could correspond to direct contact; they can be a part of
IHP. The Outer Helmholtz Plane (OHP) consists of solvated ions (usually cations) at the
closest distance of approach from the electrode surface. The OHP thus consists of
partly ionized electrolyte molecule dipole layers.
The size of the ions forming the outer Helmholtz plane (OHP) is such that the
sufficient number of them cannot neutralize the charge on the electrode. Therefore, the
remaining charges are held with increasing disorder as the distance from the electrode
surface increases and the electrostatic forces become weaker and dispersion by
thermal motion is more effective. These less ordered charges forcing opposite to that on
the electrode constitutes the diffuse part of double layer. Thus, all the charges, which
neutralize on the electrode, are held in a region between OHP and the bulk of
electrolyte. The additional charges required to neutralize the total charge on the
electrode forms the Gouy-Chapman layer or diffuse layer.
1. Ionic transport
2. Discharge
69
a. In the electrolyte
b. Near the electrode
c. At the electrode
70
1000 A
Discharge
Electrode
Electrolyte Ionic
transport
D d dc
j zF C D cv …….. (2.16)
RT dx dx
Where, F is the Faraday’s constant, is the viscosity of the electrolyte, R is the gas
constant and D is the diffusion coefficient. The three terms in the parenthesis
respectively describe the contributions of migration, diffusion and convection processes
to the mass transport towards the electrode.
electrons from the cathode (or donates electrons to the anode). This ionic discharge
occurs between 10 to 1000 Å from the electrode.
The entire pathway for the growth can be divided into following steps (figure 2.4) [2]
The preparative parameters directly affect the structural, morphological and optical
properties of the electrodeposits. The various preparative parameters like substrate,
applied field and current density, bath temperature, complexant and pH of the bath etc.
should be controlled to obtain uniform, smooth and stoichiometric electrodeposits [14-
15]. Some preparative parameters are discussed below.
i. Substrate:
The rise in bath temperature enhances the rate of diffusion and increases ionic
mobility, hence the increase in conductivity of the bath. The increase in temperature
increases the rate of crystalline growth favoring the coarse deposits. This increase in
crystal size corresponds to decrease in polarization. At higher temperature, current
densities increase, which increases the rate of nucleation, hence fine-grained, smooth
deposits can be obtained. The rise in bath temperature decreases the hydrogen over
voltage so facilitates the evolution of gas, as well as precipitation of basic salts. The
opposing effects make it difficult to predict the choice of bath temperature, however, it
can be optimized by performing actual experiments.
iii. Current Density:
At lower current densities (or over-potentials) the discharge of ions occurs slowly,
so the growth rate decreases but increases the crystallinity forming closely packed
structures. As the current density is raised, the nuclei formation rate will increase and
the deposits become fine grained. At higher current densities, the rate of discharge of
ions becomes greater compared to rate of supply of ions and there is duplicity of ions
near the cathode, which favours the growth perpendicular to the substrate surface.
Usually spongy, dendritic growth can be observed under this condition. Secondly, at
very higher current densities, hydrogen evolution occurs at faster rate, which interferes
the crystal growth and spongy, porous deposits may be obtained. This can also favour
the precipitation of hydrous oxides or basic salts due to increase in local pH.
75
In order to operate a bath with optimum efficiency and maintain the desired
physical properties of the deposit, control of pH of plating bath is necessary. Besides
too low pH may lead accumulation of hydroxide ions in the vicinity of the cathode and
consequent precipitation of basic salts, which may get included in electrodeposition,
thereby altering deposit properties. All aqueous solutions contain H+ ions, infact in every
deposit from an aqueous bath, there is a possibility of the hydrogen gas evolution at the
cathode due to H+ ions. It takes place, the efficiency of metal deposition is lowered. As
this efficiency and hydrogen discharge potential partly depends upon hydrogen ion
concentration, at low pH, the bath permits the use of higher current density to produce a
sound deposit with relatively high efficiency.
vi. Addition Agents:
The unstable metal ions are capable of combining chemically with neutral
molecules and with ions of opposite sign to form stable complex ion. The combination is
through the covalent bond, when neutral molecules interact with positively charged
metal ions to yield negatively charged complex ions. Complex compound in a plating
bath serves two purposes. Firstly they make possible to maintain a high metal
concentration but low metal ion concentration. The complex ions of the complex
compound serve as reserves and continuously supply of the simple ions necessary for
the discharge at the cathode occurs. A low metal ion concentration enables the
production of deposits with small grains and improves the throwing power. Secondly,
complex formation enables us to enhance appreciably the solubility of slightly soluble
salts.
77
Part-B
Thin Film Characterization Techniques
2. B.1 Introduction
t1
This means that at very high sweep rates capacitive current must be subtracted in order
to obtain accurate values of the rate constant.
The kinetics of electrode reactions does not measure the rate of electron transfer
itself, as this is an adiabatic process, following Frank-Condon principle, and occurs in
79
approx. 10-16s. What it measures is the time needed for the species, once they have
reached the interfacial region, to arrange themselves and their ionic atmospheres into
position for electron transfer to be able to occur. According to kinetics of the reactions
there are three types of reactions,
1. Reversible
2. Irreversible
3. Quasi reversible
Reversible system
Fig. 2.6 shows a typical curve for linear sweep voltammetry recorded for
reversible reaction of the type O + ne- R. The curve can be understood in the
following way. On reaching a potential where the electrode reaction begins, the current
rises as in a steady state voltammogram. However, the creation of a concentration
gradient and consumption of electroactive species means that, continuing to sweep the
potential, from a certain value just before the maximum value of the current, peak
current, the supply of electroactive species begins to fall. Owing to depletion, the current
then begins to decay, following a profile proportional to t-1/2 which is shown in Fig.2.9,
similar to application of potential step. Fig. 2.7 shows the typical cyclic voltammetry for
reversible system.
Normalized current
reversible system.
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Normalized current
reversible system
Ip 2 ……….(2.18)
Ep independent of
Ep- Ep/2 = 56.6/n Mv ………(2.19)
And for cyclic voltammetry alone
Irreversible System
In the case of an irreversible reaction of the type O + ne- R. liner sweep and
cyclic voltammetry lead to the same voltammetry profile, since no inverse peak appears
on inverting the scan direction.
81
Normalized current
The extent of irreversibility increases with increase in sweep rate, while at the
same time there is a decrease in the peak current relative to the reversible case and an
increasing separation between anodic and cathodic peaks. On increasing sweep rate,
there is less time to reach equilibrium at the electrode surface; reactions which appear
as reversible at low sweep rates, can be quasi reversible at high sweep rates. Fig. 2.9
shows the effect of increasing irreversibility on the shape of cyclic voltammogram.
t = m / A.b . ...........(2.22 )
where, ‘m’ is the mass of the film deposited on area ‘A’ of the substrate and ρb is the
density of the material in the bulk form. The mass ‘m’ of the film has been measured by
using a single pan microbalance. As reported in many studies [19, 20], the thin film
density varies between 0.74 to 0.87 times the bulk densities owing to the porosity.
Hence a correction factor of 0.8 is applied to the bulk density in equation 2.22.
Basically there are two types of optical transitions that can occur at the
fundamental edge of the crystalline semiconductor, direct and indirect. Both involve the
83
where A is a constant depending upon the transition probability for direct transition, n =
1/2 or 3/2 depending on whether the transition is allowed or forbidden in the quantum
mechanical sense. Eg is the optical gap.
Let’s visualize a situation given in Fig. 2.10 (b) where interband transition takes
place between different kstates. Since these must satisfy the momentum conservation
laws, the only way such transition can take place is through the emission or absorption
of a phonon with wave vector q i.e.
k' q = k + K 2.24
The transitions defined by equation (2.10) are termed as indirect transitions. For
indirect transitions [22]
The band gap energy ‘Eg’ is determined by extrapolating the linear portion of the
plot of (h)n against h to the energy axis at = 0.
84
E Conduction Conduction
Band Band
k'
h = Eg
k k
O k' k
k
Valance Band Valance Band
(a) (b)
Fig. 2.10 - “Direct interband optical transitions” for a) direct band and b) indirect
band semiconductors. The transitions are represented by vertical arrow.
85
Detector
Diverging Slit
X-ray Receiving Slit
Source
2
Sample
For thin films, the powder technique in conjunction with diffractometer is most
commonly used. In this technique the diffracted radiation is detected by the counter
86
tube, which moves along the angular range of reflections. The intensities are recorded
on a computer system. The‘d’ values are calculated using relation (2.8) for known
values of , and n. The X- ray diffraction data thus obtained is printed in tabular form
on paper and is compared with Joint Committee Power Diffraction Standards (JCPDS)
data to identify the unknown material. The sample used may be powder, single crystal
or thin film. The crystallite size of the deposits is estimated from the full width at half
maximum (FWHM) of the most intense diffraction line by Scherrer's formula as follows
[28]
0.9
D 2.27
cos
where, D is crystallite size, is wavelength of X-ray used, is full width at half maxima
of the peak (FWHM) in radians, is Bragg's angle. The X- ray diffraction data can also
be used to determine the dimension of the unit cell. This technique is not useful for
identification of individuals of multilayer or percentage of doping material.
Scattered Radiations
Detector
Note that the detector is orthogonal to the direction of the incident radiation, so
as to observe only scattered light. The source needs to provide intense monochromatic
radiation, and usually laser. The criteria for a molecule to be Raman active are also
different to other types of spectroscopy, which required permanent magnetic dipole
moment, at least for diatomic molecules. A molecule will only be Raman if the following
gross selection rule is fulfilled.
The oscillating electric field of a photon causes charged particles (electrons and,
to a lesser extent, nuclei) in the molecule to oscillate. This leads to an induced electric
dipole moment, µind,
88
This induced dipole moment then emits a photon, leading to either Raman or
Raleigh scattering. The energy of this interaction is also dependent on the polarizability:
By comparison with the equation for the interaction energy for other forms of
spectroscopy, it can be seen that the energies of Raman transitions are relatively weak.
To counter this, a higher intensity of the exciting radiation is used.
For Raman scattering to occur, the polarizability of the molecule must vary with
its orientation. One of the strengths of Raman spectroscopy is that this will be true for
both heteronuclear and homonuclear diatomic molecules. Homonuclear diatomic
molecules do not possess a permanent electric dipole, and so are undetectable by other
methods such as infrared.
2.1 Rotational
J=±1 ……….2.29
J=±2 ………..2.30
2.2 Vibrational
= ±1 ………2.31
intensity.
Consider a light wave as a stream of photons each with energy h When each
photon collides with a molecule, many things may happen, 2 of which are
considered below:
This is when the photon simply 'bounces' off the molecule, with no exchange in
h
Source Molecule
h
90
This is when there is an exchange of energy between the photon and the
h
Source Molecule
hr hr
3) Raman Scattering
The molecule may either gain energy from, or lose energy to, the photon. In the
diagram below, 3 energy states of the molecule are shown (E1, E2, E3). The molecule is
originally at the E2 energy state. The photon interacts with the molecule, exciting it with
an energy h. However, there is no stationary state of the molecule corresponding to
this energy, and so the molecule relaxes down to one of the energy levels shown. In
doing this, it emits a photon. If the molecule relaxes to energy state E1, it will have lost
energy, and so the photon emitted will have energy hr1, where h1 > h. These
transitions are known as anti-Stokes transitions. If the molecule relaxes to energy state
E3, it will have gained energy, and so the photon emitted will have energy hr2, where
hr2 < h. These transitions are known as Stokes transitions
For rotational spectroscopy, both Stokes and anti-Stokes transitions are seen.
For vibrational spectroscopy, Stokes transitions are far more common, and so anti-
Stokes transitions can effectively be ignored [29].
Electron Beam
Secondary Electrons
Electromotive force
Transmitted Beam
The signals are transferred from point to point and signal map of the scanned
area is displayed on a long persistent phosphor C.R.T. screen. Change in brightness
represents change of a particular property within the scanned area of the specimen [31].
The ray diagram of scanning electron microscope is shown in Fig. 2.17. The scattering
cross section for back-scattered electrons is given as [32],
2
30 Z
Q 16.2 10 E cot 2 2.32
Here the cross-section is proportional to Z2. Hence, the back-scattered electrons are
used for the Z contrast or for compositional mapping.
Surface transport phenomena are well known to have a strong influence on the
electronic properties of bulk semiconductors. When transport takes place through thin
specimens, the carriers are being subjected to considerable scattering by the boundary
surface in addition to normal bulk scattering. This additional scattering will reduce the
effective carrier mobility below the bulk value and will thus give rise to quantum size
effects. A study of these size effects can yield information on the electronic structure of
a surface and is therefore of considerable fundamental and practical importance. These
phenomena play an important role in the transport properties of semiconducting film of
about 1m thickness and having carrier concentration upto 1018 cm-3. Surface transport
phenomena in bulk semiconductor have received much attention in recent years. An
excellent review of the subject is given by Pulliam et al. [34]. The important transport
properties i.e. electrical resistively, thermoelectric power (TEP) are discussed below.
96
a) Electrical Conductivity:
The use of thin films as resistors, contacts and interconnections has lead to
extensive study of conductivity, its temperature dependence, the effect of thermal
processing stability and so on. Investigations of the electrical resistivity as a highly
structure sensitive properties make it possible to gain insight into the structural and
electrical properties of the metal film which is important from both the theoretical and
practical point of view. The contact techniques are most widely used for the
measurement of resistivity. These techniques include two-point probe, four point probe
and the spreading resistance methods. The two-point method is simple and easy to use.
In this technique a constant current I is passed through a sample of known dimensions
(cross-sectional area ‘A’). And the d.c. voltage ‘V’ between two fixed position probes
(separation‘d’) measured either with impedance voltmeter or potentiometrically. For
uniform sample resistively is given by
Where E is the activation energy for the conduction is Boltzmann constant and 0 is
the pre exponential constant depending on the material.
Fig. 2.18 A and 2.18 B shows photograph and schematic diagram of the
electrical conductivity measurement unit. The two brass plates of the size 10 x 5 x 0.5
cm are grooved at the centre to fix the heating elements. Two strip heaters (65 Watts)
were kept parallel in between these two brass plates to achieve uniform temperature.
The two brass plates are then screwed to each other. The sample was mounted on the
upper brass plate at the centre. To avoid the contact between the film and the brass
plate, a mica sheet was placed between the film and brass plate. The area of the film
97
was defined and silver emulsion (paste) was applied to ensure good electrical contact to
the films. The working temperature was recorded using a Chromel-Alumel thermocouple
(24 gauge) fixed at the centre of the brass plates. Testronix model 34 C (power supply
unit ) was used to pass the current through the sample. The potential drop across the
film was measured with the help of Meco 801 digital multimeter and current passed
through the sample was noted with a sensitive 4 digit picoammeter (Scientific
equipment, Roorkee DPM 111).The measurements were carried out by keeping the film
system in a light tight box, which was kept at room temperature.
proper shielding of the TEP unit, which also minimises to some extent, thermal radiation
losses. The mean temperature was measured with a Meco 801 digital multimeter while
the differential thermal gradient and thermoelectric voltage were measured with digital
Testronix microvoltmeter.
Fig. 2.19 b. Cross sectional view of the thermoelectric power measurement unit.
100
(a)
contact distance
Attractive force
Figure 2.20 Inter-atomic force versus distance curve for the operation of AFM
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