Thin Films
Thin Films
Thin Films
Chapter – II
Part – A
2.A.1 Introduction
Technological progress of modern society depends on the material
science and engineering community's ability to conceive the novel materials
with extraordinary combination of physical and mechanical properties [1,2].
Modern technology requires thin films for different applications.
Thin films are thin material layers ranging from fractions of a nanometer
to several micrometers in thickness. Electronic semiconductor devices and
optical coatings are the main applications benefiting from thin film construction.
Some work is being done with ferromagnetic thin films as well for use as
computer memory. Ceramic thin films are also in wide use. The relatively high
hardness and inertness of ceramic materials make this type of thin coating of
interest for protection of substrate materials against corrosion, oxidation and
wear. In particular, the use of such coatings on cutting tools may extend the life
of these items by several orders of magnitude. The engineering of thin films is
complicated by the fact that their physics is in some cases not well understood.
In particular, the problem of rewetting may be hard to solve, as there is ongoing
debate and research into some processes by which this may occur.So a thin
film is defined as a low dimensional material created by condensing, one by
one, atomic/molecular/ionic
species of matter. The thickness is typically less than several microns[3].
Thin - less than about one micron (10,000 A0, 1000 nm)
Film - layer of material on surface. If no substrate it is foil.
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
49
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, polarisers,
temperature controller in satellite, super conducting films, anticorrosive and
decorative coatings[4].
Thin film technology is a relatively young and ever growing field in the
physical &chemical sciences which is confluence of materials science, surface
science, applied physics, applied chemistry. Thin film technology has its
objectives in the provision for scientific bases for the methods & materials used
in thin film electronics.Additionally; it provides a sufficient data in the area of
applications to permit for understanding of those aspects of the subject that
might still be termed an ‘art’. Thin film of metals were probably first prepared in a
systematic manner by Michael Faraday, using electrochemical methods. Thin
films have a no. of applications in various fields.Few of them are
A.R.coatings,solar energy converters,transistors,coating, technology,
interference filters, polarisers,narrow band filters,solar cells,photoconductors,IR
detectors, waveguide coatings ,temp. Controlled aerospace devices,
photothermal solar coatings (such as black chrome, Nickel, cobalt etc.)
Magnetic films in recording device, superconducting films, microelectronic
devices, diamond films, and high coatings are used for engineering applications,
corrosion resistive thin film coatings and decorative thin film coatings etc. The
enormous flexibility provided by the thin film growth processes allows the
fabrication of desired geometrical, topographical, physically crystallographic &
metallurgical microstructures into two or less dimensions and to study the
structure sensitive properties[5].
50
techniques are broadly classified under two heading as listed in Table 2.A.1 [
12 ].
B). 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. In order to evaporate materials in a vacuum, a
vapour source is required that will support the evaporant and supply the heat of
vaporisation while allowing the charge of evaporant to reach a temperature
sufficiently high to produce the desire vapour pressure, and hence rate of
evaporation, without reacting chemically with the evaporant. To avoid
contamination of the evaporant and hence of growing film, the support material
itself must have a negligible vapour pressure and dissociation temperature of
the operating temperature [15,16].
C). Sputtering
If a surface of target material is bombarded with energetic particles, it is
possible to cause ejection of the surface atom: this is the process known as
53
PHYSICAL CHEMICAL
B] Spray pyrolysis:
This is a thermally stimulated reaction between the clusters of liquid
vapour atoms of different spraying solutions of the desired compound onto a
substrate maintained at elevated temperature. The sprayed droplets on
reaching the hot substrate undergo pyrolytic decomposition and form a single
crystal or cluster of crystallites of the product. The other volatile byproducts and
excess solvents escape in the vapour phase.
The thermal energy for decomposition, subsequent recombination of the
species, sintering & recrystallisation of the crystallites is proved by hot
substrate. The nature of the fine spray droplets, with the help of a carrier gas
depends upon spray nozzle. The growth of a film by a spray pyrolysis is
determined by nature of the substrate, solution as well as spray parameters.
The films are general strong and adherent, mechanically hard, pinhole free &
stable with temperature and time. The morphology of the films is general rough
and that will depend upon the spray conditions. The surface of the substrate
gets affected in the spray process and the choice is limited to glass, quartz,
ceramics or oxides, nitride or carbide coated substrates.
Among the methods mentioned in the Table 2.1, the chemical methods are
economical and easier than that of the physical methods. But there is no ideal
method to prepare thin films, which will satisfy all possible requirements.
Among the chemical methods, the chemical bath deposition(CBD) method is the
most popular today because large number of conducting and semiconducting
thin films can be prepared by this technique. It is also popular due to its
simplicity and low cost. In this technique, the thin films can be deposited on
different substrates like glass, ceramic, metallic etc. Many studies have been
conducted over about three decades on chemical bath deposition(CBD) method
for the preparation of thin films. Thereafter, due to good productivity of this
technique on a large scale and simplicity of the apparatus, it offered most
attractive way for the formation of thin films of metal oxides, metallic spinal type
oxides, binary chalcogenides, ternary chalcogenides, superconducting oxides
etc. It is simple and low cost technique and has capability to produce large area
of high quality adherent films of uniform thickness[20-27].
Part - B
Characterization Techniques.
2.B.1. Introduction
In the past years the advancement in science has taken place mainly
with the discovery of new materials. Characterization is an important step in the
development of exotic materials. The complete characterization of any material
consists of phase analysis, compositional characterization, structural and
surface characterization, which have strong bearing on the properties of
materials. In this section different analytical technique used to characterize our
thin films are described with relevant principles of their operation and working.
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 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
A) Reversible system
Fig. 2.B.3 shows a typical curve for linear sweep voltammetry (LSV) recorded
for reversible reaction of the type O + ne- R.
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.B.3, similar to application of potential
step. Fig. 2.B.4 shows the typical cyclic voltammetry (CV) for reversible system.
B) 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.
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
65
Cyclic Voltametery (CV) is the most widely used technique for acquiring
qualitative information about electrochemical reactions taking place at the
electrode - electrolyte interface. It offers a rapid location of redox potentials of
the electroactive species in agitated or quiescent electrolyte and convenient
evaluation of the effect of media upon the redox process[30-34].In CV the
potential is continuously changed as a linear function of time in potential window
+ volts VS SCE and resulting current response is recorded. The resulting
current versus potential plot is termed as a cyclic voltammogram. A smooth
curve indicates that no well defined phase change occur during the reaction. It
is assumed that only the oxidized ionic species are present initially, the mass
transfer under concentration gradient is diffusion controlled and Fick’s law of
diffusion holds good for both oxidized and reduced ionic species. The redox
potentials are predicted by Nernst equation given by,
66
During a negative potential scan (coloration) in the first half cycle, as the
applied potential approaches the characteristic reduction potential (Epc)
predicted by Nernst equation, the cathodic current attains a peak value (Ipc). At
least 90/n mV beyond the peak, the direction of applied potential is reversed.
This helps in locating the presence of another reducible species in the bath.
During the reverse positive scan (bleaching) the reduced ionic species get
oxidized and with similar trend the anodic current a peak value (Ipa) at an
oxidation potential (Epa). If the redox reaction is reversible i.e. maintain the
surface concentrations of oxidized and reduced species as per the Nernst
equation, the voltammogram is symmetrical otherwise it is asymmetrical.
D) Diffusion Coefficient;
n = Ionic charge
A = Area of film
nFAD1 2c∞
I f (t ) =
(πt )1 2 --------------- (2.3)
1/2
It indicates the decrease of the current with t , which is shown in
½
Fig.2.B.6. Such a i(t ) constancy is often termed a “Cottrell behavior”
68
The time required for the transition from colored to bleached state or
vice-versa under the application of voltage pulse is termed as response or
switching time. Though the magnitude of response time depends upon end use
demand, a minimum switching time is necessary in advanced opto-Electronic
EC devices.
B) Chronocoulometry (CC)
Instead of studying the current with time, we can integrate the current and study
the variation of charge with time: this is called as Chronocoulometry.
intercalated and deintercalated in the two successive steps applied for constant
time.
Reversibility;
α o (hν − E g ) n
α= − − − − − − − − − − − (2.8)
hν
where Eg is the separation between bottom of the conduction and top of the
valence band, hν is the photon energy, ν is constant and is equal to 1/2 or 3/2
depending on whether transition is allowed or forbidden and αo is a constant
depending upon the transition probability for direct transition. For allowed direct
transitions n =1/2 and for allowed indirect transition ν = 2. Thus if the plot of
(αhν)2 against hν is linear then the transition is direct allowed. The band gap
energy Eg is determined by extrapolating the linear portion of the curve to the
energy axis at α =0.
E Conduction Conduction
Band r Band
k'
h ν = Eg
r r
k r r k
O k' k
r
k
Valance Band Valance Band
(a)
Fig. 2.B.8.- “Direct interband optical transitions” for a)(b)
direct band and b)
indirect band semiconductors. The transitions are represented by vertical
arrow.
processes absorb or release energy and are thus measurable by DTA or DSC,
but not all energy-change processes are accompanied by changes in weight.
This difference in the two techniques enables a clear distinction to be made
between physical and chemical changes when the samples are subjected to
both DTA and TGA tests. In general, each substance will give a DSC or DTA
curve whose shape, number and position of the various endothermic and
exothermic features serve as a means of qualitative and quantitative
identification of the substance. When an endothermic change occurs the sample
temperature lags behind the reference temperature because of the heat in the
sample. The initiation point for a phase change or chemical reaction is the point
at which the curve first deviates from the base line. When the transition is
complete thermal diffusion brings the sample back to equilibrium quickly. The
peak (or minimum) temperature indicates the temperature at which the reaction
is completed. Endotherms generally represent physical rather than chemical
changes. Sharp endotherms are indicative of crystalline rearrangements, fusion,
or solid-state transition for relatively pure materials. Broader endotherms cover
behavior ranging from dehydration, temperature-dependent phase behaviors to
melting of polymers. Exothermic behavior (without decomposition) is associated
with the decrease in enthalpy of a phase or chemical system. Narrow exotherms
usually indicate crystallization (ordering) of a metastable system, whether it is
supercooled organic, inorganic, amorphous polymer or liquid, or annealing of
stored energy resulting from mechanical stress. Broad exotherms denote
chemical reactions, polymerization or curing of thermosetting resins. Exotherms
with decomposition can be either narrow or broad depending on kinetics of the
behaviour. The area of exotherms or endotherms can be used to calculate the
heat of the reaction or the heat of a phase formation.
Specifications
It is SDT-2960 from TA Instruments, USA. It is capable of
performing both differential Scanning Calorimeter (DSC) and Thermo
Gravimetric Analysis (TGA) at the same time. Differential Thermal Analysis
(DTA) can also be carried out using SDT 2960. It measures the heat flow and
weight changes associated with transitions and reactions in material over the
temperature range from RT to 1500°C. These experiments can be carried out in
75
either of the optional environment like N2, O2, Ar or air at pre decided flow-rate
(ml/min) and heating rate (°C/min). The gas-switching accessory is used to turn
on and off or to switch between two different purge gases during SDT
experiment. Heat-flow accuracy is equal to 1% where as DTA sensitivity is
0.001°C and that of weight is 0.1µ gm. This SDT- 2960 controller is connected
to PC and the special software makes the thermal analysis. It stores the data as
well as runs the analysis programs [37].
Applications
Melting point, crystallization behavior, glass transition temperature,
thermal stability, dehydration, oxidation, phase-transition, specific heat, reaction
kinetics etc can be determined.
0 .9 λ
D= 2.6
β cos θ
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 [45]. The ray diagram of scanning electron
microscope is shown in Fig. 2.B.11. The scattering cross section for back-
scattered electrons is given as [23],
2
−30 Z φ
Q = 16.2 ∗ 10 E cot 2 ---------- 2.7
Electron Beam
Secondary Electrons
Electromotive
force
Transmitted
Beam
Fig. 2.B.10- Variety of interaction products evolved due
to interaction of electron beam and sample
79
energy dispersion analysis is very useful because the intensities are increased
about 100-Fold [46]. The resolution however, of an energy dispersion
instruments is as much as 50 times less than the wavelength dispersion
spectrometer using a crystal; thus overlapping of lines from nearby elements
may occur. If a sample is irradiated with X-rays of sufficiently high energy, it will
emit fluorescent radiation. This radiation may be analysized in an X-ray
spectrometer and the elements present in the sample identified by their
characteristics wavelengths. Study of thin films, ferrites, composites, biological
samples and pharmaceutical samples are the common application areas.
The thickness of film is the most significant parameter that affects the
properties of the thin films. It may be measured either by in-situ monitoring of
the rate of the deposition or after the film is taken out form deposition chamber.
Technique of the first type often referred to as monitor methods generally allow
both monitoring and controlling of deposition rate of film thickness. Any known
physical quantity related to film thickness can be used to measure the thickness.
The method chosen should be convenient, reliable and simple. One of the most
convenient surfaceprofilometer and reliable method for determining film
thickness in this method, area and weight of the film are measured.
measure
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 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.
B) Thermoelectric Power (TEP)
If some metal contacts are applied to the two ends of a semiconductor
and if one junction is maintained at higher temperature than the other, a
potential difference is developed between the two electrodes. This
thermoelectric or Seebeck voltage is produced partly because
i) The majority carriers in the semiconductor diffuse from hot to cold
junction, thus giving a potential difference between the ends of the specimen.
This voltage builds upto a value such that the return current just balances the
diffusion current when a steady state is reached.
ii) Other part which contributes to the thermoelectric voltage is the contact
potential difference between metal and semiconductor, which occurs at two
junctions.
In the semiconductor, if the charge carriers are predominantly electrons,
the cold junction becomes negatively charged and if the charge carriers are
positive holes, the cold junction becomes positively charged. The magnitude of
the developed voltage is proportional to the difference in temperature between
the hot and cold junction, if the temperature difference is small. From the sign of
the thermoelectric voltage it is thus possible to deduce whether a given
specimen exhibits n-or p-type conductivity.
The thermoelectric power (TEP), which is defined as the ratio of thermally
generated voltage to the temperature difference across the piece of
semiconductor, gives the information about the type of carriers in the
semiconductor.
Fig. 2.B.15(A) and 2.B.15(B) shows photograph and schematic diagram
of the TEP measurement unit. Thermoelectric power measurement apparatus
consist of two brass blocks. One brass block was used as a sample holder-cum-
heater. Other brass block was kept at room temperature. The hot and cold
junction was kept thermally isolated by inserting an insulated barrier between
the junctions. The size of the film used in this study was 40 mm x 12.5 mm x
85
circuit conductions. The counter field is at its maximum and is the open circuit
voltage; Voc is given by the equation,
On the other hand, the counter electrode is being in the same electrolyte, the
photo voltage acts as a driving force for the electrons to move under the short-
circuit conditions from the semiconductor electrode to the counter electrode and
a regenerative cell is formed and is shown in Fig. 2.B.19. The short- circuit
current is given by the equation-
The electrons promoted to the conduction band drift towards the interior,
while the holes, the minority carriers, come to the surface of the semiconductor.
Here they encounter the reduced form of the redox couple in the solution. The
component is oxidized by the holes, transported to the counter electrode and
therefore gets reduced. This reduction is driven by the external connection from
the semiconductor[57].
Fig. 2.B.19. Current flow and energy level diagram for n- type
semiconductor PEC cell
Cells
The PEC cells are very similar to the Schottky type solid state solar cells.
The principle of charge transfer reaction at the semiconductor – electrolyte
interface forms the basis of various types, of photoelectrochemical solar cells.
Depending on the net free energy change (∆G) in the overall system, PEC cells
can be divided into three categories.
These cells consists of such a redox couple that the total cathodic and
anodic reactions do not lead to net chemical change i. e. a change in the net
free energy, ∆G = 0. The electrodes do not participate in the chemical reaction,
they only serve as a “shuttle” for the charge transfer mechanism.
At the semiconductor electrode,
The above cell is the regenerative type PEC cell used for direct production of
electricity.
Effectively two redox couples are present and a net chemical change
takes place in the system by converting the optical energy in to chemical
energy. The photoelectrolysis cells and some electrochemical storage cells
belong to this category. Some examples of reaction for the above type are
hν
H2O H2 + ½ O2 --------- 2.17
hν
CO2 + H2O CH2O + O2 ---------- 2.18
Chemical energy
In these cells, similar to above two redox couples are present such that a net
chemical changes take place. Hence ∆G < 0 and the optical energy provides the
activation energy for the chemical reaction. Example for photocatalytic cell is
hν
N2 + 3H2 2 NH3 --------------- 2.19
2.B.12.3 Requirements of Photoelectrochemical (PEC) Cells
The requirements, expected for achieving good performance of the PEC cells
are as follow:
A) Semiconductor photoelectrode
B) Electrolyte/redox couple
Pm
η= ------------ 2.20
E×A c
2.B.12.5 Fill Factor
This is the ratio of the maximum power point (Imax maximum short circuit
current, Voc Maximum open circuit voltage) divided by the open circuit voltage
(Voc) and the short circuit current (Isc):
I max Vmax
FF= ------------- 2.21
Isc Voc
2.B.12.6 Advantages of Photoelectrochemical (PEC) Solar Cell
(a)
contact distance
(tip –to-sample separation)
(b)
non- contact
Attractive force
Figure 2.B.20 Inter-atomic force versus distance curve for the operation of AFM
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