08 - Chapter 2
08 - Chapter 2
08 - Chapter 2
substrate patterning, under bump metallurgy, thin film filters and optical coatings for
fiber optic telecommunication systems, high speed machining and grinding, solid
lubrication and heat dissipation as well as in bio-active coatings for medical implant.
Aside from traditional applications, thin film technology is also closely tied to
nanotechnology, which is one of the key technologies of the near future. Nano
industries. Thin film coating is already an important part of precision engineering and
it will play an ever-increasing role in nanotechnology. Thin films play a dominant role
surfaces and thin films overlaying them has been carried out for many years. But
recently, it has become increasingly important in several fields of study. The study of
thin surface films has the advances in solid state physics since 1930. Generally the
films have thickness between 0.1µm and 300µm and must be chemically stable,
adherent well to the surface, and uniform, pure and low density of imperfections.
There are a number of different techniques that facilitate the deposition or formation
of very thin films (of the order of micrometers or less) of different materials on a
39
silicon wafer (or other suitable substrate). These films can then be patterned using
include silicon dioxide (oxide), silicon nitride, polycrystalline silicon and aluminum.
Materials that can be deposited as thin films include noble metals like gold.
Electrochromic materials are able to change their optical properties in a reversible and
persistent way under the application of a voltage pulse. These materials are currently
of interest for displays, rear-view mirrors and smart windows. Basically this arises
from the numerous inherent characteristics of nucleation and growth of thin film. The
enormous flexibility provided by the thin film growth processes allows the fabrication
structures in two or lesser dimensions. These features are increasingly being exploited
2. The diffusion of such atoms and molecules to some distance before being
3. The incorporation involves reaction of the absorbed species with each other
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6. Finally diffusion occurs within the bulk of the film and with the substrate.
The distinction between thin-film and thick-film technology is that the former
particles.
waveguides. Thin film device for windows, mirrors, rechargeable Li ion batteries and
space applications have become an essential part of modern technology [1, 2]. A thin
/ion/ cluster of species condensation process is defined as “Thin film”. Thin film
materials may also be formed from a liquid or paste, which is called as “thick film” A
great advantage with a thin film device, is the small amount of material used and the
compact volume of the device. In as energy efficient window in a warm climate for
example, a coating i.e., transparent to visible light but reflecting in the near IR region
semiconductors, insulators or dielectrics etc. and for this purpose various preparative
techniques have also been developed. Newer methods are also being evolved to
improve the quality of the deposits with maximum reproducible properties and
41
Thin film deposition can be broadly classified as either physical vapor
under physical methods, where the deposition takes place after the material to be
process. The gas phase chemical processes such as conventional chemical vapor
deposition, photo CVD and plasma-enhanced CVD comes under chemical methods.
Thermal oxidation is a chemical thin film process in which the substrate itself
provides the source for the constituent of the oxide. Liquid phase chemical techniques
pyrolysis and liquid phase epitaxy. Molecular beam epitaxy (MBE) is a sophisticated,
finely controlled evaporation technique performed in ultra high vacuum. There are
other method based on the application of an ion or ionized cluster source, and these
deposition makes use of a reactive component for the deposition of compound films
[5]. The choice of a preparative technique is, however, guided by several factors
particularly the melting point of the charge, its stability, desired purity and
characteristics of deposits etc. and these can often be achieved by several methods [6].
Thus various methods can be used for MIO film deposition. But the most widely
reported techniques in the literature and most widely used in industry are DC/RF
magnetron sputtering, pulsed laser deposition and spray pyrolysis. Extract details
about the various thin film preparation techniques are given by Maisel and Glang[7]
and Chopra[8]. In this study, MIO films were produced by RF-magnetron sputtering
presented in detail. In addition, since the properties of MIO depend strongly on the
42
that each deposition technique with its associated controlling parameters should yield
films with different characteristics. Some of these issues are discussed briefly.
EVAPORATIVE METHODS
Vacuum Evaporation Molecular-beam epitaxy (MDL)
Conventional vacuum evaporation Reactive evaporation
Electron-beam evaporation
GLOW-DISCHARGE PROCESSES
• Sputtering •Plasma Processes
Diode sputtering Plasma-enhanced CVD
Reactive sputtering Plasma oxidation
Bias sputtering (ion plating) Plasma anodization
Magnetron sputtering Plasma polymerization
Ion beam deposition Plasma nitridation
Ion beam sputter deposition Plasma reduction
Reactie ion plating Microwave ECR plasma CVD
Cluster beam deposition (CBD) Cathodic arc deposition
GAS-PHASE CHEMICAL PROCESSES
• Chemical Vapor Deposition (CVD • Thermal Forming Processes
CVD epitaxy Thermal oxidation
Atmospheric-pressure CVD (APCVD) Thermal nitridation
Low-pressure CVD (LPCVD) Thermal polymerization
Metalorgainc CVD (MOCVD)
Photo-enhanced CVD (PHCVD)
Laser-induced CVD (PCVD)
Electron-enhanced CVD Ion implantation
LIQUID-PHASE CHEMICAL TECHNIQUES
• Electra Processes • Mechanical Techniques
Electroplating Spary pyrolysis
Electroless plating Spray-on techniques
Electrolytic anodization Spin-on techniques
Chemical reduction plating Liquid phase epitaxy
Chemical displacement plating
Electrophoretic deposition
43
2.3.1. Pulsed laser deposition
One of the newer techniques for depositing thin films makes use of the
interaction of laser beams with material surfaces. Lasers were used in assorted
techniques were developed to capitalize on them as a heat source for the flash
evaporation of thin films. Early experimentation with laser evaporation sources in the
the late 1980s. In its simplest configuration, a high-power laser situated outside the
vacuum deposition chamber is focused by means of external lenses onto the target
surface, which serves as the evaporation source. Irrespective of laser used, the
absorbed beam energy is converted into thermal, chemical and mechanical energy,
causing electronic excitation of target atoms, ablation and exfoliation of the surface,
and plasma formation. Evaporants form a plume above the target consisting of a
motley collection of energetic neutral atoms, molecules, ions, electrons, atom clusters,
micron sized particulates and molten droplets. The plume is highly directional and its
contents are propelled to the substrate where they condense and form a film. A single
individual films, e.g., a sintered powder compact target to deposit mixed oxide films.
MIO thin films were prepared by pulsed laser deposition technique by Kudo et al. and
usually inert, is commonly known as (cathode) sputtering. When the ejected atoms are
44
Magnetron sputtering is a magnetically enhanced sputtering technique
system, a planar cathode is backed by permanent magnets that provide a toroidal field
with field lines forming a closed path over the target (cathode) surface. The secondary
electrons generated are trapped in cycloidal orbits near the target and prevent self-
heating of the substrate. The confinement of the plasma and the resultant intense
plasma allow magnetron sputtering systems to operate at much lower pressures and
lower target voltages than are possible for RF diode sputtering. Also here the
deposition rates are relatively higher and cover large deposition areas. Low substrate
heating allows the use of a variety of substrate for a wide variety of applications.
Many coworkers [11, 12, 13, and 14] prepared MgIn2O4 thin films by sputtering
technique.
The spray method depositing thin films is quite simple; it uses inexpensive
equipment to make coatings over large areas. Unlike the other chemical solution
deposition techniques, the film is found on a substrate kept outside the solution. The
solution is sprayed onto a heated substrate, where the film is formed either by
pyrolytic or hydrolytic chemical reaction of the liquid droplets, the hot substrate
providing the thermal energy. Different techniques for spraying that have been
employed include standard sprayers using compressed argon gas as a carrier gas and
ultrasonic spraying using nozzle sprayers. Spray pyrolysis involves spraying onto hot
surface of the substrate. The heat of the substrate initiates the chemical reaction by
providing the necessary thermal energy for decomposition of reacting materials into
45
its constituents and recombination of these constituents to form desired oxide films.
The other volatile by products and excess solvents formed during this process escape
in the vapour phase. Moses Ezhil Raj et al. have deposited MIO thin films by
systhesis by S.Esther Dali, et al., [18]. The band gap was found to be 4.3 eV which is
higher than that of ITO. The conductivity was found as 1.56 x 10-3 Scm-1. The particle
size was found as 2-3 μ m. MIO has been prepared by solid state reaction by S.Esther
Dali et al., [19]. MgIn2O4 thin films were deposited on glass substrates by pulsed laser
deposition [15] technique by Atsushi kudo et.al [10]. The maximum electrical
conductivity of the film at room temperature reached 1.3 x 103 Scm-1. The carrier
concentration was 3.6 x 1021 cm-3 and mobility was 2.4cm2 V-1s-1.
Magnesium Indium Oxide thin films were deposited onto a silica glass plate
by the RF magnetron sputtering method by Hiroshi Un’no et.al. [12,14]. The highest
conductivity observed for the film post annealed under H2 flow was 2.3 x 102 S/cm,
with a carrier concentration of 6.3 x 1020cm-3 and a mobility of 2.2cm2 V-1s-1. Target
materials used were ceramics. Sputtering conditions were clearly illustrated. Optical
region.
Hideo Hosono et al. [13]. The optical and electrical properties were examined.
10-7 Scm-1 to 1.5 x 10-1 Scm-1 on implantation of H+. Electrical properties of Mg-In-
46
Oxide spinel solid solution were studied by Tanji et.al prepared by solid state reaction
[20].
Naoyuki Ueda et al [22]. Optical band gap was found to be wider than ITO (~3.4eV).
Electrical conductivity has reached almost 102 Scm-1 at room temperature with no
intentional doping.
Minami et.al [11], who prepared MgIn2O4 thin films by conventional RF magnetron
sputtering. The greatest transparency was obtained in the MgIn2O4 film. The
properties of the deposited films were reported. The resistivity decreases from 2 x 10-3
sputter- deposited thin films of MIO at room temperature increased from < 10-7 to ~
Li+ to a fluence of 2 x 1016cm-2. The efficiency of carrier generation was ~20% in the
as- implanted state and ~ 40% after annealing at 3000C for H+ and Li+ respectively.
Thickness measurements were done by stylus was ~ 1.3 μ m. The crystallite size was
5-8 nm in diameter.
47
Generation of electron carriers in insulating thin films of MgIn2O4 spinel by
Li+ implantation was done by kawazoe et.al [24]. Conductivity at room temperature
increased from σ <10-7 to ~ 101 Scm-1 upon the Li+ implantation. Two optical-
absorption bands were induced upon the implantation, one at about ~ 500nm and
another above ~ 1000nm extending to the IR region, which was attributed to plasma
(ICP) method on a film 200Å thick showed the In/Mg atomic ratio to be ~ 2.01.
high transparency and conductivity has been prepared by spray pyrolysis technique by
Moses Ezhil Raj et.al and his coworkers. For the first time [16, 17, 25] conductivity of
the film deposited at 450oC is in the order of 0.15-1.24 x 10-4 S cm-1. The properties
of MgIn2O4 films were first reported by Moses Ezhil Raj et al. Apart from the
achieve high transmittance and high electrical conductivity by Moses Ezhil Raj et al
[17]. Room temperature electrical conductivity of 1.5 x 10-5 S cm-1 has been achieved.
Hall measurements showed n-type conductivity with electron mobility value 0.95 x
10-2 cm2 V1 s-1 and carrier concentration 2.7 x 1019 cm-3. The atomic ratio of
magnesium and indium in the film is 0.46. The optical band gap is 3.82 eV.
2.5 SPUTTERING
eroded and surface atoms are removed due to collisions between surface atoms and
48
Sputtering was first discovered more than 130 years ago by Grove. At one
time sputter was regarded just as an undesired drift effect which destroys the cathode
Today sputtering is widely applied to surface cleaning and etching, for thin
film deposition, for surface and surface layer analysis and for sputter ion sources [26].
The energetic particles which cause sputtering may be ions, neutral atoms,
When the surface of solid, i.e. target, is bombarded with ion, several
1. The incident ions are reflected, probably being neutralized in the process.
2. The impact of the ion causes the target to eject a secondary electron.
3. The ion is buried in the target. This is the phenomenon of ion implantation.
5. The ion impact sets up a series of collisions between atoms of the target,
possibly leading to the ejection of one of these atoms. This is the phenomenon
of sputtering.
49
2. The momentum-transfer theory: surface atoms of the target are emitted when
Influenced factors
atoms and the sputtering yield will be surely influenced by the following factors:
2. target materials
Cathode sputtering is used for the deposition of thin films. Several sputtering
systems are proposed for thin-film deposition including dc diode, rf diode, magnetron
But here, the planar magnetron RF sputtering was used to deposit the
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6. Alloys and compounds of materials with very different vapor pressures
Several sputtering systems are proposed for thin film deposition. Among these
sputtering systems the basic model is the dc diode sputtering system. The other
of the electrodes is cold cathode and the other is anode. Top of the cathode is covered
with target materials to be deposited and reverse side of the cathode is water-cooled.
The substrates are placed on the anode. When the sputtering chamber is kept at Ar
gas of 1 x 10-1 Torr and several kilovolts of dc voltage with series resistance of 1 to 10
kΩ are applied between the electrodes, the glow discharge is initiated. The Ar+ ions in
the glow discharge are accelerated at the cathode fall and sputter the target results in
In the dc diode system the sputtered particles collide with gas molecules and
then arrive at the substrates since the gas pressure is so high and the mean free path of
the sputtered particles is less than the electrode spacing. Then the amount of the
51
W ≈ k 1 W0 / pl ……………………2.1
R≈W/ρt ...………………….2.2
where k1 is a constant, W0 is the amount of sputtered particles from unit cathode area,
p is the discharge gas pressure, 1 is the electrode spacing, ρ is the density of the
current is nearly equal to discharge current Is and the sputtering yield is proportional
to the discharge voltage Vs, the total amounts of sputtered particles becomes VsIst/pl.
Thus, the sputtered deposit is proportional to the sputering power (Vs Is t) and is
capable of depositing metal films. Inside is a pair of parallel metal electrodes, one of
negative terminal of a DC power supply and typically, several kilovolts are applied to
it. Facing the cathode is the substrate or anode, which may be grounded, biased
evacuation of the chamber, a working gas, typically argon, is introduced and serves as
the medium in which an electrical discharge is initiated and sustained. Gas pressures
usually range from a few to a hundred millitorr. After a visible glow discharge is
maintained between the electrodes, it is observed that a current flows and metal from
52
Microscopically, positive gas ions in the discharge strike the cathode and
physically eject or sputter target atoms through momentum transfer to them. These
atoms enter and pass through the discharge region to eventually electrons, desorbed
gases, and negative ions) as well as radiation (X-rays and photons) are emitted from
the target. The electric field accelerates electrons and negatively charged ions toward
cannot sustain the glow discharge because of the immediate buildup of a surface
charge of positive ions on the front side of the insulator. To sustain the glow discharge
with the insulator target, the DC voltage power supply of the DC diode sputtering is
dV
iS ≈ C .................…………..2.4
dt
where C is capacitance between discharge plasma and the target, dV/dt denotes the
time variations of target surface potential. This indicates that the increase of the
frequency increases the target ion currents. In practical system the frequency used is
13. 56MHz.
as 10-3 Torr, since the RF electrical field in the discharge chamber increases the
53
sputtering system a blocking capacitor is connected between the matching network
and the target. The target area is much smaller than grounded anode and chamber
wall. This asymmetric electrode configuration induces negative dc bias on the target.
The induced dc bias causes the sputtering in the RF system. The dc bias is in the order
Of three magnetron configurations, the planar one with parallel target and
anode electrode surfaces is most common [19]. In this geometry a typical DC electric
field of E ~ 100 V/cm is impressed between the target and anode plates. Small
permanent magnets are arranged on the back of the target in either ellipse-like or
circular rings depending on whether the targets are rectangular of circular in shape.
between the target and substrate, charged particles within the dual field environment
experience the well-known Lorentz force in addition to electric field force, i.e.,
→
→ md V ⎛→ → →⎞
F= = − q⎜ E + V X B ⎟ ..............……………2.5
dt ⎝ ⎠
where q, m, and V are the electron charge, mass, and velocity, respectively. First
consider the case where B and E are parallel as shown in Fig. 2.2a. Only electrons
processes. When electrons are emitted exactly normal to the target surface or parallel
to B and E, then V x B vanishes; electrons are only influenced by the E field and
simply accelerate toward the anode, gaining kinetic energy in the process. If, however
E = 0, and the electron is launched with velocity V at an angle θ with respect to the
uniform B field between electrodes (Fig. 2.2b), it experiences a force qVB sinθ in a
54
direction perpendicular to B. The electron now executes a circular motion whose
mV sin θ
r= ………………………. 2.6
qB
A spiral electron motion ensures and in corkscrew fashion the electron returns
to the same radial position around the axis of the field lines. If the magnetic field was
not present, such off-axis electrons would tend to migrate out of the discharge and be
The case where electrons are launched at an angle to parallel and uniform E
and B fields is shown in the (Fig. 2.2c). Helical motion with constant radius occurs,
but because of electron acceleration in the E field the pitch of the helix lengthens with
time. Time-varying fields complicate matters further and electron spirals of variable
radius can occur. Clearly magnetic fields prolong the electron residence time in the
Perpendicular Fields
greater electron confinement is achieved. The geometry is shown in Fig. 2.2d, where
E is still normal to the cathode while B, which is directed into the page (+ z direction),
lies parallel to the cathode plane. Electrons emitted normally from the cathode ideally
do not even reach the anode but are trapped near the electrode where they execute a
periodic hopping motion over its surface. Physically, the emitted electrons are initially
accelerated towards the anode, executing a helical motion in the process; but when
they encounter the region of the parallel magnetic field, they are bent in an orbit back
55
to the target in very much the same way that electrons are deflected toward the hearth
in an electron beam evaporator. The analysis for this behavior is not difficult and
starts with the equations for electron motion in the three perpendicular directions.
Coordinate positions of the electron above and along the cathode are y and x,
d2x dy
me 2
= qB ..............……………..2.7
dt dt
2
d y dx
me 2 = qE – qB dx/dt ………………..............2.8
dt dt
d2z
me =0 ………………………2.9
dt 2
By solving these coupled differential equations it is readily shown that the parametric
qE (1 − cosϖ c t )
y=- …………………......2.10
meϖ c2
Et ⎛ sinϖ ct ⎞
x= ⎜1 − ⎟ ……………………..2.11
B ⎜⎝ ϖ c t ⎟⎠
where ωc= qB/me. Known as the cyclotron frequency, ωc has a value of 2.8 x 106B Hz
where electrons repeatedly return to the cathode at time intervals of π/ωc. The same
surface. Electron motion is strictly confined to the cathode dark space where both
fields are present; however, electrons stray into the negative glow region where ‘ is
small, they describe a circular orbit before collisions may drive them either back into
the dark space or forward toward the anode. Confinement in crossed fields prolongs
the electron lifetime over and above that in parallel fields, enhancing the ionizing
efficiency near the cathode. A denser plasma and larger discharge currents result.
56
2.6 THIN-FILM NUCLEATION
small but highly mobile clusters or islands is observed. In this stage the prior nuclei
incorporate impinging atoms and subcritical clusters and grow in size while the island
density rapidly saturates. The next stage involves merging of the islands by a
denuding of the substrate where further nucleation can then occur. Crystallographic
facets and orientations are frequently preserved on islands and at interfaces between
deposition, the channels fill in and shrink leaving isolated voids behind. Finally, even
the voids fill in completely and the film is said to be continuous. This sequence of
events occurs during the early stages of deposition, typically accounting for the first
growth modes: (1) island (or Volmer-Weber), (2) layer (or Frank Van der Merwe),
and (3) Stranski Krastanov, which are illustrated schematically in Fig.2.3. Island
growth occurs when the smallest stable clusters nucleate on the substrate and grow in
three dimensions to form islands. This happens when atoms or molecules in the
deposit are more strongly bound to each other than to the substrate. Metal and
semiconductor films deposited on oxide substrates initially form such islands. The
opposite characteristics are displayed during layer growth. Here the extension of the
formation of planar sheets. In this growth mode the atoms are more strongly bound to
57
the substrate than to each other. The first complete monolayer is then covered with a
somewhat less tightly bound second layer. Providing the decrease in bonding energy
is continuous toward the bulk-crystal value, the layer growth mode is sustained. The
combination of the preceding two modes. In this case after forming one or more
monolayers, subsequent layer growth becomes unfavorable and islands form. Film
growth by the S-K mode is fairly common and has been observed in metal-metal and
metal-semiconductor systems.
Penning in 1936. A wide variety of thin films can be made with little film
copper on which planar targets of any material bounded to a copper backing plate can
shield with a Teflon spacer and is kept in position using a stainless-steel nut. The
magnets are mounted outside the shield. The whole assembly is affixed to a stainless-
steel base plate, which is placed in a bell jar in which sputtering is carried out. The
discharge voltage is 300 to 800V where the maximum sputtering yield per unit energy
is obtained.
In this present work, the sputtering instrument used for coating the MIO film
was the Planar Magnetron RF/DC HindHivac sputtering system (Model-12” MSPT)
58
in a mechanically pumped stainless steel chamber. The schematic representation of
A 2-inch diameter and 5mm thick, MIO target of 99.99% purity from “Super
Conductor Materials, Inc, USA” and a corning glass substrate is loaded inside the
chamber. The photograph of the HINDHIVAC sputtering unit used for preparing thin
grounded while a radio frequency (13.56 MHz) AC voltage is applied to the target. A
capacitor is connected between the RF source and the sputtering system. Here, the
front surface of the cathode is covered with target materials to be deposited. The
substrates are placed on the anode. The sputtering chamber is filled with sputtering
gas, typically argon gas. The glow discharge is maintained under the application of rf
potential. The Ar+ ions generated in the glow discharge are accelerated at the cathode
fall (sheath) and sputter the target, resulting in the deposition of the thin films on the
substrates.
A specific pressure of gas, in this case about 5x10-2 torr of Ar, is maintained
during the sputtering process. The strong AC electric field accelerates electrons that
collide with Ar molecules, ionizing some of the Ar molecules and producing more
electrons to start a glow discharge (plasma). In the plasma the Ar molecules get
ionized. The Ar ions and electrons bombard the target alternatively as the AC field
changes polarity. Since electrons are much lighter and thus have greater mobility than
positive ions, the target draws a much higher electron current than ion current under
the same potential. Therefore, the capacitor in the circuit is always recharged more
rapidly by electron current than ion current. When the AC frequency is sufficiently
high (> 1MHz), the net effect of this inequality of mobility of positive ions and
59
“DC offset” of the AC voltage. Since the time dependence of the AC voltage is
approximately a sinusoidal function, the DC offset reduces the positive target bias to a
very small fraction of the full amplitude. The positively charged Ar thus has a net
acceleration towards the target and bombards the target almost continuously. Due to
gas law of working pressure, the sputtered particles traverse the discharge space
The most important difference between RF and DC systems is that the former
the Fig. 2.6. The semicylindrical shaped deposition chamber is made up of stainless
steel, which is a cold water cooled. It includes two plane cicular sputter sources
Thus, the use of RF sputtering for the deposition of thin films is of great
[30].
deposition occurs, a pumping system, a gas supply system and a power supply system.
Permanent magnets are placed at the back of the sputter sources in a suitable
arrangement for the production of the required magnetic field. The sputter sources are
deposited. At a distance of about 6 cm above the sputter sources and parallel to them
60
there is a substrate holder, which can be rotated by the user. On the substrate holder,
plane circular sample holders with a diameter of 9 cm are fixed which can be easily
transferred outside of the chamber for placing and exchanging the samples, which
form the substrate for the deposited material. In our unit we are using rotary vane
pump and oil diffusion pump to attain the vacuum in the deposition chamber
approximately 10-6 mbar. The following are the internal operations of the rotary and
The rotary piston and rotary vane pumps are the two most common devices
used to attain reduced pressure. In the rotary piston pump gas is drawn into the keyed
shaft rotates the eccentric and piston. There the gas is isolated from the inlet after one
Hind Hivac coating unit is having direct driven rotary vane type vacuum
pump. The rotary vane pump contains an eccentrically mounted rotor with spring
loaded vanes. During rotation the vanes slide in and out within the cylindrical interior
through an exhaust valve into the atmosphere. The whole stator/rotor assembly is
submerged in suitable oil. Single stage vane pumps have an ultimate pressure of 10-2
Torr, and two stage pumps can reach 10-4 Torr. Rotary pumps are frequently used to
produce the minimal vacuum required to operate both oil diffusion and
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(ii) Vapor pump or oil diffusion pump
This is the main pump to obtain the desired high vacuum. Diffusion pumps are
designed to operate in the molecular flow regime and can function over pressures
Diffusion pumps have been constructed with pumping speeds ranging from a
few liters per second to over 20,000 lit/sec. Pumping is achieved through the action of
a fluid medium (typically silicon oil) that is boiled and vaporized in multistage jet
assembly. As the oil vapor stream emerges from the top nozzles, it collides with and
imparts momentum to residual gas molecules, which happen to bound into the pump
throat. These molecules are thus driven towards the bottom of the pump and
compressed at the exit side where they are exhausted. The pump fluid should have a
high molecular weight so that each molecule carries considerable momentum and can
therefore make effective collisions with several gas molecules before all its
momentum is lost. It should have a very low pressure. Silicon oil DC 704 satisfies
these requirements.
The sputtering gas (Ar) is introduced into the chamber for the deposition
process. The gas flow is controlled constantly throughout the sputtering process. The
pressure of the chamber can be measured by two manometers (pressure gauges) which
cover two different regions of pressure values. The pirani type manometer is used for
measuring pressures in the region from atmospheric pressure to 1×10-4 mbar, whereas
for lower pressures until 1×10-6 mbar, the penning type manometer is used.
The substrate selection and cleaning procedures are the special art in thin film
62
quality films with reproducible properties. It exerts a decisive influence on the film
The nature and surface finish of the substrate are extremely important because
they greatly influence the properties of films deposited on to them. Glass, quartz and
substrates of alkali halides, mica, MgO, semiconductors etc are used for epitaxial
growth. The most important consideration in all these cases is that the deposit layers
must be adherent to the substrates and these should not peel off from the substrates
under the normal conditions of stress and strain, mechanical or thermal to which the
deposits are exposed during their uses. Substrate selection mainly depends on the type
of thin film to be deposited and also the process by which the film is prepared. Many
times a thin film scientist has to restrict his experiments because of lack of proper
substrate for the desired process. In general the following information may be noted
before selecting the substrate for the thin film deposition. [31, 32, 33]
1. Type of substrates
c. Metals
2. Rigid or flexible
3. Structure
4. Melting point
5. Hardness
63
6. Thermal conductivity
7. Thermal expansion
8. Transmitting region
The substrate can be selected keeping the end use and the properties of the
evaporated/sputtered films.
composition. The major advantage of glasses is that smooth surface can be achieved
vary significantly in regard to volume resistivity, loss tangent and softening points.
Their poor thermal conductivity and the difficulty of obtaining intricate shapes
including holes preclude the use of glasses for many electronic applications. Glass has
high modulus and non-zero coefficient of thermal expansion. Glasses are generally
multicomponent solids that are chemically bonding such that there are no free
depends on the nature of the substrate, the type of contaminants, and the degree of
64
oils and airborne particulate matter are examples of frequently encountered
layer, but a mild attack of the substrate material itself is often tolerate and ensures
handling or the use of solvents and must therefore be applied outside the vacuum
system. The physical cleaning methods are generally conducted in situ by installing
stirring action of the shock waves created in the solvent. Thus, solvent saturated with
impurities is continually carried away from the substrate surface and fresh, less
saturated liquid is admitted. Mechanical vibrations induced in the substrate further aid
which affect the efficiency of ultrasonic cleaning are numerous. The frequency of
vibration, applied power, type and temperature of the solvent, its surface tension and
viscosity, and the presence of nucleating particles and dissolved gases are factors
which play a role. Low frequency ultrasonic agitation was most effective in removing
This method is likely to attack the substrate surface. Acid cleaners react with
contaminants such as grease and some oxides to convert them into more soluble
compounds. The effectiveness of the solvent is the probably more dependent on the
65
(iii) Vapor greasing
The samples are kept in the bath until they reach the vapor temperature and then they
are removed. The residual alcohol on the surface is evaporated immediately and the
This is the most widely used technique to clean substrates in situ and
roughening of the substrate surface, as well as deposition of foreign material from the
counter electrode. If it is felt that these effects are not detrimental and sputter cleaning
changes of the substrate surface are brought about by one or more of the following
mechanisms:
recombination.
bombardment.
66
4. Volatization of organic residues by chemical reaction with dissociated oxygen.
Very often a substrate material has desirable bulk properties but its surface is
may be possible to upgrade the surface by an extra finishing step. The principle of
these procedures is to coat the substrate with a layer of another material which allows
well and adds the desired property without losing the attractive features of the original
substrate.
Cleaning in detergent solution was less effective than either of the other
recontamination can occur unless stringent precautions are taken. Typically, the last
step in substrate cleaning is rinsing in deionized water. As the latter may contain
traces of salts or organic matter, withdrawal of the substrate should be conducted such
that a minimum of liquid adheres to the surface. If storage cannot be avoided, dust-
In the present work, the corning 7059 glass plates were chosen as substrates
for the deposition of MIO thin films for their high optical and low electrical
conduction characteristics.
remove the unwanted impurities normally present on the surface of the glass plates
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(i) The glass substrates are washed in Sodium thiosulphate solution (extran) by
scrubbing the surfaces with the cotton swab till they pass the breathe figure
(ii) The glass slides are then rinsed thoroughly in deionized water to remove any
(iii) Then the substrates are soaked in chromic acid and heated to about one hour to
dissolve the fine silica layer formed on the surface and to make a new surface
(iv) Finally the substrates are placed in the Ultrasonic cleaner then they are rinsed
thoroughly in deionized water and dried with acetone. Now the glass
controlled substrate holder. However, the heat of the target heats the surface of the
substrate. In order to reduce the effect of the heat, the surface of the target must be
substrate.
It is noted that the temperature rise of the substrate depends on the type of
sputtering system. The temperature rise at magnetron is lower than that of the RF
diode, since the secondary electrons from the target are trapped by the transverse
magnetic field near the surface of the target. The temperature rise at the magnetron
68
It is clearly that the mobility of adatoms and clusters, which is in proportion
to their energy, on the substrate will be increased with increasing the substrate
temperature. Hence, the substrate temperature influences the microstructure and the
used for measuring substrate temperature: the temperature differences between the
substrate and the substrate holder are measured for the dummy substrates. The
substrates are closely mounted on to the substrate holder, the temperature of the
2.10 TARGETS
available for the production of sputtered thin films. Targets come in a variety of
shapes and in assorted sizes. Ceramic and oxide targets are generally prepared by hot
pressing of powders. The elemental and metal targets generally have purities of
99.99% or better, whereas those for the nonmetals have typical upper purity limits of
demanded together with stringent stoichiometries. While the metal targets usually
attain theoretical densities, lower densities are achieved during powder processing.
density targets, which are prone to greater arcing rates, emission of particulates, and
69
release of trapped gases, nonuniform target erosion, and deposition of generally
inferior films. Prior to use, targets must be bonded to a cooling backing plate to avoid
purchased from “Super Conductor Materials, Inc, USA” a 2- inch diameter and 5mm
technique using HINDHIVAC 12” MSPT RF/DC magnetron sputtering unit which
contains 500W RF generator. The de-greased and well cleaned glass plates were used
as the substrates and mounted on the substrate holder of the sputtering chamber which
is facing the sputtering source and parallel to the surface of the target and having the
heating elements to control the substrate temperature during the film deposition. The
target was placed on the base plate of the sputtering source. The target was fixed on
the magnetron sputtering source with a stainless steel backing plate which is designed
The whole magnetron source with the target was covered with the guard ring
cover of the magnetron. There is a shutter which separates the target and the
substrates. This helps in preventing the contamination of the target during substrate
loading and unloading, protects the substrates during pre-sputtering. Initially the
Now the chamber was closed and evacuated using the rotary and oil diffusion
pumps. After achieving the required vacuum i.e. high vacuum of the order of 5 x 10-6
mbar, the sputtering process was started. As the magnetron source and the wall of the
70
sputtering chamber were water cooled, the water cooler and the water circulating
being an inert gas which does not react with either the target or the substrate is
introduced into the chamber at a specified pressure. This gas serves as the source of
Ar+ ions. RF power supply is switched and stabilized to the required specific power
which induces the required DC bias levels. This bias is an indication of sheath
potential and is good sign of ion bombardment energy. With the shutter closed, the RF
power, Ar gas flow and the substrate temperature were stabilized with the constant
glow discharge, since all the parameter depends on each other. Once the above
parameters were stabilized, the target was pre sputtered for 15 mins prior to every
deposition. After the stabilization and pre-sputtering shutter was opened and allowed
films were deposited by varying the substrate temperature and the RF power. The
deposited films were pin hole free, uniform, transparent and well adhesive nature with
substrates. The RF power was varied as 50W, 100W, 150W, 200W. The substrate
temperature was kept as RT, 100 0C, 150 0C, 200 0C and 250 0C. The target to
substrate distance was kept 6cm throughout all the coating. Duration of the deposition
2.12 CONCLUSION
method and describes about the functions of various pumps that have been employed
in the coating unit to create the desired vacuum. The substrate and the cleaning
selections clearly demonstrate some basic qualifications for the substrates. A detailed
method for the preparation of MIO films is also described in this chapter.
71
The various preparative conditions such as source to substrate distance,
deposition rate pressure level, and substrate temperature were altered and optimized
for good quality and device oriented films. The sequential characterization studies on
the films have been carried out to explore their various properties and are summarized
72
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75