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Introduction
1.1 General
The semiconductor property was first observed in 1833 by Michael Faraday when
he discovered that the electrical resistance of silver sulphide increases with temperature
as compared to a decrease, in metals. The first concept of semiconductors was
introduced by Kenigsberger as Conductors which have the electron conductivity and
whose resistance is greatly affected by temperature, will be called semiconductor[1], in
year 1914. Shockley, Brattain and Bardeen, in 1947, demonstrated their invention of a
point transistor after that a huge number of semiconductor-based microelectronic devices
have been fabricated and manufactured throughout the world.
Now it is difficult to imagine a world without desktop laser printers, cellular
telephones, pagers, global positioning, CD-ROMs, DVD players, laser fax machine, and
todays combination of different information technologies that together comprises
Information superhighways. Compound semiconductor such as Gallium-Arsenide (GaAs)
and Indium-Phosphide (InP) have brought about or enabled all of these microelectronic,
optoelectronic, and wireless marvels.
Compound semiconductors are critical to the success of many technologies that
have opened new markets.. Some of the common semiconductor devices are based on
compound semiconductor substrates for such application as high speed digital
electronics, high frequency analog electronics, lasers, Light Emitting Diodes (LED).
Todays markets that have high-growth rates for using compound semiconductor in
optoelectronic and wireless systems for civilian application. This large growth requires
newer properties to be explored.
Silicon has a long history as a semiconductor material, whereas silicon is the most
popular material used today to make electronic devices, the compounds are considered a
category of semiconductors that perform functions beyond the physical limits of the
electronic properties of silicon. When it comes to light gathering or light emitting
properties, the compounds are unsurpassed by silicon which is a very poor light emitting
material [2]. The flexibility in the properties gives the compound semiconductors an
added benefit.
1.2
Objectives
2.
3.
To grow thin films of zinc oxide and optimize the growth conditions to yield
good quality films.
4.
1.3
Chapter 1.
This chapter gives a brief history of development of semiconductor technology,
objectives of the work carried out, and discuss the organization of thesis report.
Chapter 2.
This chapter contains brief introduction to semiconductors, compound
semiconductors and discuss in details about the material properties and application of
Zinc oxide and compares zinc oxide with some of the other competing compound
semiconductors.
Chapter 3.
This chapter gives an overview of current growth technologies used to deposit
thin films of various semiconductors is given. A emphasize is given on Chemical Vapor
Deposition (CVD).
Chapter 4.
This chapter deals with details of fabrication of the Chemical Vapor Deposition
(CVD) system and the precursor used for deposition of the films.
Chapter 5.
This chapter gives experimental details involved in film growth, and the
techniques used for characterization of grown films.
Chapter 6.
This chapter discus the results obtained after characterization of grown films
during the course work.
Chapter 7.
This Chapter contains conclusion drawn from the work carried out during the
course work and recommendations for future work.
Chapter 2
Valance band
Valance band
Valance band
BG
BG
Conduction band
~1eV
Conduction band
~15eV
Conduction band
Conductor
Semiconductor
Insulator
Table 2.1: The III-V binary compounds (compound semiconductors are highlighted)
Group III
Group V
N
BN
P
BP
As
BAs
Sb
BSb
Al
AlN
AlP
AlAs
AlSb
Ga
GaN
GaP
GaAs
GaSb
In
InN
InP
InAs
InSb
Out of all these compounds only few are potential semiconductors. Boron and
nitrogen compounds, for example, have been included only for sake of completeness.
Aluminum compounds are not very stable and usually disintegrate with time. The six
most important semiconductors are GaP, GaAs, GaSb, InP, InAs, and InSb.
Most of the III-V semiconductors have zinc blend crystal structure. Eight valance
electrons are shared between a pair of nearest atoms, so that on an average each of the
atoms has four valance electrons. This suggests that the bonding has a covalent character.
However, since the elements of group III are more electropositive, and those of group V
are more electronegative than group IV elements, the bonding in III-V compounds has a
partial ionic character as well, as an effect the band gap of III-V compound
semiconductors is larger than those of group IV elemental semiconductors.
Table 1.2: The II-VI Binary Compounds (compound semiconductors are highlighted)
Group II
Group VI
Zn
O
Zn O
S
ZnS
Se
ZnSe
Te
ZnTe
Cd
CdO
CdS
CdSe
CdTe
Hg
HgO
HgS
HgSe
HgTe
The crystal structure of II-VI groups shows variations and is rather complex. CdS
and CdSe crystallize in the hcp(**) wurtzite structure, and ZnTe and CdTe in zinc blend,
where as ZnS and ZnSe can exist in both these forms. The bonding in these structures is
mixture of both ionic and covalent types. This is because the average number of valance
electrons per atom is still four, but VI atoms are considerably more electronegative than
group II atoms, and this introduces ionicity.
have band gap which corresponds to visible spectrum of radiation and finds applications
in light emitting diodes.
A major problem with compound semiconductors is that there preparation in
single crystal form is difficult, also due to difference in vapor pressure of these materials.
One material may vaporize more rapidly than other, causing excess of other type of
atoms. These other type of atoms may get trapped interstitially in the lattice or may
precipitate out to form a second phase. Either of these disturbs stoichiometry.
The III-V or II-VI compound semiconductor have general formula AB where A is
group III (or group II) element and B is group V (or group VI) element. However many
of these compounds have identical structure and similar lattice constants. Such
compounds shows complete solubility in each other and structures of the form A xB1-xC
are also possible, where C is a group V (or VI) element (depending on A and B) , with x
ranging from 0 to 1. Similarly growth of crystal having two different non metals (group V
or VI) is also possible. Properties of such compounds vary smoothly with composition.
The Zinc oxide wurtzite structure, as show in figure 1.2, consists of one
hexagonal lattice containing the Zinc atoms and one hexagonal lattice containing the
oxygen atoms. The two sub lattices interpenetrate into each other. Each atom of zinc is
tetrahedrally surrounded by four atoms of oxygen.
Stoichiometric zinc oxide is dielectrics, based on the wide band gap of the
material, the resistivity () of undoped Zinc oxide is expected to be very high. However
mostly Zinc oxide exhibits n-type conductivity with electron concentration ~10 17 cm3 due
to excess of zinc atoms.
10
4.75
c-axis direction
2.92
The electron mass is 0.28 and the hole mass is 1.8.(**) [5]
Zinc Oxide has many interesting properties, which makes it very attractive candidate for
future semiconductor industry. Some of the important properties are listed below.
2.4.1
electromagnetic spectrum. The band gap is direct in nature; this gives it many interesting
applications in optoelectronic devices.
2.4.2
2.4.3
semiconductor, in other words, a Coulomb correlated electron hole pair. The binding
11
energy associated with such a pair is called exciton binding energy. The exciton play very
important role in optical properties of semiconductor and enhances the light emission
properties.
The Zinc oxide has highest exciton energy of 60 meV [8], which is very large as
compared to other competitors like GaN which has exciton binding energy of 29 meV[9].
It can be noted here that exciton binding energy for Zinc oxide is greater than the thermal
noise of 26meV at room temperature,
temperature.
2.4.4
Hardness
Zinc oxide is hardest of II-VI semiconductor materials. It has a hardness of 4.5 on
mohs scale [10]. This indicates that its performance will not be degraded as easily as the
other compounds through the appearance of defects.
2.4.5
Transparent nature
Like all metal oxides, Zinc oxide is transparent in nature for visible light [11]. The
deficiency of oxygen atoms in the zinc oxide provides free charge carriers and the
material acts like an electric conductor. By properly controlling oxygen content, one can
control the electrical conductivity of Zinc oxide. This conductivity and transparent
behaviour gives the material a very interesting and rare combination of properties.
12
2.4.6
Ferro-electric effect
The ferroelectric effect is an electrical phenomenon whereby certain ionic crystals
may exhibit a spontaneous dipole moment. The term ferroelectricity refers to the
similarity with ferromagnetism, in which a material exhibits a permanent magnetic
moment. Zinc oxide can be made ferroelectric by making ternaries with it with
Manganese [12]. Thus it finds application in magnetic sensors and most importantly
upcoming field of spintronics.
2.4.7
Piezoelectric effect
Piezoelectric effect is the property of certain crystals of generating an electric
charge when placed under mechanical stress, or of being deformed when an electrical
charge is placed across it. High Piezoelectric Effect of 1.2 C/m 2 [13]is observed in Zinc
oxide. This is among highest of all semiconductors.
2.4.8
Non-toxicity
Zinc oxide is an echo friendly chemical and has a long history of application in
medical field and cosmetics due to its ability to absorb the UV radiation coming from
sun. The material is also constantly used in various ointments and sunscreens. Thus, it
can be expected to be hazard free for nature.
Many other interesting properties have been observed like good adhesion with
many material surfaces, Radiation resistance to , , and radiations etc.
Here is comparison of key properties of Zinc oxide with those of competing
compound semiconductor materials currently in use:
13
Band-
parameters
gap
Exciton
Dielectric
binding
constant
Energy of
Crystal
Material
Cohesion
Structure
Energy
energy
(eV)
ZnO
ZnS
Wurtzite
Wurtzite
Zinc
a
3.25
3.82
ZnSe
c
5.21
5.26
1.89
1.59
(m eV)
59
30
(0)
8.75
9.60
2.7
1.29
20
9.10
1.43
--
4.2
12.9
3.39
2.86
2.24
3.17
21
--
8.90
9.66
(eV)
3.37
3.80
5.66
5.65
blend
Zinc
GaAs
GaN
6h-Sic
Blend
Wurtzite
Wurtzite
3.19
3.18
5.18
15.12
Indeed Zinc oxide has a unique combination of high values for energies of band
gap energy, cohesion and exciton stability.
14
2.5 Applications
The enormous potential for use of Zinc oxide in optoelectronic applications can
be explained with reference to above mentioned properties and table 2.3. Although the
material has a long history of applications in electrical and electronic industry, but it is
gaining large attention these days in field of semiconductors. Some of them are
mentioned here
2.5.1
source. Implementation of Light Emitting Diode and Laser Diode has already been
reported[14]. It is expected to replace red lasers by blue ones. Using blue light as a
replacement for red light one can get better performance, like in case of CD readers one
can store around four times more data.
2.5.2
Transparent conductors.
The Zinc oxide is used as transparent conducting oxide (TCO) in many
applications like solar cells, LCD displays TFT panel displays [11] etc.
2.5.3
violate region. This gives optical detectors made of Zinc oxide a special property that is
they are blind to visible spectrum of light. The optical detector thus fabricated has
strategic application in defense for UV guided missiles.
15
2.5.4
Sensors.
The Zinc oxide can be used as sensor for sensing various parameters like
Chemical sensors [25]: Sensor for oxygen content or alcohol content. Surface
resistivity of the material is very sensitive to Oxygen or alcohol content, due to this
dependence on oxygen it can act like a good Oxygen sensor or alcohol detectors.
Mechanical Sensor: Sensor for mechanical forces, pressures etc. The Zinc oxide
shows large/high piezoelectric effect and can be used as mechanical sensor and also finds
application in MEMS.
2.5.5
transistor used for multiplexing is embedded along with the pixel itself. This needs the
transistor to be transparent. The Zinc oxide can be used to fabricate transparent Thin Film
Transistors, and successful fabrication of TFT using Zinc oxide has been reported [15].
2.5.6
material with different band gap. The band gap of Zinc oxide can be tailored by making
ternaries.
16
2.5.7
oxide can have both ferroelectric as well as semiconducting properties this makes
material suitable for spintronics applications.
2.6
flexibility, and stability. This all gives the material a leading edge over other materials.
Some of them being as follows:
2.6.1.
temperature. In fact it has highest exciton binding energy in the class of II-VI and III-V
semiconductor materials. The high exciton binding energy gives the Zinc oxide superior
optical properties and the excitonic stimulated light emission can be obtained up to a
temperature of 550 K
2.6.2.
17
2.6.3.
2.6.4.
Radiation resistant
The Zinc Oxide is radiation resistant to , , and radiations[17]. This gives zinc
oxide strategic importance in nuclear war fare, space applications where radiation levels
are very high. The zinc oxide is even more radiation resistant than GaN(**)same [17].
2.6.5.
makes detectors fabricated from Zinc oxide to give superior spectral response for ultra
violate radiation.
2.6.6.
for ZnSe, 32.60 for GaAs, 51.37 for Si. This indicates stability of the zinc oxide crystal.
18
Chapter 3.
Growth Technologies
3.1
Introduction
Deposition technology can well be regarded as the major key to creation of
devices such as computers, since microelectronic solid state devices are all based on
material structures created by thin film deposition. Electronic engineers have
continuously demanded films of improved quality and sophistication for solid-state
devices, requiring a rapid evolution of deposition technology. Another important reason
for rapid growth of deposition technology is the improved understanding of physics and
chemistry of films, surfaces, interfaces and microstructures, which has been made
possible by the remarkable advances in the analytical instrumentation during past 30
years.
A good example of the crucial importance of deposition technology is the
fabrication of semiconductor devices, an industry that is totally dependent on the
formation of thin solid films of a variety of materials by deposition from the gas, vapor,
liquid, or solid phase. Subsequent steps in fabrication process create electrical structures
that require the deposition of an insulating or dielectric layer such as oxide, glass, or
nitride by one of several methods like chemical vapor deposition (CVD), process, by
plasma enhanced chemical vapor deposition (PECVD) or by any one of a number of
sputtering deposition methods. The deposition of conductor films for contact formation
and interconnection can be accomplished by vacuum evaporation or sputtering. CVD
19
3.2
Some of important and especially useful in thin film deposition methods are listed
bellow:
Evaporative Methods
Vacuum Evaporation
Glow-Discharge Methods
Sputtering
Plasma Processes
Reactive sputtering
Plasma-enhanced CVD
Magnetron sputtering
Plasma Oxidation
20
Atmospheric-pressure CVD
Thermal oxidation
Low-pressure CVD
Thermal polymerization
Metal-Organic CVD
Photo-enhanced CVD
3.2.1.
Mechanical techniques
Electroplating
Spray pyrolysis
Electroless plating
Spray-on techniques
Electrolytic anodization
Evaporation technologies
Although one of the oldest techniques used for depositing thin films, thermal
evaporation or vacuum evaporation is still widely used in the laboratory and industry for
deposition of metals and alloys. The material is first converted to vapor by boiling or
sublimation, this vapor is then transmitted from source to substrate. The vapor is
condensed to a solid film on the substrate surface.
Evaporation technology covers a large range of varying chemical reactivity and
vapor pressure. This variety leads to a large diversity of source components including
21
3.2.2.
represent a rich source of processes used to deposit and etch thin films. Many processes
for film depositions employ this phenomenon.
The two classes of deposition processes using the phenomenon are sputtering
process and plasma process.
22
3.2.3.
Chemical Vapor
23
Thin films that can be prepared by CVD cover a tremendous range of elements
and compounds. Organic, organometallic and inorganic reactants can be used as starting
materials. Gases are preferred because they can be easily metered and distributed to
reactor. Liquid and solid reactants must be vaporized without decomposition at suitable
temperature and transported using a suitable gas through heated tubes to the reaction
chamber.
Many variants of CVD are in use, some are:
In LPCVD, particle
contamination is reduced and film uniformity and conformality are better than
conventional Atmospheric Pressure Chemical Vapor Deposition (APCVD).
Keeping reactor at low pressure minimizes autodoping, a major problem in
Atmospheric Pressure Chemical Vapor Deposition (APCVD).(**)[24]
24
It is seen that the vapor phase reactants R nM and E Rm are thermally decomposed
at elevated temperatures to form non volatile product ME which is deposited on
substrate and the volatile product RR is carried away by the carrier gas to
exhaust. High quality films of Zinc oxide have been grown using MOCVD
process[26].
25
3.2.4.
26
Chapter 4
Introduction
Chemical Vapor Deposition (CVD) has established itself as an important epitaxial
crystal growth technique [28] yielding high quality Low Dimensional Structures (LDS)
for fundamental semiconductor physics research and useful semiconductor devices, both
electronic and photonics. The growth of compound semiconductors results by introducing
metered amount of the precursors into a quartz tube that contains a substrate placed on a
heated susceptor. The reaction takes place close to the heated substrate or in many cases
on the substrate itself to produce the thin film. CVD is attractive as it may be used for the
deposition of very high crystalline quality layers and can be scaled up for the mass
production with relative ease. Another important feature of CVD system is the high
growth rates that can be attained [29]. It can produce heterostructures, multi-quantum
wells (MQW) and super lattice (SL) with very abrupt switch on and switch off transitions
in composition as well as in doping profiles in continues growth by rapid changes of the
gas composition in the reaction chamber.
4.2
CAT Indore. The system is designed to use Zinc acetylacetonate as precursor. The
27
precursor being solid, a carrier gas is needed to carry its vapors to reaction chamber. The
carrier gas used here is Nitrogen gas from a high purity (99.995%) nitrogen cylinder.
The setup is divided in three major parts
1. Reaction chamber.
2. Connecting lines
3. Bubbler
Substrate
Heater
Product
gases
28
Vertical reactors is a system in which fresh process gas enters the process space
through a central port as shown in figure 4.1 and mixes with the depleted gas as it flows
radially outwards over the wafer surface . The fresh process gas stimulates a current
which flows from the center of the plate, reacts at substrate surface, and flows toward the
exhaust of the reaction chamber.
Heater
Product
gases
Reactant
gases
Substrate
In horizontal reactor the process gas flows horizontally over the substrate. The
front side is exposed to fresh supply of reactants whereas rear side gets lower
concentration of reactants, this leads to uneven thickness of coating. To avoid this tiled
substrates are used. A horizontal reactor geometry is shown in figure 4.2.
For the present system a vertical reactor is designed, due to its relative ease in
fabrication, simple to use, and better uniformity of coating with relatively less efforts.
29
Inlet for
Oxygen
Outlet for
Product
gases
Reactor body
Threaded
holes for
screw
O Ring
Reactor base
Figure 4.3: The Vertical Reactor Geometry Used in CVD System Fabricated
30
The reactor has two inlets, one for precursor other for oxygen. There is one outlet
for exhaust of waste gases as shown in figure. At the junction of inlets, the gases are
mixed and travel downwards. The reactor body is kept in a conical shape next to the
entrance of the gases so as to provide a streamline flow of gases. The mixture propagates
downwards where a heater with the substrate is placed.
The reactor chamber is made up of quartz. Besides being transparent, quartz has
the advantage that it can withstand higher temperature, which makes it possible to go to
higher growth temperatures as compared to glass during deposition.
The reactor is cleaned in organic solvent, acid washed for hour and finally
cleaned in water and organic solvents before assembly. The assembly of the reactor
chamber and the heater are shown in the figure 4.3.
An aluminum stand is used to keep the heater vertical. The stand consists of an
annular ring which is supported by four rods , as shown in the figure 4.4. Over the rods
there is a threaded disk that holds the heater.
31
The heater is positioned in middle of the reactor. This allows the gases to mix
properly prior to reaction, and this also maintains a safe distance from exhaust, as some
uneven flow may be present near exhaust.
The stand is mounted over a nylon base, which supports the quartz reactor wall.
This joint is made air tight by using an O ring in the flanged coupling.
Heater
body
Holder
Electrical
connection for
power and
Thermocouple
32
4.2.2 Bubbler
The primary task of bubbler is to maintain study flow of precursor vapors to the
reaction chamber. Prior to discussion of bubbler details the properties of the precursor
used are mentioned here.
The precursor used for CVD system fabricated is Zinc acetylacetonate. Chemical
structure for the compound is shown in figure 4.6.
CH3
O-C
Zn
CH
O=C
CH3
2
33
Benign nature
easy to handle
Nitrogen gas is used to carry the vapors of the precursor to the reaction chamber.
This is done in a bubbler where nitrogen is bubbled through the precursor.. A small
furnace initially was used to maintain precursor at higher temperature. The construction
of the furnace is shown in figure 4.7.
High
temperature
zone
Ceramic
mount
Glass
wool
Steel
Container
Kanthal
wire
Figure 4.7: The Furnace Construction.
The furnace was prepared using kanthal wire wound over a ceramic muffle. This
ceramic muffle was then placed in a cylindrical container made up of steel. The space
between the ceramic and steel container was filled with glass wool, which is a very good
thermal insulator and prevents the surface from heating to higher temperatures. For the
34
furnace in this application, the outer surface temperature is not more than 50C; if
furnace temperature was maintained at 120 C. Controlling the current through the
heating coil controlled the temperature of furnace. A PT100 sensor was used to measure
the temperature. The sensor is placed on the body of the bubbler to be placed inside the
furnace. A digital ON OFF controller was used to control the temperature with accuracy
of 3C. Inside the furnace there is a constant temperature zone where the bubbler can be
placed.
Outlet
Heating coil
Inlet
Copper pipe
Steel
container
Precursor
35
Initially the bubbler was made of steel container. On the top two quarter-inch
copper tube were brazed through as shown in the figure 4.8. Nitrogen gas enters from one
of the copper tube into the bubbler where it gets saturated by precursor vapors. Other
copper tube carries out this saturated gas. This tube is maintained at high temperature by
winding kanthal tape over it.
This kind of setup for bubbler was very cumbersome and slow in response also
refilling of precursor was difficult. To overcome all these problems, a bubbler with a
different heating scheme was redesigned.
It is important to note that here the bubbler is required to maintain at temperature
well below 150C (around 110C). It is known that Teflon tapes could withstand more
than this temperature.
36
Precursor
inlet
Gas inlet
Gas outlet
Temperature
Controller
Kanthal
tape
SS
container
Thus the furnace was replaced by directly winding kanthal tape over metal
bubbler and using Teflon tapes for isolation. A new bubbler was designed with a
cylindrical body. At the top two quarter-inch tubes are brazed as before. Ferule connecters
are attached at outlets of these quarter inch tubes, and a inch tube is also brazed which
can be used to refill the precursor. At the time of working this inch tube was sealed as
shown in figure 4.9.
37
Over the vertical walls of the container a thick layer of Teflon tape is wound.
Over this layer kanthal tape is wound. The tape is wrapped around very carefully by
keeping it tight enough, but if tape is stressed very tight then it may cut the Teflon tape
beneath and may short with metal which is below the Teflon layer; Whereas if kanthal
tape is not tight enough then on heating it may expand and may loose the gripe and get
loosened. Also the spacing between adjacent kanthal tape windings is maintained
constant. This is important for uniform heating.
It is difficult to solder kanthal tapes to copper wires, thus the copper wire was
press fitted to make electric connection. To isolate the kanthal tape another layer of
Teflon tape is wound. This layer prevents any electric shocks and prevents kanthal tape
from external tempering.
PT100 is used as temperature sensor. It is placed at bottom plate of cylinder. The
position of sensor is chosen such that it is placed away from heating coils, the censor lies
just below precursor and thus gives the temperature of precursor more accurately, also
center of bottom plate is a symmetric point and the temperature will be unbiased to
distance from heating coil.
4.2.3.
Gas lines.
Gas flows in the system are managed through gas lines or lines. Gas flows
through cylinder to bubbler, and then bubbler to reaction chamber, are maintained
through lines. There are many joints in line, joints are generally vulnerable to leakages
and thus these joints decide the pressure it can handle leak free.
38
The line carrying precursors, which are solid at room temperature, are vulnerable
to choking problem.
temperature solves the problem. Either maintaining whole system at high temperature or
heating the specific lines can be used to keep the lines from chocking.
Rotameter
Regulator
O
X
Y
G
E
N
Gas
Cylinder
Heated line
N
I
T
R
O
G
E
N
Reaction
Chamber
Bubbler
Bubbler
In the system inch copper tube are employed as lines. Ferules are employed for
connections as they can handle low pressures without considerable leaks.
39
The outlet of nitrogen cylinder is split into two lines using a T connector. Each
of these lines is connected to bubbler through flow meters. The flow meters used here are
rotameter type and have an inbuilt control knob to adjust the flow through.
The gas coming out of bubbler carries vapors. To avoid condensation of the
vapors in lines itself the lines needs to be maintained at higher temperature. This is done
by winding heating coil around the tubes carrying precursor.
Here it can be observed that temperature of the tube has to be maintained at
around 120C, and thus Teflon tape can be used here. Teflon tape is wound over copper
pipe to form a thick layer. Then kanthal tape is wind evenly over this Teflon layer. Over
this kanthal tape another layer of Teflon is wind to prevent shock and external
disturbance to kanthal tape. The electrical connections are done as for bubbler.
This technique cannot be directly applied at joints, valves. It was observed that if
these joints are not heated, the precursor starts settling on the internal walls, which may
lead to choking of lines. To heat these joints a kanthal tape mesh is used. First a piece of
kanthal tape is wound by Teflon tape of sufficient thickness. This makes the tape
electrically insulating. A mesh (net) is made out of this kanthal tape as shown in
figure 4.11 and now this net can be placed surrounding joints. And electrically these net
are placed in series with other heating coil on copper pipes. This prevents settling of
precursor inside the tubes.
40
Teflon winded
Canthol tape
Figure 4.11: The Teflon Coated Kanthal Tape Mesh Used for Heating.
To keep wiring handy banana pin connectors are used to join adjacent mesh etc.
41
The joint between glass reactor and copper tube carrying precursor cannot be
done using either ferule or flaring. A Wilson seal arrangement is used. Copper tube is
brazed to the coupling, the glass tube along with O ring are put inside as shown in the
figure 4.12 .i).
Copper
tube
Copper
tube
Threading
O Ring
Brazing
i)
ii)
Glass
tube
Figure 4.12 : The Coupling Used to Connect A Glass Tube and A Copper Tube.
The O ring is pressed tightly between the two threaded metal blocks as shown in
figure 4.12.ii) This O ring then isolates the glass rod from outside environment.
42
43
PT100
For line
temperature.
sensing
Power for
line
heater
Heated line
Reaction
Chamber
Bubbler
Cu(acac)2
To K-type
Thermocouple
PT100
Power for
heater
Bubbler
Zn(acac)2
Power for
bubbler
Controller
220V
44
Chapter 5
Experimental Details
5.1. Introduction
The CVD setup built provides the necessary conditions required to obtain thin
films of Zinc oxide. The system provides an environment, where the required growth
parameters can be adjusted to obtain good quality films. After the setup is fabricated, it is
required to set all the growth parameters to proper values to obtain Zinc oxide films. This
is done by growing films with systematic variations in growth conditions to obtain
optimal quality films.
Bubbler Temperature
The bubbler temperature governs the vapor pressure of the precursor material and
thus amount of precursor coming out with the carrier gas. The Zinc Acetylacetonate melts
at 124oC and thus bubbler temperature is varied between 95 oC to 120 oC, as to avoid
melting of precursor.
45
2.
Substrate Temperature
The substrate temperature is one of the most important growth parameter. The
reaction temperature at the substrate decides the reaction dynamics at the surface. The
precursor reacts at temperatures above 250 oC in oxygen to give zinc oxide. The
temperature of substrate has to be maintained above 250 oC.
3.
Line Temperature
4.
Oxygen Flow
Oxygen is required for cracking Zinc Acetylacetonate. The flow rate of oxygen decides
the amount of oxygen present in the reaction chamber. The presence of oxygen vacancies
in the film governs the resistivity of the film obtained.
5.
Nitrogen Flow
The flow rate of the nitrogen controls the amount of precursor entering the reaction
chamber. The nitrogen flow rate is maintained between .5 to 2 lpm.
46
During the work more than 50 films were grown. The growth conditions of some
of the important films grown are given as follows:
Oxygen
Nitrogen
Bubbler
Substrate
Flow
Flow
Temperature
Temperature
(lpm)
2
2
2
2
2
2
(lpm)
.5
.5
.5
.5
.5
.5
(oC)
108
108
108
108
108
110
(oC)
400
500
450
550
600
420
It was observed that after charging the bubbler, first few runs deliver bad quality
films. To avoid this, the bubbler prior to use is pre heated to a high temperature (at 115
o
47
48
5.4
Characterization techniques.
1.
Absorption spectrum
Absorption spectra are a very useful technique for characterization of transparent
semiconductor films due to its simplicity and ease, and are used routinely in this
dissertation work.
The photons of known wavelength are targeted on the film. Photons with energy
greater than band gap energy are absorbed whereas the photons with energy less than the
bandgap energy are transmitted. This transmitted light is observed using a photo detector.
For semiconductor materials one can observe a steep rise in absorption coefficient around
bandgap if wavelength is decreased.
The absorption spectrum gives information about the energy bandgap of the
semiconductor, the sharpness of the band edge gives idea about the quality of the film.
49
One can observe a hump in absorption spectra near band edge for Zinc oxide, this is due
to excitons.
The spectrometer UV-3101PC was used for taking measurements. The
spectrometer was used in transmittance mode, and a absorption spectrum in the
wavelength range of 2000 to 300 is recorded.
The transmission spectrum can be used to obtain the film thickness of the film.
The film thickness can be calculated using following formula
n
1
1
1 2
Where
d is film thickness
n is no of fringes observed
is refractive index of the film.
1wavelength of first
minima/maxima
2 is wavelength of last
minima/maxima
50
2.
X-Ray diffraction
X-Ray diffraction is a non-destructive tool to characterize microstructural
properties of semiconductor thin films such as crystallite size, strain and crystallographic
orientation. The high resolution X-Ray diffraction [30] technique has become essential
tool for characterizing semiconductor.
The machine used for X-Ray analysis is PANalytical X-Pert MRD. The Copper
K line was used (= 1.5405) for X-Ray diffraction. The machine was used in -2
mode to observe diffraction pattern.
Various characteristic peaks of Zinc oxide were observed and Full Width at Half
Maximum (FWHM) was measured.
The mean grain size can be calculated using Debye Scherrer formula:
d .9
B cos
Where
d is mean grain size
is wavelength of X-Ray used.
B is corrected FWHM in radians
is Bragg diffraction angle
2FWHM 2Crctn
Where
B is corrected FWHM
FWHM is observed FWHM in
radians
Crctn is correction factor for the
instrument used
51
3.
52
4.
mobility. The measurement is based on the Hall Effect discovered by E. H. Hall in 1879.
He found that if a magnetic field is applied perpendicular to the direction of current flow
in a conductor, an electric field perpendicular to the current and magnetic field is created.
VH
w
ls
l
VC
y
x
Figure 5.1: The Hall-Bar Configuration for Resistivity and Hall Effect
Measurements.
Ey
jx B
1
ne
Where
Where
53
E
Eyy is
is electric
electric field
field in
in yy direction
direction
jjx current
density in x direction
x current density in x direction
B
B is
is applied
applied magnetic
magnetic field
field
nn is
carrier
density
is carrier density
ee is
is charge
charge of
of electron
electron
Vx
j
1 E y 1 Vc w
x
Ex
neE x B E x B V H l
Where
Vc is potential difference in x
direction.
VH is Hall voltage.
l is length across which Vc is
measured.
w is the width of sample.
Ex is electric field in x direction.
VH
4
3
1
2
Figure 5.2:An Arbitrary Shape Used for van der Pauw Measurements
Let
54
Rij , kl
V kl
I ij
Where
Iij is current entering in contact i
and leaving from contact j
Vkl is Vk-Vl
d R 21,34 R32, 41
f
ln 2
2
arccos h
exp
Q 1 ln 2
f
2
Here Q = R21,34/R32,41, if this ratio is greater than unity; otherwise Q= R32,41/ R21,34
The Hall coefficient RH is calculated as
RH
d
B
R31, 42 R 42,13
In order to minimize errors, it is useful to average over current and magnetic field
polarities.
Then
RH
d 1
R31, 42 ( B) R13, 42 ( B) R42,13 ( B) R 24,13 ( B)
B8
55
The measurements were carried out for at room temperature. These measurements
were done using two Kiethley 236 Source-measurement units.
5.
Photoluminescence (PL)
The PL measurements were made at room temperature. The excitation source
used was He-Cd laser ( = 325nm). The emitted light was dispersed using a 0.5m
monochromator and detected using a Photo multiplier Tube.
56
Chapter 6
57
The exciton peaks are highlighted. The most prominent Exciton features are
observed in film grown at 450oC.
It can be seen that the slope of absorption at the band edge is better for the sample
grown at 450oC.
The sample thickness was calculated using the fringes observed in transmission
spectrum. The Table 6.1 shows the thickness calculated.
58
484
450(S45)
321
500(S43)
490
550(S50)
373
59
We find that the film deposited at 450 oC is predominantly oriented along the c
axis {strong (002) peak} but the other peaks, like (100) and (101) are also visible (JCPDS
no. 80-0075). At a deposition temperature of 500oC, the film obtained is mainly oriented
along the c axis and only a very small signature of (101) peak is observed. At a deposition
temperature of 550oC, the film is observed to be strongly c axis oriented. Figure 6.4 is a
60
plot of the calculated value of I(002)/I for different deposition temperatures. The value
of I(002)/I is an indication of the degree of orientation of the film. For the values of
I(002)/I close to 1, the films are highly c axis oriented.
We also find another X-ray peak, which is assigned to the (200) peak of the ZnO 2
phase (JCPDS no.13-0311). At a deposition temperature of 600oC, we find that the
crystalline quality reduces drastically resulting in very low intensity X-Ray peaks.
It can be seen that, as temperature is increased the sharpness of the peak increases,
this is reflected by decrease in FWHM as shown in the Figure 6.5, figure 6.5 shows
variation of FWHM with deposition temperature.
61
The grain sizes for above mentioned films are calculated, and are given in table
6.2
Table 6.2: Grain Size As Calculated from FWHM.
Deposition Temperature
Grain size
(oC)
(nm)
450
244
500
320
550
392
Resistivity and Hall measurement for samples grown at temperature 450 oC, and
500oC, and 550oC taken. The lowest resistivity of 5.8x10-2 ohm cm was observed for
sample grown at 500oC, also the sample showed a highest mobility of 3cm 2/VSec(**)
amongst the four samples mentioned.
Change this part after looking at the data.
63
SEM of sample deposited at 400oC is done, and the pictures obtained are shown in
figure 6.7.
64
Here one can observe hexagonal crystallite structure, which is expectedly due to
wurtzite structure of Zinc oxide.
65
6.5. Photoluminescence
Figure 6.9 gives the RT Photoluminescence (PL) data for the samples deposited at
different temperatures where it is found that the most intense PL is observed in the
sample deposited at 450oC.
1.0
Deposition temperature
o
450 C
o
500 C
o
550 C
PL Intensity (au)
0.8
0.6
0.4
x 10
0.2
**
0.0
400
500
600
700
800
wavelength (nm)
Figure 6.9: Room temperature PL data of ZnO films deposited at different substrate
temperatures. Beyond 510nm, the data is magnified by a factor of 10 indicating the
absence of deep centre luminescence.
66
67
Chapter 7
7.1. Conclusion
A working Single Source Chemical Vapor Deposition (SSCVD) system for
deposition of Zinc oxide thin films was successfully fabricated during the course of this
work. Zinc oxide films are deposited using the above-mentioned fabricated CVD system,
under various deposition conditions. Using this system, some growth parameters have
been optimized. The X-ray, optical absorption, photoluminescence, SEM, and electrical
characterization studies of some of these films have been carried out in this work.
Effect of deposition temperature on film quality was studied. Good exciton peak
and strong Room temperature PL was observed at lower deposition temperature
(~450oC). Although all the ZnO films were preferentially oriented along the c-axis the
highest oriented ZnO films, (oriented along the c axis) were obtained at higher
temperatures (~550oC). Furthermore with an increase of deposition temperature from
450oC to 550oC, the XRD (002) peak width decreases, indicating the formation of larger
size grains at higher deposition temperatures. We thus find that inspite of having oriented
films with larger grain sizes at high deposition temperatures (550 oC), the optical
properties degrade with deposition temperature, possibly due to the formation of certain
non-radiative recombination centers at high deposition temperatures. Furthermore, we
find that a second undesirable phase ZnO2 is formed at 550oC deposition temperature.
68
Use it for multiple materials to get ternary and quaternary semi conducting
materials.
69
ACKNOWLEDGEMENT
70
Accelerator Workshop staff for providing Workshop facilities at a brisk pace when ever it
was needed.
I certainly cannot thank enough but I truly appreciate all my friends Saurav,
Shatish, Vinod, Randhir, Shanti, Sandeep, Surrender, Laxmikant, and Rajeev who have
been like family members to me. I cannot conclude my acknowledgement without
expressing my indebt ness to my parents. It was through their blessing and love that I
could complete my work. I take this opportunity to dedicate this thesis to my beloved
parents.
Place - Roorkee
(Shreeniwas Daulatabad)
71
Page
No.
Title
Chapter 1 Introduction
1.1 General.
1.2 Objective
1
2
3
2.1 Semiconductor
2.2 Compound Semiconductor
5
5
6
10
11
2.5 Applications
2.6 Advantages of Zinc oxide over other semi conducting materials
15
Chapter 3
Growth Technologies
3.3 Introduction
17
19
20
21
22
23
26
Chapter 4
Fabrication of Chemical Vapor Deposition System
4.3 Introduction
4.4 The CVD system Design
27
27
4.4.1
Reaction Chamber
28
4.4.2
Bubbler
33
38
42
Chapter 5
Experimental Details
5.4. Introduction
45
72
45
47
49
6.
Absorption spectrum
49
7.
X-Ray diffraction
8.
51
52
9.
53
10.
Photoluminescence
56
57
60
63
64
6.10.Photoluminescence
66
68
69
REFERENCES
ANNEXURE
73
List of Figures
Figure
No.
2.1
2.2
11
4.1
A Vertical reactor
29
A Horizontal reactor
30
31
32
4.5
33
4.6
34
4.7
35
4.8
36
4.9
37
4.10
40
4.11
41
42
44
54
58
59
61
63
64
65
66
67
4.3
Title
74
Page
No.
6
55
62
68
List of Tables
Table
No.
Title
The III-V binary compounds
Page
NO.
8
9
75
15
48
60
63
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