Chapter 1

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

The following objectives are set for present work.

1.

To study the properties of the material Zinc oxide.

2.

To fabricate a Chemical Vapor Deposition (CVD) system for deposition of

thin films of zinc oxide.

3.

To grow thin films of zinc oxide and optimize the growth conditions to yield
good quality films.

4.

To characterize the films obtained.

1.3

Organization of the thesis.

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

The Compound Semiconductor: Zinc Oxide

2.1 Semiconductor
Semiconductors are a group of material with electrical characteristics between
metals and insulators. The electrical characteristics of semiconductor can be altered to a
dramatic extent by several ways including doping, temperature, optical excitation, stress
and other ways. This as well as other reasons make semiconductors the material of choice
for many electronic devices. Current electronic devices such as IC including
microprocessor used in personal computer, lasers, communication devices and a vast
array of other electronic devices are made using semiconductors.

Valance band
Valance band
Valance band
BG

BG
Conduction band

~1eV

Conduction band

~15eV

Conduction band

Conductor

Semiconductor

Insulator

Figure 2.1: Band diagram for Conductors, Semiconductors, and insulators.

Semiconductors are a group of materials typically referring to group IV elements of the

periodic table or combination of group III and V elements or combination of group II and
VI elements. Band theory can be used to classify the metals, semiconductors, and
insulators. Metals are class of materials which has valance and conduction band
overlapped, the insulators are those materials with high energy band gap between the
valance band and the conduction band, and semiconductor materials are those materials
with small band gap typically of the order of 1eV as shown in figure 1.1.
Some elements and many compounds show semiconductor behavior at room
temperature. Semiconductors from group IV are called elemental semiconductor because
they are composed of only one element. These semiconductors include Silicon (Si) and
Germanium (Ge). Some compounds of group III and group V elements as well as group
II and group VI elements shows semiconductor behavior at room temperature and are
called compound semiconductor.
The elemental semiconductors have achieved a high popularity due to its
relatively simple technology. Once germanium was most widely used semiconductor
material. It was then replaced by silicon due to its superior quality over germanium.

2.2 Compound Semiconductor

The search for new semiconducting materials with better properties still
continues, and the result is compound semiconductor. The compound semiconductors
show superior properties to silicon. The application of these compound semiconductors in
semiconductor industry is restricted due to relatively complex technology required for
growth and fabrication of devices and high costs involved. In spite of all these reasons,

the compound semiconductors promise to outperform silicon industry by performing the

tasks which are beyond the physical limits of silicon.
Most of the studied compound semiconductors come primarily from compounds
of elements from group III and group V of periodic table or compounds of elements from
group II and group VI of periodic table. Some IV-VI compounds also exhibits
semiconducting properties, but most of them have a small band gap that limits there use
to infrared detectors and lasers [3].
Following tables Table 2.1 and Table 2.2 shows the possible compounds that can
be formed from III-V group and II-VI group respectively.

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.

The technical importance of these compound semiconductors is that they provide

a wider choice of band gap in comparison to elemental semiconductors. Some of them
8

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.

2.3 The Zinc Oxide

Zinc Oxide is an II-VI group semiconductor material. The material is gaining
much attention in recent years, due many of its useful and highly flexible properties. Zinc
oxide has a wide direct band gap and a hexagonal wurtzite crystal structure.[4].

Figure 2.2: Wurtzite crystal structure.

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

2.4 Zinc Oxide material properties

Zinc oxide has molecular mass of 81.389 amu (**), and its specific gravity at
room temperature is 5.642 g/cm3. Zinc oxide has a melting point of 2250K (**). Zinc
oxide crystal has cell parameters as a=.325nm and c=.520nm at room temperature and
room temperature linear thermal expansion coefficients are
a-axis direction

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

Energy band gap

Zinc oxide has a band gap of 3.4eV [6], which falls in ultra-violate region in

electromagnetic spectrum. The band gap is direct in nature; this gives it many interesting
applications in optoelectronic devices.

2.4.2

Chemical (Stoichiometric) stability

Zinc oxide like many other oxides, is chemically stable[7]. This is important

property for deciding the life of the device manufactured.

2.4.3

Exciton binding energy

An exciton is a bound state of an electron and a hole in an insulator or

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,

it mean excitons in zinc oxide are stable at room

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

Table 2.3: Properties of some of the Compound Semiconductors.

Lattice

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

Light emitting devices.

Due to a band gap of 3.4 eV Zinc oxide finds applications as ultra-violet light

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

Solar blind ultra violate light detector.

The Zinc oxide has a band gap situated at the boundary of visible light and ultra

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

Transparent Thin Film Transistor (TFT).

In modern flat panel displays Active Matrix Display technique is used, where a

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

Quantum well devices.

Quantum well device can be fabricated by stacking thin layers of semiconductor

material with different band gap. The band gap of Zinc oxide can be tailored by making
ternaries.

16

2.5.7

Material for Spintronics.

The Zinc oxide shows ferromagnetism if doped with Magnesium oxide. Thus zinc

oxide can have both ferroelectric as well as semiconducting properties this makes
material suitable for spintronics applications.

2.6

Advantages of Zinc oxide over other semi conducting materials

The material exhibits a good combination of attractive unique properties,

flexibility, and stability. This all gives the material a leading edge over other materials.
Some of them being as follows:

2.6.1.

High exciton binding energy.

The Zinc oxide has high exciton binding energy, which is 59 meV at room

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.

Band gap can tailored

One of key advantage of using compound semiconductor is the

band gap of material can be tailored [16]to desired values depending

on the requirements. For Zinc oxide this is achieved by making ternary
with other elements like magnesium (band gap 7.8eV) .

17

2.6.3.

Larger operating temperature range

The zinc oxide has a large band gap. This enables the device fabricated from zinc

oxide to with stand a wide temperature range as compared to other semiconductor

material like silicon.

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.

Low Dark Current

The high band gap of material gives it advantage of very low dark current. This

makes detectors fabricated from Zinc oxide to give superior spectral response for ultra
violate radiation.

2.6.6.

Large Shear Modulus

The zinc oxide has very large shear modulus of 45.5 Gpa as compared with 18.35

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

processes are especially suitable if polysilicon, polycides, or refractory metals are to be

deposited.

3.2

Classification of deposition technologies

There are a large number of deposition technologies for material formation [18].

Some of important and especially useful in thin film deposition methods are listed
bellow:

Evaporative Methods

Vacuum Evaporation

Electron beam evaporation

Molecular beam epitaxy (MBE)

Glow-Discharge Methods
Sputtering

Plasma Processes

Reactive sputtering

Plasma-enhanced CVD

Magnetron sputtering

Plasma Oxidation

Ion bean Deposition

Cathodic arc deposition

20

Gas Phase Chemical Processes

Chemical Vapor deposition(CVD)

Thermal forming Processes

Atmospheric-pressure CVD

Thermal oxidation

Low-pressure CVD

Thermal polymerization

Metal-Organic CVD

Photo-enhanced CVD

Liquid-Phase Chemical Techniques

Electro Processes

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

resistance-heated filaments, electron beams, crucible heated by conduction, radiation, or

rf-induction, arcs or lasers. Additional complications may include high vacuum, precise
substrate motion (to ensure uniformity) and need for process monitoring.
Molecular beam epitaxy (MBE) : MBE is a sophisticated ,finely controlled
method for growing single crystal epitaxial films in a high vacuum (10 -11torr)[19]. The
films are formed on single crystal substrates by slowly evaporating the elemental or
molecular constituents of the film from separate Knudsen effusion source cell (deep
crucibles in furnace with cooled shrouds) onto substrates held at a temperature
appropriate for chemical reaction, epitaxy, and re evaporation of excess reactants. The
furnace produces atomic or molecular beam of relatively small diameter, which are
directed towards heated substrate. Fast shutters are interposed between the source the
substrate. By controlling this shutters, one can grow superlattice with precisely controlled
uniformity, lattice match, composition, dopant thickness and interfaces down to the level
of atomic layers. Growth of high quality Zinc oxide have been reported using Molecular
Beam Epitaxy [20].

3.2.2.

Glow Discharge Technologies

The electrode and gas phase phenomena in various kinds of glow discharges

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

In Sputtering process the ejection of surface atoms from an electrode surface by

momentum transfer from bombarding ions to surface atoms, forms an epi layer. Since the
surface atoms comes out and thus this process can also be used for etching, or surface
cleaning. Growth of c-axis oriented films using sputtering have been reported(**).[21]
In Plasma process, the fact that some chemical reactions are accelerated at a
given temperature in presence of energetic reactive-ion bombardment, is the basis of
processes for surface treatments such as plasma oxidation,and plasma nitriding etc.
Growth of ZnO nanotubes and nano wires have been reported using this technique.(**)
[22]

3.2.3.

Gas Phase Chemical Process

Method of film formation by purely chemical processes in gas phase or vapor

phase includes chemical vapor deposition and thermal oxidation.

Chemical Vapor

Deposition (CVD) is a material synthesis process whereby constituents of vapor phase

react chemically near or on a substrate surface to form a solid product. The deposition
technology has become one of the most important mean for creating thin film and coating
of a very large variety of materials essential to advanced technology(**)[23], particularly
solid state electronics where some of the most sophisticated purity and composition
requirements must be met. The main feature of CVD is its versatility for synthesizing
both simple and complex compounds with relatively ease and at generally low
temperatures. Both chemical composition and physical structure can be tailored by
control of reaction chemistry and deposition conditions.

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:

1. Low Pressure Chemical Vapor Deposition (LPCVD): Reactor operates at a low

pressure (typically 0.1 to 10 torr) for LPCVD system.

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]

2. Photo Enhanced Chemical Vapor Deposition (PHCVD): PHCVD is based

upon the activation of reactants in the gas phase or vapor phase by
electromagnetic radiation, usually short wave ultra violate radiation. Selective
absorption of photons by reactant molecules or atoms initiates the process by
forming reactive free radical species that then interact to form a desired film
product.

24

3. Metal Organic Chemical Vapor Deposition (MOCVD): The growth of thin

layer of compound semiconducting materials by the copyrolysis of various
combinations of organometallic compounds and hydrides, known generically as
metal-organic chemical vapor deposition. Preparation of all II-VI, III-V
semiconductors has been successfully demonstrated by MOCVD [25].

organometalic compound RnM where M is a II ,III group element and E R m

where E is a element from V,VI group of periodic table and R n, Rm being methyl,
ethyl radical or a hydrogen atom are taken as precursors. The general over all
chemical reaction that occurs during the MOCVD process can be written as
R n M v ER ' m M v ME s nRR' v

As an example reaction involve in formation GaAs is given below:

AsH 3 Ga(CH 3 ) 3 GaAs 3CH 4

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.

Liquid phase Chemical Techniques

The growth of inorganic thin films from liquid phase by chemical reaction is

accomplished primarily by electrochemical processes(which include anodization and

electroplating), and by chemical deposition process. Another class of film forming
method from the liquid phase is based on chemically reacting films that have been
deposited by mechanical techniques. mechanical techniques for deposition coating from
liquid media, that are subsequently reacted chemically, to form the inorganic thin film
product are spraying, spinning, dipping and dragging, flow coating, and roller coating
etc. Chemical reaction of the coating residue, often by thermal oxidization, hydrolysis, or
pyrolysis produces desired solid film. Growth of Zinc oxide films have been reported
using this technique [27].

26

Chapter 4

Fabrication of Chemical Vapor Deposition

System
4.1

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

The CVD system Design

To obtain Zinc oxide thin films on a substrate, a CVD system was fabricated at

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

4.2.1 Reaction Chamber

Reaction chamber provides an isolated environment for reactants where they react
to produce required product.
There are two types of reactors
1) Vertical reactors
2) Horizontal reactors
Reactant
gases

Substrate

Heater

Product
gases

Figure 4.1: A Vertical Reactor

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

Figure 4.2: A Horizontal Reactor

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

The reaction chamber consists of

1. Reaction chamber wall
2. Heater and its support.

The major roll of the reaction chamber body is

1) To prevent the reactants from interacting with outside environment.
2) To provide proper structure for inlet and outlet of reactants.
3) To maintain proper concentrations of reactants surrounding the heater,
where they react.

Inlet for precursor

Zn(acac)2

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.

Figure 4.4: The Heater Stand Used in The Reactor.

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

Figure 4.5: The Heater Geometry Used in Reactor.

We have used an SS resistive heater. The heater has cylindrical geometry as

shown in the figure 4.5 and has a diameter of 2.5 inches, which makes maximum
allowable substrate size up to 2 inches. The heater is mounted in vertical fashion. The
heater has an inbuilt K-type thermocouple. The temperature of heater can be increased
without damaging up to 800C in oxygen ambient.

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

Figure 4.6: Chemical Structure of Zinc Acetylacetonate.

The Zinc acetylacetonate is white crystalline powder at room temperature with a

melting point of 124 oC. The material has low vapor pressure at room temperature, but
has sufficiently high vapor pressure at elevated temperatures. The Zinc acetylacetonate
reacts with oxygen at high temperature to give Zinc oxide. Although there are some other
precursors available to obtain Zinc oxide by CVD technique like Dimethyl Zinc (DMZn),
Diethyl Zinc (DEZn)[31] etc. , but Zinc acetylacetonate has some advantages over them,
as mentioned:

33

Benign nature

easy to handle

Doesnt catch fire spontaneously (as DMZn, DEZn )

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

Figure 4.8: A Bubbler Used for Solid Volatile Precursor.

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

Figure 4.9: The Bubbler Design Used for CVD Fabricated.

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.

Maintaining the temperature of the line more than bubbler

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.

The lay out diagram for CVD is shown in figure 4.10.

Rotameter
Regulator
O
X
Y
G
E
N

Gas
Cylinder

Heated line

N
I
T
R
O
G
E
N

Reaction
Chamber

Bubbler

Bubbler

Figure 4.10: The Layout Diagram.

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

4.3. Control and Monitoring

Apart from these blocks a control system is needed to control the temperatures of
various units as mentioned. This is done using an ON OFF digital controller. The
controller has a least count of 0.1C for PT100 temperature sensor and 1 C for K-type
thermocouple input. The set point can be set with accuracy of 1C. The controller drives
output through a relay. The relay can handle a maximum current of 3Amp at 220V rms.
The controller displays the process temperature and this allows one to monitor the
temperatures of substrate and bubbler. Although the digital ON OFF controller has
hysteresis option to avoid race around condition (high speed switching of output relay),
but it is not required to use it for the system as the heating and cooling processes are slow
enough to avoid high frequency switching, also the PT100 is placed away from heating
coil, this distance adds a delay in control mechanism and further decreases the frequency
of switching. In the case of lines the sensor is placed at a point, where while heating,
lowest temperature is observed, this ensures sufficient high temperature in line so that
precursor dont condense at any point in the line. The connection diagram is shown in
figure 4.13.
Rotameters are employed to control and monitor the flow of gases. The rotameters
used has a range of 0-2 lpm.

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

Figure 4.13: The Connection Diagram.

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.

5.2. Growth parameters

For the system fabricated, there are five parameters that can be controlled as
mentioned below.
1.

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

The temperature of lines carrying precursor vapors has to be maintained at a temperature

more than that of bubbler temperature to ensure the precursor dont condense or deposit
inside the line. The line temperature doesnt play any role in film growth and is not
critical parameter. The temperature of heated line is maintained at 120 oC as bubbler
temperature is not supposed to be more than this.

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.

The oxygen flow rates is

maintained in a range of 0 to 2 liters per minute (lpm)

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:

Table 5.1: Growth. Parameters for Some of The Films Deposited.

Sample
Number
S33
S43
S45
S50
S47
S20

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

5.3. The sequence of operations

The growth zinc oxide layer on substrate comprises of following steps in given
order:
1. Charging of bubbler with precursor
The bubbler is charged if adequate amount of precursor is not present in side the
bubbler. The bubbler is charged with 5 gm of zinc acetylacetonate. The cap is screwed air
tight and is checked for any leakages.

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

C) for half an hour.

47

2. Clean the substrates

The substrates are acid washed using following procedure:
The substrates are washes using detergent soap; this removes any grease or oil
layer present on the substrate. The substrate then is kept in concentrated HCl acid to
remove any metallic or other dust particles. The substrate is then boiled in
trichlroethylene (TCE) and acetone for 10 minutes each.

3. Heat the lines and substrate

The lines should be heated to its set point, prior to heating of bubbler. This is done
to ensure that any material entering the line dont deposit on its walls. The substrate
heater is also turned on simultaneously as its takes long time to attain the given
temperature, which is in range of 350 oC to 600 oC.

4. Heat the bubbler and start gas flow

After the temperature of line reaches the set point, the bubbler heater is turned on.
The nitrogen and oxygen flow is started after the temperature of bubbler and substrate is
stabilized at there respective set points. The deposition starts with the flow of gases.

5. Stop substrate heating, bubbler heating

After growth period is complete the substrate heater and bubbler heater are
switched off.

48

6. Stop oxygen flow and nitrogen flow

The oxygen flow is turned off after the growth is over. The nitrogen flow is
stopped after the bubbler temperature falls down to 50 oC. This is done to avoid any
settlement of precursor in the tubes.

7. Stop line heating

After nitrogen flow is turned off the line heating is stopped. As there is no
precursor coming out from bubbler into the lines, it is safe to turn off the line heating.

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.

Scanning Electron Microscopy (SEM)

The SEM is one of the most useful and versatile instruments for the investigation

of surface tomography, microstructure features, etc. It provides a pictorial display of the

surface layer with a high resolution greater than that possible in a optical microscopy.
The principle involved in imaging is to make use of the scattered secondary
electrons when a finely focused electron beam impinges on the surface of the specimen.
At the point of contact several processes may take place by which electrons, photons, etc.
may be emitted. In SEM the secondary electron are primarily used. These generally have
very low energy say less than 50eV compared to tens of kilo electron Volts of the primary
electrons and hence only those secondary, which are generated at surface layers, can
leave the surface. These secondary electrons are sensed.
The basic instrument consist of an electron source, a series of lens system to
produce finely focused electron beam on the specimen surface, two pair of deflection
coils at right angle to each other and connected to saw tooth wave generator system so
that the electron beam describes a rectangular zigzag raster. The emitted secondary
electrons are collected a collector which is amplified and then fed to a cathode ray
display tube (CRT), where the surface patterns can be observed.
The (SEM machine name Philips X-40) was used to obtain images of the zinc
oxide films deposited using the fabricated system. As the conductivity of films is not
sufficient for SEM, a thin film of gold is deposited over the specimen films.

52

4.

Hall mobility, resistivity measurement.

Hall measurements yield the information about the carrier concentration and

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.

The hall coefficient RH is defined as

RH

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

The Hall mobility can be calculated as

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.

The measurements were made by a four probe method in the Van-der-Paaw

geometry, and substrates are cut in rectangular shape.

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

Then the resistivity of the sample can be calculated as follows:

d R 21,34 R32, 41

f
ln 2
2

Where f is determined from a transcendental equation:

1
ln 2
Q 1
f

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

R13, 42 ( B ) R31, 42 ( B ) R 24 ,13 ( B ) R 42 ,13 ( B )

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

Results and Discussion

6.1. Absorption spectrum

The transmittance and absorption spectrum of the films grown at deposition
temperature 400 oC, 450 oC, 500 oC, and 550 oC are shown in figure 6.1.

Figure 6.1: Absorption Sectrum of Zinc Oxide Aound Bndgap

57

The exciton peaks are highlighted. The most prominent Exciton features are
observed in film grown at 450oC.

This suggests that the film grown at substrate

temperature of 450oC is having better optical properties as compared to other deposition

temperatures.

Figure 6.2: Transmittance spectrum of Zinc Oxide around bandgap

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

Table 6.1: The Film Thickness Calculated Using Absorption Fringes.

Sample
Film thickness
Deposition
calculated
Temperature
(nm)
(oC)
400(S33)

484

450(S45)

321

500(S43)

490

550(S50)

373

59

6.2. X-Ray Diffraction

X-Ray Diffraction of films grown at deposition temperature 450 oC, 500oC, 550oC,
and 600oC was done to observe the effect of growth temperature on the crystalline quality
of the film. The X-Ray diffraction of the samples is as shown in figure 6.3.

Figure 6.3 : Comparison of Crystalline Quality As A Function of Growth Temperature

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.

Figure 6.4: Variation of I(002)/I with Deposition Temperature

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.

This indicates improvement in

crystalline quality of the film and increase in the grain sizes.

61

Figure 6.5: Variation of FWHM with Deposition temperature.

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

6.3. Hall and resistivity measurements

62

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.

Variation of resistivity of the sample with deposition temperature is as shown in

Figure 6.6.

Figure 6.6: Variation of Resistivity With Deposition Temperature.

It can be seen that optimal deposition temperature for growing the films of lower
resistivity is in range of 450oC to 500oC.

63

6.4. Scanning Electron Microscopy

SEM of sample deposited at 400oC is done, and the pictures obtained are shown in
figure 6.7.

Figure 6.7: SEM Picture of Sample S20 Grown at 420oC.

64

Figure 6.8: Highlighting hexagonal structure

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

* Laser Plasma Lines

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

Figure 6.10: The Room temperature PL intensity maxima as a function of deposited

temperatures.
Thus it is found that although the crystalline quality of the Zinc oxide layers
improve with increase in deposition temperature, the PL intensity reduces. This is most
probably due to the generation of non-radiative carrier recombination centers at high
growth temperatures that reduce the PL intensity. Another significant observation in the
RT PL data for all the samples is that, none of the films have any luminescence from deep
centers in the visible part of the spectrum. 10K PL of the sample deposited at 450 oC also
shows no visible PL from the deep centers in the visible part of the spectrum.

67

Chapter 7

Conclusions and Recommendations

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

7.2. Scope of future work

This thesis discusses the fabrication of CVD system, and optimization of certain
parameters to obtain good quality films. As future work following work is suggested

Optimize flow rates.

Use it for multiple materials to get ternary and quaternary semi conducting

materials.

Use different substrates.

69

ACKNOWLEDGEMENT

I express my deep sense of gratitude and indebt ness to my supervisor Professor

R. Nath, Department of Physics and Mr. T. Ganguli, Center for Advanced Technology,
Indore whose invaluable guidance, perspective criticism and gracious suggestion have
been indispensable in the successful completion of the present dissertation. I would also
like to thank Dr. Tarun Sharma, Dr Vijay Dixit of Center for Advanced Technology,
Indore. I feel too short of dictum to thank them for encouraging and inspiring me
constantly through the whole period of my dissertation. I would also like to thank them
for giving me opportunity to express my views freely and for nourishing ideas with
clarity of thoughts. I am thankful to Dr. K.C. Rustagi and Shri T.P. Nathan of Center for
Advanced Technology, Indore for providing me a very healthy and supportive
atmosphere.
I acknowledge Dr. A.K. Srivastava for doing the SEM characterization of
samples, I acknowledge Dr. Vijay Dixit and Mr. Ravi Kumar for their help in electrical
characterization, I acknowledge Mr. A.K. Karnal and Mr. Bagare for sharing there
experience and the help provided for construction of the furnace. I acknowledge
Dr. Tarun Sharma and Mr. Sanjay Porwal for Photoluminescence measurements of the
samples. I acknowledge Mr. Nakul and Mr. Sandeep Kamboj for providing a very
friendly, helpful, and supportive environment. I acknowledge Mr. U.K. Ghosh, Mr.
Jayaprakash Mr. J.K. Badjatya for their support and help throughout the course of work. I
would specially like to thank Mr. L.Sudarshan and Mr. U.S. Mehto and all other

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.

Date June 30, 2005

Place - Roorkee

(Shreeniwas Daulatabad)

71

Page
No.

Title
Chapter 1 Introduction
1.1 General.
1.2 Objective

1
2
3

1.3 Organization of the thesis.

Chapter 2

The Compound Semiconductor Zinc Oxide

2.1 Semiconductor
2.2 Compound Semiconductor

5
5
6

2.3 The Zinc Oxide

10

2.4 Zinc Oxide material properties

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

3.4 Classification of deposition technologies

20

3.4.1. Evaporation technologies

21

3.4.2. Glow Discharge Technologies

22

3.4.3. Gas Phase Chemical Process

23

3.4.4. Liquid phase Chemical Techniques

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

4.3.3. Gas lines.

38

4.4. Control and Monitoring

42

Chapter 5
Experimental Details
5.4. Introduction

45

72

5.5. Growth parameters

45

5.6. The sequence of operations

47

5.5 Characterization techniques.

49

6.

Absorption spectrum

49

7.

X-Ray diffraction

8.

Scanning Electron Microscopy

51
52

9.

Hall mobility, resistivity measurement.

53

10.

Photoluminescence

56

Chapter 6 Results and Discussion

6.6. Absorption spectrum

57

6.7. X-Ray Diffraction

60

6.8. Hall and resistivity measurements

63

6.9. Scanning Electron Microscopy

64

6.10.Photoluminescence

66

Chapter 7 Conclusion and Recomendations

7.1. Conclusion
7.2. Scope of future work

68
69

REFERENCES
ANNEXURE

73

List of Figures
Figure
No.
2.1

Band diagram for Conductors, Semiconductors, and insulators.

2.2

Wurtzite crystal structure.

11

4.1

A Vertical reactor

29

A Horizontal reactor

30

The vertical reactor geometry used in CVD system Fabricated

31

The heater stand used in the reactor

32

4.5

The Heater geometry used in Reactor

33

4.6

Chemical structure of Zinc acetylacetonate

34

4.7

The furnace construction

35

4.8

A bubbler used for solid volatile precursor

36

4.9

The bubbler design used for CVD fabricated

37

4.10

The lay out diagram

40

4.11

The Teflon coated Kanthal tape mesh used for heating

41

The coupling used to connect a glass tube and a copper tube

42

The connection diagram.

44

The Hall-bar configuration for resistivity and Hall effect measurements

An arbitrary shape used for van der Pauw Measurements

54

Absorption Spectrum of Zinc Oxide Around Bandgap

58

Transmittance spectrum of Zinc Oxide around bandgap

59

Comparison of Crystalline Quality As A Function of Growth

Temperature
Variation of I(002)/I with Deposition Temperature

61

Variation of FWHM with Deposition temperature

63

Variation of Resistivity With Deposition Temperature

64

SEM Picture of Sample S20 Grown at 420oC

65

Highlighting hexagonal structure

66

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
The Room temperature PL intensity maxima as a function of deposited
temperatures

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

The II-VI binary compounds

Properties of some of the Compound Semiconductors.
Growth. Parameters for some of the films deposited.
The Film Thickness Calculated Using Absorption Fringes
Grain Size As Calculated from FWHM

75

15
48
60
63

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