AN ELECTRON-CYCLOTRON-RESONANCE PLASMA APPARATUS FOR

HYDROGENATED AMORPHOUS-SILICON THIN FILM PRODUCTION

by
CRAIG C. YOUNG, B.S. in M.E., B.S. in E.E.

A THESIS

IN

ELECTRICAL ENGINEERING

Submitted to the Graduate Faculty

of Texas Tech University in
Partial Fulfillment of
the Requirements for
the Degree of
MASTER OF SCIENCE
IN
ELECTRICAL ENGINEERING

Approved

December, 1990
 73
^'^^^ ACKNOWLEDGMENTS

I would like to thank my committee members. Dr. Thomas

Trost, Dr. Magne Kristiansen, and Dr. Shubhra Gangopadhyay, for
their time and devotion towards this research. A special heart-
felt thanks goes out to my committee chairman. Dr. Thomas Trost,
without whose guidance and perseverance I would not have been
able to attain my goals.
I would also like to thank everyone associated with the
Pulsed Power Laboratory for their cooperation and diligence. A
special thanks to Kim Zinzmeyer, Chris Hatfield, Ellis Loree, and
John Bridges for the use of their ears and their endless assistance
towards the completion of this research.
To my wife Victoria, I cannot express the gratitude that she
so deserves. I am eternally indebted to her for the
encouragement, understanding, and support she gave during this
period. Because you have walked beside me along my path, I will
strive to tread upon yours.

11
 CONTENTS

ACKNOWLEDGMENTS ii
ABSTRACT v
TABLES vi
nOURES vii
CHAPTER
I. INTRODUCTION 1
II. AMORPHOUS SILICON 3
Introduction 3
Amorphous Silicon 6
Hydrogenated Amorphous Silicon Properties . . . . 8
The Role of Hydrogen 8
Bandgap and Carrier Transport 8
Doping 11
Absorption 12
Hydrogenated Amorphous Silicon Solar
Cell Structures 14
The Need For Photovoltaic Energy Conversion ..14
Advantages of Amorphous Silicon Solar Cells ..15
Types of Solar Cell Structures 16
Solar Cell Conversion Efficiency 22
Stability 24
Conclusion 24
III. BASIC ELECTRON-CYCLOTRON-RESONANCE
PLASMA THEORY 27
Introduction 27
Microwave ECR Breakdown 28
Microwave ECR Energy Coupling 30
Energy Transfer 30
•• •
111
 Power Absorption in a Magnetic Field 32
Magnetic Mirror Effects 38
Conclusion 40
IV. SYSTEMLAYOUT 41
ECR Apparatus 41
Safety Interlocks 48
V. RESULTS AND CONCLUSION 53
Thin-Film Production 53
Parameter Effects 57
ECR Apparatus Improvements 62
Conclusion 66
REFERENCES 67

IV
 ABSTRACT

Chlorinated hydrogenated amorphous silicon (a-Si:H,Cl) films

and hydrogenated amorphous silicon carbide (a-SiC:H) films have
been produced using a microwave electron-cyclotron-resonance
(ECR) plasma deposition apparatus. The sophisticated ECR system
has performed reliably, producing very stable plasma discharges
for different gases, microwave powers, flow rates, magnetic field
strengths, and discharge pressures. Twenty-two a-Si:H,Cl films
and nine a-SiC:H films were produced using a silicon tetrachloride
(SiCU) liquid source and a proprietary liquid source, courtesy of
the J. C. Schumacher Company. The a-Si:H,Cl films have shown
high photoconductivity to dark conductivity ratios comparable to
good quality glow-discharge-prepared a-Si:H films; they are thus
suitable for solar cell fabrication. The a-SiC:H films have shown
high carbon contents with optical bandgaps on the order of 2.4 eV.
 TABLES

1. Applications of Amorphous Silicon 4

2. Sample Parameters For Silicon Tetrachloride 54
3. Sample Parameters For Proprietary Liquid Source . .5 7

VI
 HGURES

1. Average annual cost of photovoltaic modules.

(Reflects large orders (> 1000) of large modules
(> 30 Wp)) 6
2. Energy bands in a semiconductor. The density of
states (a) N(E)=0 in the bandgap of a crystalline
semiconductor and (b) N(E)7tO in the mobility gap
of an amorphous semiconductor 10
3. Schematic diagram of a-Si:H solar cells, (a)
Heterojunction structure with boron doped p-layer,
and phosohorus doped n-layer. (b) p-i-n structure
with doped microcrystalline (^c) n and p layers . . . 1 9
4. Stacked p-i-n type heterojunction structure 20
5. A large-area series-connected hydrogenated
amorphous silicon solar cell array 21
6. Microwave energy transfer in a discharge volume . . 3 1
7. (a) Electric field drift for an electron in crossed
electric and magnetic fields, (b) Electron motion
atECR 37
8. Plasma confined between magnetic mirrors 38
9. Schematic diagram of the experimental ECR plasma
deposition apparatus 42
10. Magnitude plot of axial magnetic field aligned with
microwave ECR deposition system. The peak to
minimum ratio is 1.3. Magnitude plot provided by
a magnet coil current (IB) of 300 A 43
11. (a) Sample holder showing feedthrough connections.
(b) Sample plug showing substrate mounting . . . .46
12. Closed-loop pressure control system 49
13. Deposition rate as a function of magnet coil current
at 0T=6 SCCM, P=2.6 mTorr, and Rsici4=16.7% . . . .5 9

Vll
14. Deposition rate as a function of plasma discharge
pressure at 0 T = 1 O SCCM, I B = 3 0 0 A, and
RsiCl4=10% 61
15. Deposition rate as a function of plasma discharge
pressure at 0 T = 3 3 SCCM, I B = 3 0 0 A, and
RsiCl4= 10% 62
16. Deposition rate as a function of SiCU relative flow
rate at 0 T = 1 O SCCM, I B = 3 0 0 A, and P=4.7 mTorr . .6 3
17. Deposition rate as a function of SiCU relative flow
rate at 0 T = 3 O SCCM, I B = 3 0 0 A, and P=11.4 mTorr . .6 4

Vlll
 CHAPTER I
INTRODUCTION

The objective of this research is the construction and testing

of a system to produce quality hydrogenated amorphous silicon
(a-Si:H) films using a new processing technique. This technique
utilizes a microwave electron-cyclotron-resonance (ECR) plasma
deposition apparatus. The system has a number of advantages
over its counterparts (e.g., glow dischage, sputtering, etc.) which
will be discussed in the chapters to come. The main advantage of
using an ECR system is that dense plasmas can be generated at
low processing pressures. The system allows the user to
manipulate various operating parameters so as to optimize the
deposition process. It is planned that various gases will be used
in the system. So far, silicon tetrachloride (SiCU) has been used as
the silicon source gas to avoid the risks of toxic/explosive silane
gas. A controlled mixture of silicon tetrachloride and hydrogen
gas is used to deposit chlorinated a-Si:H films (a-Si:H,Cl). A
proprietary source, from J. C. Schumacher company, is also used to
deposit carbon alloy a-Si:H films (a-SiC:H).
Since production of amorphous silicon films is the main
thrust for this research, a brief background of the material is
covered in Chapter II. A discussion of amorphous silicon solar
cells is also covered in this chapter.
The next chapter deals with microwave ECR theory where
the topics of ECR breakdown and microwave energy coupling are

1
discussed. The power absorption for an ECR plasma is examined
and compared to the power absorption necessary to maintain a
plasma in the absence of a magnetic field.
The system layout is illustrated and described in Chapter IV.
A novel arrangement for the microwave source is shown which
allows the ECR plasma to operate at very low impressed electric
fields. This is important since films produced at low absorbed
powers need to be investigated.
Effects of processing parameters on the plasma and film
deposition are discussed in Chapter V. A number of graphs are
shown to illustrate some of the processing parameter effects upon
the deposition rate. Conclusions and suggestions towards future
system improvements are also given.
 CHAPTER n
AMORPHOUS SILICON

Introduction
In the short span of a little more than a decade, the
electronic industry has seen the birth and evolution of a truly
spectacular technology, the development of hydrogenated
amorphous silicon (a-Si:H) as a new electronic material. The
technology has advanced from almost total obscurity to the point
of having established a viable position in the marketplace. The
cumulative substrate area coated per year with amorphous silicon
is more than 100,000 m2/year and may exceed ten times that
amount by century's end.^
As early as 1968, researchers were investigating amorphous
silicon for its photoelectronic properties. Not until 1974, though,
did the material finally display the capability to be used in
electronic devices. During this year RCA scientists fabricated the
first photovoltaic cell containing a-Si:H material, which was
patented in 1977.2-3 Since that time amorphous silicon has
become a mature technology covering a wide array of applications
and products, as shown in Table 1.
The photovoltaic cell is the most important of the
amorphous silicon devices listed in Table 1. Forty percent of
worldwide photovoltaic production is now amorphous silicon.5
The technology is growing to become one of the most promising
renewable energy resources for the future.
Table 1: Applications of Amorphous Silicon

Products Commercially Available

Device Product

Photovoltaic cell Calculators, watches, etc.

Photoreceptor Electrophotography, LED printers
Photoconductor Color sensors, light sensors, etc.
Image sensor Contact-type image sensors
Solar control layer Heating reflecting float glass
Anti-reflecting/antistatic layer Television screens
Thin-film transistor (TFT) Displays, televisions

Other Proposed Applications

Image pick-up tubes Passivation layers

Position sensors Charge-coupled devices
FETs for logic circuits Strain gauges
FETs for ambient sensors Photolithographic masks
Fast detectors and modulators
Diodes
Bipolar transistors
Optical Waveguides
Optical recording
LED's
 Hydrogenated amorphous silicon (a-Si:H) has shown
excellent characteristics for use not only in solar cells, but in
photosensitive devices,^ and thin-film tran sis tors. "^ The world-
wide interest, stimulated by the development of the a-Si:H solar
cell, has led to considerable advances in the understanding of a-
Si:H properties and fabrication. The rapid growth of amorphous
semiconductor technology is due to the material's amorphous
nature, and excellent optoelectronic properties.
For amorphous silicon solar cell technology to compete with
conventional energy sources, it must first demonstrate better cell
efficiency ( 10-15% range ), improved stability, and reduced cost
(less than $2 per peak watt (Wp)). Conversion efficiencies of 12%
for single-junction laboratory cells (l-cm2), and 13.7-15.6% for
multi-junction laboratory cells have been obtained.8-^o At
present, commercial solar cell modules stabilize at conversion
efficiencies of about 5% after one year of operation.
In the past, photovoltaic power has failed to compete in
traditional power generation markets due to high manufacturing
costs. Only recently has the technology made strides in competing
cost-wise, in some areas, with conventional energy sources.
Figure 1 shows the yearly decline in photovoltaic module cost
which is down from $13AVp in 1980, to $3.80AVp in 1988.5
When the selling price reaches $3AVp, solar cells become
cost effective with diesel motors in remote applications such as
irrigation and village power. Grid connected photovoltaic power
generation becomes economically viable for supplying peakpower
when prices decrease to about $2/Wp. However, for photovoltaics
to compete with nuclear and coal-fired generating plants, the
average selling price must decrease to less than $0.50/Wp.5

$/Wp

1980 1981 1982 1983 1984 1985 1986 1987 1988

YEAR

Figure 1. Average annual cost of photovoltaic modules.

(Reflects large orders (> 1000) of large modules (> 30 Wp)).

Amorphous Silicon
Crystalline silicon is characterized by both short and long-
range order, and an indirect bandgap. Amorphous silicon is
noncrystalline and lacks long-range periodic ordering. There
exists however, short-range ordering up to the third and fourth
nearest neighbors which is approximately the same as that for
crystalline silicon. The short-range order is directly responsible
for observable semiconductor properties such as optical
absorption edges and activated electrical conductivities.
The lack of long-range order in amorphous silicon (a-Si) is
the consequence of a very large density (lO^^ to 1020 cm-3) of
defects that exist primarily from broken bonds between the
silicon atoms. These unsaturated or 'dangling' bonds correspond
to atoms missing neighbors at those sites where periodicity is lost.
As a result, even though the nearest neighbor configuration
is similar to that in crystalline silicon, the effect of disorder in
amorphous silicon has a profound influence on its electrical and
optical properties. The disordered atomic structure of amorphous
silicon causes the material to act more like an insulator than a
semiconductor. The large defect density of gap states provides
fast nonradiative recombination centers that result in poor
electronic properties.
The high defect density in the gap of pure a-Si films makes
it impossible to change the position of the Fermi level by
introducing donor or acceptor type (e.g., phosphorus or boron,
respectively) dopants. This results from the fact that a change in
the position of the Fermi level requires a change of the state of
charge for an extremely large number of defect states. This
change in the state of charge cannot be compensated because the
 8
defect states act as trapping centers for charged carriers.
Therefore, the Fermi level is 'pinned' by the gap states in pure
amorphous silicon.

Hydrogenated Amorphous Silicon Properties

The Role of Hydrogen
In order to effectively dope amorphous silicon, unpinning of
the Fermi level is necessary. This is done by alloying the a-Si
with a passivating agent. Hydrogen seems the most logical choice
for this purpose. The incorporation of hydrogen passivates bonds
that would otherwise be dangling bonds, thereby dramatically
reducing the density of localized states (DOS) in the gap.
Hydrogenated amorphous silicon (a-Si:H) has a DOS less than 10^6
c m " 3 e V - l , which is a density of defects as low as that found in
good quality single crystal semiconductors.
The low density of localized states in a-Si:H produces
desireable device properties, including a relatively long minority-
carrier diffusion length. With passivation of the dangling bonds,
doping of the material can be carried out to produce p-type and
n-type semiconductors.

Bandgap and Carrier Transport

The nature of a-Si:H puts certain limitations on the
electronic properties which are not present in crystalline
semiconductors. This is due to the disordered atomic structure
inherent in amorphous materials but which is absent in the
periodic array of atoms of a crystal.
Energy band theory successfully predicts the semiconductor
properties of crystalline solids in terms of the conduction and
valence energy bands, Ec and Ey in Figure 2(a). These bands
describe the number of quantum states at each energy that
electrons and holes can occupy. The bands correspond to energies
where the densities of states that the electrons and holes can
occupy are high, and the charge carriers in these 'extended' or
'nonlocalized' states can move freely through the material.
Between the conduction and valence energy bands, the density of
states drops to zero, so that no electrons or holes with energies
that would be in the bandgap can exist. This results in the well-
known semiconductor 'forbidden gap' or 'bandgap.' The periodic
nature of crystalline material allows the charge carriers to have
large mean free paths, which results in high minority carrier
mobilities of the electrons and holes.
The atomic disorder inherent in amorphous semiconductors
causes distinct differences between them and crystalline
materials. The absence of long range order introduces many
imperfections, so that the carrier mean free paths become
significantly lower than in the crystalline materials. When the
disorder increases to the extent that the mean free path is
approximately equal to the interatomic distance, the charge
carriers become localized. The energy at which the mean free
path approximately equals the interatomic distance is called the
 10

Defect
States

T
> >

Bandgap

Tail
States

(a) Density of States (cm'^eV'^) (b) Density of States (cm'^eV'^)

Figure 2. Energy bands in a semiconductor. The density of

states (a) N(E)=0 in the bandgap of a crystalline semiconductor
and (b) N(E):?tO in the mobility gap of an amorphous
semiconductor.

critical energy, and represents the boundary between localized

and nonlocalized states. The resulting energy bands look similar
to those in crystalline semiconductors and are shown in Figure
2(b) where Ec and Ey are the critical energies for the conduction
and valence bands.
While a crystalline semiconductor has no energy states
available within the bandgap, an amorphous semiconductor has a
continuum of localized states. As charge carriers move within the
bandgap they are trapped by the tail states. This trapping slows
down the mobility of the carriers during conduction, to values
between 10-^ and 10-3 cm^V-^s"!. Within the conduction and
 11
valence bands carrier transport occurs via extended states with a
much higher mobility, 1 to 10 cm^V-ls'l, but significantly lower,
by a factor of 100 or more, than those in crystalline
semiconductors. So it is not the absence of states that gives rise to
the bandgap in an amorphous semiconductor but the very low
mobility within the gap. Therefore, the gap is more accurately
referred to as a mobility gap, and the carrier mobility is a trap
controlled transport property. This low mobility limits the
applications of amorphous semiconductors to areas where speed is
not of importance.

Doping
The ability to dope a-Si:H is the critical component that
allows it to be used in semiconductor devices. The low density of
midgap states allows the conductivity of hydrogenated amorphous
silicon to be modulated by doping. As in the case of crystalline
silicon, a-Si:H can be made n+ or p+ by the incorporation of
phosphorus or boron into the films. The doping efficiency in a-
Si:H is not as high as in crystalline silicon due to the
accompanyment of defects with the incorporation of dopants, and
the eventual pinning of the Fermi level by the tail states.
Doping a-Si:H with boron or phosphorus alters the transport
properties, reduces the minority carrier diffusion length, and
increases the density of states in the gap. In a solar cell, heavy
phosphorus doping leads to a decrease in the open-circuit voltage
(Voc) and to a lower short-circuit current density (Jsc)- The
 12
decrease in both VQC and Jsc reduces the overall conversion
efficiency of the cell. Heavy boron doping has the deleterious
effect of reducing the photoconductivity, by introducing a series
resistance. Here again, the cell conversion efficiency is sacrificed.
Nevertheless, the conductivities of intrinsic (undoped) a-Si:H of
10-8 to 10-12 i2-lcm-l can be increased to - 10-2 Q-lcm-l through
doping.

Absorption
The disorder and hydrogen content in a-Si:H makes its
optical properties quite different than those of crystalline silicon.
The absorption coefficient for amorphous silicon, in the
wavelength region corresponding to the solar spectrum, is an
order of magnitude higher than that for crystalline silicon.
The magnitude of the absorption coefficient depends upon
whether the semiconductor material used is amorphous or
crystalline. For crystalline material, the absorption coefficient also
depends upon whether it is a direct or indirect semiconductor. In
an indirect gap semiconductor, such as crystalline silicon, the
probability of light absorption is much less than for a direct gap
semiconductor. An excited electron in an indirect semiconductor
must go through a momentum change as well as an energy change
in order to reach the conduction band. For GaAs, which is a direct
gap semiconductor, an electron with energy equal to the bandgap
can make the transition from the valence band to the conduction
band without a necessary change in momentum. This satisfies the
 13
conservation of momentum requirement, thereby giving direct
gap semiconductors a much higher absorption coefficient. Since
amorphous silicon has no long-range order, the momentum
conservation rule does not apply. This results in a much larger
absorption coefficient for amorphous silicon.
The disordered structure in a-Si:H produces a larger optical
gap (-1.7 eV) than in crystalline silicon (-1.1 eV). This allows a-
Si:H films to absorb a significantly greater amount of light in a
comparable thickness. This means that an a-Si:H fllm needs a
layer less than 1 jim thick to absorb solar radiation at
wavelengths less than 0.7 jim, while its crystalline counterpart
needs a layer more than 20 times as thick. Therefore, amorphous
silicon, unlike crystalline silicon, can be used to make thin-film
solar cells.
The two most important mechanisms for the absorption of
light by a semiconductor are the excitation by a photon of an
electron from the valence band to the conduction band and
transitions within a band. The first mechanism, referred to as the
fundamental absorption, converts radiation into free electrons and
holes when a photon of energy, equal to the energy gap Eg, i s
absorbed. Only one electron-hole pair is generated for a photon
with energy larger than Eg. The excess energy is dissipated as
thermal energy and contributes nothing to the conversion process.
The second process is referred to as free carrier absorption where
the energy of a free carrier is increased and not used in the
photovoltaic conversion process.
 14

An increase in the hydrogen content causes the optical gap

to increase and the corresponding absorption to decrease.
Therefore, a low hydrogen content is needed to optimize the
optical gap; whereas a rather high hydrogen concentration is
required to eliminate the dangling bonds and to obtain good
electronic properties. The opposite is true for doping. It has been
found that doping, with donors and especially with acceptors,
increases the absorption coefficient and decreases the optical
bandgap.

Hydrogenated Amorphous Silicon

Solar Cell Structures
The Need For Photovoltaic Energy Conversion
In the not too distant future, renewable energy sources will
have to play a much larger role in meeting the world's energy
demands. Solar energy is attractive since it represents an
inexhaustible source, unlike depletable fossil fuels such as coal,
gas and oil. However, if solar energy is to be competitive with
other methods of power generation, the cost must decrease and
the operating conversion efficiency increase.
The importance of solar cells cannot be understated; since
their potential for large-scale power generation, capable of
meeting terrestrial energy requirements, is immense. Almost
everywhere on earth a typical house roof covered in solar cell
panels can supply enough electrical power for that household.
 15
The world's future population growth will occur in the third world
developing countries along with an increased demand for
electrical energy. The world's population presently stands at
approximately 5.5 billion, and will tower well above the 6 billion
mark by century's end. At that time, 40% of the world's
population will live in rural villages inside third world countries,
where stand-alone electrical energy generation serves as the most
practical solution to the estimated future lack of centralized
generation. Solar energy may prove to be very attractive in such
situations.
From an ecological point of view, solar cells can help fulfill
the need for clean renewable energy resources. Clean renewables
can conceivably reduce the global warming effects due to
hydrocarbons, dramatically decrease the conscious onslaught
against the world's forests, and extend the lifetime of the earth's
natural resources for generations to come.

Advantages of Amorphous Silicon Solar Cells

Amorphous silicon solar cells have a number of distinct
advantages over their crystalline counterparts; these are listed as
follows:
(i) Amorphous silicon has an absorption coefficient about
one order of magnitude greater than crystalline silicon in the
maximum solar energy wavelength region near 500 nm. This high
absorption coefficient allows a-Si solar cells to be constructed with
 16
an optically active region on the order of one micrometer thick,
instead of the necessary 20 jim for crystalline silicon.
(ii) Because less semiconducting material is needed in the
construction of amorphous silicon solar cells, and the growth
temperature is low (200 to 400 °C), the energy requirements in
the manufacturing process are much smaller. This savings reduces
the energy pay-back period.
(iii) Inexpensive substrate materials such as glass or
stainless steel can be used to deposite amorphous silicon since the
semiconductor has a noncrystalline lattice structure.
(iv) The lack of long-range periodic order in amorphous
silicon allows greater control of physical constants such as the
energy gap.
(v) Their fabrication processes are well suited to automated
large-scale, continuous, mass-production thin-film techniques.

Types of Solar Cell Structures

There are three basic types of amorphous silicon solar cell
structures, the Schottky barrier, the p-i-n, and the heterojunction.
The Schottky barrier solar cell has the simplest structure and
exhibits reasonable conversion efficiencies (5.5%)ii. It consists of
a transparent Schottky contact with a high work function, such as
platinum, on an intrinsic a-Si:H layer. Below the intrinsic layer is
a thin phosphorus doped a-Si:H layer deposited onto a metal
substrate. The drawback with Schottky barrier cells is that they
severely degrade in the presence of moisture, therefore causing
 17
stability problems. Better cell efficiencies are realized with p-i-n
junctions and heterojunctions.
Doped hydrogenated amorphous silicon exibits extremely
small minority carrier lifetimes. This is due to the large
concentration of defects incurred during doping. Therefore, p-n
junctions do not exhibit good conversion efficiencies. To obtain
better cells, the addition of an intrinsic a-Si:H layer, in a p-i-n
configuration, is used. The intrinsic layer is approximately fifty
times as thick as the p and n regions. The low density of gap
states (<10l6 cm-3) in the intrinsic layer allows the junction to
have a large depletion width with a high minority carrier lifetime.
Most of the light absorption occurs in the intrinsic layer
generating more carriers to participate in the conversion process.
In p-i-n device construction, a transparent conductive oxide
(TCO) such as indium tin oxide (ITO) is deposited onto a glass
substrate. In order to increase light utilization and thus the cell's
current, the surface of this film is textured.^^ Texturing reduces
the optical reflection of the incoming sunlight and increases the
optical path length in the material. The ITO film is followed by a
thin boron doped layer (10-30 nm), an intrinsic layer (300-600
nm), and a phosphorus doped layer (10-30 nm). The structure is
completed with the deposition of a metal reflector/contact, such as
silver or aluminum. Although p-i-n cells exhibit efficiencies at or
above 6%, a boron doped top layer is not very appropriate
because of the material's large absorption coefficient. The
extremely short minority carrier lifetime inherent in this layer
 18
will also degrade the cells efficiency. These effects drastically
reduce the conversion efficiency, especially in the short
wavelength range.
The problems with the p-type layer are corrected by
replacing it with a hydrogenated amorphous silicon carbide film
(a-SiC:H). Since the carbon doped film has a different bandgap
than intrinsic a-Si:H, a heterojunction is formed at the interface.
Carbon alloyed a-Si:H is a wide bandgap material (1.9 eV) that is
transparent to incident light. The layer increases the open-circuit
voltage of the solar cell by reducing carrier recombination at the
p-i junction.
Figure 3 illustrates two types of a-Si solar cell structures.
The p-i-n cell is the most common structure used in commercial
products. The heterojunction solar cell shown in figure 3(a) is
fabricated by first depositing a thin silicon-dioxide (Si02) buffer
layer on glass, and then depositing a 600 nm thick transparent
conducting oxide layer of tin-oxide (Sn02). This textured layer
enhances light trapping over the visible wavelength range and
reduces the series resistance of the cell structure. The p-type
layer (10 nm) is a boron doped wide bandgap a-SiC:H film. The
intrinsic a-Si:H layer is typically 250-500 nm thick with a slight
amount of boron doping to allow for better intrinsic behavior
under illumination. The n-type layer is a phosphorus doped a-
Si:H film about 20-30 nm thick. The rear contact is an evaporated
or sputtered aluminum. Manufacturers have achieved conversion
 19

h\)

Glass
SiO.
SnO,
a-SiC:H
a-Si:H

(a)

h\)

\ic SiC:H

a-Si:H

jxc Si:H n

(b)

Figure 3. Schematic diagram of a-Si:H solar cells, (a)

Heterojunction structure with boron doped p-layer, and
phosohorus doped n-layer. (b) p-i-n structure with doped
microcrystalline (|ic) n and p layers.
 20

efficiencies of 12% by replacing the rear aluminum contact with

an ITO/silver contact.^
Another commercially used amorphous silicon structure is
that shown in Figure 3(b). The substrate is stainless steel foil with
both the n-layer and p-layer doped microcrystalline (|ic) Si:H.
This configuration produces a flexible solar cell commonly found
in credit card-size calculators. Another flexible a-Si structure is
shown in Figure 4. In this case, two p-i-n structures are stacked
in tandem. The thicknesses of the a-Si:H layers are adjusted so
that the currents from the two cells are similar. For large-area
modules, the films are patterned to series-connect the cells as
shown in Figure 5.

h\)

••irro.
^c SiC:H P
a-Si:H i

^ic Si:H n
^ic SiC:H P

a-Si:H

^ic Si:H
Istainless steel!

Figure 4. Stacked p-i-n type heterojunction structure.

 21

Metal

a-Si:H
(p-i-n)
Glass Substrate rro

Figure 5. A large-area series-connected hydrogenated

amorphous silicon solar cell array.

Conversion efficiencies of 13.7% and 15.6% have been

obtained in multijunction laboratory cell structures that utilize a
narrow bandgap layer (a-SiGe:H:F and CdS/CuInSe2 layers,
respectively) to increase the collection efficiency in the red and
near infrared region. Since a-Si:H has a bandgap of about 1.7 eV,
most of the incident infrared radiation is passed through this
layer. Varying the concentration of germanium from 0 to 100%,
the optical bandgap of a-SiGe:H can be changed from 1.7 to 1.1 eV.
Unfortunately, only low levels of germanium can be incorporated
before the alloying seriously deteriorates the electronic properties
of the material. This deterioration is also common to carbon alloys
with high levels of doping. As a result, a-Si:H alloy solar cells can
 22

be fabricated with good electronic properties having optical

bandgaps between 1.45 and 1.9 eV.i3

Solar Cell Conversion Efficiency

There are several conditions that must be satisfied for
amorphous silicon solar cells to operate efficiently. First, the
optical absorption coefficient must be sufficiently large to absorb
a significant fraction of the solar energy in the film. For films on
the order of 1 jim in thickness, the absorption coefficient, a, must
be greater than 10^ cm-1 over at least the visible portion of the
solar spectrum. Second, the photogenerated electrons and holes
must be efficiently collected by contacting electrodes on both
sides of the semiconductor film. This implies that the minority
carrier diffusion length be comparable to the film thickness.
Third, a large built-in potential is necessary since it determines
the output voltage of the cell. This potential is generated by the
formation of a semiconductor junction such as a heterojunction, a
p-i-n junction, or a Schottky barrier. Finally, the total solar cell
series resistance must be kept small so that the IR drop is a small
percentage of the output voltage. Contributions to the series
resistance come from the bulk resistivity, the contacts, the current
collection grids, and the electrical wiring.
The conversion efficiency of a solar cell is defined as the
ratio of the maximum electrical power (Pm) to the power of the
incident light (Pi), both measured in Wcm-2. The equation can be
written as
 23

-_Jn.Vn,_(FF)JscVoc
^ Pi Pi • ^'^

where Jm and Vm are the output current density and voltage for a
cell operating under maximum output power conditions, and Pi is
the total power incident on the cell (Pi» 100 mWcm-2 for the sun
directly overhead on a clear day; AMI condition). Jsc is the short
circuit current density of the cell, and VQC is the open circuit
voltage of the cell. The fill factor (FF) is defined by

(FF) = imYm_, (2)

J'SC
sr V^ /OC

with a theoretical achievable value as high as 0.85. However,

series resistance effects will lead to considerably lower fill factors
of less than 0.75.
Several authors have estimated a theoretical limit on the
conversion efficiency for a-Si:H solar cells.i^ The maximum
conversion efficiency is found to be approximately 18%. The
upper limits for the three factors that determine the conversion
efficiency where calculated to be Voc«l V, Jsc=22 mAcm-2, and
FF«0.80. Higher efficiencies are possible if the density of states is
reduced.
 24
Stability
Optical degradation is the most important obstacle to
overcome if a-Si:H solar cells are to become a promising energy
source. This degradation is known as the Staebler-Wronski
effect. 15 It is a phenomenon, common to all amorphous silicon
alloys, of light-induced photoconductivity decrease. This
phenomenon seems to originate from the breaking of weak Si-Si
bonds by nonradiative recombination of photogenerated
carriers. 16-18 The breaking of weak bonds creates a large number
of metastable dangling bonds that degrade the cells
photoconductivity. This degradation seems to be self-limiting
though, since the number of created dangling bonds will saturate
and cause the collection width to decrease and saturate to a
smaller value.
Therefore, the degradation problem can be circumvented to
a point by keeping the device thickness approximately equal to
the smallest collection width attained. Another means of reducing
the degradation effects is to keep impurities, such as oxygen and
carbon, below 10+20 cm-3 in the intrinsic layer. Stability problems
tend to improve by increasing the deposition temperature, and
decreasing the hydrogen content, i'*

Conclusion
Thin film a-Si:H solar cell structures are rapidly closing the
gap in becoming a viable alternative energy source. In the last
decade, the overall cost to manufacture a-Si:H solar cell modules
 25
has steadily declined (presently less than $3.80/Wp). During this
same period, the efficiencies for small-area laboratory cells (1-
cm2) have been reaching the theoretical limit. The manufacturing
cost still needs to drop to about $2/Wp in order for utility-scale
power generation to be economically practical. Even though
laboratory cells have shown high conversion efficiencies, large
power modules (1 m2) have only achieved stable efficiencies of
6%. Therefore, improvements in manufacturing techniques are
still needed with future research directed at a better
understanding of the physics underlying film deposition and
growth.
Several key areas have been identified as vital to the
successful development of amorphous silicon thin-film solar cells.
The first area involves improved device quality through careful
material preparation, tight processing control, and state-of-the-art
high vacuum equipment and techniques to reduce contamination.
The second area is the development of high-quality small bandgap
films using amorphous silicon-germanium alloys. A third
important issue is amorphous thin-film deposition kinetics. This
requires an understanding of particle bombardment and
deposition parameters on the film's electronic properties.
Improved processing parameters are needed to reduce the
number of localized states in the gap and to decrease the tail-state
effects. A fourth is the development of numerical models to
simulate device behavior. This will allow the ability to analyze
thin-film solar cells without constructing complete devices. The
 26

final, and major area of concern, is the improvement of long-term

device stability. The fundamental issue here is the light-induced
photoconductivity degradation or Staebler-Wronski effect. An
improved overall understanding of the physics behind the
material is necessary if amorphous silicon is to become a practical
alternative energy source.
 CHAPTER III
BASIC ELECTRON-CYCLOTRON-RESONANCE
PLASMA THEORY

Introduction
Microwave electron-cyclotron-resonance (ECR) plasma
discharges have become an area of increasing interest due to their
use in many plasma processing applications. Electron cyclotron
resonance (ECR) plasmas have been utilized for the last 25 years
in various fields of plasma technology. This technology, borrowed
from fusion!9 and electric propulsion plasma,20 has developed into
an attractive plasma discharge process relevant to semiconductor
manufacturing. This technology offers a number of desirable
characteristics, including high plasma densities (=10^^-10!^ cm'^),
high degree of ionization (10% and higher), electrodeless nature,
low gas pressures (lO'^^-lO'-^ Torr), compatibility with active and
corrosive gases, and stability of operation. Another important
feature is the ability to produce high-quality films at low
deposition temperatures.
The low-temperature and low-pressure microwave ECR
plasma process is becoming attractive for use in many
semiconductor applications, and constitutes a possible means of
meeting stringent processing requirements. Although microwave
ECR plasma systems are being increasingly used for thin-film
deposition, similar systems, for other uses, have been developed;
e.g., plasma stream and reactive ion beam etching,2i sputtering-

27
 28
type ECR plasma deposition,22 ion implantation,23 and diamond-
film production.24 The movement towards smaller, faster, more
densely packed semiconductor devices has spurred a need for
more accurate processing techniques. In order to improve these
techniques for both etching and deposition, better uniformity,
lower damage levels for thinner structures, and lower deposition
temperatures are needed, while still yielding high quality films at
high throughputs.
Various types of films have been deposited using microwave
ECR plasma discharges. The general trend is that films can be
deposited at lower temperatures than for CVD or conventional
plasma-CVD processing, with comparable or better film quality.
Although deposition rates are generally low, progress has been
made in scaling these upward through higher flow rates and
greater microwave power.

Microwave ECR Breakdown

ECR plasma absorption occurs when microwave energy is
coupled to the natural resonant frequency of electrons in the
presence of a static magnetic field. In any gas there is a small
number of electrons present due to ionization by cosmic rays or
some other phenomenon. When the electron cyclotron frequency
in a magnetic field, which is defined as

0)ce=eB/me, (3)
 29
(where e = electron charge, B = static magnetic flux density, and
mc = electron mass) equals the microwave excitation frequency
(co), resonance occurs. This resonance efficiently transfers energy
from the electromagnetic field to the electrons. The ECR coupling
takes place within a small, thin volume, commonly known as an
ECR layer. Within this layer most of the applied power is
absorbed; producing high-energy electrons necessary to sustain a
discharge at low operating pressure. The accelerated electrons
move out of the ECR layer throughout the discharge volume
collisionally dissociating and ionizing the neutral gas. The result is
a low-pressure, almost collisionless, plasma that can be varied
from a weakly to a highly ionized state by changing discharge
pressure, gas flow rates, and input microwave power.25
For a standard 2.45-GHz magnetron the corresponding static
magnetic field needed is 0.0875 T. Several reasons have made
2.45 GHz the frequency utilized in all the ECR processing work
reported to date. The magnetic field required for resonance at
this frequency is relatively easy to obtain with ordinary water-
cooled solenoidal electromagnets. The magnetron, hardware and
power supplies are readily available for this operating frequency.
The densities obtained are high enough to be useful in present
materials processing applications.
 30

Microwave ECR Energy Coupling

Energy Transfer
In an arbitrary microwave plasma discharge, the energy
from the electromagnetic field is absorbed by both the electron
and ion gas. In most cases though, direct energy transfer to the
ion gas can be neglected (except for ion cyclotron resonance) due
to the low mobility of the ions. This is because the work imparted
to a charged particle by an electric field varies inversely with the
particle mass.
Ions can still have an effect on plasma dynamics. As
electrons are extracted from the discharge region, primarily along
the magnetic field lines, an electrostatic potential is created that
tends to pull positive ions in the same direction. Although direct
energy transfer is negligible in an ion gas, ions do undergo circular
Larmor gyration about the magnetic field lines. However, the
greater mass of the ions causes them to have an orbital radius
much larger than that of the electrons. For an argon ion having
kinetic energy of 5 eV transverse to a magnetic field of 0.0875
Tesla, the Larmor radius is about 23 mm (as compared to 0.1 mm
for an electron). This large orbital radius will cause the ion gas to
loose most of its energy through collisions with the chamber walls.
For an ECR discharge, the electron gas is excited directly by the
microwave electric field. The electrons continuously gain energy
and are accelerated. Neutral and ion gases acquire energy by way
of collisions with the heated electron gas. This ECR energy
transfer process for a discharge volume is shown in Figure 6.
 31
Discharge
Container
Radiation Wall
Losses

Joule Heating
and ICR
Heating

MICROWAVE
ELECTRIC
FIELD

Elastic
and
Inelastic
Collisions

Heat
Radiation Conduction
Losses and
Convection

Figure 6. Microwave energy transfer in a discharge volume.

 32

Through the interaction with the electron gas, the neutral

and ion gases interchange energy by way of collisions, and
transfer energy to the walls through heat conduction and
convection. Therefore, losses from the discharge have a direct
dependence upon the electron density, pressure, gas type, and
discharge geometry.

Power Absorption in a Magnetic Field

Without the presence of a static magnetic field, a plasma
discharge is pressure dependent. Therefore, at low pressures
(<100 mTorr), it is difficult to sustain a discharge without high
applied electric fields. With the addition of a static magnetic field
high power absorption, even for very low applied electric fields, is
easily obtained.
The equation of motion of an electron will now be used to
study the absorbed microwave power in both cases, with and
without a static magnetic field. Newton's law along with an added
term that represents the momentum loss of the electron due to
collisions with ions and neutrals is known as the Langevin
equation and is given by

- ^ mv" = -e [E + v" X B] - m\)eV^, (4)

dt

where v" is the average directed velocity, e is the electron charge,

and x>c is the effective collision frequency for electrons. The
 33

effective collision frequency refers to the fact that an electron

loses all its directed motion an average of De times per second.
Initially, the magnetic field is not applied and the
microwave energy is represented by an oscillatory electric field

E = Eo ei^^ (5)

Neglecting transients, and solving for the steady-state solution,

where v" has the same time dependence. Equation (4) becomes

jcomv = -eE - m-OgV . (6)

Rearranging,

v= ^-fiE (7)
m(\)e-i-jo))

This is the average directed velocity, or drift velocity, under the

influence of an electric field. The conduction current density due
to the electric field is equal to

J = -Ne7e= ^^^ E . (8)

m(\)e + jco)

The conductivity of the medium due to the electrons is:

^^__N£_e ^ ^^^
m(\)e + jco)
 34
The conductivity and the applied electric field is now used to
write the expression for the absorbed power density for the
electron gas as

Pabs = R e ( a ) E ^ (10)

where Re(a) is the real part of the conductivity, given by

Re(a) = N ^ (V") (11.

This term for the conductivity shows the explicit

dependence of the absorbed power on vjod. With the density and
electric field held constant. Equation (11) has a maximum when
co^De- The effective collision frequency, VQ, varies directly with the
gas pressure. For the case of hydrogen, \)e ~ 4.9 x lO^p, where p =
gas pressure in Torr at 300 K. Therefore, maximum microwave
power absorption is discharge-pressure dependent, and good
microwave energy coupling is possible in a coUisional heating
process.
For very low pressures, <100 mTorr, the mean free path
between electron-neutral and electron-ion collisions becomes very
long, \)e«co, and Equation (10) becomes

Pabs = ^ (VCO) E^ • (^2)

 35
In order to sustain a discharge at low operating pressures, and
without the presence of a static magnetic field, high plasma
densities and high applied electric fields are required. With the
inclusion of an ECR static magnetic field the discharge process is
greatly simplified.
With the field included, the complete steady-state Langevin
equation is given as

(De-Hjco)m\r=-e [E + v"x B] . (13)

For the simple case where the electric field is perpendicular to the
static magnetic field, the absorbed power by the electron gas
becomes

Pabs=^^f^[ ^ -+ 1 -]E^ . (14)

2 m ^ 2 + (co-COce) 'Ol + (cO+COce)

If the collision frequency is reasonably small with respect to the

frequency of the applied electric field, a)e<<co, Equation (14)
becomes

Pabs=^^^[ 1 -]E'. (15)

2 m ^ 2 + (co-COce)

Equation (15) will peak in a resonant manner if the frequency of

the applied electric field approaches the electron cyclotron
 36
frequency (co=coce). This indicates a high power absorption even
with very low impressed electric fields.
This is the ECR condition under which the motion of an
electron in the magnetic field is in synchronization with the
applied oscillatory electric field. An electron with co=(Oce will feel

the usual Lorentz force ev X B and begin to drift in the direction

normal to E and B. This is the well known electric field drift, VE,
and is illustrated in Figure 7(a). In the first quarter cycle of the
electron's orbit, the electron will gain energy from the increasing
electric field, and accelerate in the plane normal to the magnetic
field. The electron's Larmor radius is increasing at this time.
During the second quarter of the orbit, when the electric field is
decreasing, the electron will also accelerate, but at a lower rate
than it did during the first quarter cycle. The final half orbit
produces the same effects only in the opposite direction.
Therefore, at ECR, an electron is subject to continuous acceleration
by the electric field. Electrons with the "right" phase will gain
energy; whereas electrons with the "wrong" phase will lose
energy. The motion that the electron makes is shown in Figure
7(b). The increasing orbit and speed of the electron is limited by
a collision with another particle, a collision with a wall, or
movement out of the ECR region.
It should be noted, however, that as the discharge pressure
increases, pure ECR heating gives way to collisional heating. As
the pressure is increased the collisional frequency -Oe approaches
 37
ExB
i Electric
Field
t Drift,

E-*^ ®B
(a)

(b)

Figure 7. (a) Electric field drift Ve, for an electron in crossed

electric and magnetic fields, (b) Electron motion at ECR.

the excitation frequency co, and Equation (14) becomes

approximately equivalent to Equation (10). This shows that
higher pressures render the influence of the magnetic field
useless towards the heating of the electron gas. Thus, at higher
pressures the energy absorption process becomes collisional and
 38
the magnetic field has little influence on the heating of the
electron gas. Therefore, ECR is a coupling technique for low-
pressure discharges where the electrons can orbit many times
between collisions, or at least Ve^coce-

Magnetic Mirror Effects

Most ECR plasma discharge systems employ a nonuniform
static magnetic field commonly known as a magnetic mirror. The
name refers to the fact that this field configuration can reflect
charged particles entering a high-field region. Therefore, a pair of
coils that form two magnetic mirrors can confine a plasma. This
effect works both on ions and electrons. Figure 8 illustrates this
scheme where the magnetic field is highest in the throat (Bm) and
weakest at the midplane (BQ). A magnetic mirror is produced
either by permanent magnets or magnetic coils.

Figure 8. Plasma confined between magnetic mirrors.

 39
The basis for plasma confinement in a magnetic mirror is
the invariance of the magnetic moment, ^i. The magnetic moment
for a gyrating particle is defined as

^i =4-mv//B . (16)

As a particle moves into regions of stronger or weaker

fields, its Larmor radius changes, but ji has to remain constant.
Therefore, the particle's perpendicular velocity Vi must increase
during periods of increasing magnetic field. Since energy must be
conserved, the parallel velocity v„ has to decrease. If the
magnetic field is high enough in the throat, the parallel velocity
will become zero; and the particle is reflected back to the weak-
field region.
In the absence of an electric field, a charged particle moving
into a converging field will spiral with ever decreasing transverse
orbits until it is reflected. The particle will then reverse direction
and spiral back into the weak-field region with increasing orbit.
When a transverse microwave electric field is present in the
magnetic mirror, acceleration of the electrons takes place when
they pass through the ECR region where co=o)ce- Outside this ECR
region, the electrons experience little or no energy absorption as
indicated from Equation (15); and will experience the usual mirror
force.
 40
Confinement of the plasma is not perfect. A particle with
Vi=0 will have no magnetic moment and feel no force in the
direction of the field. A particle with a small ratio of
perpendicular velocity to parallel velocity will also escape if the
maximum field at the throat is not large enough.

Conclusion
From the previous discussion, an ECR plasma offers a
number of desireable characteristics; the most notable being an
efficient means of producing high-quality films at low deposition
temperatures. The electrodeless and electron-cyclotron-heating
nature of the plasma is suitable for many processing applications.
The ECR plasma is easily maintained, even for very low applied
electric fields.
Because the ECR process accelerates high-energy electrons,
the electron energy distribution will be non-Maxwellian. This
makes the form of the distribution dependent upon the applied
electric field, and the size and shape of the ECR layer. Therefore,
the electron energy distribution can be controlled by the applied
electric field and the magnetic mirror configuration. This control
over the ECR plasma helps to slow down the electrons prior to
striking the substrate. This is favorable since most plasma
processing applications do not desire high-energy electrons.
 CHAPTER IV
SYSTEMLAYOUT

ECR Apparatus
A schematic diagram of the ECR plasma deposition apparatus
is shown in Figure 9. The ultra-high-vacuum system is made
entirely of stainless steel. The discharge chamber, with an inside
diameter of 13.3 centimeters, is located inside two sets of magnet
coils. The magnet coil current is supplied by a Hobart type M-600
dc motor-generator arc welder. The coils are used to provide a
magnetic field in a dual magnetic mirror configuration; a
magnitude plot of the field along the chamber axis is shown in
Figure 10. The axial magnetic field strength is adjusted so that
the field is greater than the ECR value at the coil locations, and
decreases with axial position as shown. Positioning the microwave
input to the chamber at the location of the left coil set, places the
waveguide window in the region of greatest magnetic field
intensity. This positions the intense ECR layer away from the
waveguide window.
Microwave power is generated by a 2.45 GHz continuous-
wave power source (with a Matsushita 2M137 magnetron) and
introduced into the discharge chamber via a rectangular
waveguide and quartz vacuum window. The incident microwave
power can be continuously varied up to 1 kW. The incident power
Pine and reflected power Pref are both measured using a dual
directional coupler and power meters.

41
 42

C/3

os D > ... 3
«->
hi
cd

a.
a
o

O
a.

a.
X

e
o
CO

ON

(11
3
00
 43
1000
^X=^ ^V - ECR
>^

•-3 C
o Q
Is

0 10 20 30 Distance (cm)

Langmuir probes

Sample
Holder
Microwave
Source

Viewport
Magnet
Coils

Figure 10. Magnitude plot of axial magnetic field aligned

with microwave ECR deposition system. The peak to minimum
ratio is 1.3. Magnitude plot provided by a magnet coil current ( I B )
of 300 A.

A four-stub tuner is used to match the ECR discharge load

for different discharge conditions. A unique feature of the
microwave system is the use of a three-port circulator and
dummy load as an attenuator instead of an isolator.
A circulator is designed to protect the magnetron from large
reflected power conditions that could damage or shorten the life
of the device. The three-port circulator is normally configured
 44
with the microwave input at port 1, the discharge load at port 2,
and a matched dummy load at port 3. In this arrangement, all the
power entering port 1 leaves port 2, and all the reflected power
from the nonlinear plasma load exits port 3 into the matched
dummy load. This isolates the magnetron from the nonlinear
discharge and allows it to operate into a matched load
independent of discharge variations. The drawback for this
configuration occurs when trying to operate the magnetron at
output power levels below 50 Watts. Below this value, magnetron
operation is unstable with similar consequences for the plasma
discharge. Since the plasma deposition process needs power in
the range of 10 to 50 Watts, some method of providing stability is
needed.
In the method we have chosen, the circulator and dummy
load are configured as an attenuator, with the connections to ports
2 and 3 interchanged and a stub tuner added with the dummy
load (see illustration in Figure 9). This allows the magnetron to
operate at high powers (500 W) where its output is stable. A
portion of the applied power to the dummy load is reflected by
the stub to the discharge chamber. This allows low microwave
power, in the range of 0-50 Watts, to be applied to the discharge
chamber without magnetron instability problems. Adapting the
microwave system in this manner produces a controllable, stable
discharge for different operating conditions.
Numerous flanges and viewports provide locations for the
connection of gas pressure gauges, Langmuir probes, gas input.
 45
and discharge observation windows (viewports) as shown in
Figure 9. Two MKS type-1159B mass flow controllers are used to
maintain a prescribed flow for the hydrogen and liquid-source
gases in units of standard cubic centimeters per minute (SCCM).
Argon and helium are connected at the other two inputs, and are
used as inert discharges for cleaning and plasma diagnostics. The
gas flow rates for these inputs are controlled by a
Granville/Phillips variable leak valve. Single and double
Langmuir probes are used to measure radial profiles of the
plasma density and temperature at the two locations shown in
Figure 9.
The sample holder is located 15 centimeters downstream
from the right magnet coil set. Figure 11(a) shows a detailed
drawing of the sample holder. It contains an electric heater that
can regulate the substrate temperature from room temperature to
425 °C. The holder is electrically isolated from the chamber and
can be kept at the floating potential or rf biased. A thermocouple
placed inside the holder is used to monitor the substrate
temperature. A water-cooled Maxtek type TM-IOOR thickness
monitor is located above the sample holder. The thickness
monitor provides a direct display, at high update rates, of film
thickness and deposition rate during deposition. This allows for
improved manual control of the vacuum film deposition process.
A manual shutter is used to cover the sample to prevent
deposition during discharge tuning and after completed
processing. A number of pilot holes are drilled in the holder to
 46

HEATER THERMOCOUH^
SHUTTER
CaSTTROL BIAS
\

I • 11

4-^
CERAMIC
I I
SPACERS

SAMPLE
PLUG
PORT

c
TOP VIEW

FRONT VIEW
(a)

SAMPLE
PLUG

CRYSTALLINE GLASS
SILICON SUBSTRATE SUBSTRATE
l/4"xl/2" ea.
(b)

Figure 11. (a) Sample holder showing feedthrough

connections, (b) Sample plug showing substrate mounting.
 47
prevent outgasing from the internal cavities. Feedthroughs to the
sample holder are introduced through a six-way port (see Figure 9
for details). Sample insertion is performed by way of the load-
lock section and substrate feedrod.
Two substrates, one glass and the other crystalline silicon,
are fastened to the substrate plug illustrated in Figure 11(b). The
procedure for inserting the substrates into position in the
discharge chamber prior to film deposition is as follows: The plug
containing the substrates is attached to the end of the feedrod
inside the load-lock chamber, the chamber is closed and
evacuated, the gate valve between the load-lock chamber and the
discharge chamber is opened, the plug is pushed into place in the
sample holder by means of the feedrod, the feedrod is withdrawn
to the load-lock, and the gate valve is closed. A Cajon™ 0-ring
fitting provides the vacuum seal for the feedrod.
There are two vacuum pump systems attached to the
apparatus. One, connected to the load-lock, is composed of a
Pfeiffer-Balzers turbo-molecular vacuum pump in tandem with a
Kinney type KTC-21 roughing pump. Two MDC type pneumatic
gate valves are used to isolate the load lock from the system. This
setup is used to pump down the load-lock during sample insertion
and extraction, and to obtain base pressures in the neighborhood
of 5 X 10"^ Torr. The other pump system, connected behind the
sample holder location, is composed of a high throughput Kinney
type MB403 roots blower (66 liters/second at 10"^ - 1 Torr) in
tandem with a Kinney type TCS-21 roughing pump. This vacuum
 48
system is operated during film deposition because of its high flow
rate capability, and because of the contaminant exhaust gases.
An MKS type 253A exhaust control valve is located at the
input of the roots blower. The valve is part of a closed-loop
pressure control system as illustrated in Figure 12. The control
system consists of a MKS type 390 Baratron guage connected to a
MKS type 170M-6C and type 170M-25C electronics unit and
readout. The Baratron is also connected to an MKS type 252
exhaust valve controller. The control system varies the exhaust
valve opening in order to hold the discharge operating pressure at
a set-point level set by the operator. This arrangement creates a
very flexible system in which the microwave power and gas flow
rate are held constant while the discharge operating pressure is
varied. This allows "mapping" of the plasma discharge process
over a wide array of discharge parameters.

Safety Interlocks
Safety is an important issue since toxic/corrosive silicon
tetrachloride gas, and flammable hydrogen gas is used. The ECR
apparatus contains a number of safety interlocks to aid the
operator in the event of a system failure. These interlocks are in
place in case a failure occurs in the gas, coolant, microwave, or
vacuum systems.
Hydrogen is a colorless, odorless, tasteless, nontoxic, and
flammable gas. Because hydrogen is lighter than air, it has a
tendency to accumulate in the upper portions of confined areas.
 49

O
c
o
o
<D
3
t/i

CI.
O
I

CO
O
u
(S

(L>
3
00
 50
Concentrations of hydrogen between 4% and 75% by volume in air
are relatively easy to ignite by a low-energy spark and may cause
explosions. The amount of hydrogen gas during operation is well
below the flash-over concentration; but for safety precautions, the
exhaust gas is diluted with nitrogen gas prior to exiting the
roughing pump stage. The ECR apparatus is enclosed in a framed
plastic room which is vented to atmosphere by way of an exhaust
fan through a charcoal filter. A section of the vent is also used to
remove exhaust gases from the vacuum systems. This
arrangement allows for a safe operating environment, where an
operator(s) can quickly exit and seal off the enclosure in case of
an uncontrolled gas leak.

The magnet coils, microwave circulator, and dummy load

require a reliable source of cooling water. To accomplish this, the
inlet water line is run through a filtration unit to prevent
sediment buildup, and a one inch diameter water line provides an
ample supply of cooling water for the system. Pressure switches
are located at the cooling inlet lines to the magnet coils and the
microwave circulator and dummy load. They are adjusted to
shut-off the microwave power supply and magnet coil current in
case of lost coolant flow, low coolant flow, or failure of the
operator to open the coolant valves. The microwave source also
has an additional cut-off switch that monitors the magnetron's
operating temperature. The magnetron is cooled by forced air
from a blower. In the case of blower failure, the temperature
 51
switch will shut off the microwave power supply and prevent
overheating and eventual destruction of the magnetron.
An instrument rack houses a series of manual switches that
allow the operator to control the two pneumatic gate valves near
the load-lock, the gas inlet valves at the flow controllers, and the
gas inlet valve at the chamber. All these switches are in series
with a single manual switch in case of an emergency shut-down.
The roots blower, the turbo-molecular pump, and the two
roughing pumps are operated from a series of relays that are also
controlled by a single cut-off switch. This setup allows the
operator to rapidly isolate the discharge chamber from the gas
sources and vacuum pump systems in the event of some type of
system failure.
An HPS series 145 VACUUM SENTRY™ safety valve is
installed between the turbo-molecular pump and roughing pump.
The safety valve protects the vacuum system in the event of
power failure by isolating the evacuated chamber and turbo-
molecular pump and venting the roughing pump. This keeps air
from the chamber, avoids oil backup, and allows the motor to
restart the roughing pump more easily when power is restored.
The valve operates with atmospheric pressure and activates upon
loss of electrical power. A solenoid valve is connected in parallel
with the roughing pump's electrical supply. When the electrical
power is on, the solenoid valve is held closed, keeping the safety
valve open and the vacuum chamber evacuated. Interruption of
electrical power to the mechanical pump causes the solenoid valve
 52
to open and admit atmospheric air into a portion of the valve.
This closes the safety valve before vacuum pressure is lost in the
chamber. The force needed to keep the safety valve shut is
provided by the pressure differential between the atmosphere
and the vacuum chamber. A series of small orifices admit air into
the inlet of the roughing pump to prevent oil back-flow.
 CHAPTER V
RESULTS AND CONCLUSION

Thin-Film Production
The deposition system operating parameters and deposition
rates, and the conductivity ratios for the thin-film samples
produced from silicon tetrachloride (SiCU) and hydrogen (H2) gas
are shown in Table 2. Because of the numerous operating
parameters involved it is necessary to vary one parameter at a
time while holding the remaining constant. This will allow
mapping of each processing parameter in order to determine
optimum settings. The substrate was electrically grounded for all
samples produced, and the magnetic field was provided by a
constant coil current ( I B ) of 300 Amps for all but three of the
samples produced. This results in the magnetic field plotted in
Figure 10. Dark conductivity (od), photoconductivity (oph), and
infra-red spectroscopy were used to characterize the films. For
the first four samples the total gas flow rate ( 0 T ) and the relative
gas flow rates (RsiCU and RH2) were varied to determine the
optimum setting according to the conductivity ratios. The
microwave power was set at 25 Watts for three of the first four
samples. A problem with the stability of the plasma discharge for
the first sample occurred during deposition and resulted in a film
with a poor conductivity ratio. Even though the plasma discharge
was quite stable during the deposition process for the third
sample, a poor film was deposited. The second sample, after

53
 54
Table 2: Sample Parameters For Silicon Tetrachloride ^

Sample RH2:Rsia4 0T Power T«A Press. IB CTph /c J Stability

^ (%) (seem) (W) (^C) (A/s) (mTorr) (A)

1 71-29 7 20-40 285 1.3 1.8 300 17 poor

2 90-10 10 25 285 1.6 7.6 300 48330' good
3 83-17 6 10 250 1.0 3.5 330 poor film good
4 97-3 33 25 285 0.5 11.9 300 7 good
5 90-10 10 25 285 3.0 4.3 300 poor film good
6 90-10 10 40 285 1.2 7.6 300 97 good
7 90-10 10 25 285 2.0 7.6 300 354 good
8 90-10 10 30 285 3.7 4.8 300 462 good
9 90-10 10 15 285 4.6 4.6 300 111 good
10 90-10 10 30 310 3.9 4.3 300 1869 good
11 90-10 10 25 310 4.0 4.7 300 36 good
12 90-10 10 20 310 2.2 4.2 300 88 good
13 90-10 10 15 310 1.7 4.0 300 9 good
14 90-10 10 10 315 1.2 4.0 300 fair
15 90-10 10 25 285 2.3 4.1 300 good
16 90-10 10 25 60 3.0 4.8 270 good
17 90-10 10 25 100 3.4 4.5 300 good
18 90-10 10 25 200 3.4 4.3 300 good
19 90-10 10 25 400 2.4 4.9 300 fair
20 90-10 10 25 285 3.2 4.6 300 good
21 90-10 10 25 285 1.6 4.6 240 good
22 90-10 10 25 285 2.7 5.0 300 good

1 Courtesy J. C. Schuma
! cher Companjf

2post-a nnealing
 55
annealing, produced a conductivity ratio of 48,330. This opto-
electronic property is comparable to good quality glow discharge
a-Si:H films. The annealing process relaxes the film structure and
improves the silicon-hydrogen bonding, thereby reducing the
density of states. The conductivity ratio prior to annealing was
found to be 140.
Because sample 2 showed a high photoconductivity, the
relative flow rate for SiCU of 10% was used for all remaining
samples produced. The microwave power was the next parameter
varied for samples 5 through 9. The substrate temperature (Tsub)
was increased from 285 °C to 310 °C for the next five samples (10
thru 14), with the microwave power again being the parameter
varied. A second SiCU gas source was used for samples 15
through 22 since the first source was suspected of being
contaminated with oxygen. For samples 15 through 19 the
substrate temperature was varied from no substrate heating to
400 °C in increments of 100 °C. Samples 15 and 20 through 22
were produced to investigate the reproducibility of the process.
It is important to note that the deposition rates for the six
samples made under identical conditions (sample's 2,5,7,15,20,and
22) were not very consistent with each other. It is believed that
this is caused from film buildup on the chamber walls as the
overall processing time increases. The film previously deposited
on the walls becomes partially etched during the deposition
process, and contributes to the deposition process. Observations
 56
have shown that the deposition rates increase for later runs at the
same operating conditions.
The operating parameters, deposition rates, and conductivity
ratios for the samples produced from a proprietary liquid source,
courtesy of the J. C. Schumacher company, and hydrogen gas are
tabulated in Table 3. All samples produced from this gas source
contained a very large amount of carbon which produced poor
quality films. These carbon alloyed amorphous silicon films (a-
SiC:H) could possibly be used as a window layer (wide bandgap
material) in p-i-n type solar cells. The first two samples were the
initial samples produced in the ECR deposition apparatus. They
were produced prior to the installation of the circulator and
dummy load; at a time when the plasma discharge conditions
were very poor. The poor discharge condition was believed to be
caused by unstable magnetron operation at the low applied
powers. The remaining seven liquid source (L.S.) samples were
produced after the circulator and dummy load were installed, at
which time the discharge process improved remarkably. The
relative flow rates for the liquid source ( R L . S . ) gas and hydrogen
( R H 2 ) g^s were varied so as to investigate the percent carbon
content in each film. The total gas flow rate and substrate
temperature (Tsub) were held at their respective values for the
seven samples. The applied power, operating pressure, and
magnet coil current also stayed relatively constant as shown in
Table 3. From the table, the deposition rates (rd) remained
relatively constant for samples 3 through 9, although the
 57
Table 3: Sample Parameters For Proprietary Liquid Source-

Sample RH2:RL5. 0T Power Tgub Press. IB Stability

#
(%) (seem) (W) (A/s) (mTorr) (A)

1 50-50 20 55 275 5 13.3 300 poor

2 75-25 40 68 275 5 19.2 300 poor
3 93-7 30 25 285 1.5 11.2 300 good
4 90-10 30 25 285 2.2 25 300 good
5 90-10 30 25 285 2.5 25 300 good
6 90-10 30 25 285 2.5 24 300 good
7 72-28 30 25 285 2.5 25 270 good
8 50-50 30 25 285 2.8 25 300 good
75-25 30 20 285 2.8 15.5 300 good
'

J. C. Schumacher Company

deposition rates did appear to be on the rise as seen by the slight

increase for samples 8 and 9.

Parameter Effects
The opto-electronic properties of electron-cyclotron-
resonant plasma discharge films are dependent upon many
deposition parameters such as the discharge pressure, gas flow
rate, absorbed microwave power, substrate temperature, and
magnetic field. The hydrogen concentration in hydrogenated
amorphous silicon films depends upon some of these deposition
conditions. In general, the hydrogen content will decrease as the
substrate temperature increases.26 The loss in hydrogen content
 58
as the substrate temperature increases causes the density of
defect states to increase.27
Films deposited at low substrate temperatures (< 200 °C) do
not exibit good elctronic properties. These films contain dihydride
(SiH2) and trihydride (SiHs) chains which act as recombination
centers. Above 200 °C the hydrogen exists in monohydride (SiH)
form. It is this fundamental change to monohydride bonding at
higher substrate temperatures that has a major effect on the
reduction of the density of states and, therefore, an improvement
in the opto-electronic properties of the material. When a-Si:H
films are heated to temperatures greater than «350 °C, the
hydrogen evolves from the material, and the density of states
increases, causing a reduction in the opto-electronic properties.
Hydrogen content will also increase with an increase in applied
power, and decreases with an increase in discharge pressure.
In the following discussion the deposition rate is graphically
displayed as a function of the various processing parameters. In
Figure 13 the deposition rate is plotted as a function of the
magnet coil current at various absorbed microwave powers (Pabs)-
For an absorbed power of 8 watts, the deposition rate does not
seem to be affected by an increase in the magnetic field, as long as
it is above the threshold value (IB = 1 8 0 A, B M « 0 . 0 6 3 T ) . It is not
until the applied power is further increased that an increase in
the magnetic field begins to affect the deposition rate, the rate
then displays a peak.
 59

TH (A/S)

2 •
« Pabs=8W
• Pabs=10W
° Pabs=15W
A Pabs=50W
1 -

0
360
IrfA)

Figure 13. Deposition rate as a function of magnet coil

current at 0 T = 6 SCCM, P=2.6 mTorr, and RsiCU-

For the present ECR apparatus setup, a layer of enhanced

brightness always forms outside the magnetic mirror
configuration (between the second magnet coil set and the
viewport, see Figure 9). We take this to be an ECR layer. At low
magnetic field settings the ECR layer takes the shape of a thin disc
that covers the cross section of the discharge chamber. When the
magnetic field is increased, the ECR disc layer propagates towards
the sample holder, following the 0.0875 Tesla magnitude of the
flux density, and gradually forms into a donut-like shape touching
 60
the chamber wall. This change in the ECR layer probably changes
the makeup of the particle flux incident on the substrate and thus
the film deposition rate. The maximum seen in the deposition-
rate curves may be due to high energy particles being slowed by
the chamber wall. A slowing of the particles allows more
deposition than etching to occur. Additionally, the general
increase in deposition rate with absorbed power seen in Figure 13
is probably due to an increase in the ion density caused by the
higher power.
Figures 14 and 15 show the deposition rate plotted versus
the discharge pressure, at various absorbed powers, for total flow
rates ( 0 T ) of 10 SCCM and 33 SCCM, respectively. The relative
flow rate for the SiCU gas is 10% and the magnet coil current is
300 Amps. These two graphs show that the deposition rate, at
fixed absorbed power, is relatively constant for different
discharge pressures. The increase in the deposition rate, at a
constant pressure, for higher absorbed power is probably due to a
more efficient discharge produced by a greater ion density.
Figures 16 and 17 illustrate the deposition rate versus the
SiCU relative flow rate (RsiCu) at various absorbed powers. Figure
16 is for a total flow rate of 10 SCCM at a discharge pressure of
4.7 mTorr, and a magnet coil current of 300 Amps. From the plots
of Figure 16, for fixed absorbed power, it is easily seen that the
deposition rate increases to a maximum with increasing percent
SiCU gas in the discharge. The maximum deposition rates occur
approximately at 50% SiCU relative flow rate for the higher
 61
r^CA/s)

o Pabs=5W
• Pabs=10W
Pabs=15W
-• Pabs=20W
A Pabs=25W

30 40
P (mTorr)

Figure 14. Deposition rate as a function of plasma discharge

pressure at 0 T = 1 O SCCM, I B = 3 0 0 A, and RsiCl4= 10^^-

applied powers. For concentrations of SiCU above 50% the

deposition rate gradually drops until etching occurs. This
phenomenon is probably due to the increased number of chlorine
ions in the plasma discharge.
Figure 17 is for a total SiCU gas flow rate of 30 SCCM at a
discharge pressure of 11.4 mTorr. The curves for the deposition
rate follow a similar pattern as that discussed for Figure 16;
except that the deposition rates for relative flow rates beyond
50% are not shown since the maximum lies at 30%.
 62
^Akls)
8

6 -
o Pabs=5W
• Pabs = 10W
4 - ° Pabs=15W
A Pabs=20W
A Pabs=25W

2 -

Figure 15. Deposition rate as a function of plasma discharge

pressure at 0 T = 3 3 SCCM, I B = 3 0 0 A, and RsiCl4= 10%-

ECR Apparatus Improvements

There are a number of different areas in which possible
additions and changes to the apparatus can be, and already have
been, made in an attempt to improve the discharge process; and
ultimately to obtain better quality a-Si:H films. Relatively high
levels of metallic contaminants have been found in ECR deposited
samples which originate from the part of the stainless steel
chamber exposed to the high density ECR plasma discharge.28 It
 63
r^CA/s)

» Pabs=5W
• 'abs=10W
Pabs =
"n ''abs=15W
P.Ko=
A Pabs=20W
A Pabs=25W
• Pabs=30W
• Pabs =35 W
• Pabs=40W

100

Rsicif'')

Figure 16. Deposition rate as a function of SiCl4 relative flow

rate at 0 T = 1 O SCCM, I B = 3 0 0 A, and P=4.7 mTorr.

was found that these metallic impurity levels can be greatly

reduced by covering the stainless steel chamber wall at the ECR
layer with an anodized aluminum sleeve. We have had a number
of anodized aluminum sleeves fabricated, and these are ready for
future thin film production. Confinement of the ECR discharge
between the magnetic-mirror producing coil sets can be
accomplished by placing a stainless steel screen to the right of the
second magnet coil set (see Figure 9). This will prevent the
microwaves from propagating beyond the magnet coil and setting
 64
r.CA/s)
12

o Pabs =5 W
• Pabs=10W
8 -
D Pabs=15W
• Pabs=20W
A Pabs=25W
Pabs=30W
4 - Pabs=35W
Pabs=40W

^SiClf)

Figure 17. Deposition rate as function of SiCU relative flow

rate at 0 T = 3 O SCCM, I B = 3 0 0 A, and P=11.4 mTorr.

up a discharge beyond the magnetic-mirror section. The

acquisition and installation of a stainless-steel screen is currently
being performed for future a-Si:H film production, and to
investigate its effects upon film deposition.
Another possible improvement involves redesigning the
sample plug (see Figure 11(b)). The crystalline silicon and glass
substrates are held in place by four small screws. From visual
inspection of the deposited films, it is apparent that the screws
affect the film deposition near their location. Concerning the
 65
sample feedrod, during sample insertion slight leakage can be
observed from the chamber pressure readout. The leakage occurs
at the single 0-ring that seals the feedrod. Although vacuum
grease and 0-ring replacement minimizes this problem, a different
type of feedrod seal is suggested. The addition of a hinged load-
lock door for sample insertion and retrieval is another possible
improvement; currently, much time is wasted removing and
replacing many bolts. For the liquid source gas flow rate, a more
sensitive mass flow controller is necessary to improve the
repeatability of the flow setting. This improvement has just been
accomplished by reducing the range of the mass flow controller
reduced. A new temperture controller is being fabricated in order
to obtain improved constant substrate temperatures, and also to
extend the heating element lifetime.
The most important improvement needed is to replace the
silicon tetrachloride gas source with silane (SiH4) gas. This will
eliminate the chlorine from the discharge, and produce pure
hydrogenated amorphous silicon films. Work is presently being
done to accomplish this task. Safety precautions have to be taken
into account when converting over to silane due to the explosive
nature of the gas. Accomplishing this changeover will give Texas
Tech University the distinction of having the only microwave ECR
plasma apparatus producing a-Si:H films in the country.
A new toroidal ECR deposition system is in the final
construction stage. The new system will perform the same task as
that of the ECR deposition system discussed earlier. The magnetic
 66
field is obtained from electrically insulated, water-cooled, copper
tubing wrapped around the exterior of the toriodal chamber. This
new toroidal chamber will replace the deposition chamber and
magnet coil sets shown in Figure 9. However, all other
subsystems will remain the same.

Conclusion
This microwave ECR plasma deposition plasma apparatus has the
ability to operate with different source gases, flow rates,
microwave powers, magnetic field strengths, operating pressures,
and sample temperatures and voltages. The system has also
shown the ability to produce stable, repeatable, and controllable
plasma discharges for a wide range of processing parameters. The
microwave ECR plasma deposition apparatus has shown promising
results in producing a-Si:H,Cl films that are comparable to a-Si:H,Cl
films produced by the glow discharge process. With the added
improvements mentioned above, and the eventual changeover to
silane gas, the ECR apparatus will be in a position to produce high
quality a-Si:H films.
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