Ho Thesis

THE DESIGN AND MODIFICATION OF A SPUTTER SYSTEM FOR DC
REACTIVE SPUTTERING OF ALUMINA AND ZIRCONIA THIN FILMS
A Thesis
Submitted to the Graduate Faculty of the

Louisiana State University and
Agricultural and Mechanical College
in partial fulfillment of the
requirements for the degree of
Master of Science in Mechanical Engineering
in
The Department of Mechanical Engineering
by
Diane Van Ho
B.S., Louisiana State University, 2008
August 2011
DEDICATION
I would like to dedicate this thesis to
my parents, Nghia Thy Ho and Huong Thu Dinh,
my brother, Charlie Ho, my extended family, and
my boyfriend, Edward Scheuermann.
Through their love, support and encouragement,
I had the strength to pursue and complete my Master’s degree.
ii
7 ACKNOWLEDGEMENTS
First of all, I would like to offer my sincerest gratitude to my advisors, Dr. Shengmin Guo
and Dr. Muhammad Wahab, for their advice, continuous support and encouragement
throughout this research project. I am grateful for the faith they had in me and that they
pushed me to my limits during the research process. I also would like to thank Dr. Dorel
Moldovan for serving on my committee and for his influence and advice during my
academic studies.
This research was partially funded by NASA/LEQSF(2009-12)-PHASE3-03 and NASA
Award Number NNX09AP72A and partially by the Louisiana Space Consortium
(LaSPACE). I would like to acknowledge Dr. John P. Wefel for his help in securing the
funds for my Graduate Student Research Assistance award through LaSPACE and his
support for my research and future career.
Sincerest thanks go out to Dr. Dimitris Nikitopoulos for all his advice and
encouragement throughout my graduate studies. Dr. Nik has always supported my
ideas for graduate department events. I would also like to thank Diane Morgan for all
her help with graduate forms and sending emails for me. I would also like to
acknowledge the ME staff for all their hard work and all the ME professors for providing
me with a quality education in both my undergraduate and graduate studies.
I would like to acknowledge the following companies that have provided technical
support, general knowledge and materials that helped propel this research: Denton
iii
Vacuum, LLC (James Chung), Angstrom Sciences (Mark Bernick), Capital Valve &
Fitting Co., Inc. (Andy Carroll), Collins-Oliver (Wanda), and John Fenn.
I would also like to give my sincerest gratitude to all my friends, who have all been very
supportive of my research and helped me remember the good times in life. I specifically
want to thank Ranran Liu for all his time, help, and guidance throughout my research.
Without his help, I could not have gotten as far as I have today. I want to acknowledge
and thank all of my lab mates for helping me with any problems I had: Monica
Bohorquez de Silva, Luping Li, Peigen Zhang, Jiangdong Liang, Li Wang, Dr. Kaiyang
Wang, and Dongsheng Guan. To my classmates, Calicia Johnson, Brooks Lowrey,
Lance Brumfield, Jean-Philippe Junca-Laplace, James Dupree, Sai Rao and Tat
Acharya, who struggled alongside me to get through our graduate courses, I am grateful
for their companionship and support. To my best friends who are always there for me
through all the tough times as well as the fun times, Farren Ancar, Sara Terrebonne
Daigle, Tony Daigle, Dat Nguyen, Lauren Mine Smith, Diana Kauveiyakul, and Angel
Alvarez, graduate school was a lot easier with them in my life.
Finally, I would like to give my deepest gratitude to my whole family, who has given me
unconditional love and unwavering support. I specifically want to thank my uncle,
Benedict Lim, for encouraging me to pursue an engineering degree. I would not be
where I am today without all of them.
iv
8 TABLE OF CONTENTS
ACKNOWLEDGEMENTS ............................................................................................... iii
LIST OF TABLES ........................................................................................................... vii
LIST OF FIGURES ........................................................................................................ viii
ABSTRACT .....................................................................................................................xi
CHAPTER 1: INTRODUCTION ....................................................................................... 1

1.1 Motivation ........................................................................................................... 1
1.2 Brief History of Thermal Barrier Coatings (TBCs) .............................................. 1
1.2.1 Fabrication and Application of TBCs ........................................................... 3
1.3 Brief Sputtering History ...................................................................................... 5
1.4 Thesis Overview................................................................................................. 6
CHAPTER 2: BACKGROUND ON SPUTTERING .......................................................... 8

2.1 Glow Discharges ................................................................................................ 8
2.1.1 The DC Glow ............................................................................................. 14
2.1.2 A DC Discharge Model .............................................................................. 15
2.2 Sputter Yield..................................................................................................... 17
2.3 Sputter Theory ................................................................................................. 19
2.3.1 Evaporation Theory ................................................................................... 20
2.3.2 Momentum Transfer Theory ...................................................................... 21
2.4 Diode Sputtering .............................................................................................. 22
2.5 Magnetron Sputtering ....................................................................................... 25
2.6 Reactive Sputtering .......................................................................................... 27
CHAPTER 3: LITERATURE SURVEY .......................................................................... 33

3.1.1 Alumina Reactive Sputtering ..................................................................... 37
3.1.2 Zirconia Reactive Sputtering...................................................................... 41
CHAPTER 4: EXPERIMENTAL METHODS .................................................................. 46

4.1 The Sputter System ......................................................................................... 46
4.1.1 Current Sputter System ............................................................................. 46
4.1.2 Modified Sputter System............................................................................ 49
4.2 System Maintenance ........................................................................................ 50
4.3 Experimental Procedures ................................................................................. 50
4.3.1 Metallic Sputtering ..................................................................................... 51
4.3.2 Reactive Sputtering ................................................................................... 52
4.4 Mini-chamber Design ....................................................................................... 54
CHAPTER 5: EXPERIMENTAL RESULTS ................................................................... 58

5.1 Metallic Sputtering ............................................................................................ 58
v
5.3 Sputtering with Mini-Chamber .......................................................................... 84
5.4 Sputtering with Ceramic Target ........................................................................ 85
CHAPTER 6: DISCUSSION AND FUTURE WORK ...................................................... 86

6.1 Discussion ........................................................................................................ 86
6.2 Future Work ..................................................................................................... 88
REFERENCES .............................................................................................................. 92
VITA .............................................................................................................................. 96
vi
9 LIST OF TABLES
Table 5.1.1: Average deposition rate for metallic thin films. .......................................... 62
Table 5.2.1: EDS results of alumina and zirconia thin films at varying O2 flow. ............. 76
Table 5.2.2: Deposition rates for alumina and zirconia thin films at different O2
flow. ......................................................................................................................... 78
Table 5.2.3: XPS results for alumina and zirconia samples at varying O2 flow
without ion etching. .................................................................................................. 80
Table 5.2.4: EDS results for the same alumina and zirconia samples as in Table
5.2.3. ........................................................................................................................ 81
Table 5.2.5: XPS results for one sample of alumina and zirconia with ion etching. ....... 83
vii
10 LIST OF FIGURES
Figure 1.2.1: Engine test of coating on one blade for 100 hours by Bartoo and
Clure in 1953 [Miller, 2007] ......................................................................................... 2
Figure 1.2.2: Comparison of thermal spray and EB-PVD thermal barrier coatings
[Miller, 2007]. .............................................................................................................. 3
Figure 1.2.3: Schematic of thermal barrier coating system [Padture, 2011]. ................... 4
Figure 2.1.1: The current density versus voltage in a DC glow discharge [Vossen
and Cuomo, 1978]. ..................................................................................................... 8
Figure 2.1.2: An illustration of current versus voltage in a DC glow discharge

[Mahan, 2000]. .......................................................................................................... 10
Figure 2.1.3: The luminous and dark regions of a DC glow discharge [Mahan,
2000]. ........................................................................................................................ 14
Figure 2.1.4: (a) Schematic diagram of a DC sputtering discharge; (b) the

electrostatic potential profile as a function of distance from the cathode
[Mahan, 2000]. .......................................................................................................... 15
Figure 2.4.1: Circuit schematics of a sputtering system with DC (left) and RF

(right) power supply [Mahan, 2000]........................................................................... 25
Figure 2.5.1: Depiction of the magnetic and electric field on a magnetron cathode
[Mahan, 2000] ........................................................................................................... 26
Figure 2.6.1: Simple reactive sputtering geometry [Rossnagel, 2002]. ......................... 28
Figure 2.6.2: Hysteresis loops for deposition rate and discharge voltage with
increasing reactive gas flow [Rossnagel, 2002]. ....................................................... 30
Figure 2.6.3: Gas geometries for (1) mixed inert and reactive gas at target and
(2) inert gas at target and reactive gas at substrate. ................................................. 32
Figure 3.1.1: Hysteresis curve for mass flow control of reactive gas [Sproul et al.,
2005]. ........................................................................................................................ 36
Figure 3.1.2: Hysteresis curve for partial pressure control of reactive gas [Sproul
et al., 2005]. .............................................................................................................. 36
Figure 4.1.1: Denton Vacuum Explorer 14 sputtering system. ...................................... 46
Figure 4.1.2: Top view of schematic representation of Denton Vacuum sputter

system [Denton Vacuum manual]. ............................................................................ 47
viii
Figure 4.1.3: Computer-controlled touch panel on sputter system. ............................... 48
Figure 4.1.4: Additional gas lines on modified sputter system....................................... 49
Figure 4.4.1: Schematic of mini chamber setup by Scherer and Wirz. .......................... 55
Figure 4.4.2: Mock-up of a mini chamber design using aluminum foil and shield. ......... 57
Figure 4.4.3: Separate oxygen nozzle placed closer to substrate holder. ..................... 57
Figure 5.1.1: XRD result for aluminum film on glass slide. ............................................ 58
Figure 5.1.2: XRD result for zirconium on glass slide. ................................................... 59
Figure 5.1.3: SEM micrograph of as-sputtered aluminum film on silicon wafer. ............ 60
Figure 5.1.4: SEM micrograph of as-sputtered zirconium film on silicon wafer. ............ 61
Figure 5.1.5: SEM micrograph of cross section of aluminum film on silicon wafer. ....... 61
Figure 5.1.6: SEM micrograph of cross section of zirconium film on silicon wafer. ....... 62
Figure 5.2.1: Typical hysteresis curve for reactive magnetron sputtering [ Koski et
al., 1999]. .................................................................................................................. 64
Figure 5.2.2: Hysteresis curve for reactive sputtering of aluminum oxide,

presented as reactive gas flow rate versus target voltage. ....................................... 65

presented as reactive gas flow rate versus sputter pressure. ................................... 65
Figure 5.2.4: Hysteresis curves for (a) mass deposition rate of zirconium oxide,
(b) target voltage, and (c) partial pressure of oxygen as a function of oxygen
flow rate [Venkataraj et al., 2002].............................................................................. 66
Figure 5.2.5: Hysteresis curve for reactive sputtering of zirconium oxide,

presented as reactive gas flow rate versus target voltage. ....................................... 67

presented as reactive gas flow rate versus sputter pressure. ................................... 68
Figure 5.2.7: XRD result of aluminum oxide on glass slide. .......................................... 69
Figure 5.2.8: XRD result of zirconium oxide on glass slide. .......................................... 69
Figure 5.2.9: SEM surface image of alumina thin film with 1.8 sccm O2. ...................... 70
ix
Figure 5.2.10: SEM surface image of alumina thin film with 2.0 sccm O2. .................... 70
Figure 5.2.11: SEM surface image of alumina thin film with 2.1 sccm O2. .................... 71
Figure 5.2.12: SEM micrograph of zirconia thin film surface with 1.8 sccm O2. ............ 72
Figure 5.2.15: SEM micrograph of the surface structure for zirconia film sputtered
at 150 W with RF power [Sethi et al., 2009]. ............................................................. 74
Figure 5.2.16: SEM micrograph of zirconia surface and cross section at 5% O2

[Gao et al., 2000]. ..................................................................................................... 75
Figure 5.2.17: SEM micrograph of alumina thin film cross section for 1.8 sccm
O2. ............................................................................................................................. 76
Figure 5.2.18: SEM micrograph of zirconia thin film cross section with 2.0 O2. ............. 77
Figure 5.2.19: XPS aluminum spectrum for alumina sample without ion etching. ......... 78
Figure 5.2.20: XPS zirconium spectrum for zirconia sample without ion etching. ......... 79
Figure 5.2.21: XPS spectrum for alumina sample after ion etching. .............................. 81
Figure 5.2.22: XPS spectrum of zirconia sample after ion etching. ............................... 82
Figure 6.2.1: Various views of the mini chamber over the sputter gun. ......................... 90
Figure 6.2.2: (Left) View of mini chamber over sputter gun, (Right) view of mini
chamber with shield .................................................................................................. 90
Figure 6.2.3: Representation of reactive gas inlet made of stainless steel tubing. ........ 91
x
11 ABSTRACT
Yttria-stabilized zirconia (7% YSZ) is the most used material for thermal barrier coatings
(TBCs) to reduce the conductive heat transfer on turbine blades, but it is not resistant to
infrared radiation. In order to reduce radiation heat transfer, alternating materials, such
as alumina and zirconia, can be used to fabricate multi-layer coatings in which each
layer is optimized to reflect a targeted range of wavelength. This research aims to
fabricate these multi-layer coatings by reactive magnetron sputtering.
Reactive magnetron sputtering is the sputtering of an elemental target in the presence
of a reactive gas that will react with the target material to form a compound on the
substrate. Although reactive magnetron sputtering has high deposition rate, a major
disadvantage of reactive magnetron sputtering is target poisoning, which leads to very
low deposition rates.
In this research the flow control of reactive gas method has been used to complement
the setup of the current sputtering system. First, pure aluminum and zirconium thin films
are deposited and analyzed for film structure and properties. Then, alumina and zirconia
thin films are reactively sputtered.
The films are analyzed using XRD and SEM to determine the crystallography and
surface structure. The XRD results of the metallic thin films for aluminum and zirconium
shows the peaks corresponding to FCC and HCP crystal structure, respectively. The
XRD results of the alumina and zirconia films do not contain any peaks, indicating an
amorphous structure. XPS results give elemental compositions for the films from which
the stoichiometry can be determined. The composition of the films is analyzed for before
xi
and after ion etching of the surface. The XPS results concluded that the films were
under stoichiometric.
More experiments need to be performed to determine the best ratio of inert and reactive
gas in order to produce stoichiometric films. Modifying the current system could help to
improve the quality of the films by utilizing a pulsed-DC power source, an arc
suppression system, the partial pressure control of the reactive gas, and other
instruments to properly measure the film properties.
xii
1 CHAPTER 1: INTRODUCTION
1.1 Motivation
Thermal barrier coatings (TBCs) are ceramic coatings applied to metal components in
gas turbine engines or rocket engines that are exposed to high temperatures in order to
extend the service life of that component. Even though research in this area began over
60 years ago, many researchers are still trying to find ways to improve TBCs for
engines operating at even higher temperature ranges to achieve higher efficiencies. The
current work aims to modify a sputter system to incorporate reactive sputtering
capabilities and to fabricate alumina and zirconia thin films by reactive magnetron
sputtering. Eventually, this process can be used to optimize the thickness of the
individual layers of multi-layer thermal barrier coatings in order to reduce the infrared
radiation passing through the TBCs.
1.2 Brief History of Thermal Barrier Coatings (TBCs)
This brief history was obtained from a NASA paper written by Robert A. Miller [Miller,
2007]. A form of thermal barrier coatings have been around since the 1940s when they
were first introduced as frit enamel coatings for turbine blades by W.N. Harrison, D.C.
Moore, and J.C. Richmond of the National Bureau of Standards in 1947. As early as
1948, one of the first frit coatings was tested on turbine blades in an engine. Bartoo and
Clure tested a coating in an engine for 100 hours in 1953 (Figure 1.2.1). The Air Force
led the development of frit coatings in the 40s, 50s, and 60s. Working with industrial
partners, NACA, now NASA began using TBCs in the development of LH2/LOx rocket
engines in 1956. In 1960, the first flame sprayed coating used for rocket applications
1
was the RokideTM thermal barrier coatings on the XLR99 rocket engine nozzles of the X-
15 developed by L.N. Hjelm and B.R. Bornhorst. The RokideTM TBC had a zirconia top
coat and a nickel chrome bond coat. In the 1960s and early 1970s, Sal Grisaffe
conducted materials-oriented thermal spray research using alumina, zirconia (calcia and
possibly yttria stabilized), and hafnia for nuclear rocket applications.
Figure 1.2.1: Engine test of coating on one blade for 100 hours by Bartoo and
Clure in 1953 [Miller, 2007]
Since 1970 plasma sprayed TBCs were used in commercial combustors. S. Stecura,
C.H. Liebert, and F.S. Stepka played key roles in the development of the “modern”
thermal spray coatings in the mid-1970s. These coatings, which survived a J-75 engine
test, used yttria to stabilize zirconia and a MCrAlY type bond coat. Electron-beam
2
physical vapor deposition (EB-PVD) TBCs were introduced onto turbine blades in 1989
and remain the coating of choice for first-stage turbine blades (Figure 1.2.2).
1.2.1 Fabrication and Application of TBCs
TBCs are typically deposited using two common processes: air plasma spraying and
electron-beam physical vapor deposition. As mentioned before, plasma spray
technique, a form of thermal spray, was developed in the 70s, and EB-PVD was
introduced in the early 90s. Nowadays it is more common to use EB-PVD for TBC
deposition because it offers superior thermo-mechanical properties and lifetime
performance over plasma spray process [Kelly, 2006]. A thermal barrier coating system
usually consists of three layers: the ceramic top layer, a thermally grown oxide (TGO)
layer, and a bond coat layer to the substrate (Figure 1.2.3).
Figure 1.2.2: Comparison of thermal spray and EB-PVD thermal barrier coatings
[Miller, 2007].
3
The most common ceramic material for the top layer is yttria-stabilized zirconia, which
has low thermal conductivity, a high coefficient of thermal expansion and is chemically
inert to combustion atmospheres [Leyens, 1999].
Figure 1.2.3: Schematic of thermal barrier coating system [Padture, 2011].

The bond coat, typically made with MCrAlY-type compositions or aluminides, must
provide sufficient bonding between the ceramic top coat and the superalloy substrate
and should have corrosion resistance. The chromium and/or aluminum in the bond coat
also provide oxidation protection to the metal blades by forming an oxide scale.
The first applications of ceramic coatings were used on aero turbine blades in the 1940s
and then on rocket engines in the 1960s. They are commonly used on combustion
liners, turbine vanes, and turbine blades to protect the components from the harsh
environment. The TBCs have also found application in the automotive industry. They
are used to coat components of the exhaust system, such as exhaust manifolds,
turbocharger casings, exhaust headers, downpipes, and tailpipes. The most recent
4
research has been on the development of multi-layer TBCs to protect against radiation
heat transfer as engine temperatures are rising to increase efficiency.
In order to fabricate these new multi-layer TBC structures using reactive sputtering, the
process of sputter deposition needs to be studied. A brief sputtering history will be
presented to give a full background on sputter deposition.
1.3 Brief Sputtering History
Cathodic sputtering is the phenomenon of the cathode electrode disintegration under
the bombardment of the ionized gas molecules when an electrical discharge is passed
between electrodes at a low gas pressure [Holland, 1956]. Over a century ago, early
investigators of electrical discharges in gases observed that the wall of a glow discharge
tube became coated with a metallic deposit in the negative electrode region [Mattox,
2003]. W.R. Grove was the first to study what came to be known as “sputtering” (and
sputter deposition) in 1852 [Grove, 1852]. This film deposition from a glow discharge
was also observed by M. Faraday in 1854 and Julius Plücker in 1858 [Plücker, 1858].
Prof. A.W. Wright of Yale University published a paper in the American Journal of
Science and Arts in 1877 on the use of an “electrical deposition apparatus” to form
mirrors and study their properties [Wright, 1878]. C.J. Overbeck reported the deposition
of compounds by sputtering in a reactive gas (“reactive sputter deposition”) in 1933 for
use as optical coating [Overbeck, 1933]. In 1936 F.M. Penning [Penning, 1936]
proposed the “crossed field” (electric and magnetic) electron trap to enhance plasmas in
sputtering from cylindrical-hollow (inverted) magnetrons and cylindrical-post magnetrons
[Penning and Mobius, 1940].
5
Although our basic understanding of this complex subject is incomplete, sputtering is a
very mature technology, as evidenced by the many applications of the process. Some
examples given by Parsons of these applications are magneto-optical storage media,
compact disks, planarized coatings for multilayer circuits, optical multilayer coatings for
mirrors and filters, solar control and low emissivity window coatings, conductors and
barrier layers for very large scale integrated circuits, solar cells, diamond-like coatings,
transparent conducting electrodes, amorphous optical films for integrated optics
devices, luminescent films, microcircuit photolithographic mask blanks, wear-resistant
coatings for cutting tools, and decorative coatings [Parsons, 1991]. Parsons also gives
some reasons for using sputtering: excellent film uniformity; surface smoothness and
thickness control; deposition of films with nearly bulk-like properties; versatility; good
adhesion; high rates, which are comparable to evaporation. For film deposition there are
two categories of sputter sources: glow discharge (diode, triode, and magnetron) and
ion beam. This research uses glow discharge sputter sources for the sputtering
process.
1.4 Thesis Overview
In this chapter the motivation for the current work was presented. A brief history and the
applications of thermal barrier coatings were discussed. Also, a brief sputtering history
was presented.
Chapter 2 talks about the background of glow discharges and different sputtering
techniques. Some sputter theories are presented. Various sputter deposition
arrangements are revealed and comparisons made. Reactive sputtering is examined
and compared with conventional sputtering techniques.
6
Chapter 3 goes into more details about DC reactive magnetron sputtering of alumina
and zirconia thin films. The works of other authors are presented in order to compare
their results with findings from the current work.
Chapter 4 introduces the sputtering system and modifications the author made on the
system. The system maintenance is also reviewed to show the many obstacles the
author faced during this research. The chapter concludes with the details of the
experimental procedures for metallic and reactive sputtering.
Chapter 5 provides the experimental results from metallic sputtering of aluminum and
zirconium and reactive sputtering of alumina and zirconia. These results are then
compared to findings of other authors.
Chapter 6 summarizes the current research project and provides recommendations for
future work.
7
2 CHAPTER 2: BACKGROUND ON SPUTTERING
Sputtering is a technology that was discovered in the 1850s, but was not widely used
until the technology advanced in the 1940s. Sputtering stems from the investigations of
glow discharges, which is why the basic principles of glow discharges are presented in
this chapter. An understanding of the fundamental physics behind glow discharges will
lead to greater comprehension of the sputtering process.
2.1 Glow Discharges
The glow discharge phenomena relevant to diode sputtering will be described in this
section. The schematic in Figure 2.1.1 represents the characteristics for the applied
voltage as a function of current for a DC discharge formed in a low-pressure gas with a
high-impedance DC power supply.
2
4
Figure 2.1.1: The current density versus voltage in a DC glow discharge [Vossen
and Cuomo, 1978].
8
Vossen and Cuomo [Vossen and Cuomo, 1978] described the four distinct regions of
this process: Townsend discharge (1), normal discharge (2), abnormal discharge (3),
and arc (4). Initially, a very small current flows when a voltage is first applied due to the
presence of a small number of ions and electrons from some external source (i.e.
radiation). Because all of the charge present is moving, the current is nearly constant,
but as the voltage is increased, charged particles acquire sufficient energy to produce
more charged particles by collisions with the electrodes and neutral gas atoms. The
current steadily increases as more charge is created, but output impedance of the
power supply limits the voltage. This describes the Townsend discharge (1) region.
As neutral gas atoms become charged ions, they strike the cathode releasing
secondary electrons, which form more ions by colliding with neutral gas atoms. These
ions then return to the cathode producing more electrons that, in turn, produce more
ions. This avalanche effect continues until the number of electrons generated is just
sufficient to produce enough ions to regenerate the same number of electrons, which
yields a self-sustaining discharge. The normal discharge (2) is the region when the gas
begins to glow, the voltage drops, and the current abruptly rises. In this region, the
bombardment of the cathode is initially not uniform, but rather concentrated near the
edges of the cathode or irregularities on the surface. The bombardment gradually
covers the cathode surface as the power is increased until a nearly uniform current
density is achieved.
Further addition of power increases both the voltage and current density in the
discharge. This region is called the abnormal discharge (3), and it is the mode in which
sputtering is operated. Thermionic electrons as well as secondary electrons are emitted
9
when the current density reaches about 0.1 A/cm2, followed by further avalanche effect.
Since the voltage is limited by the output impedance of the power supply, a low-voltage
high-current arc (4) discharge forms.
Mahan [Mahan, 2000] also describes the various regions of the glow discharge but
includes more mathematical details. He gives a combination of several classic diagrams
for the representation of applied voltage as a function of current for a DC discharge in
an argon pressure range of 0.1-1.0 Torr (Figure 2.1.2). Voltage is taken to be the
dependent variable, whereas current is the independent variable.
Figure 2.1.2: An illustration of current versus voltage in a DC glow discharge

[Mahan, 2000].
The ohmic conduction and saturation (A) regime is described by low current density
and a small free electron density due to an external agent. In this region the conditions
of the discharge does not resemble the sputtering plasma. In the low current range at
higher electric fields, the current saturates as a function of the applied voltage: Isat =
10
constant. All available electrons are swept from the cathode to the anode by the electric
field. During saturation the discharge is not yet self-sustaining.
J. S. Townsend investigated that impact ionization of neutrals by electrons occurs when
the applied voltage is increased to the point where the current rises beyond the
saturation value [Mahan, 2000]. These neutral gas atoms are ionized when the
electrons are accelerated towards the anode. This process of producing more free
electrons and ions is known as the Townsend discharge (B). The ionization potential of
a neutral atom is the minimum kinetic energy required for the impact ionization process
with an ionization cross section of Si. For kinetic energies below the ionization potential,
the cross section is zero. The assumption made for the electron current coming off the
cathode is Isat. The electron current increases due to the impact ionization with distance
from the cathode (x) according to the following relation:
∙ ∙ , (2.1)
which leads to the relation:
∙ ∙
. (2.2)
Itde is the Townsend electron current, Isat is the saturation current, and n is the neutral
particle density in m-3. The electron current at any distance d between the cathode and
anode can be used to calculate the total current, Itd, in the discharge, which is constant
and independent of x:
∙ ∙
, (2.3)
11
The ion current is given by the difference in the total current and the electron current:
∙ ∙ ∙ ∙
1 (2.4)
At x=0 the maximum ion current occurs, and the ion current equals zero at the anode.
The Townsend discharge is not yet self-sustaining since the current would stop if the
ionization radiation were removed.
In the previous region, ions did not have enough kinetic energy to ionize neutral gas
atoms, but in the breakdown (C) region, they play a major role in creating charged
particles by knocking out free electrons from the cathode. This process can be defined
by the yield or secondary electron emission coefficient, γ. The yield γ is the number of
secondary electrons emitted per incident ion. An energy-independent, empirical
expression for the yield has been provided by [Raizer, 1991]:
0.016 2 , (2.5)
where Ei is the ionization potential of the cathode atom and W is the work function.
Breakdown is described as the region where the sudden drop in voltage is necessary to
maintain the discharge at a fixed current. The electron current at the anode is given by:
∙ ∙ ∙ ∙
0 (2.6)
Equation 2.6 describes the original saturation current enhanced by electron impact
ionization plus the secondary electron current, also enhanced by the electron impact
ionization between the electrodes. The increase in original electron saturation current
enhanced by impact ionization plus the increase in electron current due to the
12
secondary electron emission at the cathode also enhanced by impact ionization is equal
to the ion current at the cathode. The ion current Ibi(0) is defined as:
∙ ∙
0 ∙ ∙ (2.7)
As stated before, the total current of the discharge is constant and can be evaluated as
the electron current at some distance d between the electrodes:
∙ ∙
, ∙ ∙
. (2.8)
In breakdown, the discharge no longer depends on any external ionizing source and
transitions to a self-sustaining discharge.
The next regime after breakdown is the normal glow (D) in which discharge voltage is
constant while current varies. The current density at the cathode is not uniform; rather,
the secondary electron emission is localized at the edges and any irregularities on the
cathode surface. The ion bombardment will spread over the entire cathode surface as
the current increases at constant applied voltage. At this point the discharge begins to
have the general characteristics of the sputtering plasma.
Once the entire cathode area is used, further increase in the current can only be
achieved by increasing the yield γ and/or the cross section Si, which means that the
applied voltage is increased. This regime is known as the abnormal glow (E) where
most DC sputtering processes are operated. The final region in Figure 2.1.2 is the arc
(F) regime, which occurs as a result of extreme heating of the cathode by ion
bombardment, leading to the thermionic emission of electrons.
13
2.1.1 The DC Glow
Plasma is another name for a glow discharge, which is an electrical current flowing
through a gas that glows by light emission from the excited gas atoms. A glow
discharge has various luminous and dark characteristics observed by early researchers,
which is illustrated in Figure 2.1.3.
Figure 2.1.3: The luminous and dark regions of a DC glow discharge [Mahan,
2000].
Mahan [Mahan, 2000] states that the Aston dark space is the region where electrons
emitted from the cathode has very low energy and ions are rapidly accelerated towards
the cathode. The electrons cannot excite or ionize any gas particles due to their low
energy. According to Cobine [Cobine, 1941], the cathode glow “appears to cling to the
cathode surface.” Brown described it as a “velvety coating [resulting from] the loss of
excitation energy of the positive ions on neutralization” [Brown, 1966].
The next region is also known as the “cathode sheath” of processing plasmas, but it is
14
usually several times thicker than the actual sheath. This region, the Crookes (or
cathode) dark space, is a “region of primary interest…its thickness is approximately the
mean distance traveled by an electron from the cathode before it makes an ionizing
collision” as explained by Maissel and Glang [Maissel and Glang, 1970]. High velocity
electrons that have accelerated across the cathode fall and low velocity electrons from
impact ionization of neutral gas atoms are both present in this region.
In the negative glow region, enhanced visible emission is due to the larger cross section
of secondary electrons for excitation of neutrals. Electrons lose their energy in the
negative glow region, so that when they arrive in the Faraday dark space, they are not
able to neither excite or ionize any neutral gas atoms nor gain any more kinetic energy.
The rest of the luminous region is called the positive column. Here electrons can gain
enough kinetic energy from the small electric field in order to excite neutral gas atoms
again as they move towards the anode. Ions with sufficient kinetic energy can also
bombard the anode and emit secondary electrons, which then excite neutrals,
producing the anode glow.
2.1.2 A DC Discharge Model
Consider a pair of electrodes in which the cathode is the electrode that attracts cations
(positive ions) from the plasma and the anode is the electrode that attracts anions
(electrons). (a) is a schematic representation of a DC discharge and (b) illustrates the
potential profile.
To model a practical discharge, the current density to the cathode is taken to be jion,
which may be enhanced by secondary electron emission, and the current density to the
15
anode is the negative of this value:
(2.9)
In order to achieve these currents, the following relations must be true:
≪ (2.10)
and
, (2.11)
where vcat and van are the voltages of the cathode and anode respectively, VDC is the
applied voltage, Vf is the floating potential, and Vp is the plasma potential. Thus, this
leads to the frequent observation that the plasma is the “most positive” body in the main
current path of the discharge [Mahan, 2000].
(a) (b)
Figure 2.1.4: (a) Schematic diagram of a DC sputtering discharge; (b) the

electrostatic potential profile as a function of distance from the cathode [Mahan,
2000].
16
Using the expression for the current density for when the applied voltage is less than
the plasma potential ⁄ , the expression for the
plasma potential relative to the anode can be obtained:
(2.12)
When the anode is grounded, van = 0. In a practical model, the anode area is much
larger than the surface area of the cathode, which increases the plasma potential. The
potential drop across the cathode sheath is known as the cathode fall:
. (2.13)
This means that a value greater than the applied voltage is the maximum possible
kinetic energy with which ions strike the cathode. Also, the sputtering power density is
given by: ∙ .
The plasma body is separated from the cathode and anode by the sheaths, which are
high-electric field regions. Figure 2.1.4(b) shows the resulting electrostatic potential as a
function of position between the electrodes.
2.2 Sputter Yield
The most fundamental parameter of all sputtering processes is the sputtering yield,
which was previously defined as the number of atoms emitted from the cathode surface
per incident ion. The threshold for sputtering is approximately equal to the heat of
sublimation, and the sputter yield increases with incident ion energy in the energy range
of 10-5000 eV [Almen and Bruce, 1961]. The erosion rate of sputtering targets and
17
approximately the deposition rate of sputtered films can be determined by the sputtering
yield. A compilation of sputtering yields for various elements is published in [Vossen,
1978]. Sputtering yields of metals rarely differ by more than a factor of 10 under similar
conditions. However, over the years more recent developments and error corrections
have led early data to be regarded as obsolete. Probably the most recent
comprehensive compilation of sputter yield data for elemental targets was done by
Matsunami et al [Matsunami et al, 1984]. They prepared graphs of yield as a function of
energy using a database of all published sputter yield measurements available in early
1983. An empirical curve for the yield as a function of projectile energy Y(E) was plotted
in addition to the actual data points obtained from literature. The empirical yield formula
of Matsunami et al. is given by:
.
∗ .
0.42 ∙ ⁄ ∙ 1 , (2.14)
. ⁄ ⁄
where Us is the sublimation energy, α*,Q, Eth are empirical parameters, se and sn are the
inelastic and nuclear reduced stopping cross section respectively, mp and mr are the
projectile mass and recoil ion mass respectively, E is the projectile energy, and Zp and
Zr are the atomic number of projectile and recoil ion respectively. The empirical
parameters can be calculated using the following formulas:
. .
∗
0.08 0.164 ∙ 0.0145 ∙ (2.15)
and
18
.
, ∙ 1.9 3.8 ∙ 0.134 ∙ . (2.16)
Lindhard’s nuclear, sn, (elastic) and the inelastic, se, reduced stopping cross section are
approximated by:
. √ .
(2.17)
. √ . . √
and
⁄ ⁄ ⁄
⁄
0.079 ∙ ⁄ ⁄ ∙ ⁄ ⁄ ⁄ , (2.18)
where the reduced energy is defined by
.
⁄ ⁄ ⁄ ∙ . (2.19)
2.3 Sputter Theory
One of the first theories of cathode disintegration was the belief that heated gas trapped
in small cavities in the metal exerted sufficient pressure to blow particles out of the
cathode. However, Baum disproved this theory by showing that sputtered material
exited the cathode in atomic form with high thermal velocities [Baum, 1927]. Lamar and
Compton [Lamar and Compton, 1934] believed in the momentum transfer theory and
explain sputtering as a mechanical “bumping off of surface atoms by ions which have
penetrated below the surface and rebounded.” While some may call sputtering
“momentum transfer” process, it is really an energy transfer process in elastic collisions
19
during which momentum must be conserved [Mahan, 2000]. In 1940 Penning and
Mobius discovered that the sputtered atoms were sufficiently excited under intense
ionizing conditions in a magnetic field to emit characteristic spectra [Penning and
Mobius, 1940]. This was seen through the sputtering of copper where the discharge
was a greenish hue. In modern sputtering theory discussion, there are two groups of
such theories. One group of researchers, such as Blechschmidt and v. Hippel, state that
at the point of impact of the positive ions, sputtering is due to local heating and thermal
evaporation of the cathode atoms [Blechschmidt and Hippel, 1928]. Strong evidence
against a universal thermal mechanism is due to the lack of yield dependence on target
temperature [Bohdansky et al., 1987]. Another group of investigators argue that
sputtering is due to the emission of atom-on-ion impact as seen in the same manner as
secondary electron emission. Langmuir and Kingdon advanced this impact theory in
order to describe the sputtering of thorium from a tungsten surface [Kingdon and
Langmuir, 1923].
2.3.1 Evaporation Theory
Starr [Starr, 1939] has done an investigation of the evaporation theory of sputtering. He
has reported that an empirical relation exists between the rate of sputtering of various
metals and the total heat WH required to evaporate the metal [Holland, 1956]. Starr
states that the sputtering rate for fixed glow discharge conditions follow:
/ (2.20)
where Q is the mass sputtered per ampere-hour and C is a constant depending on the
discharge conditions. He also argues that the theory of localized high temperature with
20
thermal evaporation predicts an exponential relationship, whereas a linear relationship
is given by the theory of direct momentum transfer of the impinging ions with the metal
atoms. Starr believed that sputtering is a double evaporation process. Initially, the
sputter rate of emitted metal atoms by direct energy transfer due to ion bombardment is
inversely proportional to the total heat of evaporation Q ~ 1/WH. After leaving the
cathode surface, the metal vapor condenses into a fine aggregate (metal powder).
Additional exposure to the heat of ions and electrons near the cathode surface would
cause re-evaporation into the residual gas. Starr does not give any experimental
evidence of this theory.
2.3.2 Momentum Transfer Theory
Wehner’s research in the 1950s was one of the most important works on sputtering
because it provided a satisfactory explanation of the energy exchange mechanism
between the bombarding ions and cathode atoms [Wehner, 1954]. He argued that
evaporation theory cannot explain the dependence of the sputtering rate on the angle of
incidence of the positive ions. Wehner used Hg+ ions impinging at normal incidence to
bombard a target (of different metals) in order to measure the minimum ion energy for
sputtering. He obtained that the heat of sublimation was proportional to the product of
∗
the momentum transferred at the threshold energy from the ion to the metal atom
along with the bulk sound velocity of the metal. The threshold energies can be
calculated from
∗ .
(2.21)
21
∗
where is in eV, Mg and Mm are the atomic weights of the ion and metal respectively,
vs is the bulk sound velocity of the metal in cm/sec, and WH is the heat of sublimation of
the metal in Kcal/mol. Wehner states that [Holland, 1956]:
“The significance of the sound velocity here, although not yet fully
understood, is obviously to introduce the elastic constants of the
material, which determine what part of the transferred energy with the
momentum directed to the inside of the material arrives at the surface
with a momentum reversed in direction. This part has to be at least equal
to the binding energy of a surface atom before sputtering ensues.”
Now that the sputtering background and theory have been introduced, the next
sections will cover the different types of sputtering processes.
2.4 Diode Sputtering
The simplest sputter source is the planar diode. The diode electrodes are the target
(cathode) and the substrate (anode) within a vacuum chamber. Typically, the target is
disk-shaped with a diameter of about 5 to 10 cm and is thermally mounted to a water-
cooled backing plate or directly water-cooled. The anode is the substrate or the
chamber walls and is usually separated from the target by a few centimeters. A current
flowing through a low pressure gas is called a discharge. Plasma, also known as the
fourth state of matter, is a partially ionized gas, and some plasmas are also glow
discharges, in that they glow with light emission from excited atoms [Mahan, 2000].
There are three fundamental sputtering arrangements: a direct-current (DC) diode
discharge, a capacitive radio-frequency (RF) diode discharge, and a planar magnetron
22
with either a DC or RF discharge. In diode sputtering, energetic ions from the plasma of
a gaseous discharge bombard the target and cause neutral target atoms to be ejected
through momentum transfer. The ejected target atoms impinge on the substrate forming
a coating. The target is the cathode of the discharge connected to either a DC or RF
negative voltage supply, and the anode is usually grounded. Argon gas, which
maintains a pressure on the order of 1 Torr, is typically the inert gas used as the
medium for the plasma. As argon ions collide with the target surface, secondary
electrons are emitted from the surface. These electrons are accelerated back across the
sheath and gain significant energy, which is used to form more ions to sustain the
discharge [Rossnagel, 2002]. The power supply can either be a high-voltage DC source
or a high voltage RF source. The standard frequency used in the RF source is 13.56
MHz due to government communications regulations. The mean ion current density to
the target is on the order of 1 mA/cm2 for both DC and RF sources. However, for RF
source, the amplitude of the total RF current is an order of magnitude (or more) higher.
Generally, an RF discharge can operate in the same way as a DC discharge, but the
difference is that the applied RF voltage oscillates with time. In addition, to develop the
necessary DC self-bias, a blocking capacitor is placed in series with the powered
electrode. A matching network is utilized to optimize power transfer from the RF source
to the plasma [Mahan, 2000].
DC diode plasmas have typically been used for sputtering etching of samples placed on
cathode surface or sputtering deposition of cathode material onto samples placed on
the anode. However, DC plasmas are infrequently used because it is relatively slow
compared to other deposition techniques and requires conductive electrodes to allow
23
the flow of the current. Using an RF source has some advantages over DC source, such
as high deposition rates at lower voltages and lower sputter pressures and sputtering of
insulating targets. below shows the circuit schematics of DC (a) and RF (b) sputtering
arrangements [Mahan, 2000].
The efficient use of target material is an advantage of diode sputtering since the diode
electrodes can be large and the electric field between them is uniform, so the ion flux is
nearly constant over the target. However, inefficient use of secondary electrons is a
major disadvantage of diode sputtering. Also, the substrate temperature significantly
increases due to the bombardment of the growing film, and diodes have low deposition
rates compared to other sputter sources that are capable of low pressure operation
[Parsons, 1991]. Although film deposition was discovered through investigations of glow
discharges, diode sputtering is not commonly used since the development of the
magnetron.
Figure 2.4.1: Circuit schematics of a sputtering system with DC (left) and RF

(right) power supply [Mahan, 2000].
24
2.5 Magnetron Sputtering
As previously mentioned, Penning and Mobius [Penning and Mobius, 1940] first
introduced the concept of cylindrical-hollow magnetrons in 1940. They found that
sputtered atoms under the intense ionizing conditions obtained in a magnetic field were
sufficiently excited to emit characteristic spectra. Since then many configurations have
been developed to advance this technology. The most notable work on post cathode
magnetron sputtering was done by A.S. Penfold and J.A. Thornton in the 1970s. The
planar magnetron has been established as the embodiment of a high deposition rate
sputtering source. J.S. Chapin first introduced the planar magnetron in 1974 even
though this “obvious” solution eluded discovery and implementation for more than 30
years [Waits, 1978]. Several manufacturers had various versions of the planar
magnetron sputtering source commercially available by early 1975. The planar
magnetron is just the classical DC or RF diode sputtering arrangement with the addition
of permanent magnets directly behind the cathode. There are various geometries but all
magnets are arranged in such a way that the magnetic field lines are parallel to the
cathode surface and perpendicular to the electric field lines (Figure 2.5.1). This causes
the secondary electrons to drift in a closed path in the direction, also known as
the Hall Effect, trapping the electrons near the cathode surface. This arrangement
results in enhanced ion bombardment and sputtering rates for both DC and RF
discharges.
A typical planar magnetron configuration is where a disk-shaped target (cathode) having
a toroidal plasma ring facing and parallel to a fixed substrate holder (anode). RF planar
magnetron sputtering allows the use of insulating targets and direct or reactive
25
deposition of dielectric films. However, due to the complexity of the RF power supply
and the difficulty of ensuring an efficient RF ground, the choice for deposition of
electrically conducting materials is DC planar magnetron sputtering.
Figure 2.5.1: Depiction of the magnetic and electric field on a magnetron cathode
[Mahan, 2000]
Waits [Waits, 1978] reports that argon pressures of 0.5-30 mTorr and DC voltages of
300-700 V are typical operating parameters for DC planar magnetrons. RF planar
magnetrons can operate at much lower voltages than their RF diode counterparts.
Although RF magnetrons are necessary for sputtering insulating targets, they are about
half as efficient as DC magnetrons. For a given power, RF planar magnetron deposition
rate is constant (±10%) and independent of pressures ranging from 1-20 mTorr.
Parsons lists typical magnetron characteristics: cathode current density of 20 mA/cm2,
discharge voltage 250 to 800 V, minimum pressure of about 1 mTorr, and target-to-
26
substrate distance vary from a few centimeters to 20 cm (about 6 cm is typical). One of
the disadvantages of the planar magnetrons is poor utilization of the target material,
which is typically 20-30% of the starting target material [Parsons, 1991].
Some applications listed by Waits for planar magnetron deposition are: decorative or
functional coatings on plastic, anticorrosion or abrasion-resistant coatings on metals,
large-scale integrated circuits, thermal printheads, and on a smaller scale, coating of
heat sensitive biological samples.
2.6 Reactive Sputtering
G.A. Veszi introduced the term “reactive sputtering” in 1953 [Veszi, 1953]. The
sputtering of a metal target in the presence of a reactive gas to form a compound is
known as reactive sputtering (Figure 2.6.1).
Dielectric films can be sputtered from an insulating target comprised of the desired
compound from an RF sputter source or by reactively sputtering a metal target with a
suitable reactive gas using either DC or RF sputter sources. For example, reactive
sputtering is commonly used for the deposition of oxides and nitrides. The
disadvantages of directly sputtering dielectric films from a ceramic target using RF
power is that the deposition rate is very low compared to elemental deposition and
target cracking due to the poor physical stability of the compounds.
Reactive sputtering is usually the preferred method because of the following
advantages [Parsons, 1991]:
 Metal targets can be machined;
27
 Metal targets have high thermal conductivity and, therefore, can handle high
power densities without cracking;
 Different types of dielectrics can be fabricated by choosing different reactive gas
mixtures; and
 High-rate techniques give deposition rates comparable to those of pure metals.
Figure 2.6.1: Simple reactive sputtering geometry [Rossnagel, 2002].

Another reason for using reactive sputtering with metal targets is the ability to use DC
power instead of RF for high rate, controlled deposition. The disadvantage of using
metal targets in reactive sputtering is that the target surface can also react with the gas
to form an insulating thin film on the surface, which drastically alters the sputtering
28
process. During reactive sputtering, the target operates in two states: metallic mode and
compound mode. Metallic mode is characterized by high target voltage and low gas
pressure leading to high deposition rates. Compound mode is when a thin ceramic film
forms on the target surface leading to low target voltage at high gas pressures. It is
desirable to operate in the transition region between these two modes. In order to
determine where this transition region lies, the hysteresis effect must be observed to
determine the critical partial pressure of the reactive gas. Figure 2.6.2 below illustrates
the hysteresis phenomena where deposition rate and discharge voltage are plotted as a
function of reactive gas flow rate.
As reactive gas flow rate is increased, the deposition rate and discharge voltage are
nearly constant as the reactive gas is being absorbed by the sample and chamber walls
becoming partially oxidized. As the reactive gas is further increased, there is a certain
point (fc) where stoichiometric films are formed. This is the critical flow point (fc), and it is
also a point of unstable operation. Any further increase of reactive gas will cause an
insulating film to form on the cathode surface since the saturated films will not be able to
absorb any more reactive gas.
Even if the reactive gas flow rate is reduced, it will not return to the same path because
now the target is operating in compound mode. Only when the reactive gas has been
significantly reduced so that the oxide layer will be sputtered off, the target will return to
metallic mode. That is why reactive sputtering should occur in the transition region
between these two states just before the critical point at the knee of the curve. Because
this point is unstable and difficult to control, there are several methods to fix this
problem [Rossnagel, 2002]:
29
 Feedback control of the reactive gas;
 Increased pumping speed;
 Dual cathodes;
 Gas pulsing;
 Sample/cathode separation; and
 Oscillating deposition-oxidation.
Figure 2.6.2: Hysteresis loops for deposition rate and discharge voltage with
increasing reactive gas flow [Rossnagel, 2002].
30
It is common to introduce a mixture of inert and reactive gas into the vacuum chamber
at some arbitrary point during reactive sputtering. However, for high rate reactive
sputtering, consideration of gas delivery pipe geometry can allow for better process
control. There are two geometries that can be considered for deposition of nitrides and
oxides. Figure 2.6.3 depicts these two gas geometries [Parsons, 1991].
In gas geometry (1), a mixture of inert and reactive gas is uniformly introduced over the
cathode surface. This configuration is useful for high-rate deposition of nitrides because
it utilizes the intense discharge region near the cathode to generate ions and other
reactive species. Since oxygen is highly reactive with most metal surfaces, gas
geometry (2) is better suited for oxide deposition. In this configuration the inert gas is
uniformly introduced over the cathode surface while the reactive gas is distributed
around the substrate region. This helps to minimize the oxygen partial pressure in the
near-cathode region. The application of a negative substrate bias can maximize the
reaction at the substrate surface.
The next chapter studies the works of other investigators on reactive sputtering of
alumina and zirconia in order to compare sputter systems, sputter parameter, and
sputtered film results with the results of this investigation.
31
Figure 2.6.3: Gas geometries for (1) mixed inert and reactive gas at target and (2)
inert gas at target and reactive gas at substrate.
32
3 CHAPTER 3: LITERATURE SURVEY
Reactive sputtering was studied for the fabrication of alumina and zirconia thin films
because it offers many advantages for high deposition rates and good film properties.
The cost effectiveness of using reactive sputtering of metal targets over direct sputtering
of ceramic targets was a major constraint for this research.
Reviews [Holland, 1956; Parsons, 1991; Vossen and Cuomo, 1978; Mahan, 2000;
Rossnagel, 2002; Schwartz, 1963] of various deposition processes of thin films
including sputtering and reactive sputtering have been compiled to cover many
investigations in this field. This author aims to incorporate reactive sputtering capability
into an existing vacuum sputter system in order to produce ceramic thin films.
Schwartz [Schwarts, 1963] describes the important characteristics of reactive sputtering
and why it is being utilized more in industry, especially for integrated electronic circuitry.
Schwartz also points out some mechanisms of reactive sputtering, gives details on
experimental techniques, and compiles experimental investigations on using reactive
sputtering for resistive films, insulating films, and semiconductor films.
Hollands and Campbell [Hollands and Campbell, 1968] sputtered thin films of tantalum
in mixed argon/oxygen atmosphere (total pressure of 3.0 x 10-4 Torr) and found that
oxygen partial pressure was the controlling factor for other film parameters, such as
deposition rate, density, electrical properties, and electron diffraction. They concluded
that there exists a critical oxygen pressure in which below this point, tantalum metal is
sputtered and reaction occurs at the substrate and above this point, reaction at the
33
target forms an oxide surface from which tantalum oxide is sputtered. Through
experiments, they found that the deposition rate was independent of oxygen
concentration up to an oxygen pressure of approximately 1.25 x 10-4 Torr at which the
deposition rate fell from 2.6 x 10-5 to 6.0 x 10-6 g/min. Using a target of 1 cm2 area, the
growth rate was measured and recorded. At room temperature in 100% argon, the
growth rate was 14 Å/min and rose to a maximum rate of 32 Å/min at 6.0 x 10-5 Torr,
and then it significantly declined in 100% oxygen to 4 Å/min. They formulated that with
increasing partial pressure of oxygen, at any given temperature and constant deposition
rate, the degree of oxidation of the sputtered films will increase. Therefore, they came to
the conclusion that chemisorption equilibrium precedes the rate-determining step of
oxide growth. They found that at a constant temperature the rate of oxidation will be
approximately proportional to the square root of the oxygen pressure [Hollands and
Campbell, 1968]. The following equation expresses this statement:
⁄ , (3.1)
where K is the chemisorption equilibrium constant and R is the gas constant. They also
studied the effects of substrate temperature above and below the critical pressure, and
also presented supporting evidence for their conclusions.
Sproul et al. [Sproul et al., 2005] gives a more comprehensive review of the control of
reactive sputtering processes by comparing different methods of reactive gas control.
The simplest method is flow control of the reactive gas; however, the deposition rate
can be very low and film properties are not optimal. The more desirable method is
partial pressure control, but this is more complex since it requires active feedback
34
control. This method allows the target to be operated in the transition region between
metallic mode and compound mode. The authors state that using a pulsed DC or mid-
frequency AC power supply can prevent arcing during the sputtering of insulating films.
In order to obtain high deposition rates and optimum film properties, reactive sputtering
must take place in the transition region between the metallic and compound states of
the target. The process is unstable in the transition region for flow control of the reactive
gas. Observing the hysteresis effect for flow control, a sudden transition region can be
seen on a graph with increasing reactive gas flow rate. Using partial pressure control,
there are three basic feedback signals that have been used since the mid-1980s: optical
emission spectrometer, mass spectrometer, and cathode voltage. There is a continuous
transition between the metallic mode and compound mode when using partial pressure
control of the reactive gas. Therefore, there is an advantage in using partial pressure
control over mass flow control. Sproul et al. illustrated this difference by showing the
hysteresis curves for flow control (Figure 3.1.1) and partial pressure control (Figure
3.1.2).
Shinoki and Itoh [Shinoki and Itoh, 1975] investigated the mechanism of RF reactive
sputtering by mass spectrometry. They modeled the reactive process and found that
there was an abrupt step-like decrease in the sputtering rate at a definite partial
pressure of reactive gas. They concluded that the reaction process in RF reactive
sputtering is highly influenced by the gettering action of sputtered atom deposits.
Gettering is the process by which unwanted impurities are removed by providing an
alternative location (“a getter”) where they prefer to reside [http://dunham.ee.washington
.edu/ee528/notes.getter.pdf].
35
Figure 3.1.1: Hysteresis curve for mass flow control of reactive gas [Sproul et al.,
2005].
Figure 3.1.2: Hysteresis curve for partial pressure control of reactive gas [Sproul
et al., 2005].
36
3.1.1 Alumina Reactive Sputtering
Aluminum oxide (Al2O3) films have been produced for many applications in the
mechanical, optical, and electronics industries due to their excellent properties, such as
chemical inertness, mechanical strength and hardness, transparency, high abrasive and
corrosion resistance, and insulating and optical properties [Deshpanday and Holland,
1982; Koski et al., 1999].
Deshpanday and Holland investigated the reactive magnetron sputtering of aluminum in
Ar-O2 mixtures to determine the conditions for preparing oxide films with low optical
absorptance using both DC and RF power sources [Deshpanday and Holland, 1982].
They used an aluminum target (99.9% purity) of 75 mm (~ 3”) diameter, a target to
substrate distance of 40 mm (1.6”) and an erosion track mean diameter of 52 mm (2”).
The chamber pressure was vacuumed to 10-5 Torr with a gas pressure of 20 mTorr
when O2 was increased to 10% of total pressure. The presented tables for both DC and
RF reactive magnetron sputtering of aluminum target with values for deposition rate,
optical reflectance, transmittance, and absorptance of the Al2O3 films. They found that
with increasing O2 concentration, the deposition rate decreases in both DC and RF
reactive magnetron sputtering. Alumina films with absorptance less than 1.0% by DC
magnetron sputtering were possible in a 10% Ar-O2 mixture. The absorptance
decreased with increasing power at 10% O2 concentration. However, with RF
magnetron sputtering, the film absorptance increased with increasing O2 concentration
as well as power input. They used the Abelès method to measure the refractive index of
the films, which considers the film to have negligible absorptance. Since all the films
had some absorptance, they found that the films with the highest transmittance had a
37
refractive index of 1.61-1.62 for films evaporated using electron beam heating. They
concluded that for most oxidized films deposited stoichiometry was not completely
achieved.
Sproul et al. [Sproul et al., 1995] showed that it was possible to deposit aluminum oxide
coatings by DC reactive magnetron sputtering when using an arc suppression system.
They state that “Coatings such as aluminum oxide (Al2O3) are almost impossible to
deposit by conventional reactive DC magnetron sputtering because of the strong
interaction of the oxygen with the target surface that leads to very rapid oxide
compound formation on the target surface.” Arcing is very common and particularly
violent for reactive DC sputtering, and it can result in damage to the power supply.
Some investigators have used RF power to overcome the issue of arcing, but the
deposition rate is very slow, typically 2%-3% of the metal deposition rate at the same
power. Some researchers have also found that pulsed DC power supplies work well in
reactive sputtering; however, they can be quite expensive. Therefore, Sproul et al.
investigated a cheaper alternative – an arc suppression unit placed between the DC
magnetron power supply and the target. They also used this arc suppression unit in
conjunction with an automatic feedback control of the reactive gas.
For their experimental methods, the following system parameters were used: base
pressure of 5 x 10-7 Torr, argon as inert gas, etching pressure of 8 mTorr and sputter
pressure of 4 mTorr. The substrates used were glass slides and M2 tool steel, and they
were at a floating potential during deposition. The glass slides were etched for 1 minute,
and M2 tool steel were etched for 5 minutes with 1.5 kW of RF power. The target power
was set to 2 kW for all deposition runs. An Advanced Energy SPARC-LE 20 kHz unit
38
was used for the arc suppression. Partial pressure control of the reactive gas is used to
overcome poisoning of the target surface. They characterized the alumina films by
measuring the film hardness, film thickness and roughness, crystallographic structure,
and transmittance and absorbance of the film. Very clear, insulating films were
deposited at a partial pressure of 0.08 mTorr and showed very little difference between
the glass slide and the coating. The average refractive index of the film was found to be
1.6.
Koski et al. [Koski et al., 1999] also deposited aluminum oxide films using DC reactive
magnetron sputtering on glass slide, silicon wafer, stainless steel, and polycarbonate
substrates. The main disadvantages of reactive sputtering are poor deposition rate due
to target poisoning, hysteresis phenomena, arcing and inhomogeneity. To reduce target
poisoning and arcing, they controlled target voltage rather than power during deposition.
A pulsed DC power supply was used to minimize arcing.
Koski et al. [Koski et al., 1999] used an Alcatel reactive physical vapor deposition (PVD)
apparatus for depositing the films. They chemically cleaned the substrates in an ethanol
ultrasonic bath for 5 to 15 minutes to remove organic contaminants. The target was pre-
sputtered in a pure argon atmosphere of 1.0 Pa (7.5 x 10-3 Torr) for 10-20 minutes in
order to remove any oxide contaminants. They used a 6-inch diameter aluminum
(99.999 at.%) target. The system also contained a differentially pumped quadrupole
mass spectrometer for leak detection, residual gas analysis, and deposition control.
Argon gas was introduced in the target housing, while oxygen was introduced in the
immediate vicinity of the substrate holder using a home-made circular gas inlet located
1-2 cm from the substrates. The substrate bias voltages were between 0 V and -200 V.
39
The target voltage was between 310 V and 405 V, and the power was between 1000
and 1500 W. An Advanced Energy SPARC-LE V Accessory was used to handle arcing.
A Taylor-Hobson profilometer was used to measure film thickness right after deposition.
Stoichiometric aluminum oxide films were transparent, while metal-rich films were black
or brown. SEM (Scanning Electron Microscope) was used to study the surface
structure, and AFM (Atomic Force Microscope) was used to image the surface
topography and detect surface roughness. XRD was used to gather information on
crystallographic structure, and a RBS (Rutherford Backscattering Spectrometer) was
used for composition analysis and density measurements. Nanoindentation was used to
measure the nanohardness and elastic modulus of the thin films.
At a voltage of 405 V, the deposition rate of the transparent film was 215 nm/min, which
is 77% of the metallic deposition rate. All deposited films had an amorphous structure
since the deposition temperature is lower than the crystallization temperature of
aluminum oxide, 400ºC. The surface roughness on silicon substrates as measured by
AFM were between 0.72 and 2.64 nm. As substrate bias increased and sputtering gas
pressure increased, the surface roughness increased. The O/Al ratio, which depends on
the target voltage, was between 1.30 and 1.72. The density decreased with increasing
target voltage, and it is also dependent on sputtering gas pressure and substrate bias
voltage. Hard thin films occur at low pressures and have higher compressive stress
levels. The authors concluded in their findings, “Low sputtering gas pressures and low
bias voltages led to aluminum oxide thin films with a high hardness and low intrinsic
stress. High sputtering gas pressure, high substrate bias voltage and low target voltage
led to dense aluminum oxide thin films.”
40
3.1.2 Zirconia Reactive Sputtering
Zirconium oxide (ZrO2) films have been used in a wide range of applications that include
laser mirrors, broadband interference filters, ionic conductors, oxygen ion conductors for
sensor and fuel cell applications and thermal barrier coatings. The properties of
zirconium oxide that make them desirable for these applications are high melting point,
oxidation resistance, excellent thermal stability, high refractive index, and good ionic
conductivity in the Y-stabilized cubic phase [Venkataraj et al., 2002].
Venkataraj et al. [Venkataraj et al., 2002] deposited zirconium oxide thin films by DC
reactive sputtering onto silicon substrates at room temperature from a metallic
zirconium (Zr) target in an argon-oxygen atmosphere. Sputtering was performed using a
3” Zr target at room temperature with constant cathode current of 900 mA and a
pressure of 0.8 Pa ( 6 mTorr). Oxygen flow was varied between 0 and 4 sccm. The
target to substrate distance was maintained at 70 mm (2.75 inches). The substrates
used were glass slide and silicon wafer. Various methods were used in order to
characterize the thin films, such as Rutherford backscattering spectroscopy, X-ray
diffraction, X-ray reflectometry, atomic force microscopy, and optical spectroscopy.
Deposition rate was plotted against oxygen flow, which was increased from 0 to 4 sccm.
It can be seen that there is a sudden drop between 2.7 and 2.8 sccm. This indicates the
transition region between metallic and compound mode of the target. In metallic mode
(below 2.7 sccm O2) the films have a nearly constant deposition rate of 1.6 nm/s, while
the sputter rate of the films sputtered in compound mode drops to 0.2 nm/s. The
stoichiometry of the films was determined by Rutherford backscattering experiments. It
was found that films sputtered in the metallic mode were under-stoichiometric. The
41
sample sputtered in the transition region had an O/Zr ratio of 1.75, which is approaching
stoichiometric zirconia. Films sputtered in compound mode (above 2.8 sccm) were fully
oxidized with a stoichiometry of Zr1O2.1±0.3. The films were observed to have a well-
ordered crystalline phase of ZrO2 with monoclinic structure rather than an amorphous
structure.
Koski et al. [Koski et al., 1999] deposited zirconium oxide thin films by pulsed DC
reactive magnetron sputtering on glass slide, silicon wafer, and stainless steel
substrates using an ALCATEL PVD system. The substrates were cleaned in an ethanol
ultrasonic bath for 15 minutes, and the target was pre-sputtered in argon for 15 minutes
to remove any contaminants from the surface. A 6 inch diameter zirconium target was
used in argon pressures between 0.30 and 1.0 Pa (2.25 x 10-3 and 7.5 x 10-3 Torr).
Oxygen was the reactive gas introduced near the substrate holder. The target to
substrate distance was 70 mm (~2.76 inch). Target power controlled deposition process
was used while arcing was suppressed by using an Advanced Energy SPARC-LE V
Accessory with a pulsing frequency of 30 Hz.
Koski et al. [Koski et al., 1999] used the same instruments to measure the thin film
properties that were used in the measurement of aluminum oxide thin films. The partial
pressure of oxygen was between 0.07 and 0.10 Pa (5.25 x 10-4 and 7.5 x 10-4 Torr), and
the power density was 1000 W (5.48 W/cm2). As the sputtering gas pressure was
increased, the deposition rate increased from 35 to 135 nm/min/kW. Deposition rate
was also affected by substrate bias voltage. As the substrate bias voltage was
increased from a floating to -150 V, the deposition rate was increased from 50 to 95
nm/min. The deposition rate is also dependent on the target power, and as the target
42
power increased from 500 to 2000 W, the deposition rate increased from 50 to 455
nm/min. Below a power of 1500 W, the thin films were colorless and transparent;
however, at higher powers of 1750 and 2000 W, they films were partly brown and totally
black, respectively. They also found that the surface roughness was inversely
proportional to the nanohardness, and the roughness was lower for biased samples
versus floating bias samples. At lower pressures, the thin films were found to have high
hardness and low surface roughness. For example, at 0.50 Pa the nanohardness and
surface roughness was found to be 17.8 GPa and 2.9 nm, respectively. The
nanohardness of thin films of thicknesses 500 nm to 1µm increased up to 19 GPa. With
increasing substrate bias voltage and decreasing sputtering gas pressures, the elastic
modulus was found to increase from 210 to 231 GPa. The black thin films had an O/Zr
ratio of 1.6. The differences in the crystallization of thin films could be related to the
argon ion energy. The stoichiometric transparent films had a preferred monoclinic
structure whereas the under-stoichiometric black films had a preferred tetragonal phase.
Reactive sputter deposited zirconium oxide films with an amorphous structure can be
annealed for crystallization of the monoclinic phase.
In summary, the authors concluded that the deposition rate of the thin films increased
as a function of target power density as well as increasing sputter pressure and
substrate bias voltage. Zirconium oxide films with low nanohardness, rough surfaces,
and low elasticity were observed with increased sputter pressure. Hard, elastic,
stoichiometric and dense thin films with smooth surfaces were produced when the
substrate was biased during deposition.
Sethi et al. [Sethi et al., 2009] produced zirconium oxide films on silicon and glass
43
substrates by reactive sputtering using pulsed-DC and radio frequency (RF) power
sources. The chamber was evacuated to a base pressure of 1 x 10-4 Pa (7.5 x 10-7 Torr)
using a turbomolecular pump. A zirconium target 3” diameter was pre-sputtered for 5
minutes with 50 W in pure argon at 0.7 Pa (5.25 x 10-3 Torr). The total pressure was
kept constant at 0.7 Pa. Two power sources were used: pulsed direct current at 150
kHz and radio frequency at 13.56 MHz. The substrates were mounted on a copper base
plate, and substrate temperature was measured using a chromel-alumel thermocouple.
The target to substrate distance was fixed at 89 mm (3.5 inches). The target voltage
was measured using an oscilloscope. Film thickness was measured using a Tencor
Alpha-Step 500 surface profiler. XRD, SEM, and EDS were used to characterize the
properties and structure of the film.
The structure of the zirconia films were compared for the two power sources from XRD
results. Both sources produced films with the monoclinic ZrO2 phase; however, the RF
sputtered films had the presence of a minor phase of tetragonal ZrO2 as well as larger
crystallite size at the same power and pressure. Crystallite size increases with
increasing pressure except for films that are prepared at lower powers and higher
pressures. Deposition rate was also observed to increase with increasing power. Films
prepared at 0.2 and 0.3 are oxygen deficient, which was confirmed by EDS. The Zr:O
ratio was 1.3 instead of the desired 0.5 of Zr:O. However, a Zr:O ratio of 0.6 was found
for films prepared at 6.0 Pa. A liquid N2 substrate-cooling system was implemented in
order to determine the effect of substrate temperature on crystallization. The crystallite
size at room temperature was larger than that at low temperatures for high power. The
deposition rates for pulsed DC sputtering dropped from 117 to 37.8 Å/min at 400 W and
44
from 25.2 to 15.6 Å/s at 200 W at a constant pressure of 0.7 Pa. The growth mode,
which defines the crystallization and stoichiometry of the films, is controlled by
sputtering pressure, power, and oxygen content. The thickness of the films was found to
be critical; zirconia films under 50 nm were mainly amorphous.
45
4 CHAPTER 4: EXPERIMENTAL METHODS
4.1 The Sputter System
This chapter will describe the maintenance and modification of the current sputter
system. It will also focus on the experimental procedures done to obtain thin film
coatings. Finally, a discussion of a mini chamber design for separating inert and
reactive gas will conclude this chapter. Metallic thin films were produced by direct
current (DC) planar magnetron sputtering of metal targets while oxide thin films were
produced by introducing oxygen as a reactive gas.
4.1.1 Current Sputter System
The sputter system used in this work is a Denton Vacuum Explorer 14 planar
magnetron sputtering system shown in Figure 4.1.1.
Figure 4.1.1: Denton Vacuum Explorer 14 sputtering system.
46
The vacuum chamber is a cylinder of 30.5” ID x 18” high made from stainless steel. The
top plate of the chamber lifts open to allow access to the targets and substrates.
Attached to the center of the top plate is a rotating, water-cooled substrate fixture
designed to mount 4” to 6” wafers. The chamber can be mounted with up to six
cathodes, as shown in Figure 4.1.2, but the system used only has four cathodes, which
are in a cross configuration.
Figure 4.1.2: Top view of schematic representation of Denton Vacuum sputter

system [Denton Vacuum manual].
The sputter source configuration consists of a planar cathode (target) that is parallel to
an anode surface, which is usually grounded, that serves as a substrate holder. All four
sputter sources are manufactured by Angstrom Sciences and are 4” diameter, indirect-
cooled, internal “stalk-mount” planar magnetron sputter sources optimized for straight-
on deposition. However, three of the sputter sources have standard magnetics and one
has enhanced magnetics for magnetic targets. Two kinds of power supplies were used:
47
three Advanced Energy MDX 1.5 kW DC power supplies and one Seren 600W RF
power supply and matching network. Typical target sizes are 4” diameter and ¼” or ⅛”
thickness. The chamber is pumped down by a CTI Cryogenics CryoTorr 8 cryogenic
pump connected to an Edwards XDS 10 dry scroll pump for rough pumping. The
chamber base pressure reaches less than 1.0e-7 Torr, which is detected by an Inficon
BPG400 vacuum gauge. The sputter pressure is detected by an MKS 627B Baratron®
absolute capacitance monometer. An MKS Type 2179A mass-flo® controller (MFC)
regulates argon gas flow into the chamber. The system includes a programmable logic
controller with a color touch panel. The experimental parameters, such as gas flow rate,
power, and sputtering pressure can be controlled and viewed on this panel. (Figure
4.1.3).
Figure 4.1.3: Computer-controlled touch panel on sputter system.
48
4.1.2 Modified Sputter System
In order to do reactive sputtering, the current system had to be modified to introduce
reactive gases into the vacuum chamber. The current system had a 4-way manifold for
the addition of other gases. Argon was already connected to the system, but oxygen
and nitrogen need to be added. Argon and oxygen/nitrogen will be mixed inside the
chamber via single tubing during reactive sputtering. An MKS Type 247D four-channel
power supply/readout and two MKS Type 2179A mass-flo® controllers were purchased
to control the reactive gases. The Type 2179 MFCs have a positive shutoff valve
solenoid valve, which is opened with compressed air. Plastic tubing was used to route
compressed air to the MFCs and ¼” stainless steel tubing was used for gas flow into the
chamber (Figure 4.1.4).
Plastic tubing
for air
SS tubing
for gases
Figure 4.1.4: Additional gas lines on modified sputter system.
49
4.2 System Maintenance
The system maintenance is not known for these previous years since the previous
professor has left the university. During the modification and initial experimentation
phase, the author has come across many components that needed to be replaced or
repaired. The water filters for the cooling system had not been replaced for at least
three years. The once clear filter housing was completely black, and filter particulates
were getting into the water lines. The cryogenic compressor adsorber is recommended
to be replaced every 12 months but had not been replaced since the system was
purchased. The Inficon BPG400 was not properly detecting the vacuum pressure
because the filament of the hot cathode was broken and needed to be replaced.
Cathode shields and shutters needed to be sand/bead blasted to remove the layers of
deposition after a long time of sputtering. An additional viewport was added in order to
see the sputtering process on the RF gun. Also, a gas feed through was installed in
order to separate argon and reactive gas inside the chamber. These maintenance
issues did not all occur at the same time. They were discovered gradually over time as
the author was doing experiments with the machine. Due to wait time for parts and
repair, experimental results have been delayed longer than the author had wished.
Because the machine was not up to par for operation, any coatings produced during this
time could not yield accurate results.
4.3 Experimental Procedures
This section will describe the procedures carried out for metallic and reactive sputtering
of thin films. In both cases the substrates used were microscope glass slides and silicon
wafers. Pure aluminum and zirconium targets (99.999 % and 99.2% purity, respectively)
50
were used. Argon is used as the inert gas, and oxygen is used as the reactive gas. The
user must follow the check list and operating procedures posted on the sputter system
before beginning any experiment to ensure that the system will not be damaged during
sputter operation.
4.3.1 Metallic Sputtering
For metallic sputtering, the desired metal target is installed on a sputtering gun with the
desired power source (DC or RF). The substrates are cleaned with ethanol or acetone
in an ultrasonic bath for 10-15 minutes. They are dried off with compressed air from an
aerosol can. Then, the substrates are mounted on the substrate holder depending on
how many tests will be performed. The system is allowed to vacuum for a minimum of
two hours but is usually vacuumed overnight. Once the base pressure is below 1e-7
Torr, the vacuum pressure is low enough for sputtering to take place. Then argon flow
rate is set, and gas is introduced to the chamber, which will increase the chamber
pressure. The sputter pressure is determined by the flow rate of the gas and can be set
to a desired pressure using the high vacuum valve in pressure control mode (PCM).
Typical sputter pressures are around 5-10 mTorr, and in order to decrease the sputter
pressure, the high vacuum valve should be opened. After the pressure is fixed, the
power for the corresponding gun is turned on. Viewports allow the user to see the
plasma inside the chamber. In an argon atmosphere, the color of the glow is typically
purple. The target is usually pre-sputtered for at least 10 minutes to remove any oxide
layer that might have formed when opening the chamber. Pre-sputtering means that a
sputtering process with the shutter closed or on a facet that does not contain any
substrates so that the coatings are not contaminated.
51
This system allows for multiple guns to be used at the same time in order to do multi-
layer coatings. Usually, this can be programmed to run automatically. If the user is only
making single layer coatings, the system can be run in manual mode. The current and
voltage is monitored throughout the experiment to make sure it stays constant. The
deposition rate varies depending on the material system. By varying the time, the
thickness of the coating can be changed. When the desired thickness has been
achieved, the power and gas are turned off. The system is allowed to pump for about 30
minutes before opening the chamber so that the coating will be cooled down to mitigate
the formation of oxide layer from reacting with the air. The samples are then analyzed
using X-ray diffraction (XRD) and scanning electron microscopy (SEM) with energy-
dispersive X-ray spectroscopy (EDS).
4.3.2 Reactive Sputtering
Reactive sputtering procedures are similar to metallic sputtering with the addition of the
reactive gas into the chamber. However, it is difficult to perform reactive sputtering
when using DC power since it is easy to poison the target surface. Poisoning means
that an oxide layer forms on the surface and prevents target atoms from sputtering off.
Therefore, the maximum oxygen flow rate before poisoning occurs must be determined
and a hysteresis test must be performed. Before any oxygen is introduced into the
chamber, the target is pre-sputtered in a pure argon atmosphere for a minimum of 15
minutes to the clean the target surface of contaminants or any oxide layer. The sputter
pressure, current and voltage are recorded as a baseline to determine when poisoning
occurs. While the target is sputtering in pure argon, 1.0 cm2/min of oxygen is sent into
the chamber via the MFC. The target is allowed to sputter in the argon-oxygen mixture
52
for 5 minutes. Again, the sputter pressure, current and voltage are recorded. Oxygen
flow rate is slowly increased in increments of one until there is a sudden change in the
voltage. For example when using an aluminum target, there is a sudden decrease in
voltage when the target is poisoned. The point just before this decrease is the optimum
flow rate for reactive sputtering. Once the optimum flow rate has been determined, the
oxygen is turned off and the target is sputtered in pure argon for 10-15 minutes. Then,
oxygen is re-introduced into the chamber, mixed with argon, and reactive sputtering
takes place. The plasma can be seen through the viewports. For the case of aluminum
oxide, the plasma glow is purple when in a pure argon atmosphere but changes to a
white color when oxygen is mixed in. The plasma should be carefully watched for any
discontinuities (flashing or turning off and on), which can be a sign of arcing or
poisoning of the target. If this happens the system should be turned off so that the
sputtering guns do not get damaged. If the current and voltage stays approximately
constant throughout the duration of the test, then there is a possibility of a good coating.
In order to determine the components of the coating, the sample should be analyzed
using EDS or X-ray photoelectron spectroscopy (XPS) for elemental composition. XRD
was also used to determine the crystallographic structure.
Various tests were done with reactive sputtering in order to improve the stoichiometry of
the thin films. The target to substrate distance was varied using a rod and plate
apparatus to move the substrates closer to the target. Also, a separate gas line for
oxygen was installed in order to introduce oxygen closer to the substrate holder to
reduce oxidation on the target surface.
53
4.4 Mini-chamber Design
During reactive sputtering, the formation of stoichiometric films on the substrate occurs
during the transition of the target from metallic mode to compound mode. This means
that the deposition rate is determined by the sputter yield of the compound, which is
much lower than the sputter yield of most elemental metals. In order to remedy this
problem, researchers have investigated separate control of target and substrate
processes. Schiller et al. proposed using rapid motion of the substrate between the
deposition and oxidation regions in the sputtering system [Schiller et al., 1979]. For the
sputtering indium tin oxide from a metal target, Maniv et al. used a combination of a
geometric baffle between the target and the substrate and an auxiliary RF discharge
coupled to the substrate to support the reactive process [Maniv et al., 1983]. For the
deposition of non-absorbing oxides, such as Al2O3 and SiO2, at high deposition rates,
Scherer and Wirz used a similar set up to Maniv et al. with the exception of the RF
discharge. Instead, they used an additional DC discharged produced between the baffle
and the substrate by electrodes working at positive voltages of about 40 V [Scherer and
Wirz, 1984]. The schematic representation of their reactive DC sputtering arrangement
is shown in Figure 4.4.1.
The experimental details explaining the schematic is provided in Scherer and Wirz’s
[Scherer and Wirz, 1984] paper. The shield (12) is about 20 mm from the target surface
(2) and also has variable apertures. Argon (5) is introduced near the cathode surface
while oxygen (7) is introduced between the shield and the substrate (13). Using this
configuration the authors observed very stable process conditions for the deposition of
Al2O3 and SiO2. They found the static deposition rate of Al2O3 to be 36 Å/sec at a
54
dissipated power of 12 W/cm2. The theoretical deposition rates of Al2O3, SiO2, and
Ta2O5 compared well with the measured values.
1. Magnetron cathode PK 75
2. 75 mm diameter target
3. DC power supply
4. Vacuum chamber
5. Argon gas inlet
6. Argon gas supply
7. Oxygen gas inlet
8. Oxygen gas supply
9. Stainless steel mini-chamber
10. Simple electrode system
11. DC power supply
12. Shield with variable aperture
13. Substrate
Figure 4.4.1: Schematic of mini chamber setup by Scherer and Wirz.

The configuration for this research was based loosely on the design by Scherer and
Wirz [Scherer and Wirz, 1984]. It contains a stainless steel mini-chamber around the
sputtering gun with an interchangeable shield of varying aperture sizes. The stainless
steel shield will be about one inch from the target surface. There will also be a fixed port
on the mini-chamber wall for argon gas to be introduced near the target surface.
Stainless steel, quarter-inch tubing will be bent into a circular shape of about 4” in
55
diameter for the reactive gas inlet system. It will also contain 0.5 mm holes spaced
every 20 mm on the inside of the circular tubing. The gas inlet will be placed about 2 cm
from the substrate holder.
Before manufacturing the test chamber, a temporary test chamber was mocked up
using the cathode shield already on the gun and heavy duty aluminum foil for the shield
(Figure 4.4.2). The cathode shield was extended 1” past the target surface. Plastic
tubing was used to route the argon gas inlet to the cathode shield. A 37 mm diameter
hole was cut out of a sheet of aluminum foil and then placed over the cathode shield to
imitate the shield with an aperture. A separate gas line for oxygen was installed and
mounted on the chamber lid so that the reactive gas would be introduced near the
substrate holder (Figure 4.4.3). Metallic and reactive sputtering tests were done to see if
any plasma formed and deposition would still occur using the mini-chamber design.
56
Figure 4.4.2: Mock-up of a mini chamber design using aluminum foil and shield.
Figure 4.4.3: Separate oxygen nozzle placed closer to substrate holder.
57
5 CHAPTER 5: EXPERIMENTAL RESULTS
5.1 Metallic Sputtering
Aluminum and zirconium films were sputtered on glass slide and silicon wafer from 4”
metallic targets in DC magnetron sputtering. The films were analyzed using a Rigaku
MiniFlex benchtop XRD machine. The following data was collected over the range of
20º to 110º to determine the crystal structure of the as-sputtered aluminum film (Figure
5.1.1).
Aluminum
300
(1 1 1)
250
Intensity (counts)
200
150
(2 0 0) (2 2 0) (3 1 1)
100
(2 2 2)
50
0
15 25 35 45 55 65 75 85 95 105
2 Theta (deg)
Figure 5.1.1: XRD result for aluminum film on glass slide.
58
The aluminum film is shown to have peaks that correspond to a face-centered cubic
(FCC) crystal structure belonging to the space group Fm-3m. The three peaks with the
highest intensity are found at 38.5º (1 1 1), 44.7º (2 0 0), and 78.2º (3 1 1). The lattice
parameters can be calculated using the Miller Indices; however, XRD software called
MDI Jade Easy Quant XRD was used to find the Miller Indices and lattice parameters.
Since aluminum is a cubic structure, the lattice parameters a = b = c = 4.050 Å. The
XRD result for an as-sputtered zirconium film on glass slide over the range of 30º to 90º
is shown in Figure 5.1.2. The three peaks with the highest intensity are found at 35.5º (1
1 0), 63.8º (3 0 0), and 50.9º (2 0 1), where the angle is 2θ and the Miller Indices are in
parentheses. These peaks correspond to a hexagonal closed-packed (HCP) crystal
structure with a space group of P6/mmm. The corresponding lattice parameters are a =
5.039 Å, b = 5.039 Å, and c = 3.136 Å.
Zirconium
1300
(1 1 0)
1200
1100
Intensity (counts)
1000 (3 0 0)
900
800
700 (2 0 1)
(1 1 1) (1 1 2)
600 (0 0 2) (2 2 0) (3 1 1)
500
400
300
25 35 45 55 65 75 85 95
2 Theta (deg)
Figure 5.1.2: XRD result for zirconium on glass slide.
59
An FEI Quanta 3D FEG SEM system was used to characterize the film surface structure
and to measure the film thickness. Figure 5.1.3 is an SEM micrograph of the surface
structure of an as-sputtered aluminum film on silicon wafer. The surface shows large,
faceted grains in a porous structure. This image was taken at 25,000X magnification.
Figure 5.1.3: SEM micrograph of as-sputtered aluminum film on silicon wafer.

The as-sputtered zirconium film on silicon wafer can be seen in Figure 5.1.4. This film
shows a denser surface with smaller, faceted grains as compared to the aluminum film.
This film was also taken at 25,000X magnification. The cross section of both aluminum
and zirconium films were captured in the SEM. The deposition rate was calculated
based on the average thickness of the film divided by the deposition time. Figure 5.1.5
and Figure 5.1.6 show the cross section of aluminum and zirconium films, respectively.
Table 5.1.1 gives the average deposition rate for each film with a target to substrate
distance of about 10 cm.
60
Figure 5.1.4: SEM micrograph of as-sputtered zirconium film on silicon wafer.
Figure 5.1.5: SEM micrograph of cross section of aluminum film on silicon wafer.
61
Figure 5.1.6: SEM micrograph of cross section of zirconium film on silicon wafer.
Table 5.1.1: Average deposition rate for metallic thin films.
Average
Sputter Film Deposition
Power Deposition Deposition
Material Pressure Thickness Rate
(W) Time (min) Rate
(mTorr) (µm) (nm/min)
(nm/min)
Al 200 5.0 1.015 30 33.8
33.53
Al 200 11 3.99 120 33.25
Zr 150 4.8 3.83 120 31.92
31.74
Zr 150 4.8 3.786 120 31.56
There are many factors that can influence the deposition rate such as power density in
the erosion area, size of erosion area, cathode surface condition, cathode temperature,
target to substrate distance, target material, applied voltage and current density, gas
density, and sputter pressure. Some of these parameters are interrelated, such as
pressure, power density, and size of the erosion area. Holland [Holland, 1956] writes
that voltage and current density controls the deposition rate, which in turn is depended
62
on the gas density. He states, “Since the temperature of the residual gas may increase
appreciably as the sputtering proceeds, the gas pressure must be adjusted to maintain
a constant gas density and hence constant voltage and current density [Holland, 1956].”
In a water-cooled cathode, Penning and Moubis [Holland, 1956] found that the
sputtered material on the substrate increased, meaning the deposition rate increased,
when the current density was increased to increase the discharge temperature. As
stated by Waits [Waits, 1978] in the chapter on Planar Magnetron Sputtering, the
deposition rate is directly proportional to the target power. He also writes that “if all the
factors affecting deposition rate can be held constant, then the rate will be constant and
reproducible.”
From Table 5.1.1 this statement is proven true for zirconium. All the parameters were
kept the same and the film thickness and deposition rate remained nearly constant
around 32 nm/min. For the aluminum case, the sputter pressure and deposition time
were changed to see if there would be a change in deposition rate. However, it can be
seen that the deposition rate is also nearly constant around 34 nm/min.
For reactive sputtering, a quick hysteresis test should always be performed prior to
sputtering in order to determine the critical reactive gas flow rate. The critical reactive
gas flow rate indicates the transition region between the metallic and compound states
of the target. Many investigators have observed the hysteresis phenomena in reactive
sputtering. Koski et al. [Koski et al., 1999] indicates that in a typical hysteresis curve
(Figure 5.2.1) for power controlled deposition, the target voltage and total pressure were
63
depended on the oxygen gas flow rate. When the oxygen flow rate reached the value of
f1, the target voltage dropped dramatically and the total pressure increased.
Figure 5.2.1: Typical hysteresis curve for reactive magnetron sputtering [ Koski et
al., 1999].
As seen in Figure 5.2.2 and Figure 5.2.3, the hysteresis curves for power controlled
deposition agree with the findings of Koski et al [Koski et al., 1999]. The parameters for
this experiment are 300 W DC, starting sputter pressure of 5 mTorr in argon, and
oxygen flow rate from 0 to 10 sccm. The critical point occurs at 3 sccm where the
voltage drops drastically and the pressure starts to increase. Upon decreasing the
oxygen flow rate, the voltage and pressure take a slightly different path but goes back to
the initial voltage and pressure values.
64
Aluminum Oxide V vs O2
380
Increasing O2
360
Decreasing O2
340
Voltage (V)
320
300
280
260
0 1 2 3 4 5 6 7 8 9 10 11
O2 flow rate (sccm)

presented as reactive gas flow rate versus target voltage.
Aluminum Oxide P vs O2
12
Increasing O2
11
Decreasing O2
10
Pressure (mTorr)
9
8
7
6
5
4
0 1 2 3 4 5 6 7 8 9 10
O2 flow rate (sccm)

presented as reactive gas flow rate versus sputter pressure.
65
Venkataraj et al. [Venkataraj et al., 2002] demonstrated the behavior of mass deposition
rate, voltage, and partial pressure of reactive gas with respect to reactive gas flow for
zirconium oxide thin films. Figure 5.2.4 presents the hysteresis behavior of these
parameters that are dependent on reactive gas flow. In all three graphs the critical point
is between 2.7 and 2.8 sccm O2 flow. The voltage (b) and partial pressure of oxygen (c)
suddenly increase at this point transitioning into the oxide mode.
Figure 5.2.4: Hysteresis curves for (a) mass deposition rate of zirconium oxide,
(b) target voltage, and (c) partial pressure of oxygen as a function of oxygen flow
rate [Venkataraj et al., 2002].
The parameters for the zirconium hysteresis test are 150 W DC, starting pressure of 5
mTorr in argon, and oxygen flow rate from 0 to 8 sccm. Figure 5.2.5 displays the oxygen
flow rate versus target voltage. From this plot, it can be seen that the voltage suddenly
66
increases at the critical flow of 2.0 sccm. A similar trend for the sputter pressure can be
seen in Figure 5.2.6 where the pressure increases rapidly at 2.0 sccm entering into the
compound mode.
Zirconium Oxide V vs O2
340
330
Increasing Oxygen
Target Voltage (V)
320
Decreasing Oxygen
310
300
290
280
270
260
0 0.5 1 1.5 2 2.5 3
O2 flow rate (sccm)

presented as reactive gas flow rate versus target voltage.
X-ray diffraction was used to determine the crystallography of the films. Figure 5.2.7
shows the XRD result for the aluminum oxide sample as well as the standard peaks for
γ-Al2O3. Since no distinguishing peaks can be seen, the film has an amorphous
structure. The XRD result for the zirconium oxide sample with peaks for monoclinic-ZrO2
can be seen in Figure 5.2.8. This result also shows no identifying peaks, which
correlates to an amorphous structure of the zirconia film. It can be concluded that thin
films deposited by reactive sputtering have an amorphous structure. Some investigators
have post-heat treated or annealed their samples in order to obtain a crystalline
structure. C.M. Chiang and L.S. Chang found that the alumina thin films have a more
67
crystalline structure with increases in RF power density due to the bombardment of
secondary electrons and ions. The growth of crystallites is enhanced by the increase in
surface diffusivity of atoms when the film is heated up [Chiang and Chang, 2005].
Zirconium Oxide P vs O2
8
Increasing Oxygen
7.5
Decreasing Oxygen
7
Pressure (mTorr)
6.5
5.5
4.5
4
0 2 4 6 8
O2 flow rate (sccm)

presented as reactive gas flow rate versus sputter pressure.
SEM was used to capture the surface structure of the alumina and zirconia thin films.
Images of the cross section were also taken in order to measure the thickness and
determine the deposition rate for DC reactive magnetron sputtering of metallic targets.
The surface images of alumina thin film samples on silicon wafer with different oxygen
flow rates of 1.8 sccm O2 (Figure 5.2.9), 2.0 sccm O2 (Figure 5.2.10), and 2.1 sccm O2
(Figure 5.2.11) during reactive sputtering are depicted below. The images are all taken
at 50,000X magnification, and all films sputtered with 200 W DC power at 5 mTorr
sputter pressure. From XRD results, the alumina films were found to have an
68
amorphous structure, which is commonly seen in thin films. This can also be confirmed
by the dense, continuous surface structure of the films compared with the faceted,
grains of the aluminum film.
[051911Al2O3200W2hr.raw]
600
49-0134> Al2O3 - Aluminum Oxide
500
400
Intensity(Counts)
300
200
100
0
20 30 40 50 60 70 80 90 100 110
2-Theta(°
Figure 5.2.7: XRD result of aluminum oxide on glass slide.
[0429ZrO2M150W1hr.raw]
65-1025> ZrO2 - Zirconium Oxide
600
500
Intensity(Counts)
400
300
200
100
0
20 30 40 50 60 70 80
2-Theta(°
Figure 5.2.8: XRD result of zirconium oxide on glass slide.
69
Figure 5.2.9: SEM surface image of alumina thin film with 1.8 sccm O2.
70
There is a difference seen from the films increasing oxygen content form 1.8 sccm to
2.0 sccm. A more porous structure with cracks can be seen in the surface structure of
the film with 2.0 sccm O2. As noted by findings from Chiang and Chang [Chiang and
Chang, 2005], “the effects of target poisoning and plasma reduction with increasing
oxygen flow rate over 3 sccm become dominating. The outcome of both is the porous
structure of aluminum oxide thin films.” This means that once the target transitions from
metallic to compound state, target poisoning effects the deposition rate and also the
crystallinity of the target material. For 2.1 sccm O2 in Figure 5.2.11, the film is very
dense with very small grains, similar to the surface structure of the film with 1.8 sccm
O2. There is an explanation for the difference in the surface structure of the film with 2.0
sccm O2. If the target surface was poisoned, this could explain the difference in surface
structure and why the film with 2.0 sccm O2 is more porous. The oxygen flow rate of 2.1
sccm was chosen because it was around the critical point during the hysteresis test.
71
The objective is to sputter at the maximum flow rate first in order to get the most oxygen
reaction to produce stoichiometric films.
Below in Figures 5.2.12 - 5.2.14 the surface structure of zirconia thin films on silicon
wafer were captured by SEM for varying oxygen flow rates of 1.8 sccm O2 (Figure
5.2.12), 2.0 sccm O2 (Figure 5.2.13), and 2.2 sccm O2 (Figure 5.2.14). All images were
captured at 50,000X magnification, and all films were sputtered at 150 W DC power at
4.8 mTorr sputter pressure.
Figure 5.2.12: SEM micrograph of zirconia thin film surface with 1.8 sccm O2.
Figure 5.2.12 exhibits varying grain sizes, which indicates that smaller grains
agglomerate to form bigger clusters. These clusters then form a continuous film over the
substrate surface. In the film with 2.0 sccm O2, the surface structure appears porous
with individual small grains forming a continuous film. Then when oxygen flow is
increased to 2.2 O2, the film is denser but with the same approximate grain size. Again,
the porosity of the film may or may not be attributed to the poisoning effect of the target.
72
73
However, the author cannot definitely say that this is the reason for the difference in
surface structure due to lack of knowledge and reference from other investigators. The
author believes that these films may have been deposited in the different modes of the
target. The lowest oxygen content is closer to the metallic mode while the highest
content is just before the compound mode. The middle oxygen content is most likely to
be in the transition region between the two modes, which may account for the porosity
of the films. However, Sethi et al. [Sethi et al., 2009] investigated the crystallization of
zirconia films with RF sputtering. They found a porous structure consisting of tapered
crystallites separated by voids at high sputtering pressures and low power (Figure
5.2.15). Gao et al. [Gao et al., 2000] also sputtered zirconia thin films using RF power
with varying O2 concentrations. The SEM image shows a porous structure with small
grains (Figure 5.2.16). The grain size and surface structure from findings of Sethi et al.
and Gao et al. look similar to the findings of this author.
Figure 5.2.15: SEM micrograph of the surface structure for zirconia film sputtered
at 150 W with RF power [Sethi et al., 2009].
74
Figure 5.2.16: SEM micrograph of zirconia surface and cross section at 5% O2
[Gao et al., 2000].
The samples above were analyzed using EDS in order to determine the composition of
the films. Table 5.2.1 gives a summary of the ratios found for each sample. For the
alumina films, the ratio of oxygen to aluminum increases with increasing oxygen
content. The zirconia films also show increasing oxygen to zirconium ratio with
increasing oxygen content; however, there is a slight error between 2.0 and 2.2 sccm
O2. This is a very small difference and could be attributed to human error as well and
inaccuracy of EDS to measure oxygen content. The main point here is that the ratio is
increasing with increasing oxygen content. Although none of these films are
stoichiometric alumina or zirconia, they are a form of alumina and zirconia films that are
under stoichiometric. The difficulty in obtaining stoichiometric films is determining the
correct ratio of inert to reactive gas as well as other interrelated parameters, such as the
target power, sputter pressure, substrate to target distance, and target voltage and
current density. This analysis just provides the conclusion that reactive sputtering can
75
be achieved even though the process is unstable using DC power. Other system
configurations and parameters must be modified and properly controlled in order to
obtain stoichiometric films with good film structure and properties.
Table 5.2.1: EDS results of alumina and zirconia thin films at varying O2 flow.
EDS Analysis for Film Composition
O:Al ratio (Al2O3 = 1.5) O:Zr ratio (ZrO2 = 2)
1.8 sccm O2 0.627 1.8 sccm O2 0.996
2.0 sccm O2 0.772 2.0 sccm O2 1.18
2.1 sccm O2 0.931 2.2 sccm O2 1.14
Figure 5.2.17 and Figure 5.2.18 show the SEM micrographs of the cross section of
alumina and zirconia films, which were used to measure the thickness and determine
deposition rates.
Figure 5.2.17: SEM micrograph of alumina thin film cross section for 1.8 sccm O2.
76
From the SEM images of the film cross section, thicknesses were measured and then
divided by the deposition time in order to determine the deposition rates of alumina and
zirconia from metallic targets at different oxygen flow rates.
Figure 5.2.18: SEM micrograph of zirconia thin film cross section with 2.0 O2.
The average deposition rate of alumina is around 43 nm/min. It would be closer to 42
nm/min if the deposition rate of the film with 2.0 sccm O2 were not 44 nm/min. This
increase could be due to human error in measuring the film thickness. Overall, the
deposition rate seems to stay nearly constant for alumina films with increasing oxygen
flow. The average deposition rate of zirconia film was calculated to be 22 nm/min;
however, there is a large error in this calculation. This is probably due to the cross
section image captured for the film with 2.2 sccm O2. The cross section must have been
tilted at an angle so that the true thickness was not measured and the deposition rate
was much lower. The deposition rate for the film with 2.0 sccm O2 seems more accurate
and corresponds to the deposition rate of metallic zirconium.
77
X-ray photoelectron spectroscopy was used to analyze the chemical composition of
alumina and zirconia films of varying O2 content. Using analysis software XPSpeak 4.1,
the spectrum peaks can be separated based on the binding energy to determine the
chemical composition.
Table 5.2.2: Deposition rates for alumina and zirconia thin films at different O2
flow.
Sputter O2 Film Deposition
Power Deposition
Material Pressure Flow Thickness Rate
(W) Time (min)
(mTorr) (sccm) (µm) (nm/min)
Al2O3 200 5.0 1.8 2.5454 60 42.42
Al2O3 200 5.0 2.0 3.9732 90 44.15
Al2O3 200 5.0 2.1 5.085 120 42.38
ZrO2 150 4.8 2.0 1.8979 60 31.63
ZrO2 150 4.8 2.2 1.106 90 12.29
Aluminum (2.0 O2)

40000
35000 Raw Intensity

Background
30000
Al-Al, 2p
Intensity (cps)
25000
Al-O, 2p
20000
15000
10000
5000
0
68 70 72 74 76 78 80 82
Binding Energy (eV)
Figure 5.2.19: XPS aluminum spectrum for alumina sample without ion etching.
78
Figure 5.2.19 is a graph of the aluminum spectrum detected from an alumina sample
with 2.0 sccm O2 content. The blue solid line is the original raw spectrum from the XPS
machine, and the red dotted line is the baseline. After separating the spectrum, there
are two peaks. The green dashed line corresponds to Al-Al, 2p, which has a binding
energy of 72.65 eV based on the Handbook of X-ray Photoelectron Spectroscopy
[Wagner, 1979]. The purple dot-dashed line has a peak that corresponds to the binding
energy of 74.7 eV for Al-O, 2p. This means the aluminum detected in this peak comes
from alumina and not metallic aluminum.
Zirconium (2.2 O2)

300000
Raw Intensity
250000
Background
Zr-Zr, 3d5/2
Intensity (counts)
200000
Zr-Zr, 3d3/2
150000
100000
50000
0
176 178 180 182 184 186 188
Binding Energy (eV)
Figure 5.2.20: XPS zirconium spectrum for zirconia sample without ion etching.
The XPS spectrum for zirconium in a zirconia sample is shown in Figure 5.2.20. The
blue solid line is the original spectrum, and the red dotted line is the baseline. According
79
to the XPS handbook, there are two peaks for zirconium orbitals 3d5/2 and 3d3/2 with
binding energies of 178.7 and 181.1eV, respectively. The peaks in the plot are slightly
shifted. This was noticed during the XPS analysis and was caused by an option in the
system analysis not being checked at the start of the analysis. The spectrum for
aluminum and zirconium were analyzed for the highest oxygen content only; however,
six samples were analyzed at the same time for their chemical composition without ion
etching the surface. Table 5.2.3 summarizes the oxygen to aluminum/zirconium content.
For both the alumina and zirconia, the samples with the lowest oxygen content seem to
be over stoichiometric. This may be due to oxidation of the sample surface or error in
the system analysis. However, for the next two samples in each set, the oxygen to
aluminum/zirconium increases with increasing oxygen content. For zirconia film with 2.2
sccm O2, the film has a ratio corresponding to stoichiometric zirconia. Although this is
only a quantitative analysis in XPS, other methods should be used to verify the
composition, such as the Rutherford backscattering spectrometer. EDS analysis also
indicates an increase in ratio with increasing oxygen content (Table 5.2.4). For the
alumina sample with 2.0 sccm O2, silicon was also detected in the quantitative
measurements and was not left out. Therefore, the ratio in the table is higher than what
the actual would be without silicon.
Table 5.2.3: XPS results for alumina and zirconia samples at varying O2 flow
without ion etching.
XPS Analysis for Film Composition without Ion Etching
1.6 sccm O2 1.81 1.8 sccm O2 2.14
1.8 sccm O2 1.26 2.0 sccm O2 1.86
2.0 sccm O2 1.35 2.2 sccm O2 2.06
80
Table 5.2.4: EDS results for the same alumina and zirconia samples as in Table
5.2.3.
EDS Analysis for Film Composition
1.8 sccm O2 0.691 2.0 sccm O2 1.03
2.0 sccm O2 1.09* 2.2 sccm O2 1.07
Aluminum (1.6 O2) after Etching

80000
70000 Raw Intensity

Background
60000
Al-Al, 2p
Intensity (cps)
50000 Al-O, 2p
40000
30000
20000
10000
0
68 70 72 74 76 78 80 82
Binding Energy (eV)
Figure 5.2.21: XPS spectrum for alumina sample after ion etching.
One alumina and one zirconia sample was selected to do another XPS analysis with ion
etching of the surface since XPS can only analyze the first 10 nm of the top surface of
the sample. Because it was thought that the surface of the samples may have had
some oxidation, which increased the oxygen content, the surfaces were etched in order
to get a reading from the bulk material underneath the surface layer. Only one sample
of each was chosen due to money and time constraints. The author thought to analyze
81
the sample with the highest oxygen content; however, after the analysis was done, it
was realized that the alumina sample was for the lowest oxygen content.
Figure 5.2.21 shows the XPS spectrum for aluminum in the alumina sample after ion
etching of the surface. Once again the spectrum was separated into two peaks. The
green dashed line corresponds to the aluminum content from metallic aluminum,
whereas the purple dot-dashed line is the aluminum content from aluminum oxide.
Comparing the relative intensities of the Al2O3 sample before and after etching, it can be
concluded that the ratio of Al-Al, 2p to Al-O, 2p increases, and that the film is comprised
of both metallic and ceramic material.
Zirconium (2.2 O2) after Etching

350000
Raw Intensity
300000 Background
Zr-O, 3d5/2
250000
Intensity (counts)
Zr-O, 3d3/2
200000 Zr-Zr, 3d5/2
Zr-Zr, 3d3/2
150000
100000
50000
0
175 180 185 190 195
Binding Energy (eV)
Figure 5.2.22: XPS spectrum of zirconia sample after ion etching.
82
The separated spectrum for zirconium in a zirconia sample after ion etching is seen in
Figure 5.2.22. This time there are four peaks, two corresponding to metallic zirconium
and two corresponding to zirconium oxide, since zirconium has two orbitals shown in
the spectrum. The yellow and orange lines correspond to Zr-Zr, 3d5/2 and Zr-Zr, 3d3/2,
respectively. Zr-Zr, 3d5/2 and Zr-Zr, 3d3/2 have binding energies of 179.2 and 181.6 eV,
respectively. Zr-O, 3d5/2 and Zr-O, 3d3/2 are represented by the green and purple lines,
respectively. The binding energy of ZrO2-3d5/2 is 183.1 eV and ZrO2-3d3/2 is 185.5 eV.
Based on the relative intensities, there is more zirconium content coming from zirconium
oxide than pure zirconium.
Table 5.2.5: XPS results for one sample of alumina and zirconia with ion etching.
XPS Analysis for Film Composition with Ion Etching (25 mins)
1.6 sccm O2 2.2 sccm O2
With Etching 1.079 With Etching 1.34
Without Etching 1.81 Without Etching 2.06
For both the alumina and zirconia sample, the oxygen to aluminum/zirconium ratio
decreased meaning that the oxygen content decreased. This analysis is probably a
more accurate measurement of the composition of the samples. In order to have a more
conclusive result, analysis should have been done for all the samples to see if the trend
does follow the previous conclusion of increasing ratio with increasing oxygen content.
Access to a Rutherford backscattering spectrometer would have allowed the author to
gather more results for comparative purposes and to obtain a valid conclusion on the
composition of the constituent materials in the as-sputtered films.
83
5.3 Sputtering with Mini-Chamber
During experimentation the author had problems deposition stoichiometric films using
regular DC reactive magnetron sputtering. Many investigators have stated that this is an
unstable process and other methods must be employed to control the process. The
author came across a design by Scherer and Wirz [Scherer and Wirz, 1984], who
incorporated a mini chamber around the sputtering gun inside the sputter chamber. The
idea was to separate the reaction of oxygen from occurring on the target surface leading
to target poisoning. This author produced a mock up design to test whether plasma
would still be produced using Scherer and Wirz’s idea.
Metallic sputtering was performed to deposit aluminum and zirconium films using the
mini chamber mock up (Figure 4.4.2). Then reactive sputtering was performed to
deposit alumina and zirconia films. XRD was performed on the metallic films. In the
aluminum film, no distinguishing peaks were observed indicating an amorphous
structure. This could mean that the deposition rate was greatly reduced with the mini
chamber and thus, the film was too thin to form crystal structures. The author did not
have access to any instruments that could measure these thin films, such as a
thickness profilometer, ellipsometer, or a quartz crystal microbalance. For the zirconium
sample, there was one peak corresponding to (1 1 2) plane at 2θ = 70.8º. XRD was not
done on the ceramic samples because it was assumed to also have an amorphous
structure. However, SEM was used to view the surface structure of the ceramic films.
The alumina film shows a continuous surface with a porous structure, and the zirconia
film has a smooth surface with small amounts of grain formations.
84
5.4 Sputtering with Ceramic Target
The author attempted to sputter alumina films from a ceramic target using RF power in
order to compare the films to those deposited by reactive sputtering of a metallic target.
One sample was deposited using 300 W RF at 3 mTorr sputter pressure for three hours.
The second sample was deposited using 300 W RF at 3 mTorr sputter pressure with the
addition of 0.5 sccm O2 for two hours. SEM was used to study the surface structure of
the two alumina samples at 50,000X magnification. The surface of the alumina film from
the ceramic target showed a smooth surface with no distinguishing defects. However,
the alumina film, which had the addition of oxygen flow, showed a continuous surface
structure with small grain formations. Although the deposition rate was not measured, it
is known from literature that the deposition rate for RF reactive sputtering is much lower
than DC reactive sputtering. The film with the additional oxygen has the same size
grains as the films from DC reactive sputtering of alumina but not as dense. If sputtered
for longer time, the film deposited would have become denser and look similar to the
reactive sputtered alumina films. More samples should have been deposited in order to
have comparative results and make a better conclusion as to whether the alumina films
had the same structure. Also, XPS or EDS should have been used to determine the
composition of the film sputtered from a ceramic target. Although, the target should be
stoichiometric alumina, some investigators have said the films may come out under
stoichiometric without the addition of oxygen. Since the author did not spend much time
researching the sputtering of ceramic targets, the experiments did not yield good
alumina thin films.
85
6 CHAPTER 6: DISCUSSION AND FUTURE WORK
6.1 Discussion
New materials are being investigated in order to enhance and improve current thermal
barrier coatings, which in turn will help increase the efficiency of gas turbines and jet
engines. Presently, an old technology, reactive sputtering, was utilized in order to
research new designs for TBCs. In this work the author’s goals were to modify an
existing sputter system for reactive sputtering capabilities and to produce multilayered
ceramic thin films. The most challenging part of this research was to understand the
theory, to modify system, and to control the process. Regular maintenance of the
various components on the system was an obstacle that delayed, but did not hinder,
experimental work. Gas lines were added for nitrogen and oxygen reactive gases to be
used for reactive sputtering. Mass flow-controllers and a 4-channel power supply were
installed to control the flow of reactive gas into the sputter chamber.
Metallic sputtering was performed using both DC and RF power in order for the author
to understand the system and how the process works. Aluminum and zirconium thin
films were deposited on glass slide and silicon wafer at room temperature. XRD
analysis was utilized to determine the crystallography of the films. Aluminum was found
to have peaks consistent with FCC crystal structure with lattice parameter a = 4.05 Å.
Zirconium had peaks corresponding to HCP crystal structure with lattice parameters a =
b = 5.0309 Å and c = 3.136 Å. SEM micrographs displayed the surface structure of the
thin films. Aluminum had large, faceted grains with a porous surface structure.
Zirconium had small, faceted grains with a continuous, dense surface. The cross
section was measured for the film thickness in order to calculate the deposition rate.
86
Aluminum had a deposition rate of 34 nm/min, whereas zirconium’s deposition rate was
32 nm/min.
Reactive sputtering from metallic targets was then employed to deposit aluminum oxide
and zirconium oxide thin films on glass slide and silicon wafer at room temperature
using DC power. XRD results concluded that the ceramic films were amorphous. SEM
surface images depicted films with continuous surface and small grains. One sample
from alumina and zirconia showed a porous structure, which could be attributed to
target poisoning. The average deposition rate of alumina was found to be 43 nm/min,
and the average deposition rate of zirconia was found to be 22 nm/min. However, the
author believes there was an error in the cross section image taken in SEM, and that
the deposition rate is closer to 32 nm/min, which is similar to metallic zirconium.
Although the deposition rate for the alumina ceramic films was calculated to be greater
than the metallic films, it is more accurate to conclude that the high rate was due to
deposition in metallic mode of the target. XPS analysis of the elemental composition
found that the films were under stoichiometric.
Over the course of this research, the author has learned much about sputtering and
reactive sputtering processes. Many investigators have utilized DC reactive sputtering
because of its advantages; such has high rate deposition, metal target utilization, and
multiple dielectric combination fabrication. Through discussions with other researchers
in industry, the author learned that fabrication of stoichiometric films in this sputter
system would not be viable. Sproul et al. has stated that, for most cases, it is not
possible to operate in the transition region of the target with flow control of the reactive
gas. They also state that it is not possible to optimize rate, reproducibility, and film
87
properties with flow control of the reactive gas. The Denton Vacuum Explorer system is
likely capable of reactive sputtering, but not able to achieve stoichiometric films without
modification to the system. There are many parameters that are interdependent, which
makes it harder to determine the exact parameters that would produce the best films.
The author recommends the incorporation of a pulsed-DC power supply in order to
suppress arcing and prevent target poisoning if DC power is desired. Partial pressure
control can also prevent target poisoning by precisely controlling the reactive gas flow
since it has an active feedback control. Flow control of the reactive gas is very unstable,
and some investigators have said that it is impossible to achieve stoichiometric films.
The author also recommends acquiring the proper instruments to characterize the
structure, thickness, and properties of the sputtered thin films. Also, it was not an
objective of the author to obtain films with quality properties, but it would be required
when fabricating multi-layer coatings for new TBCs. A mass spectrometer was used by
other investigators for leak detection, residual gas analysis, and deposition control.
Substrate bias and substrate heating improved the properties of the sputtered films.
6.2 Future Work
Since the overall objective of this research group is to design and fabricate multi-layer
coatings for TBCs in gas turbines and jet engines, more experimental work needs to be
done in order to produce stoichiometric ceramic coatings. A majority of the experiments
performed by this author held most sputter parameters constant and varied only the
oxygen flow rate. However, if more experiments were to be done, the power, sputter
pressure, and target to substrate distance should be varied and compared to find the
88
right combination of sputter parameters for stoichiometric films. Also, more discussions
with other researchers, who have already accomplished this feat, should be done to
gain more knowledge about the dependency of the sputter parameters and to restrict
the number of experiments that need to be performed to find optimum films.
More time should be spent experimenting with sputtering from ceramic target in order to
determine the quality of the thin films and to have a comparison for reactive sputtering
of thin films from a metal target.
Although it was encouraged by the author’s major professor to manufacture a mini
chamber to incorporate in the sputter chamber, this was not completed due to the
limited time the author had to finish the current experiments. However, from the mock
up the author can conclude that films can be sputtered using this design if properly
installed. The author has created some drawings to represent a preliminary design for
the mini chamber. This is not a completed design and should be engineered to work
with the Denton Vacuum system. The dimensions in the picture are not true or concrete
dimensions. They are there only for scaling purposes.
The mini chamber is a concentric cylinder that will go over the sputter gun (inside
cylinder) and will be held in place with four set screws (Figure 6.2.2). A shoulder will be
milled into the wall of the mini chamber in order to hold the shield in place with hex
screws. This design is for ease of changing the aperture size in the shield. The shield
has a two-part role: one is to close the chamber off and the second is to prevent the
reactive gas from reaching the target surface. The red circle in the left image indicates a
port hole for argon gas to be introduced inside the chamber.
89
Figure 6.2.1: Various views of the mini chamber over the sputter gun.
Figure 6.2.2: (Left) View of mini chamber over sputter gun, (Right) view of mini
chamber with shield
90
The reactive gas will be introduced over the substrate holder and placed about 2 cm
from the substrate surface. Figure 6.2.3 is a representation of ¼” stainless steel tubing
gas outlet. Small holes will be drilled on the inside of the tube at an angle directed
towards the substrate.
Figure 6.2.3: Representation of reactive gas inlet made of stainless steel tubing.
Further experiments should be carried out with the mini chamber design in place to see
if stoichiometric films can be produced. If this design does not work, modifications to the
system using one of the other recommendations would most likely help further the
research in obtaining stoichiometric ceramic thin films. After stoichiometric ceramic films
have been fabricated, the researcher should begin design for multi-layer coating.
Simulation to calculate the necessary thickness of each layer to reflect a targeted
wavelength should be done in order to reflect the whole spectrum of infrared radiation.
91
7 REFERENCES
Almen, O. and Bruce, G. Nucl. Instrum. Methods. 11 (1961), 257; ibid. 11 (1961), 279.
Baum, T. Z. Phys., 40 (1927), 686.
Blechschmidt, E. and v. Hippel, A. Ann. Phys. Lpz., 86 (1928), 1006.
Bohdansky, J., Lindner, H., Hechtl, E., Martinelli, A. P., and Roth, J. “Sputtering Yield of
Cu and Ag at Target Temperatures Close to the Melting Point.” Nucl. Instr. Meth.
B18 (1987), 509.
Brown, S. C. Introduction to Electrical Discharges in Gases. New York: Wiley, 1966.
Chiang, C. M. and Chang, L. S. “Microstructure and characterization of aluminum oxide

thin films prepared by reactive RF magnetron sputtering on copper.” Surface and
Coatings Technology. 198 (2005), 152-155.
Cobine, J. D. Gaseous Conductors. New York: McGraw-Hill, 1941.
Desphpandey, C. and Holland, L. “Preparation and properties of Al2O3 films by DC and

RF magnetron sputtering.” Thin Solid Films. 96 (1982), 265-270.
Gao, P., Meng, L. J., dos Santos, M. P., Teixeira, V., and Andritschky, M.
“Characterisation of ZrO2 films prepared by rf reactive sputtering at different O2
concentrations in the sputtering gases.” Vacuum. 56 (2000), 143-148.
Grove, W.R. “On the Electrochemical Polarity of Gases,” Phil. Trans. Royal. Soc.
(London), B142, 87 (1852)
Holland, Leslie. Vacuum Deposition of Thin Films. New York : John Wiley & Sons Inc.,
1956.
Hollands, E. and Campbell, D. S. “The Mechanism of Reactive Sputtering”. Journal of

Materials Science. 3 (1968), 544-552.
http://dunham.ee.washington .edu/ee528/notes.getter.pdf. June 22, 2011.
Kelly, Matthew J. et al. “Thermal Barrier Coatings Design with Increased Reflectivity and
Lower Thermal Conductivity for High-Temperature Turbine Applications.”
International Journal of Applied Ceramic Technology. 3 (2) (2006): 81-93.
Kingdon, K. H. and Langmuir, I. Phys. Rev., 20 (1922), 108; ibid. 21 (1923), 210; ibid.
22 (1923), 148.
92
Koski, K., Holsa, J, and Juliet, P. “Deposition of aluminum oxide thin films by reactive
magnetron sputtering.” Surface and Coatings Technology. 116-119 (1999), 716-
720.
Koski, K., Holsa, J., Juliet, P. “Properties of zirconium oxide thin films deposited by
pulsed reactive magnetron sputtering.” Surface and Coatings Technology. 120-121
(1999), 303-312.
Lamar, E. S. and Compton, K. T. “A Special Theory of Sputtering.” Science. 80 (1934),

541.
Leyens, C. et al. “Influence of EB-PVD TBC Microstructure on Thermal Barrier Coating

System Performance Under Cyclic Oxidation Conditions.” Surface and Coatings
Techonology. 1999.
Mahan, John E. Physical Vapor Deposition of Thin Films. New York: John Wiley &
Sons, Inc., 2000.
Maissel, L. I. and Glang, R., eds. Handbook of Thin Film Technology. New York:
McGraw-Hill, 1970.
Maniv, S, Miner, C. and Westwood, W. D. J. Vac. Sci. Technol. 18 (2) (1981), 195-198;
ibid. 1 (3) (1983), 1370-1375.
Matsunami, N., Yamamura, Y., Itikawa, Y., Itoh, N., Kazumata, Y., Miyagawa, S.,
Morita, K., Shimizu, R., and Tawara, H. “Energy Dependence of the Ion-induced
Sputtering Yields of Monatomic Solids”. Atom. Data Nucl. Data Tables. 31 (1984),
1.
Mattox, Donald M. The Foundations of Vacuum Coating Techonology. New York:

Noyes/William Andrew Publishing, 2003.
Miller, Robert A. “History of Thermal Barrier Coatings for Gas Turbine Engines:
Emphazising NASA’s Role from 1942 to 1990” for Thermal Barrier Coatings II
sponsored by Engineering Conferences International. Cleveland: Glenn Research
Center, National Aeronautics and Space Administration, 2007.
Overbeck, C.J. J. Opt. Soc. Am., 23, 109 (1933).
Padture, Nitin. “The Ohio State University: Nitin P. Padture, Ph.D.”

http://www.matsceng.ohio-
state.edu/faculty/padture/padturewebpage/padture/research.htm. The Ohio State
University. n.d. Web. April 13, 2011.
Parsons, Robert. “Sputter Deposition Processes.” Sec II-4 in Thin Film Processes II,
edited by John L, Vossen and Werner Kern. San Diego: Academic Press, Inc.,
1991.
93
Penning, F.M. “Coating by Cathode Disintegration,” (filed December 1935 in Germany),
U.S. Patent #2,146,025 (Feb. 7, 1939); also Physica (Utrecht), 3, 873 (1936).
Penning, F.M. and J.H.A. Mobius, Proc., K. Ned. Akad. Weten., 43, 41 (1940).
Plücker, J. “Observations on the Electrical Discharge Through Rarefied Gases,” The

London, Edinburgh and Dublin Philosophical Magazine, 16, 409 (1858)
Raizer, Y. P., Gas Discharge Physics. New York: Springer, 1991.
Rossnagel, Stephen. Handbook of Thin-Film Deposition Processes and Techniques -

Principles, Methods, Equipment and Applications. 2nd Ed. Seshan, Krishna. New
York: Noyes/William Andrew Publishing, 2002.
Scherer, M. and Wirz, P. “Reactive High Rate D.C. Sputtering of Oxides”. Thin Solid
Films. 119 (1984), 203-209.
Schiller, S., Heisig, U., Steinfelder, K., and Strumpfel, J. Proc. Int. Conf. on Ion Plating
and Allied Techniques, London, July 1979. Edinburgh: CEP Consultants, 1979.
Schwartz, N. Trans. 10th Nat. Vac. Symp. Murray Hill: Bell Telephone Lab. Inc., 1963.
Sethi, G., Sunal, P., Horn, M. W., and Lanagan, M. T. “Influence of reactive sputter
deposition conditions on crystallization of zirconium oxide thin films.” Journal of
Vacuum Science Technology A. 27 (3) (2009), 577-583.
Shinoki, F. and Itoh, A. “Mechanism of rf reactive sputtering.” Journal of Applied

Physics. 46 (8) (1975), 3381-3384.
Sproul, W. D. and Christie, D. J., and Carter, D. C. “Control of reactive sputtering

processes”. Thin Solid Films. 491 (2005), 1-17.
Sproul, W. D., Graham, M. E., Wong, M. S., Lopez, S. Li, D., and Scholl, R. A. “Reactive
direct current magnetron sputtering of aluminum oxide coatings.” Journal of
Vacuum Science Technology A. 13(3) (1995), 1188-1191.
Starr, C. Phys. Rev., 56 (1939), 216.
Venkataraj, S., Kappertz, O., Weis, H., Drese, R., Jayavel, R., and Wuttig, M. “Structural
and optical properties of thin zirconium oxide films prepared by reactive direct
current magnetron sputtering.” Journal of Applied Physics. 92 (7) (2002), 3599-
3607.
Veszi, G.A. J. Brit. Instn. Radio Eng., 13, 183 (1953).
Vossen, J.L. and J.J. Cuomo. Thin Film Processes. New York: Academic Press, Inc.,
1978.
94
Wagner, C. D., Riggs, W. M., Davis, L. E., Moulder, J. F., and Muilenberg, G. E.
Handbook of X-ray Photoelectron Spectroscopy. Eden Prairie: Perkin-Elmer Corp.,
1979.
Waits, Robert K. “Planar Magnetron Sputtering.” Sec. II-4 in Thin Film Processes, edited
by John L Vossen and Werner Kern. New York: Academic Press, Inc., 1978.
Wehner, G. K. Phys. Rev., 93 (1954), 633.
Wright, A.W. “On the Production of Transparent Metallic Films by Electrical Discharge in
Exhausted Tubes,” Am. J. Sci. Arts, Vol. 13, pp. 49-55 (1877); also “On the New
Process for the Electrical Deposition of Metals and for Constructing Metal-Covered
Glass Specula,” Am. J. Sci. Arts, Vol. 14, pp.169-178 (1878)
95
8 VITA
Diane Ho was born in October 1985 in Marrero, Louisiana. She was Valedictorian of
Immaculata High School, Class of 2004. She received her Bachelor of Science in
Mechanical Engineering from Louisiana State University (LSU) in December 2008. After
graduating from her undergraduate studies, she traveled to Hong Kong, Australia and
New Zealand for six weeks. She joined the graduate program at LSU in August 2009
and will receive her Master of Science in Mechanical Engineering in August 2011. Diane
has accepted a job with Air Liquide’s ALLEX program. She will be starting her job in
Houston, Texas in August 2011. She is the elder daughter of Nghia Thy Ho and Huong
Thu Dinh and has a younger brother, Charlie Ho.
96

Ho Thesis

Uploaded by

Copyright:

Available Formats

Ho Thesis

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Ho Thesis

Uploaded by

Copyright:

Available Formats

THE DESIGN AND MODIFICATION OF A SPUTTER SYSTEM FOR DC

REACTIVE SPUTTERING OF ALUMINA AND ZIRCONIA THIN FILMS

Submitted to the Graduate Faculty of the

The Department of Mechanical Engineering

I would like to dedicate this thesis to

my parents, Nghia Thy Ho and Huong Thu Dinh,

my brother, Charlie Ho, my extended family, and

my boyfriend, Edward Scheuermann.

Through their love, support and encouragement,

I had the strength to pursue and complete my Master’s degree.

This research was partially funded by NASA/LEQSF(2009-12)-PHASE3-03 and NASA

Award Number NNX09AP72A and partially by the Louisiana Space Consortium

support for my research and future career.

encouragement throughout my graduate studies. Dr. Nik has always supported my

me with a quality education in both my undergraduate and graduate studies.

Wang, and Dongsheng Guan. To my classmates, Calicia Johnson, Brooks Lowrey,

Alvarez, graduate school was a lot easier with them in my life.

unconditional love and unwavering support. I specifically want to thank my uncle,

Benedict Lim, for encouraging me to pursue an engineering degree. I would not be

where I am today without all of them.

LIST OF TABLES ........................................................................................................... vii

LIST OF FIGURES ........................................................................................................ viii

CHAPTER 1: INTRODUCTION ....................................................................................... 1

CHAPTER 2: BACKGROUND ON SPUTTERING .......................................................... 8

CHAPTER 3: LITERATURE SURVEY .......................................................................... 33

CHAPTER 4: EXPERIMENTAL METHODS .................................................................. 46

CHAPTER 5: EXPERIMENTAL RESULTS ................................................................... 58

CHAPTER 6: DISCUSSION AND FUTURE WORK ...................................................... 86

Figure 2.1.2: An illustration of current versus voltage in a DC glow discharge

Figure 2.1.4: (a) Schematic diagram of a DC sputtering discharge; (b) the

Figure 2.4.1: Circuit schematics of a sputtering system with DC (left) and RF

Figure 2.6.1: Simple reactive sputtering geometry [Rossnagel, 2002]. ......................... 28

Figure 4.1.1: Denton Vacuum Explorer 14 sputtering system. ...................................... 46

Figure 4.1.2: Top view of schematic representation of Denton Vacuum sputter

Figure 4.1.4: Additional gas lines on modified sputter system....................................... 49

Figure 5.1.2: XRD result for zirconium on glass slide. ................................................... 59

Figure 5.2.2: Hysteresis curve for reactive sputtering of aluminum oxide,

Figure 5.2.3: Hysteresis curve for reactive sputtering of aluminum oxide,

Figure 5.2.5: Hysteresis curve for reactive sputtering of zirconium oxide,

Figure 5.2.6: Hysteresis curve for reactive sputtering of zirconium oxide,

Figure 5.2.7: XRD result of aluminum oxide on glass slide. .......................................... 69

Figure 5.2.8: XRD result of zirconium oxide on glass slide. .......................................... 69

Figure 5.2.16: SEM micrograph of zirconia surface and cross section at 5% O2

layer is optimized to reflect a targeted range of wavelength. This research aims to

fabricate these multi-layer coatings by reactive magnetron sputtering.

Reactive magnetron sputtering is the sputtering of an elemental target in the presence

disadvantage of reactive magnetron sputtering is target poisoning, which leads to very

low deposition rates.

thin films are reactively sputtered.

instruments to properly measure the film properties.

current work aims to modify a sputter system to incorporate reactive sputtering

radiation passing through the TBCs.

1.2 Brief History of Thermal Barrier Coatings (TBCs)

possibly yttria stabilized), and hafnia for nuclear rocket applications.

1.2.1 Fabrication and Application of TBCs

electron-beam physical vapor deposition. As mentioned before, plasma spray

deposition because it offers superior thermo-mechanical properties and lifetime

layer, and a bond coat layer to the substrate (Figure 1.2.3).

inert to combustion atmospheres [Leyens, 1999].