CHARACTERISATION OF THE GAS-PHASE
ENVIRONMENT IN A HOT FILAMENT DIAMOND CHEMICAL VAPOUR DEPOSITION CHAMBER USING
MOLECULAR BEAM MASS SPECTROMETRY.
By
Roland S. Tsang
A thesis submitted to the University
of Bristol in accordance with the requirements for the degree of Doctor of
Philosophy in the Faculty of Science, Department of Physical Chemistry.
August 1997
ABSTRACT
Molecular beam mass spectrometry
has proved to be capable of providing quantitative measurements of both stable
free radical gas-phase species under conditions typical in the diamond CVD
process. Due care has to be taken,
however, in the data reduction procedures because the overall system
sensitivity is critically dependent on the local temperature, pressure and
composition of the gas being sampled.
Simple empirically based correction procedures can offset such
variations in the sampling efficiency.
Armed with a sensitive gas-phase analysis technique and the necessary
data reduction procedures for the characterisation of a CVD environment,
attention was turned towards the study of the effects that different gas
additions to the standard hydrocarbon/H2 gas mixtures have on the
gas-phase reaction mechanism occurring during the CVD growth process.
First, an understanding in
the behaviour and applicability of chlorine-assisted CVD was accomplished in a
hot filament reactor. Quantitative
measurements of the composition of the gas-phase species prevailing during
diamond deposition were obtained for a variety of chlorine containing source
gases. Two forms of gas mixtures were
used: (1) 1% of a chlorinated methane (CH4-xClx, x=1-4)
in H2 and (2) 1% CH4 in H2, then introducing
chlorine varying from 1-4%. At filament
temperatures at and above the optimum for diamond growth (~2300C), the relative concentrations of the various hydrocarbon species (CH4,
C2H2, C2H4) in the gas phase are
insensitive to the choice of Cl precursor used. Furthermore, the product
distribution at these temperatures is remarkably similar to that measured when
CH4 is the precursor. For
both forms of Cl precursor gases used, chlorine is effectively reduced to HCl
at standard growth temperatures, whose concentration is proportional to the
chlorine fraction input in the feed gas.
The as-grown diamond films were analysed using AES and SEM
techniques. No chlorine was detected in
bulk structure of the films but ~1-2% was found on the diamond surface. The apparent catalytic activity of Cl atoms
in the CVD process is therefore likely to be due to its role in abstracting
surface terminating hydrogen or H abstraction of surface C-Cl, at lower
substrate temperatures.
Next, the effects of nitrogen
on the CVD diamond growth mechanism was examined. The deposition rate at optimum growth conditions depends
critically on the choice of C/N precursor used, and the origin of the
carbon-containing species. The
reactions occurring in the gas-phase seem to lead predominantly to the
formation of HCN, (except for CH4/N2 gas mixtures). The stability of this species precludes most
of the cycling of carbon during the CVD process, resulting in low rates of
diamond deposition. Thermodynamic equilibrium
calculations confirm that HCN production is highly favoured in H/C/N gas
mixtures at high gas processing temperatures.
For a 1:1 C:N ratio in the feed gas, continuous films were produced
after 6 hour deposition only by CH4/H2/N2 gas
mixtures. Incorporation of nitrogen in
the grown diamond films was very low, consistent a theoretical
calculations. At lower temperatures N2
simply acts as a spectator to the CVD process, as evidenced by the significant
increase in the C2H2 concentration and reduction in the
HCN concentration in the gas-phase compared to other N source gas
additions. At optimum filament
temperatures (~2400°C), addition of N2
to a CH4/H2 gas mixture leads to higher deposition rates
of poor quality diamond films (determined by LRS). We believe that this can be explained if N2 is acting
as a catalyst for the destruction of H atoms, thereby reducing the etching rate
of non-diamond phases on the film surface.
Thus addition of a tiny amount of N2 to the hot filament CVD
process will affect not only the gas-phase chemistry, but the growth rate, the
morphology and the quality of the resulting diamond films.
The effects of addition of
phosphine on the growth behaviour of diamond films have also been
investigated. Films were grown using
gas mixtures of 1% CH4 with increasing amounts of PH3
(1000-5000 ppm). Gas phase species
prevalent during the growth process (e.g. CH4, CH3, C2H2,
PH3 and HCP) have been monitored, quantitatively, and compared with the
corresponding growth rates, quality and properties of the resulting films.
Addition of up to 2000 ppm PH3 produced good quality diamond films
at the highest growth rates, and changed the crystal morphology in favour of
[100]. At higher PH3
concentrations (3000-5000 ppm) the growth rate decreases again, with
predominantly [111] faceted crystals and a compromise in film quality. These observations can be rationalised by
the rapidly cycling between methyl radicals and HCP molecules. At low PH3 input, an unusually
high CH3 mole fraction was observed due to additional [H] produced
as a result of rapid decomposition of PH3 to P and 3H, lending to
fast deposition rates. At high PH3
input, a reversal in growth rates was observed, which we suggest may be due to
another, competing reaction, which instead serves to deplete [CH3].
Finally, as a means to test
the validity of the MBMS data we have also employed a highly structured
computer package called CHEMKIN, using the SPIN application code to aid in the
incorporation of complex gas-phase chemical reaction mechanisms into numerical
simulations. For the first time
we have performed a simulation on a 1% CH4 in H2 mixture
as a function of filament temperature.
We find that the mole fractions predicted by SPIN for the various
hydrocarbon species (CH4, C2H2, C2H4)
in the gas phase depends critically on the amount of [H] introduced in the
initial SPIN input file, for any particular filament/substrate
temperature. Filament poisoning effects
(which reduce the effective concentration of H atoms produced at the filament)
have been taken into account in choosing an appropriate starting [H]. At growth temperatures, Dandy and Coltrin
predicted an H atom concentration of 5% at the filament (having corrected for
filament poisoning effects) which was the value we used in the input with 1% CH4
in H2. Subsequent simulation
of this gas mixture under standard growth conditions produced calculated mole
fractions of CH4, C2H2, and C2H4
that are accurate to within a factor of 1-2 compared to the measured
values. Different H atom concentrations
were introduced to the input file for different filament temperatures, and the
results obtained again were in good agreement with those measured by MBMS.
ACKNOWLEDGEMENTS
Firstly, I would like to
thank my supervisor, Professor Mike Ashfold, for his ever-enthusiastic and
valued advice during my postgraduate studies.
My very special thanks go to
Dr. Paul May, for not only being a constant source of encouragement,
inspiration and efficient proof-reading over the past three years, but also for
his excellent humour and treasured friendship.
I would also like to thank
Dr. Christopher Rego for his support and expertise during my first year PhD,
and whose work has really set the foundations not only for my project work, but
for our understanding of this area of chemistry.
I am grateful to Mr. Keith
Rosser for his technical support and advice throughout my experimental work, to
John Cole for successfully setting up the CHEMKIN computer package, and to Dr.
Thomas Badgwell of the Chemical Engineering Department at Rice University for
advice on the many aspects of the package. My special thanks also goes to Dr.
Jim Butler of the Naval Research Laboratory not only for valued discussions on
my research, but also a most delicious tub of chilli peanut butter.
Thanks go to Mr. John Dimery
for the use of the scanning electron microscope (SEM), to Dr. Charles Younes
for all the Auger analyses, and to Mr. David Jones for developing outrageously
large quantities of high quality SEM photos presented within this thesis. A
special acknowledgement must go to Mr. Tim Davis form the Physics Department.
Thanks dude for all your help and advice with these seemingly endless Raman
curve fittings and data collections, but mostly for your patience and good
humour, especially on those ‘Friday afternoons’.
I am indebted to the
legendary “BUDGIES”, namely Paul,
Stuart, Tim, Dave, Annette, and Stefan, our temporary German virgin addition, for
making the last three years so unforgettable, providing a most sparkling
research atmosphere and for many of those ‘it’ll be rude not to’ pub sessions.
To my family and friends, a
big thank you for all of your support during my years as a student. Finally an
extra special mention goes to Vicks who never ceased to believe in me. Thank
you for all your care and support during the so often underestimated task of
‘writing-up’.
“To win them, temples have
been profaned, palaces looted, thrones torn to fragments, princes tortured,
women strangled, guests poisoned by their hosts, and slaves disembowelled. Some
have fallen on battlefields, to be picked up by ignorant freebooters, and sold
for a few silver coins. Others have been cast into ditches by thieves or swallowed
by guards, or sunk in shipwrecks, or broken into powder in moments of frenzy.
No strain of fancy in an Arabian tale has outstripped the marvels of fact in
the diamond's history.”
Gardner Williams (General
Manager of de Beers ca.1890's)
“The
BUDGIES are getting rowdy…”
Jim
Butler, NRL, Diamond Conference Meal,
Tours, 1996.
“They resist blows to such an extent that the hammer
rebounds and the very anvil splits asunder, but this invincible element which
defies Natures two most violent forces, iron and fire, can be broken by ram's
blood. But it must be steeped in blood that is fresh and warm and even so, many
blows are needed.”
Pliny the Elder ca. 1
century AD.
“Je
suis vraiment desolé…”
The BUDGIES, Diamond Conference, Tours, 1996.
To mum, dad and sis.
Memorandum
The research described in
this thesis was carried out by the author in the School of Chemistry at the University
of Bristol under the supervision of Professor MNR Ashfold, Dr. P.W. May and Dr.
C.A. Rego.
The work reported herein is
original to the author, except where acknowledged by reference or special
recognition. No part of this work has been submitted previously for any degree.
CONTENTS
1. INTRODUCTION
1.1 Diamond 1
1.2 Historical overview of the CVD diamond process 3
1.3 The diamond CVD technique 4
1.4 The CVD diamond film 6
1.5 The choice of substrates suitable for growing CVD diamonds
8
1.6 Mechanism of CVD growth 9
1.7 Role of atomic hydrogen in the CVD process 11
1.8 Gas-phase chemistry involved in the CVD process 12
1.9 Characterisation of the CVD process 13
1.10 Summary of the work performed on hot filament CVD systems. 14
1.11 References 17
2.1 Introduction 20
2.2 Scanning Electron Microscopy (SEM) 21
2.3 Laser Raman Spectroscopy (LRS) 21
2.4 Auger Electron Spectroscopy (AES) 23
3. EXPERIMENTAL
3.1 Introduction 25
3.2 Hot filament CVD reactor 26
(a) The filament 26
(b) The substrate 27
(c) Gas phase composition 28
(d) Gas flow system 30
3.3 Molecular beam mass spectrometry of diamond CVD
34
3.4 Molecular beam mass spectrometer design 35
(a) Choice of sampling cone orifice diameters 38
(b) Two stage differential pumping 39
(c) Hiden HAL/3F PIC 100 quadrupole mass spectrometer 40
3.5 Characterisation of the mass spectrometer 50
(a) Energy scale calibration 50
(b) MS calibration 51
(c) Mass discrimination 52
(d) Temperature dependence of MS sampling efficiency 54
(e) Thermal diffusion effects 56
(f) Dissociation patterns 56
(g) Ionisation cross sections and potentials 57
(h) Detection of radical species
58
(i) Procedure for obtaining quantitative measurements of
CH3 radicals
59
3.6 Step-by-step procedure for converting MBMS raw data into
species
mole fractions 62
(a) Stable gas phase species 62
(b) Methyl radicals 66
3.7 References 72
4.1 Introduction 74
4.2 Cracking patterns of CH4 75
4.3 Cracking patterns of C2H2 76
4.4 Gas phase composition as a function of filament temperature
for 1% CH4 in H2 77
4.5 Discussion of errors 78
4.6 Gas composition as a function of filament temperature
for a variety of hydrocarbon precursor gases 79
4.7 Analysis of the films grown using 0.5% and 1% CH4
in H2 79
4.8 Appendix: Experimental Data 83
5.1 Introduction 87
5.2 Experimental Details 91
(a) Deposition experiments 91
(b) Film analysis 91
(c) Gas phase composition measurements 92
5.3 Analysis of the diamond films 94
5.4 Gas composition versus filament temperature for a variety of
chlorine
containing precursor gases in H2 99
(a) Chloromethane (1% CH3Cl in H2) 99
(b) Dichloromethane (1% CH2Cl2 in H2) 99
(c) Trichloromethane (1% CHCl3 in H2) 100
(d) Tetrachloromethane (1% CCl4 in H2) 100
5.5 Gas composition versus filament temperature for various CH4/Cl2/H2
containing gas mixtures 104
5.6 Gas composition versus filament temperature using 1% CF4
in H2 105
5.7 Discussion 106
5.8 References 112
5.9 Appendix 114
(I) Ionisation
potentials (I.P.) of the various precursor gases used 114
(II) Experimental Data 114
6.1 Introduction 122
6.2 Experimental Details 124
(a) Deposition experiments 124
(b) Film analysis 125
(c) Gas-phase composition measurements 125
6.3 Analysis of the diamond films 126
(a) Methane and Ammonia as precursor gas mixture 126
(b) Methylamine as precursor gas mixture 128
(c) Hydrogen cyanide as precursor gas mixture 128
(d) Methane and nitrogen as precursor gas mixture 132
6.4 Gas composition versus filament temperature for a variety
of C-/N-containing precursor gases in H2 139
(a) Methane and
Ammonia as source gas mixture 139
(b) Methylamine
as source gas mixture 144
(c) Hydrogen cyanide as source gas mixture 145
(d) Methane and nitrogen as source gas mixtures 145
6.5 Conclusions 152
6.6 References 154
6.7 Appendix 156
(I) Synthesis of
Hydrogen Cyanide 156
(II) Ionisation
potentials and the user selected electron energies
of the
various gas-phase species monitored 157
(III) SEM Photo Library 158
(IV) Experimental Data 166
7.1 Introduction 175
7.2 Experimental Details 176
(a) Deposition experiments 176
(b) Film analysis 177
(c) Gas-phase composition measurements 177
(d) Cracking patterns of PH3 177
7.3 Analysis of the diamond films 179
7.4 Gas-phase composition measurements 182
7.5 Discussion 185
7.6 References 189
7.7 Appendix 190
(I) Ionisation
potentials and the user selected electron energies
of the
various gas-phase species monitored 190
(II) SEM Photo Library 191
(III) Laser Raman spectra
(uv - 325 nm) of films grown using 1% CH4
in PH3/H2, the amount of phosphine
varying from 0.1%-0.5%. 205
(IV) Experimental Data 211
8.1 Introduction 226
8.2 Structure of CHEMKIN 227
8.3 Structure of the Transport Property Fitting Code
and SURFACE CHEMKIN 232
8.4 Application codes 237
(a) SENKIN 238
(b) SPIN 241
8.5 Numerical simulation of the diamond CVD process 246
8.6 Numerical simulation of the gas-phase composition vs. filament
temperature
for 1% CH4 in H2
at 20 Torr 251
8.7 Filament poisoning effects 265
8.8 References 272