1

General Introduction

The extreme hardness, high thermal conductivity, excellent infrared

transparency, and remarkable semiconductor properties (Table 1) combine
to make diamond one of the most technologically and scientifically valuable
materials found in nature.l’l-I31 However, natural diamond is rare and only
obtainable as gem stones in small sizes and at great expense. The scarcity
and high cost have motivated researchers to attempt to duplicate nature and
synthesize diamond since it was discovered in 1797 that diamond is an
allotrope of carbon.
At room temperature and atmospheric pressure, graphite is the stable
crystalline form of carbon, with an enthalpy only 2 k.I mol-’ lower than
diamond. Diamond is thermodynamically stable relative to graphite only at
high pressures, as evident from the carbon phase diagram, Fig. 1.131
Although thermodynamically feasible at relatively low pressures and tem-
peratures (Fig. l), graphite to diamond conversion faces a considerable
kinetic barrier, and the rate of conversion apparently decreases with increas-
ing pressure.121 Therefore, the early attempts to convert graphite into
diamond by simply increasing pressure were unsuccessful for over one
hundred years 111until high-pressure high temperature (HPHT) processes
came into being. The development of the HPHT processes is a result of the
extensive research during the 1940’s that built upon detailed knowledge
of the carbon phase diagram developed by 0. I. Leipunskii et al.1’1 The
HPHT synthesis of diamond essentially duplicates the natural process by
converting graphite into diamond under conditions at which diamond is the

I
2 Diamond Chemical Vapor Deposition

thermodynamically favored phase. Direct conversion of graphite to diamond

in static HPHT processes (Fig. 1) requires high pressure (>120 kbar[‘]-[3])
and high temperature (~:300O~C[‘]-[~]) to overcome the kinetic barrier and
obtain any observable conversion rate, and hence not economically viable.
The difficulties in the direct conversion spurred the development of various
processes to lower the temperature and pressure.

Table 1. Properties of CVD Diamond and Single-Crystal Diamondr2]

CVD Single-crystal
Diamond Diamond

Density (g cmm3) 2.83.51t4) 3.515

Thermal capacity at 27’C (J mot-’ K-l) 6.12 6.195
Standard entropy at 27% (J mol“ K-l) 2.428
Standard enthalpy of formation at 27’C (J mol-‘) 1.884
Effective Debye temperature at 0-827°C (K) 1860 * 10
Thermal conductivity at 25’Ca (W m-l KM’) 2100b 2200
Thermal expansion coefficient at 25-200°Cc (x 10s6 ‘C-I) _2.OI2lI51 0 .8-l .2[21[51
Band gap (eV) 5.45 5.45
Electrical resistivity (Q cm) 10’2-10’6 10’6
Dielectric constant at 45 MHZ to 20 GHz 5.6 5.7
Dielectric strength (V cm-‘) 106 106
Loss tangent at 45 MHZ to 20 GHz ~0.0001
Saturated electron velocity (x 10’ cm s’) 2.7 2.7
Carrier mobility (cm2 V’ s-l)
electron (n) 1350-1500 2200
positive hole (p) 480 1600
Young’s modulusa (GPa) 820-900d 910-1250
at 0-800”Ct61
Compression strength (GPa) 8.68-16.53
Poisson’s ratio 0.10-0.16
Coefficient of friction in air 0.035-0.3t71 0.05-O. 15
Vickers hardnessa (GPa) [varies with crystal orientation] 50-100 57-104
Index of refraction at 10 pm 2.34-2.42 2.40

a Higher than any other known materials

b Anisotropic characteristic of thermal conductivity of thick CVD diamond films may be
found in Ref. 9.
’ Lower than Invar
d Young'smodulus=89_5(1-1.04x1~(7'-20)~, (GPa), where T in “Ct*).
 General Introduction 3

Pressure, kbar

loo0 zoo0 3ooo 4ooo so00

Temperature. ‘c

Figure 1. Carbon phase diagram with temperature and pressure ranges corresponding to
various diamond synthesis processes, as indicated by the shaded areas. (Reproduced wifh
permission from ReJ 3, 0 American Chemical Society, 1989)

The first breakthrough came in 1953 when H. Liander at Allemanna

Svenska Elektriska A. B. (ASEA) in Sweden developed a HPHT processl”]
using a liquid metal solvent-catalyst at pressures and temperatures where
diamond is thermodynamically stable. Independently, the General Electric
team, F. P. Bundy and co-workers, synthesized diamond using the HPHT
technique in 1954, 1111followed by H. B. Dyer and co-workers at De Beers
Adamant Research Laboratory in South Africa .l121Through surmounting the
kinetic barrier by the solvent-catalyst reaction with a transition metal-Fe,
Ni, Co, Cr, Pt, Pd, Fe-Ni, Co-Fe,121 or Mn, Al as well as B141--the solvent-
catalytic HPHT process permits graphite to diamond conversion to occur at
conditions much nearer the graphite-diamond equilibrium line but at lower
temperatures (Fig. 1). Typically, pressures range from 50 to 100 kbar and
temperatures from 1300 to 2300”C.111131141 This technique, commercialized
by General Electric in the U.S., along with the dynamic HPHT technique, i.e.,
shock-wave synthesis, U3]industrialized by Du Pont in the U.S., provides a
reproducibility and tailorability unavailable in natural diamond in terms of
chemistry, morphology, size, shape, toughness, and other properties impor-
tant for abrasive and heat-sink applications.141 The development of the
techniques also increases knowledge ofthe carbon phase diagram, which has
4 Diamond Chemical Vapor Deposition

advanced carbon research in general. Large crystals of approximately 8 mm

diameter have been synthesized by Sumitomo Electric in Japan, and recently,
even larger single crystals, up to 17 mm, by De Beers in South Africa.[21131
Research in the HPHT synthesis of diamond is still underway in an effort to
lower production costs and produce even larger crystals.
The second breakthrough came with the discovery by W. G. Eversole
of the Union Carbide Corporation in the U.S.l141 that diamond could be
deposited on a substrate from a hydrocarbon gas or a CO/CO, mixture by
chemical vapor deposition (CVD) at low pressures and temperatures where
diamond is metastable with respect to graphite (Fig. 1). Eversole’s effort,
starting in 1949 and proceeding in parallel with the early studies ofthe HPHT
processes, led to first successful synthesis of diamond by CVD, predating the
first successful HPHT synthesis. 1151[161In 1953, H. Schmellenmeier at
Potsdam Teachers College in East Germany reported the formation of very
hard carbon films from acetylene in an electrical discharge.l171 Although
Schmellenmeier was not attempting to synthesize diamond films in his
experiments, the x-ray data of the coatings revealed crystalline diamond
present in the films. Contemporarily, B. V. Derjaguin and co-workers at the
Institute of Physical Chemistry of the Academy of Science of the former
U.S.S.R.l181 and J. C. Angus and co-workers at Case Western Reserve
University in the U.S. llgl initiated efforts to grow diamond at low pressures.
These two groups worked independently of one another, and both were
unaware of Eversole’s work. The experiments conducted by these two
groups were characterized by the co-deposition of diamond and graphite on
diamond seed crystals. The deposition processes required frequent interrup-
tions to remove accumulated graphite by hydrogen etching at temperatures
and pressures greater than 1000°C and 50 atm, or by oxidizing in air at
atmospheric pressure. 118]The typical growth rates of diamond were less
than 0.1 pm h-‘. In 1966 it was found by J. J. Lander and J. Morrison of
Bell Telephone Laboratories in the U.S. that hydrogen may permit
metastable growth of diamond by impeding the conversion of diamond to
graphite at temperatures between 900 and 1300°C.1201 They pointed out that
the growth of single-crystal diamond layers on a single-crystal diamond
substrate should be possible as long as carbon atoms are added at a rate low
enough to prevent stable graphite nuclei from forming. In 1978, E. C.
Vickery of Diamond Squared Industries in the U.S. developed a process for
growth of diamond layers on a diamond substrate,131 in which the
deposition/removal cycles were combined into a single step by using a
 General Introduction 5

mixture of 95 vol.% hydrogen and ~5 vol.% hydrocarbon in the presence of

catalysts such as Pt or Pd.
Although the average growth rates at the time were too low to be of
commercial significance, the sustained efforts of Derjaguin, Angus and their
co-workers ultimately led to the discovery of the crucial role of atomic
hydrogen to preferentially etch graphite deposits and to permit high nucle-
ation and growth rates on non-diamond substrates. This discovery was a
historic milestone in the development of diamond CVD techniques.[2’l-1241 It
was the recognition of the crucial role of atomic hydrogen that led Derjaguin
and co-workers125l to the first successful growth of diamond crystals on non-
diamond substrates at a commercially practical deposition rate (> 1 pm h-‘)
in the mid 1970’s. This was followed by the development ofvarious methods,
such as electric discharge and hot-filament, 1261to increase the concentration
of atomic hydrogen during CVD. These successes triggered considerable
interest and an extensive research effort on diamond CVD in Japan. In the
early 1980’s, the Japanese research group at National Institute for Research
in Inorganic Materials (NIRIM) synthesized individual faceted diamond
crystals at growth rates of 10 urn h-’ by microwave plasma and hot-filament
assisted CVD.1271-1291 These results, with convincing characterization
evidence by electron microscopy, x-ray diffraction, and Raman spectros-
copy, confirmed the earlier experiments and refocused worldwide attention
on the synthesis of diamond by CVD. In the past decade, a wide variety of
energetically assisted CVD processes have evolved for diamond synthesis on
various substrates at practical growth rates. 1271-1411In particular, the strong
Japanese research effort led to significant strides in the practical synthesis
and applications of polycrystalline diamond films and coatings. Deposition
areas as large as 400 cm2 have been achieved.131 Linear growth rates have
been increased to the order of hundreds of micrometers per hour,l37l and
recently to 930 pm h-l in DC plasma arc-jet CVD.1421 Diamond-coated
boring and drilling tools have been developed by Mitsubishi Metals in Japan.
High-fidelity loudspeakers for high-frequency sound with a diaphragm
coated with diamond thin film have been manufactured by Japanese Victor
Corp. and Sumitomo Electric Co. in Japan.131 The commercial production
of free-standing shapes of diamond, >lOO cm* in area and 1 mm in thickness,
has been realized by Norton and General Electric in the U.S., and others.121
The potential for economic scale-up of diamond CVD techniques
qualifies it as a viable processing alternative to the HPHT methods for
6 Diamond Chemical Vapor Deposition

production of diamond abrasives or heat sinks at a cost that is still high but
will be reduced as the technology improves. Moreover, CVD processes offer
an opportunity to exploit many desirable physical properties of diamond
(Table 1). The ability to coat a large area on a variety of substrate materials
with diamond films vastly expands the potential application areas of
diamond (Table 2) over those possible with natural or HPHT-synthetic
diamond. This capability, along with the need to explain the improbable
growth of diamond under apparently metastable conditions, has stimulated
active research into all aspects of diamond CVD in all the major industrial-
ized countries over the world. As potential applications of CVD diamond are
continuously discovered, it may be anticipated that the ultimate economic
impact of this emerging technology on the defense, space, and commercial
areas will outstrip that of high-temperature superconductors with more
immediate applications141 (Table 2).
By making an updated and systematic review of diamond CVD
processes, the objective of this book is to familiarize the reader with the
scientific and engineering aspects of diamond CVD, and to provide experi-
enced researchers, scientists, and engineers in academic and industry com-
munity with the latest developments in this growing field. The scope of the
present book encompasses the development and applications of diamond
CVD, starting with a brief description of atomic and crystal structures of
diamond and a review of the various processing techniques used in diamond
CVD. It is followed by an extensive discussion of fundamental phenomena,
principles and processes involved in diamond CVD, with emphasis on the
nucleation and early growth stages of diamond during CVD. Diamond
nucleation mechanisms, epitaxy and oriented growth are discussed on the
basis of experimental observations. The nucleation enhancement methods
developed to date are summarized. The effects of surface conditions and
deposition parameters on surface nucleation are described. Finally, theoreti-
cal and modeling studies on surface nucleation are reviewed.
 General Introduction
Table 2. Actual and Potential Applications of CVD Diamond[2][3][431-[46]
Application areas Application examples
Grinding/cutting tools Inserts
Twistdrills
Whetstones
Industrial knives
Circuit-board drills
Oil drilling tools
Slitter blades
surgical scalpels
.savrr
Wearparts Bearings
Jet-nozzle coatings
Slurry valves
Extrusion dies
Abrasive pump seals
Computer dish coatings
Engine parts
Mechanical implants
Ball bearings
Drawing dies
Textile machinery
Acoustical coatings Speaker diaphragms
D@io&corrosion protection Crucibles
Ion barriers (sodium)
Fiber coatings
Reaction vessels
Optical coatings Laser protection
Fiber optics
X-my windows
Anti reflection
W to IR windows
Radomes
Photonic devices Radiation detectors
Switches
Thermal management Heat-sink diodes
Heat-sink PC boards
Thermal printers
Target heat-sinks
Semiconductor devices High-power transistors
High-power microwave
Photovohaic elements
Resistors
Capacitors
Field-effect transistors
W sensors
7
Physical properties of diamond
utilized in the applications
greathardness
great wear resistance
high strength and rigidity
good lubricating properties
general chemical inertness
pat hardness
great wear resistance
high strength and rigidity
good lubricating properties
general chemical inertness
high sound propagation speed
high stiffness
low weight
general chemical inertness
high strength and rigidity
good temperature resistance
transparency from W
through visible into IR
good radiation resistance
large bandgap
high thermal conductivity
high electrical reaistivity
high dielectric strength
high thermal conductivity
good temperature resistance
good radiation resistance
high power capacity
good high- frequency performance
low saturation resistance