Surface Science 500 (2002) 986–1004

www.elsevier.com/locate/susc

Role of surface and interface science in chemical

vapor deposition diamond technology
L.K. Bigelow a, M.P. D’Evelyn b,*
a
Bigelow Consulting Corporation, Boylston, MA 01505, USA, formerly with Norton Diamond Film of Saint-Gobain
Industrial Ceramics, USA
b
General Electric Corporate Research and Development, P.O. Box 8, Schenectady, NY 12301, USA
Received 15 August 2000; accepted for publication 3 May 2001

Abstract
Diamond is well known as the hardest material in nature. It also has other unique bulk physical and mechanical
properties, such as very high thermal conductivity and broad optical transparency, which enable a number of new
applications now that large areas of diamond can be fabricated by the new diamond plasma chemical vapor deposition
(CVD) technologies. However, some of the most interesting properties of diamond, including the ability to be grown
over large areas by CVD processes, result not from its bulk properties but from its special and unique surface chemistry.
The surface chemistry derived properties are as remarkable as the bulk properties, and in the end may enable the
development of new applications, technologies, and industries which are at least as important as those based on the
bulk properties. Some of these surface properties are extreme chemical inertness, low surface energy, low friction co-
efficients, negative electron affinity, biological inertness, and high over-voltage electrode behavior. The surface science
and some of the interesting ongoing research in these areas are explored and illustrated, and unresolved questions are
highlighted. Ó 2001 Elsevier Science B.V. All rights reserved.

Keywords: Models of surface kinetics; Chemical vapor deposition; Growth; Surface chemical reaction; Surface energy; Diamond;
Polycrystalline surfaces

1. Introduction index and optical transparency. As an industrial

Diamond is best known for its qualities as a
gemstone and for its use as an industrial abrasive.
As a gem, diamond is highly valued because it has
a crystal structure that can be cleaved to bring out
the brilliance and fire created by its high refractive
* processes has made it possible to utilize of some of
Corresponding author. Tel.: +1-518-3877133; fax: +1-518-
3877563.
E-mail addresses: lkbigelow@aol.com (L.K. Bigelow),
develyn@crd.ge.com (M.P. D’Evelyn).
abrasive, it is unique because of its unmatched
hardness, which makes it the abrasive of choice to
grind or cut any other hard material, and the only
one that can be used to mechanically polish dia-
mond itself.
The development of large area coatings of dia-
mond by plasma chemical vapor deposition (CVD)
diamond’s unique bulk and surface properties in
new applications that were not possible with the
small stones found in nature, or with high-pressure

0039-6028/01/$ - see front matter Ó 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 3 9 - 6 0 2 8 ( 0 1 ) 0 1 5 4 5 - X
 L.K. Bigelow, M.P. D’Evelyn / Surface Science 500 (2002) 986–1004
synthetic diamond. Many of these new potential
opportunities stem not from the bulk properties
important in gemstones and abrasive applications,
but from the surface chemistry and surface prop-
erties of diamond. It is the objective of this re-
view article to examine a few of the most interesting
of these new opportunities, including specula-
tive ones, and to discuss the surface science issues
which must be explored to understand and develop
them into commercially successful new techno-
logies.
2. Diamond growth overview
Many of the most interesting features of dia-
mond, including the CVD growth process itself,
derive from the special surface chemistry of dia-
mond. These surface chemistry related properties
and processes in the end may enable the develop-
ment of new applications, technologies, and in-
dustries which are at least as important as those
based on diamond’s strength and hardness. Some
of these special surface properties are extreme
chemical inertness, low surface energy, low friction
coefficients, negative electron affinity, biological
inertness, and unique behavior when used as an
electrode in aqueous solutions.
Diamond is one of the most stable chemical
structures in nature, but graphite has an even more
favorable free energy of formation than diamond
under normal ambient pressures and temperatures.
The Gibbs free energy of formation at room
temperature and 1 atm is 2.9 kJ/mol more negative
for graphite than for diamond [1]. When carbon
condenses under other than extreme pressures, the
formation of graphite is thermodynamically fa-
vored instead of the growth of diamond. If one
were to try to transform graphite to diamond at
room temperature, a pressure of at least 16,000
atm would be required, although the kinetics of
transformation would of course be vanishingly
slow at this temperature. However, at higher
temperatures the pressure stability region of
graphite expands even further, and even higher
pressures are required to favor the growth of dia-
mond. At 1700 K in excess of 50 kbar are required
to reach the diamond stability region, which cre-
987
ates a serious technical barrier to the growth of
synthetic diamond by high pressure processes.
Despite these barriers, synthetic diamond is now
grown on a large scale in high-pressure presses
under diamond-stable conditions by dissolution of
graphite in metal ‘‘solvent-catalysts’’ and precipi-
tation of diamond. This process was developed in
the mid 1950s [2] and commercialized by General
Electric, followed soon after by De Beers and
others. The worldwide market for synthetic su-
perabrasives, including diamond and cubic boron
nitride grit, polycrystalline diamond and cubic
boron nitride (manufactured under high pressures
and high temperatures), and diamond and cubic
boron nitride powder, is approximately one billion
US dollars per year and continues to expand sig-
nificantly.
Questions remain concerning how diamond
forms in nature. Conventional models have dia-
mond growing over geological eons, 200 or more
kilometers below the surface of the earth under
high temperatures and pressures, and subsequently
being transported to the surface by primary vol-
canic intrusions. In South Africa, the type of vol-
canic rock commonly associated with diamonds is
called kimberlite, after the area where it was first
discovered. In the 1970s, in Australia, diamonds
were also discovered in a significantly different type
of volcanic intrusion known as lamproite [3]. More
recently, it has also been proposed that diamond
can form in the interior of large planets such as
Uranus and Neptune, whose atmospheres contain
CH4 , water, and ammonia, through the conversion
of methane to diamond at pressures in the range of
10–50 GPa and 2000–3000 K [4]. The authors
propose that this process of conversion to diamond
even produces enough energy to contribute to the
observed energy budget of these planets!
3. Surface chemistry of chemical vapor deposition
diamond growth
Growth of diamond by CVD [5,6] is driven by
the chemistry and kinetics of gas-phase and sur-
face reactions, rather than thermodynamics. Dia-
mond is typically grown using a dilute mixture of
a hydrocarbon such as methane in hydrogen.
988 L.K. Bigelow, M.P. D’Evelyn / Surface Science 500 (2002) 986–1004
Additional species, such as oxygen, nitrogen, flu-
orine, and chlorine, are sometimes used, but con-
sideration of the mechanistic role of the latter
species is beyond the scope of this article. Atomic
hydrogen is generated by inputting power into the
gas phase, for example, by means of a white-hot
filament, a microwave discharge, or an arc dis-
charge, which in turns reacts with the hydrocarbon
to form reactive species such as CH3 and C2 H2 .
These species are then transported to the substrate
surface, where the reactive precursors adsorb and
are subsequently converted to diamond by a series
of reactions that are still not completely under-
stood. Surface chemistry plays a crucial role in
determining the growth rate and quality of dia-
mond films, and surface science methods have
contributed significantly to the current level of
understanding of the growth mechanism.
Virtually all commercial CVD diamond is
polycrystalline, but on the atomic scale growth
takes place on single-crystal grains. The symmetry
of individual crystallites can be best understood by
reference to the crystal structure of diamond,
shown in Fig. 1. Each carbon atom is bonded to
four neighbors, and these tetrahedra are arranged
in such a way that eight atoms fit in a cube whose
edge is the lattice constant (3.567 A
). Facets on
crystals always occur perpendicular to the slowest-
growing crystallographic directions, which in CVD
diamond normally correspond to the so-called
[1 0 0] and [1 1 1] crystallographic directions [7].
Referring to Fig. 1, the ideal-structure (1 0 0) sur-
face (perpendicular to the [1 0 0] direction) com-
prises vertically oriented zig-zag chains of atoms;
as each new atomic layer is added the direction of
the chains rotates by 90°. On ideal-structure (1 1 1)
surfaces each surface atom is bonded to three
atoms below to form an array of puckered hexa-
gons. Square (1 0 0) and hexagonal or triangular
(1 1 1) facets characteristic of individual diamond
crystals (Fig. 1(d)) are also present in polycrys-
talline CVD diamond films, as shown in Fig. 2.
The properties of the film, including strength, abra-
sion resistance, fracture toughness, transparency,
surface roughness, etc., are determined by the
microstructure, including grain size and orienta-
tion, stresses, dislocations, and incorporation of
impurities. These impurities can include elements
such as nitrogen, or metals, or non-diamond
phases such as carbon atoms in a graphitic bond-
ing configuration, known as sp2 carbon. The
microstructure is in turn determined by the de-
tailed surface growth mechanism, including the
relative growth rates in the [1 0 0] and [1 1 1]
directions, v1 0 0 and v1 1 1 , respectively, and the
relative rates of generation of new crystallographic
directions (twinning or re-nucleation) versus con-
tinued growth in a given direction (homoepitaxy)
[8]. Examples of CVD diamond surface structures
that are produced by different growth chemistries
and growth conditions are shown in Figs. 2 and 3.
The polycrystalline structure of the diamond in
Fig. 2(a) is typical for many commercial coatings
on cutting tool inserts or rotary tools. The square
(1 0 0) diamond crystal faces shown in a surface
view in Fig. 2(b) and in a fracture cross-section in
Fig. 3 were grown within a transitional parameter
space between nearly pure (1 0 0) facet growth
and a mode which generates a microcrystalline
diamond morphology. The microcrystalline mor-
phology can be seen between the (1 0 0) faces in
Fig. 2, and the (1 0 0) growth columns in Fig. 3.
Our current level of understanding of the
atomic-scale mechanism of diamond CVD results
from a close interplay of experiment and modeling,
although there are a number of basic questions
that remain unanswered. Under typical diamond
growth conditions there is good evidence that most
of the carbon atoms originate from methyl radi-
cals, CH3 [6,9–11]. However, diamond growth
from acetylene, C2 H2 , occurs with a lower reaction
probability [12,13], and under more extreme con-
ditions atomic carbon, C2 , and alkyl halides can
act as diamond precursors, although the latter are
beyond the scope of this article.
What is the molecular-level mechanism by
which CH3 and/or C2 H2 become incorporated into
(1 0 0) and (1 1 1) diamond surfaces? To provide
a starting point for kinetic growth models, sev-
eral groups have examined hydrogenated (1 0 0)
and (1 1 1) diamond surfaces or facets after
quenching from growth conditions by scanning
tunneling microscopy (STM). On the (1 0 0) sur-
face, a number of authors have observed a (2
1)
reconstruction [14–16], that is, a doubling of the
surface unit cell size in one direction, as shown in
 L.K. Bigelow, M.P. D’Evelyn / Surface Science 500 (2002) 986–1004 989

Fig. 1. Lattice structure of diamond. (a) Cubic unit cell, showing fourfold bonding to each carbon atom. (b) (1 0 0) surface (ideal
structure), comprising vertically oriented zig-zag chains of first- and second-layer atoms. (c) (1 1 1) surface (ideal structure), com-
prising puckered hexagons of first- and second-layer atoms. (d) Isolated diamond crystal, with square (1 0 0) and hexagonal (1 1 1)
facets.

Fig. 4(a). (1 1 1) surfaces are often highly defective
on the micron scale, but unreconstructed (1
1)
surface domains, that is, with a surface unit cell
that is indistinguishable from the ideal structure
(Fig. 1(c)), have been observed by several groups
[15,17], as shown in Fig. 4(b). These surface
structures are well understood. The linear features
on the (1 0 0)-2
1:H surface comprise rows of
C–C dimers, in which each surface carbon atom is
bonded to one hydrogen atom and has two back-
bonds to the diamond lattice, as shown schemati-
cally in Fig. 5(a). The orientation of the dimer
rows in adjacent atomic layers is rotated by 90°
due to the symmetry of the lattice. The length of
the monohydride dimer bond has been measured

by dynamical low energy electron dif-
as 1.60 A
fraction (LEED) [18], in excellent agreement with
theory [19–21]. The vibrational modes of the C–H
990 L.K. Bigelow, M.P. D’Evelyn / Surface Science 500 (2002) 986–1004
Fig. 2. (a) Typical polycrystalline diamond coating on a cutting
tool. Growth steps, twinning, and apparent re-nucleation at
crystal plane intersections are visible. (b) Surface morphology
of CVD diamond grown in a transitional parameter space be-
tween dominant (1 0 0) (square facets) and microcrystalline
structures.
dimer species are coupled, producing symmetric
and asymmetric stretch modes at 2919 and 2899
cm1 , respectively, as observed by surface infrared
spectroscopy [22], again in excellent agreement
with theory. The (1 1 1)-1
1:H surface comprises
a simple termination of the bulk lattice, with one
hydrogen atom bonded to each surface carbon
atom, as shown schematically in Fig. 5(b). The
C–C bond lengths are essentially unperturbed, as
established by dynamical LEED [23] and X-ray
diffraction [24], and the C–H bond produces a
sharp vibrational mode at 2832 cm1 , as observed
by infrared–visible sum frequency generation [25]
and infrared spectroscopy [26].
Diamond growth models beginning from the
(1 0 0)-2
1:H and (1 1 1)-1
1:H surface struc-
tures have been proposed by a number of authors,
employing methyl radicals [27–29], acetylene [30],
or both [31–33] as assumed growth precursors.
The rate constants for most surface reactions
were estimated from analogous gas-phase reac-
tions, and relatively good agreement with experi-
mental growth rates has been achieved. A number
of global features of the surface growth mecha-
nism are well established. Incident hydrogen atoms
abstract (i.e., an Eley–Rideal mechanism) hydro-
gen from surface C–H bonds, creating dangling-
bond sites at which hydrocarbons can adsorb.
Further surface H-abstraction and rearrangement
reactions form new C–C bonds and remove the
remaining H atoms, incorporating the adsorbed
species into the diamond lattice. However, beyond
this global understanding a number of basic ques-
tions remain under active discussion. What are the
roles of different growth precursors, especially
CH3 and C2 H2 ? Are etching (removal of adsorbed
CHx species) and/or surface migration important
during growth and in producing smooth surfaces?
We consider these questions briefly in the re-
mainder of this section but defer others, such as:
why are 104 hydrogen-atom surface reactions
required for each atom of diamond deposited [6]?
The most definitive test of a diamond growth
model is to test its predictions on all experimen-
tally observed surfaces, including the growth rate
as a function of temperature and gas composition
and the surface morphology. This program rep-
resents a challenge to theory based on kinetics of
elementary surface reactions because of the large
range of time scales involved and the large number
of atoms necessary to adequately address ques-
tions of surface morphology. To date this test has
been performed only by Battaile et al. [32,33], who
considered growth from both CH3 and C2 H2 and
employed a sophisticated computer simulation
method capable of sampling a wide range of time
scales. These authors achieved reasonable agree-
ment with experimental homoepitaxial growth ki-
netics data in the [1 0 0] and [1 1 1] directions [7,34]
with two key findings. First, reasonable growth
rates in the [1 1 1] direction could only be achieved
if a significant level of C2 H2 was present in the gas
 L.K. Bigelow, M.P. D’Evelyn / Surface Science 500 (2002) 986–1004 991

Fig. 3. Fracture cross-section of the film in Fig. 2(b), showing the columnar growth of the (1 0 0) crystals, and the interspersed mi-
crocrystalline diamond. The nucleating substrate surface is at the bottom of the micrograph.

Fig. 4. STM images of (a) (1 0 0)-2
1 domains and (b) (1 1 1)-1
1 domains on CVD-grown diamond surfaces (from Ref. [15], with
permission). In (a) the surface unit cell is doubled in size in the direction perpendicular to the rows—hence the (2
1) designa-
tion—whereas in (b) the surface unit cell is identical to that of an ideal surface where the atoms are frozen in place at their bulk
positions (cf. Fig. 1(c)).
992 L.K. Bigelow, M.P. D’Evelyn / Surface Science 500 (2002) 986–1004

Fig. 5. Atomic structure models of (a) (1 0 0)-2
1 and (b) (1 1 1)-1
1 diamond surfaces. Light circles: H atoms. Larger, smaller dark
circles: top-layer, lower-layer C atoms. The 90° rotation in the direction of the dimer rows in (a) as the surface height is raised by one
atomic layer is a simple consequence of the symmetry of the diamond lattice (Fig. 1(b)).

phase in order to nucleate new layers, even though
most of the growth resulted from CH3 . Second,
[1 0 0] growth was significantly faster than experi-
ment unless etching of CHx species, by a combi-
nation of H-induced reactions and simple thermal
desorption, was assumed to be relatively facile.
The latter conclusion was supported by high-level
ab initio calculations of the energetics of several
key surface intermediates.
Experimental tests of these conclusions is made
difficult by the presence of both CH3 and C2 H2 in
virtually all diamond CVD reactors. However,
Martin and co-workers [11,12,35] have shown that
it is possible to grow high-quality diamond in
a flow tube, where the gas velocity is sufficiently
high that reactions interconverting CH3 and C2 H2
are negligible in the region of diamond growth.
Recently, D’Evelyn et al. [35] have shown that
diamond growth from H and CH3 can produce
well-faceted cubo-octahedra, as shown in Fig. 6(a).
The observation of comparable growth rates in
the [1 0 0] and [1 1 1] directions––implied by the
shapes of the crystals––despite a very low partial
pressure of C2 H2 , appears to contradict the first
conclusion of Battaile et al. Growth from H and
C2 H2 produced octahedra with a high concentra-
tion of contact twins, as shown in Fig. 6(b). The
latter results demonstrate that CH3 and C2 H2 are
not interchangeable in the growth mechanism and,
in particular, that defect-free incorporation into
the lattice is less likely with C2 H2 , at least on the
(1 1 1) surface. The apparent absence of a nucle-
ation requirement by 2-carbon species during [1 1 1]
growth suggests that the steady-state growth sur-
face has a significant coverage of adsorbed species,
i.e., does not closely resemble the (1 1 1)-(1
1)
surface, which in turn suggests that etching reac-
tions may not as facile as modeled by Battaile et al.
[33]. Further support for a more complex steady-
state growth surface comes from recent modeling
work [36] and the dependence of STM surface
images on post-growth annealing/etching in atomic
hydrogen [37].
Most diamond growth models assume that hy-
drocarbon precursors either become incorporated
into the lattice where they stick initially or else
desorb, i.e., surface migration is negligible. Yet the
facets of as-grown CVD diamond surfaces are
normally relatively smooth on the nanometer-to-
micron scale, and surface diffusion is known to be
important in the production of smooth surfaces of
many materials. Random growth on arbitrary
surface sites should produce atomically rough
surfaces, in contradiction to experiment. Frenk-
lach and co-workers [29,38] have proposed that
surface migration is significant during [1 0 0] dia-
mond growth, at least on the 5–20 A
length scale,
and facilitates the growth of dimer rows and
smooth surfaces. These predictions are supported
by semi-empirical and high-level quantum chemi-
cal calculations of the structures and energetics
of various surface intermediates and reactions
 L.K. Bigelow, M.P. D’Evelyn / Surface Science 500 (2002) 986–1004
Fig. 6. Diamond crystals grown in a flow-tube at 800 °C from
(a) H þ CH3 ; (b) H þ C2 H2 . The crystal in (a) is well faceted,
with (1 0 0) and (1 1 1) facets of similar area, which implies that
methyl radicals alone are capable of growing diamond in [1 0 0]
and [1 1 1] directions at similar rates. The crystal in (b) is ter-
minated by highly defective (1 1 1) surfaces only, which indi-
cates that [1 1 1] growth from acetylene leads to many defects
and is considerably slower than growth in the [1 0 0] direction.
[29,38]. Direct evidence for surface migration
during growth is so far lacking, but it is not clear
that the degree of smoothness observed on CVD-
grown facets can be accounted for in the absence
of migration.
Separate experiments in hydrogen plasmas
(etching, rather than growth conditions) suggest
993
that etching and surface migration can occur under
growth conditions, but this remains to be firmly
established. Hydrogen plasma treatments can pro-
duce smooth (1 0 0) and (1 1 1) surfaces under some
conditions [39–43], and can roughen [42–44] or
produce faceted pits [45,46] under other condi-
tions. Most authors have attributed the smoothing
phenomenon to etching. However, Rawles et al.
[42,43] found that the size of diamond particles
was unchanged during H-atom-induced facet for-
mation and was independent of particle packing
density and gas flow rates, and argued that this
observation supported surface migration but was
inconsistent with etching and etching/regrowth
mechanisms.
Definitive answers to the questions posed above
require further experimental and theoretical surface
science investigation. An improved fundamental
understanding of the CVD growth mechanism
should enable improvements in the quality and
decreases in the cost of CVD diamond. Particularly
valuable would be in situ measurement of the cov-
erage and type of surface hydrogen during growth;
quantification of the evolution of nanometer-scale
surface roughness; and the kinetics of etching and
surface migration induced by hydrogen atoms.
4. Properties
The chemical composition of the diamond sur-
face is important in determining certain physical
properties and for commercial applications. These
properties include friction coefficient, surface elec-
trical conductivity, surface energy for wetting and
bonding, negative electron affinity, and plasma
erosion resistance. As discussed above, the surface
bond structure and tendency to reconstruct de-
pends sensitively on the crystal orientation, growth
mode and surface treatment process.
4.1. Surface bonding
In this section we discuss the bonding and en-
ergetics of several diamond surface structures that
are or might be important for applications. More
comprehensive reviews can be found elsewhere
[19,47–49].
994 L.K. Bigelow, M.P. D’Evelyn / Surface Science 500 (2002) 986–1004
Hydrogenated diamond surfaces are important
for applications as well as in CVD growth. Several
types of studies have demonstrated that the surface
C–H bond is essentially identical to that in alk-
anes, with a bond energy of about 96 kcal/mol [50].
As noted above, the vibrational frequencies of
adsorbed hydrogen agree closely with theory. We
also saw in the previous section that abstraction of
surface hydrogen by gas-phase atomic hydrogen
plays a crucial role in the growth mechanism.
CVD modeling studies have assumed an activation
energy of about 7 kcal/mol [30,51], similar to that
in analogous gas phase abstraction reactions.
Krasnoperov et al. [52] measured an identical ac-
tivation energy for the surface abstraction reaction
on polycrystalline CVD diamond at pressures that
were high enough to reach thermal equilibrium
between the surface and the impinging gas-phase
species. A much smaller apparent activation en-
ergy has been observed under ultrahigh vacuum
conditions [53,54], which indicates that transla-
tional energy in the incoming H atom is more ef-
fective in surmounting the activation barrier than
is thermal motion of the surface atoms. The
sticking coefficient for atomic hydrogen on bare
surface sites appears to be approximately one.
The rates of desorption of H2 from the (1 0 0)-
2
1:H and (1 1 1)-1
1:H monohydride surfaces
are approximately proportional to the surface
concentration of hydrogen atoms. This behavior is
unusual on surfaces––hydrogen desorption rates
are more typically proportional to the square of
the surface concentration. The corresponding ac-
tivation energies for hydrogen desorption are 80–
88 kcal/mol [55,56] and 85–92 kcal/mol [25,57],
respectively, consistent with a C–H bond energy
near 96 kcal/mol. Following desorption the sur-
faces adopt a 2
1 reconstruction, comprising
C@C dimers linked by a r bond and a weak p
bond on (1 0 0) or p-bonded –C–C– chains on
(1 1 1) [19,47–49]. Naively, the simplest desorption
mechanism on the (1 0 0) surface would involve H
atoms on a dimer moving together and forming
an H–H bond while breaking two C–H bonds
and forming a surface p bond. However, such a
mechanism is symmetry forbidden [58] and, by
analogy to hydrocarbons, a much higher activa-
tion energy (120 kcal/mol for H3 C–CH3 !
H2 C@CH2 þ H2 [59]) might be expected. The dy-
namical nature of the H2 desorption mechanism is
as yet unknown. The first-order kinetics imply that
hydrogen tends to cluster together on the surface
rather than being randomly distributed, but the
roles of p-bonding on the clean surface, bond
strain, surface diffusion, and perhaps other factors
remain to be elucidated.
The existence of a p bond (albeit highly strained)
on the clean (1 0 0)-2
1 surface suggests that so-
called Diels–Alder chemistry––reaction between
one molecule with a C@C r þ p bond and a sec-
ond molecule with two C@C bonds separated by a
C–C r bond to form a cyclic structure––might be
possible, creating new possibilities for functional-
ization of diamond surfaces. Recent studies have
shown this to be the case. Adsorption of 1,3-buta-
diene (H2 C@CH–CH@CH2 ) occurs readily and
produces the expected –CH2 –CH@CH–CH2 –
product, as shown by infrared spectroscopy [60]
and high-resolution electron energy loss spectro-
scopy [61]. There is a twist, however, which ap-
parently results from the highly strained nature of
the surface p bond. Adsorption of a simple alkene
(cyclopentene), which is nominally symmetry for-
bidden (the analogous molecular reaction does not
take place) also occurs on the diamond surface
[62], albeit with a low sticking coefficient.
Hydrogenated diamond surfaces are stable in
oxygen or air up to a temperature of about 300 °C,
above which the surface hydrogen is progressively
replaced by surface oxygen species [63].
The chemistry of oxygen-containing species on
diamond surfaces is important and, for the most
part, analogous to that in organic molecules. Un-
fortunately, perhaps, the details are fairly complex.
Oxygenated diamond surfaces typically comprise a
combination of bridge-bonded –O– and linear
>C@O species and, if some surface hydrogen is
also present, –OH and –COOH groups [63–66].
Upon heating, adsorbed oxygen desorbs only as
carbon containing gas products, including CO and
CO2 , starting at desorption temperatures near 600
°C [67]. Desorption occurs over a wider range of
temperatures for oxygen than for hydrogen, re-
flecting a range of binding energies as would be
expected from the range of structures. Frenklach
et al. have determined the activation energy for
 L.K. Bigelow, M.P. D’Evelyn / Surface Science 500 (2002) 986–1004
desorption to be 45 kcal/mol by b-scission of a C–
C@O backbond [68].
Halogen termination of diamond might be ex-
pected to be very stable and to have useful prop-
erties, by analogy to alkyl halides and TeflonTM .
However, in contrast to the alkane-like behavior
described above, the chemistry of halogens on dia-
mond surfaces shows large departures from the
behavior of analogous alkyl halides, which have
C–X bond energies of about 116 or 82 kcal/mol for
fluorine or chlorine, respectively. Experimental
evidence indicates that desorption of F and Cl is
atomic rather than recombinative [69]. Based on
bond energies calculated with a cluster analogue of
diamond and assuming a normal pre-exponential
factor, one would predict that less than 10% of a
monolayer would desorb upon heating to tem-
peratures of 1200 or 700 °C for F or Cl, respec-
tively [70]. In stark contrast, F and Cl begin
‘‘oozing’’ (desorbing) from the surface at or below
room temperature. Fluorine begins desorbing near
room temperature but residual F has been found
by some authors to remain at temperatures as high
as 1200 °C [69,71,72]. For chlorine on diamond
(1 0 0) and (1 1 1) desorption was observed over the
range 50 to 300 °C [69], while on diamond
powder a significantly higher desorption temper-
ature range was observed, 300–1100 °C [73]. The
extremely broad range of desorption temperatures
imply a strongly coverage-dependent bond energy,
as low as 20 kcal/mol at full coverage. The bond
energies for F and Cl have been calculated as 103
and 48 kcal/mol at monolayer coverage [74],
somewhat reduced from the low-coverage results
[70]. However, it is clear that further contributions
to the destabilization of C–X bonds at high cov-
erage remain to be understood, whether from
steric repulsion, dipole repulsion, a decreasing
ability of the surface to donate charge to the more
electronegative halogen atoms, or other effects.
4.2. Surface energy
Surface termination of the diamond has im-
portant implications for many industrially impor-
tant processes such as metallization and bonding
to diamond. If the diamond is annealed at 1000 °C
in ultrahigh vacuum, the adsorbed hydrocarbons,
995
hydrogen and oxide species are removed, and the
surface reconstructs. A clean surface of C–C sat-
urated bonds is actually quite stable and unreac-
tive, at least by comparison to other materials such
as silicon. Fabis has reported on the effect of
plasma treatment of cleaned diamond surfaces
with H, O, and CF4 plasmas on the surface energy
of the diamond, and the impact that has on
polymer adhesion for electronics packaging [75].
The surface energy and the availability of elec-
trons for further bonding to materials on the
surface is strongly affected by these species termi-
nating the surface, as illustrated by the coverage
dependence of C–X bond energies. Fabis measured
the surface energy of diamond after various sur-
face treatments, using a series of liquids of differ-
ent surface tensions, following the work of Kaifu
and Komai [76]. As shown in Table 1, the O ter-
minated surface is the most wettable, and is also
hydrophilic.
Processing treatments which create polar oxy-
gen functionalities such as carbonyl (C@O) and
ether (C–O) are a key requirement for strong
bonding of polymers to diamond. In contrast,
clean high temperature annealed (1000 °C in 1010
Torr) surfaces with C@C saturated bonds, hy-
drogen terminated surfaces, and even fluorine
terminated surfaces are hydrophobic and are re-
sistant to wetting or bonding. XPS analyses re-
ported by Fabis indicate C–O and C@O surface
functional groups, and C–F (with some possible
C–O residuals) are present on the surfaces treated
with CF4 plasmas.
Table 1
Surface energy measurements of CVD diamond as a function of
surface treatment of polished samples (Ra ¼ 10 nm), from
Fabis [75]
Surface treatment XPS func- Surface energy
tional group (dynes/cm)
1000 °C: 1200 s, at 1010 C–C 22
Torr
H-plasma: 1800 s, 1 KW, C–H 28
2.45 GHz
CF4 -plasma: 1800 s, 1 KW, C–F (C–O) 38
13.56 MHz
O-plasma: 1800 s, 1 KW, C–O, C@O 50
13.56 MHz
996 L.K. Bigelow, M.P. D’Evelyn / Surface Science 500 (2002) 986–1004
The surface activity of the polymer or metal
to be bonded to diamond is of course the other
half of the equation which determines the actual
strength of the bond to a treated diamond surface.
The adherence of an epoxy polymer used in elec-
tronics plastics packaging under a series of boil/
peel cycles was found by Fabis to directly correlate
with the surface energy measurement in Table 1.
Surface treatment of the diamond after deposition
to increase its surface energy is also critical to the
adherence of blanket or patterned metallizations
for the fabrication of thermal management sub-
strates for electronic devices.
5. Applications
5.1. Surface factors in diamond friction
CVD diamond is known to have a low friction
coefficient under appropriate conditions. This is a
function of its surface termination state, and is af-
fected by prior processing and by the environment
and conditions of frictional contact, as well as the
surface roughness and crystal structure of the dia-
mond faces. In vacuum, diamond-on-diamond
sliding contact eventually leads to an increase in
friction from initial values of 0.1 to 1.4, with sig-
nificant surface damage occurring in the process
[77]. This can be attributed first to shearing and
fracture of local high spots, and then to the removal
under high local forces of the critical surface termi-
nating species, such as O or H. Those species, when
present reduce the surface energy, and prevent local
atomic attraction or actual bonding across the in-
terface of carbon atoms at contact asperities.
Those surface chemistries and structures of
the diamond surface that promote low frictional
properties are of major importance in bearing and
seal applications. These are presently under de-
velopment. They take advantage of the strong
bonding of diamond to its surface terminating
species, which reduces local bonding with the
contacting frictional face and reduces frictional
forces. In many applications, the chemical inert-
ness and low surface energy of diamond can also
prevent the build-up of deposits that would nor-
mally reduce seal life.
5.2. Diamond electrodes
The use of doped diamond electrodes in elect-
rochemical analysis and in electrochemical syn-
thesis and destruction is an area of increasing
research interest and potential industrial impor-
tance. CVD diamond has three advantages over
conventional graphite electrodes used in electro-
chemistry, according to Angus et al. [78]. These are
chemical stability and robustness, large potential
window for water stability, and low background
current densities. Boron doping at low concen-
trations produces p-type semi-conductivity at an
acceptor level 0.37 eV above the valence band [79].
At high B concentrations, in the range of 1020 –1021
cm3 , diamond becomes a semi-metal with con-
ductivities as high as 103 X cm. These conduc-
tivities can be reached with B/C ratios in the gas
greater than about 500 ppm [78].
Conductive CVD diamond can be grown on
substrates such as Si, W, and Mo by doping with
boron in the gas phase. Angus et al. [78] has sur-
veyed the literature relating the ratio B/C in the
gas phase to B/C in the grown diamond. He found
a wide range of rates of incorporation for different
deposition processes, but the amount of B incor-
porated in the diamond was usually proportional
to the ratio in the gas for a given deposition ex-
periment. In general, boron incorporation was
greater in hot filament depositions than in micro-
wave growth, and was greater on (1 1 1) surfaces
than (1 0 0) surfaces. It is speculated that there may
be more activated species on the surface of the
diamond in microwave deposition, which reduces
the concentration of adsorbed boron on the sur-
face. The presence of oxygen also greatly reduces
the incorporation ratio of boron, apparently by
oxidation of boron to B2 O3 [80].
Highly conductive diamond is desirable for
electrosynthesis and electrodestructive applica-
tions, while electrochemistry can utilize diamond
of lower conductivity. Further, higher quality di-
amond with less incorporation of non-diamond
carbon produces a broader window of water sta-
bility for electrochemistry (Fig. 7).
This figure shows the difference in range of
water stability in electrolysis experiments in 0.5 M
H2 SO4 for high quality diamond, low quality
 L.K. Bigelow, M.P. D’Evelyn / Surface Science 500 (2002) 986–1004 997

Fig. 7. Effect of type of electrode (diamond/platinum/HOPG), and of diamond quality on electrode potential range for water
decomposition. (from Angus et al. [78], reproduced by permission of the publisher of New Diamond and Frontier Carbon Tech-
nology, MYU K.K.). The horizontal axes show the electrochemical potential applied to the diamond electrodes relative to a
standard hydrogen reference electrode (SHE). The current flow (vertical axes) increases sharply at the potential at which breakdown
of the aqueous electrolyte into hydrogen (negative potential) or oxygen (positive potential) takes place. Note that the high quality
diamond electrode (a), has the widest range of negative and positive potential before breakdown of the aqueous solution (1.25 to
þ2.3 V). The low surface energy of the hydrogen-terminated surface of diamond may contribute to this behavior. The potential
range observed with lower quality diamond (b) is less than with high quality diamond, probably because the defects on the surface
are graphitic in behavior, and are more reactive. The platinum (c) and HOPG (d) electrodes result in the breakdown of the
electrolyte at lower potential limits than either of the diamond types. The importance of this behavior of diamond electrodes is that
electrochemical methods can be used to react and destroy many chemicals, such as contaminants in waste water, before actually
decomposing the water itself. Electrochemistry with CVD diamond electrodes therefore has potential as a method of waste water
treatment. CVD diamond electrodes can also precipitate heavy metal from waste water, and can power a number of chemical
reactions in water, other solutions, and molten salts, while often exhibiting much greater resistance to attack and corrosion than
other materials. Diamond electrodes can be used to detect and measure a much larger range of dissolved substances than electrodes
of other materials by measuring the breakdown characteristics of the compounds dissolved in the aqueous electrolyte. Examples of
substances that have been detected via diamond electrodes include polyalkylene glycol, dopamine, azide, sulfa drugs, and hista-
mines.

diamond, platinum, and highly oriented pyrolytic
graphite (HOPG). In this type of experiment, one
varies the electrical potential and measures the
current that flows as substances dissolved in an
aqueous solution break down or dissociate or as
the water itself is dissociated into hydrogen and
oxygen. Electrochemical reactions of dissolved
species can only be observed usefully if the water it-
self is not decomposing! For high quality diamond,
an aqueous solution evolves hydrogen at a poten-
tial of 1.25 V and oxygen at a potential of þ2.3
V, a much wider range than the corresponding
998 L.K. Bigelow, M.P. D’Evelyn / Surface Science 500 (2002) 986–1004
values of 0.0 and þ1.5 V observed with a platinum
electrode. Non-diamond carbon, which is present
in larger amounts in lower quality diamond re-
duces the range of accessible potentials to near
that observed with HOPG. The high reaction
stability of the diamond surface has been attrib-
uted to hydrogen termination [81] which, as dis-
cussed in the previous section, leads to a low
surface energy and hydrophobic behavior. How-
ever, even diamond surfaces that have been oxi-
dized by local generation of oxygen at high
positive potentials exhibit high sensitivity and
stability, which makes diamond suitable as an
electrode for electrochemical determinations under
oxidizing conditions, for example, dopamine in
ascorbic acid [81]. The importance of diamond
quality in resisting attack during electrochem-
ical processes is pointed out by DeClements and
others, following the results of their research on an-
odic polarization in concentrated KOH [82]. Low
quality diamond films are attacked at the grain
boundaries, but separate high quality film samples
showed no signs of corrosion or morphological
damage under the same experimental conditions.
Diamond electrodes can be used for analyzing
dissolved compounds that cannot be detected with
other electrodes. This is possible because the water
is dissociated at a lower potential with these other
electrodes than are the dissolved compounds. For
example, the presence of polyalkylene glycol can
be analyzed using diamond electrodes, whereas
platinum electrodes cause electrolysis of the water
before oxidation of the polyalkylene glycol, and
the reaction potential for the glycol is not reached
[78]. With diamond, the peak heights are linear
with the glycol concentration. The wide potential
window and low baseline current of diamond
make this possible.
Other electroanalytical applications have been
demonstrated on diamond that are unreliable or
impossible on glassy carbon (GC). Some of these
are detection or measurement of azide, polyam-
ines, sulfa drugs, histamines, and NADH, a co-
enzyme used in several dehydrogenase-based
biosensors [81].
A great deal of interest and research activity is
focussed on commercially developing the electro-
chemical processing capability of diamond elec-
trodes, both for, (1) the destruction of pollutants
and for, (2) the generation of desireable chemical
compounds and elements. For example, efficient
fluorination of 1,4-diflurobenzene using boron
doped diamond has been demonstrated by Okino
et al. [83]. The diamond electrodes show much
higher stability in this process than Pt or HOPG
[83]. Compton has recently showed diamond is
an excellent material for the sonoelectrochemical
production of hydrogen peroxide from oxygen
with its combination of mechanical properties and
electrode characteristics [84]. The effect of hydro-
gen plasma pre-treatment of the diamond surface
in sonoelectrochemical processing of dioxygen has
also been studied [85].
Industrial applications of the diamond elec-
trode technology are under active development for
pollution control, for example in treatment of
waste water effluent from industrial plants. The
oxidation of organic compounds to CO2 at the
surface of a diamond electrode has been demon-
strated with a current efficiency greater than
85% [86]. Experiments on the oxidation of phenol
(an example of an aromatic compound), and acetic
acid (an example of an aliphatic compound)
were successful in reducing these contaminants to
low levels (less than 3 ppm in the case of phenol).
The electrodes were not damaged or poisoned
after weeks of operation. Cyanide can also be
eliminated, especially in the presence of chlo-
ride ions, which help to catalyse the oxidation re-
action.
Large area (50
60 cm2 ) boron doped dia-
mond electrodes on substrate materials such as
titanium, zirconium, niobium, tantalum, tungsten,
and graphite have been developed [87]. Examples
of boron doped diamond electrodes produced on
these materials by the Fraunhofer Institute are
shown in Fig. 8. Further research to understand
the details of the oxidation and reduction reactions
at the diamond surface will lead to electrodes op-
timized for industrial applications. The reduction
of cadmium and copper from aqueous solutions
has also been demonstrated [88]. These toxic
metals precipitate out as fine particulates which do
not adhere to the diamond electrode, thus per-
mitting easy disposal of the precipitated metals,
and re-use of the electrodes. The clean surface that
 L.K. Bigelow, M.P. D’Evelyn / Surface Science 500 (2002) 986–1004 999

Fig. 8. Boron doped diamond electrodes on titanium, tantalum, niobium and graphite base material produced by the Fraunhofer
Institute, Braunschweig. (Reproduced by permission of New Diamond and Frontier Carbon Technology—from vol. 9, pp. 229–240.)

remains is a direct result of the low surface energy
and chemical stability of diamond.
6. Future research directions
Some opportunities for improved fundamental
understanding of diamond surface and growth
chemistry have already been given. In this section
we enumerate some novel applications.
6.1. Negative electron affinity
Diamond has the property that with certain
types of surface termination, such as clean or hy-
drogen terminated surfaces, the conduction band
minimum lies above the vacuum level at the sur-
face, and the diamond exhibits negative electron
affinity. This means there is no activation barrier
to ejection of an electron from the surface, in
contrast to most other materials, which require an
applied potential at the surface or a high temper-
ature to initiate electron emission into space. This
behavior has created considerable research interest
[89–91] because it could potentially lead to highly
efficient cold cathode emission devices, and prod-
ucts such as large area flat panel displays. The
market for field emission displays is potentially
very large market because the devices would be
bright (‘‘sun visible’’) and highly energy efficient.
However, the performance of diamond in field
emission display development to date has been
disappointing because the density of emission sites
has been too low, and the emission current has
also been too low. A factor in this is the lack so far
of an effective way to n-type dope the diamond to
support significant emission from NEA surfaces or
from impurity based conduction sites. Nanotubes
appear at present to be the most promising ap-
proach to field emission sources for flat panel
displays.
6.2. Bio-sensors and detectors
The surface and electronic properties of dia-
mond also make it a candidate for the develop-
ment of new bio-sensors and detectors, and
advanced diagnostic equipment such as in vivo
blood chemistry monitors. First of all, the extreme
inertness, especially of the hydrogen terminated
1000 L.K. Bigelow, M.P. D’Evelyn / Surface Science 500 (2002) 986–1004
diamond surface, means that diamond is the most
inert and least likely to be rejected of all materials
for both structural and sensor applications in the
body. This bio-inertness and low tendency to in-
duce blood clots has been reported many times.
Significant in vivo testing of products has not yet
begun, but there is growing activity to develop
diamond based body replacement parts, such as
permanent hip joint replacements and heart valve
components. This is an area for important future
research and commercial competition.
Troupe et al. have reported on diamond based
glucose sensors. The diamond electrodes have to
be boron doped to provide adequate conductivity
for use in this application [92]. The diamond was
doped by implantation with boron and annealed at
850 °C to provide adequate surface conductivity
(with a calculated 1
1020 atoms/cm3 at the
surface). Stability of the diamond and the boron
in the lattice was measured by immersion in de-
ionized water for four weeks at 37 °C. The con-
centration of boron in the water reached only
4 ppb, indicating virtually no leaching of boron
from the diamond surface. Several designs were
tried. A device using an oxidized, activated dia-
mond surface, with specially selected adsorbed
bio-molecules to assist in the surface reactions
provided the best sensitivity for glucose detection.
A range of new bio-agent and chemical detec-
tors have been proposed, based on the wide band
gap of diamond, in combination with its inert
and stable surface. A recently demonstrated tech-
nology with the potential to identify a wide
range of absorbed species on the diamond sur-
face and thereby detect dangerous bio-agents or
process-critical chemical constituents is called
charged-coupled deep level transient spectroscopy
(Q-DLTS). The principle is that adsorption of any
compound on the surface of the diamond will re-
sult in a change in the electronic states at the di-
amond surface, which can be characterized by its
effect on the transient response to imposed voltage
pulses. The voltage pulses may be applied by an
electrode grid on the surface of the diamond. The
surface potential energy and the density of trap-
ping centers will be characteristically different with
the adsorption of different species on the surface
of the diamond, and thus can be detected and
Fig. 9. Schematic of detector grid and design for proposed
Q-DLTS chemical and bio-agent sensor using CVD diamond.
This detector is based on the effect that adsorbed species on the
surface of a diamond film have on the transient response to
electrical pulses applied to the surface. Cyclic bias pulses are
applied to the surface via a grid, changing the charge state of
the surface and of subsurface electronic trapping centers. The
surface charge is measured by integrating the current that flows
as the surface charge decays when the bias voltage is turned off.
The charging and decaying behavior is affected by adsorbed
molecules on the surface, which can be differentiated and
identified by their characteristic effects and decay signatures.
The frequency of the pulses is varied to produce curves of
charge versus pulse duration that are characteristic of the sys-
tem and the adsorbed species.
quantified by analyzing the response to the voltage
pulses. This surface analysis technique has been
demonstrated in a detector using DLC on quartz.
Adsorbed species (isopropyl alcohol and water)
can be differentiated by the transient response to
pulses from the array of inter-digital electrodes on
the surface [93]. A schematic of one design concept
using CVD diamond is shown in Fig. 9.
It is expected in this method that the effect of
different adsorbed species on the surface will be
independent of each other, so that many agents
can be detected by a single detector. Much work
remains to characterize and catalog the effect of
each adsorbate on diamond made with different
surface textures, surface treatments, and surface
terminations. However, the Q-DLTS method is
sensitive enough to detect a charge of 2000 elec-
trons on the surface, and may be able to detect
airborne contaminants in the parts per trillion
range. Bio-agents are typically transmitted by
 L.K. Bigelow, M.P. D’Evelyn / Surface Science 500 (2002) 986–1004
aerosols. The Q-DLTS sensor is sensitive to par-
ticles. It is hoped that bio-agents such as viral
agents, toxins and spores may be detectable di-
rectly or indirectly by developing a database of
characteristic and differentiable effects on the
transient response of the diamond. Such systems,
designed with compact diamond detector sub-
strates and with an analytical database on-board
for each species of concern, should be easily por-
table. This would make the devices ideal for indi-
vidual use for working near hazardous chemicals,
or for field use to monitor and protect military and
civilian personnel against chemical or biological
agents.
The potential uses for disease control, hospital
and industrial air quality monitoring, and chemi-
cal process monitoring and control are staggering,
if the technology proves to be as sensitive as pro-
jected and also manufacturable and cost effective.
Surface science will play a key role in identifying
the important surface variables and treatments to
optimize sensitivity for different types of chemicals
and agents of interest. An added feature, which is a
benefit of the bulk properties of diamond is the
possibility to heat the detector, using a resistive
grid beneath the substrate or by another method.
This would desorb the adsorbed species from the
surface so the device could continuously monitor
and update the environment. It would become re-
useable over long periods in service.
7. Conclusion
A detailed understanding and application of
surface science is essential to the present industrial
use of diamond and to the development of the
exciting new products diamond will make possible.
An example of an important practical problem
overcome by surface studies was reviewed earlier,
the problem of metallization of diamond. Until the
factors that affect the surface energy of diamond
were understood and the solutions applied, a great
deal of difficulty and inconsistency was experi-
enced by those trying to bond patterned or blanket
metallization to diamond. However, with appro-
priate pre-treatment, excellent adherence and reli-
able product performance has been achieved. It is
1001
certain that the same principle will apply to the
development of many other new diamond prod-
ucts, including the selected ones we have reviewed
here.
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