J. Phys. Chem.

1994,98, 7073-7082 7073

Elementary Reaction Mechanism for Growth of Diamond (100) Surfaces from Methyl Radicals

Sergei Skokov, Brian Weiner,t and Michael Frenklach’

Department of Materials Science and Engineering, The Pennsylvania State University,
University Park, Pennsylvania 16802

Received: March 21, 19940

Chemical reactions of methyl radicals on (100) diamond surfaces have been investigated theoretically. Quantum-
mechanical calculations a t the PM3 semiempirical level were performed on a series of small- and large-size
clusters to explore possible reaction steps responsible for diamond growth a t conditions typical of chemical vapor
deposition. Among a variety of possible chemisorption sites considered, surface dimer radicals not only were
the most favorable on kinetic grounds but appeared to be the only type capable of sustaining the subsequent
incorporation of adsorbed methyl groups into the diamond lattice. Surface migration of H atoms, radical sites,
and chemisorbed CHz groups proved to be important for diamond growth. A new reaction mechanism of
diamond (100) growth from methyl radicals is proposed which offers a plausible explanation for the experimentally
observed fast and smooth growth of diamond surfaces. The mechanism consists of two principal features,
conversion of dimer sites into bridge sites and surface migration of bridge sites toward continuous bridge chains;
it does not require any particular order of dimer formation but establishes the governing role of surface diffusion.

Introduction is kinetically unstable under the conditions of diamond CVD.16

In spite of substantial progress in technological aspects of
chemical vapor deposition (CVD) of diamond films,’ the
underlying chemical reaction mechanism of diamond growth
remains poorly understood. Generally, Cl-hydrocarbons have
been assumed to be the sole growth species, basically following
a one-carbon-at-a-timepicture. Recent isotope labeling experi-
ments,23 reporting that about 90% of deposited diamond originates
with methane and its radicals, support this point of view. A
series of less direct experiments4echo this conclusion.
Proposals have been made by invoking CH5+ ions5 and CH4
molecules6 but without suggesting possible reactions. The
mechanism suggested by Tsuda et al. that implicated either
gaseous methyl cations7or the presence of a positive charge on
the surfaces faces two major difficulties. First, the critical role
of ions or electrostatic charges has not been corroborated by
experiment, and second, a prohibitively strong repulsion exists
among methyl groups required to be adsorbed at three neighboring
sites of the (1 11) surface. This repulsion has been computed at
different levels of theory: empirical, using Brenner p~tential;~
quantum semiempirical, using AM1 10 and ASED-MOII methods;
and local density approximation12 (LDA). It was determined in
these studies that the chemisorption energy per methyl group is
decreased by 11-23, 29, and 28 kcal/mol, respectively, when
CHI groups are placed at three adjacent (1 11) surface sites. No
stable states for a (1 1 1) surface totally covered by CH3 groups
were found in the calculations of Mehandru and Anderson.”
While the adsorptionof three neighboring methyl groups seems
to be essentially forbidden, the adsorption of two neighboring
methyl groups meets only a moderate r e p u l ~ i o n . I ~ -The~~
Abstraction of an H atom from one of these CH2 sites will be
followed by a @-scission and ultimate desorption of the
-CH=CH2 group. This sequence of events limits the rest of
the proposed CH3-basedmechanisms of diamond growth on (1 1 1)
and (1 10) surfaces.17-19
The most promising in terms of mechanistic understanding
appears to be the growth on (100) surfaces. The growth on (100)
surfaces by incorporationof CIH, hydrocarbonradicals has been
advocated from considerations of surface morphology.20.21
HarrisZ2proposed a specific reaction mechanism in which the
growth is initiated by the addition of CH3 to a radical created
on a dihydride surface. After an H atom is abstracted from the
adsorbed CH3 and another H from the neighboring surface site,
the two radicals combine, forminga next-layer diamond site. The
principal difficulty with this mechanism is the strong repulsion
exerted on the incoming CH3.23 In fact, the dihydride surface
itself, due to the repulsion between closely spaced hydrogen atoms,
was suggested to be thermodynamicallyunstable at typical CVD
conditions and to be reconstructed to a monohydride phase.24
Such reconstruction was observed e~perimentallyz”~and sup-
ported by theoretical c a l c u l a t i o n s . ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
On the basis of these considerations,it has been proposed23J4
that the growth takes place on a reconstructed, (100)-(2 X 1)
surface, initiated by the addition of CH3 to a radical site of the
surface dimer unit. Following an H abstractionfrom the adsorbed
CH3, the produced CH2 adradical is incorporated into the diamond
lattice by opening the dimer and forming a bridge between the
dimer carbons. We will refer to such a site as a CH2-bridge site
or simply, in the context of the present study, a bridge site. In
one of the proposed mechanism^,^^ the CHI adradical forms a

-
formation of a C-C bond between these two methyls encounters
a substantial potential energy barrier, 50 kcal/mol, if only one
of the two is activated by H abstraction.13 Such relatively large
C-C bond with the second carbon site of the dimer simultaneously
with the cleavage of the dimer bond. This one-step reaction was
found to possess a substantial potential energy barrier. In the
barriers are typical for the addition of a primary hydrocarbon other me~hanism,’~ the reaction proceeds in two steps: dimer
radical to a hydrogen-saturated carbon at0m.1~9~5When both opening through @-scission,
methyl groups undergo H abstraction, the C-C bond should be
formed as quickly and irreversibly as is typical of radical
~ombinati0n.I~ However, the produced - C H & H r adspecies
~~ ~~

t Department of Physics, The PennsylvaniaState University, DuBois, PA

15801.
*Abstract published in Advance ACS Abstracts, June 15, 1994. and methylene bridging the former dimer carbon atoms,
0022-3654/94/2098-7073$04.50/0 0 1994 American Chemical Society
7074 The Journal of Physical Chemistry, Vol. 98, No. 28, 1994
To avoid lengthy descriptions, we will refer to reaction l a as
dimer @-scission,reaction l b as methylene bridging, and the
sequenceof reactions 1a and 1b as “insertion”into dimer (we will
keep insertion in quotation marks to distinguish it from a carbene-
type insertion). This two-step reaction mechanism appears to be
energetically and kinetically feasible, as determined by using
empirical,34 quantum ab initio,35 and quantum semi-
empirical16potentials; for instance, the respectivepotential energy
barriers obtained in these calculations for the second step are 3.9,
8.8, and 12.3 kcal/mol. The feasibility of this reaction is further
supported by the thermodynamic stability of the dimer mono-
radica1,16*32defying in this case the @-scissionrule.
However, reaction 1 alone cannot explain the propagation of
diamond growth, as it only “fills in” the dimer sites and does not
address the growth between the nascent bridge sites. Two
proposals were made regarding this issue. In the mechanism of
Harris and Goodwin,35 after one CH3 group is “inserted” into a
dimer, another CH3 is chemisorbed to a nearby radical of the
next-row dimer and following an H abstraction forms a bridge
site next to the first one. However, as will be shown later, once
CH3 is chemisorbed to a dimer radical, it is more likely to “insert”
into that dimer than to bridge to the adjacent bridge site. To
resolve this difficulty, Zhu et al.36suggested that after the dimer
@-scissionstep and before the bridging, surface radical migration
H H
c
H
d‘‘
/ \ /H
Cd
SH2
cd
H \ ~
cd
c
H,
cd
/ \
Cd
/H tH2 H\
cd cd +d
/H H\.
Cd
takes place, followed by the eventual addition of the lone
chemisorbed CH2 group at the initial bridge site. That reaction
2 is facile was based on a relatively small endothermicity, 6 kcal/
mol, computed36 using MM3 molecular mechanics.3’ However,
the analysis indicates that reaction 2 is not effective in competing
with reaction 1b. Furthermore, neither the mechanism of Harris
and Goodwin35 nor that of Zhu et al.36can resolve the difficulty
arising from CH3 being adsorbed not at the nearby site but at
the remote site of the dimer, as shown below
HH H. H empirical potential fitted to PM3. The form and parameters of
The configuration formed in such a case of two bridge sites
separated by a void site has the geometry of a dihydride (100)
site and, as mentioned above, exerts a large steric repulsion on
the adsorption of CH3. Thus, the occurrence of reaction 3 should
result in a highly defective film or cease the growth altogether,
contrary to the experimental evidence reviewed by Harris and
Goodwin35and Zhu et A remedy to such disruptive growth,
suggested by the latter authors,36is the removal of undesirable
bridge sites by the reverse of reaction 1. This requirement,
however, should substantially slow down the growth, again
contrary to experiment. Another possibility would be to “fill in”
thevoid sites by speciesother than methyl radicals. For instance,
Imai et al.38performed PM3-levelquantum chemical calculations
Skokov et al.
Figure 1. Schematic diagram of a diamond (100) surface model used in
the MD simulations. Gray-shaded circles represent quantum mechani-
cally described carbon atoms, white circles empirical carbon atoms,
hatchedcirclesempirical carbon atoms of the thermostat, and black circles
empirical carbon atoms held in fixed positions throughout the simulations.
and found no potential energy barriers for the addition of CH or
CHI to a CllHl8 cluster simulating such a dehydrogenated void
site. Yet, the concentrations of these species are expected to be
orders of magnitude lower than that of CH3 in the deposition
zone of hot-filamentreactors,3w2Le., under the conditionscapable
of producing high-quality diamond films. In any event, we will
leave these possibilities to future studies and focus here on methyl
radicals.
The brief analysisgiven aboveshows that the growth of diamond
(100) surfaces by reactions of methyl radicals remains an open
question. The objective of the present study was to systematically
investigate the underlying chemistry and identify the most
plausible reactions responsible for the growth of diamond. Our
analysis employed for this purpose was based on semiempirical
quantum-chemical calculations, the level of theory well suited
for establishingreaction mechani~ms.~3 Specifically,we analyzed
the kinetics of the following gas-surface and surface reactions:
adsorption of CH3 at a series of possible surface sites; migration
of H atoms, surface radicals, and chemisorbed CH2 groups; and
(2)
the growth of adjacent chains of bridge sites. The results indicate
that it is imperative to consider migration of H atoms and CH2
groups for the growth of diamond. The latter process, in
particular, appeared to be responsible for the smoothness of the
growth.
Method
The reaction rate coefficients were calculated using non-
variational transition-state theory (TST).& Similarly to our
previousstudy of acetylenereactions on diamond (100) surfaces,16
the input data were obtained by quantum-chemical calculations
performed on two kinds of model clusters. The surface was
modeled by a composite cluster illustrated by the schematic
diagram in Figure 1. The central gray-shaded atoms in the top
three layers were described by a PM3 semiempirical quantum-
chemical H a m i l t ~ n i a nand
~ ~ the surrounding atoms by an
the latter were the same as reported previously.32 The basic
quantum-region clusters employed in the present study, CmH52
and C45H60, are shown in Figure 2. These quantum clusters were
embedded into 320- and 545-atom empiricalclusters,respectively.
The geometries of the CmH52 and C45Ha clusters were chosen
to accommodate different types of surface-active sites used in
analysis. A variety of such sites were created from the two surfaces
shown in Figure 2 by incorporation of appropriate atomic steps.
Minimum-energy configurations of the model surfaces were
obtained by unrestricted Hartree-Fock (UHF) calculationsusing
a combined-force molecular dynamics (MD) method, described
and tested by us previously in studies of diamond (100) surface
reconstr~ctions,3~ structures of oxygenated ( 100) surfaces,46and
reactions of acetylenewith (100) surfaces.16 In thesecalculations,
the bottom-layer atoms, shown in black in Figure 1, were held
at fixed bulk positions. Periodic boundary conditions were
Growth of Diamond (100) Surfaces
I I I I
Figure 2. Quantum-mechanically described C40H52 (top) and C45Hm
(bottom) clusters representing diamond (100) surfaces. White circles
represent top-layercarbon atoms, gray circlesbottom-layercarbon atoms,
and black circles hydrogen atoms. Surrounding empirical atoms are not
shown for clarity.
implementedby the minimum imageconvention in two dimensions
across planes perpendicularto the ( 110) directions. Temperature
control was accomplished by the method of Berendsen et al.?'
maintaining a prescribed temperature, 1200 K in the present
simulations, of the four near-bottom layers shown hatched in
Figure 1.
Transition-state geometries were found by constrained opti-
mization, where only certain atoms were allowed to relax. The
choice of relaxed atoms was dictated by the specific surface site
and reaction of interest. The other surface atoms were fixed at
the positions of the minimum-energy configuration obtained in
the MD simulations for the initial model surface. The use of
large-size clusters is beneficial in the determination of potential
energy minima; however, due to the constraints imposed by
boundary conditions of the MD simulations, vibrational frequen-
cies cannot be evaluated from these clusters reliably. To obtain
normal frequencies, the calculations were repeated using small
clusters,modeled after C9H12 examined in our previous studies.16f2
In most cases, all atoms were allowed to relax in these calculations.
Transition-state geometries for both large- and small-cluster
models were found to be close to each other, thus justifying the
use of the MOPAC48vibrational frequencies from the smaller
cluster. Low frequencies that originated from internal rotations
were substituted by appropriate free rotations with rotational
constants evaluated from computed moments of inertia. The
ability of PM3 to reproduce vibrational frequencies was tested
by Coolidge et al.?9 who found that PM3 predictions for
hydrocarbons are within a reasonable accuracy, 9.3%.
Thus, in the TST calculations, the potential energies of ground
and transition states were those obtained in large-cluster calcula-
tions and the corresponding vibrational frequencies were taken
from small-cluster calculations. Such an approach is a com-
promise between the usually adopted, ad-hoc hypothesis of
The Journal of Physical Chemistry, Vol. 98, No. 28, 1994 7075
chemical similaritySoof gas-phase and gas-surface reactions and
accurate first-principal calculations of gas-surface reaction rate
coefficients, the latter still being unrealistic for large-sizeclusters.
Results and Discussion
Before we begin the analysis, there are several issues that need
to be addressed. First, although the present method is not limited
to any specific set of conditions, for the sake of clarity, the present
study will focus on the conditions typical of diamond CVD:35~51*52
temperature 1200 K, [HI = le9mol/cm3, and [CH3] =
mol/cm3.
Second, the fraction of surface radical sites, r, can be
expressed41953 as the ratio of kb: to k&, where the latter are rate
coefficients of H abstraction,
and H addition,
reactions, respectively. Here c d represents a carbon atom of a
diamond surface. At 1200 K,the value of kFb is on the order
of54-573 X 10l2cm3 mol-' s-l and that of kzd is about 10-fold
larger.58-61 Thus, under the control of reactions 4 and 5, the
of a given surface site to be a radical is r -
fraction of surface radical sites or, equivalently, the probability
0.1.
Third, for the concentrations of gaseous H atoms and CH3
radicals adopted above, the per-site rates of H-abstraction,
- 3 x 103, R& - -
H-addition, and CH3 combination with a surface radical are
3 x 104, and ~22 1 x 103 s-1,
respectively, assuming a rate coefficient 0F4 1 X 10'3 cm3 mol-'
s-I for the radical combination. These per-site rates provide critical
time scales against which other surface reactionswill becompared.
Thus, for instance, surface reactions much faster than 3 X lo4
s-1 can be assumed to maintain the state of partial equilibrium.
Under such conditions,the knowledgeofexact rateconstant values
becomes less critical.
Finally, as mentioned in the Introduction, the two carbon atoms
of the (100)-(2 X 1) dimer unit behave rather inde~endently3~
of each other, and hence the probability of two sites chosen at
--
random both being radicals, or the probability of having a double-
radical site, is62 r2 0.01, and the per-site formation rate of such
a site is rR,Hb, 3 x 102 s-1.
Adsorption of C H 3 on (100) Surfaces. As a result of a
continuous evolution of the growing surface, an incoming methyl
radical can encounter numerous possible combinations of indi-
vidual surface sites. A series of such circumstances, those of
interest to the present study, were examined. Figure 3 depicts
them-combinations of dimer, bridge, and lone dihydride
sites-arranged into three groups: A-C. In group A, a dimer
radical to which CH3 is being added is paired with a dimer, bridge,
or dihydride site, hydrogenated or dehydrogenated. Similarly
structured is group B, where the adsorption of CH3 takes place
at a bridge radical site. Group C is designed to study the addition
of CH3 to a lone dihydride radical site.
Chemisorption energies, potential energy barriers, reaction
equilibrium constants, and reaction rate constants obtained for
the cases listed in Figure 3 are reported in Table 1. As explained
in the preceding section, the reactions enthalpies and potential
energy barriers were computed by employing large clusters with
the combined-force molecular dynamics. The vibrational fre-
quencies used in the determination of the reaction-rate and
equilibrium constants were obtained in static calculations
performed on small-sizeclusters,those depicted in Figure 4: cluster
I was used for the addition of CH3 to sites A, cluster I1 to sites
7076 The Journal of Physical Chemistry, Vol. 98, No. 28, 1994 Skokov et al.

TABLE 1: Enthalpies of Adsorption (AH), Potential Energy

Barriers (E),Adsorption (&a) and Desorption (4)Rate
Constants,and Equilibrium C~~tants ( ) for the Reactions
%
of CHSwith Different Sites on a Diamon (100) Surface at
1200 K
HH surface AH, E, kadm KW
site' kcal/mol kcal/mol cm3 mol-' s-l kd, s-l cm3 mol-'
cluster I -74.7 0.0 1.0 x 2.8 x
1013b 103 3.6 x 109
A1 -73.6 0.0 1.0 x 1013b 5.3 x 103 1.9 x 109
A2 -75.4 0.0 1.0 x 1013b 2.2 x 103 4.5 x 109
A3 -65.7 0.0 1.0 x 1013b 1.5 x 105 6.7 x 107
A4 -73.7 0.0 1.0 x 1013b 5.1 x 103 2.0 x 109
A5 -66.2 0.0 1.0 x 101136 1.2 x 105 8.3 x 107
A6 -74.1 0.0 1.0 x 1013b 4.3 x 103 2.3 x 109
cluster I1 -25.8 15.9 4.0 X lo6 4.3 X lo8 9.3 X 10-3
B1 -24.2 14.8 6.4 X lo6 3.8 X 10' 1.7 X 10-'
B2 46.8 2.4 1.2 x 109 5.4 x io6 2.2 x 102
B3 10.9 24.2 1.2 X los 1.8 X 10'3 6.7 X 10-9
B4 -30.9 8.6 8.6 X lo7 3.2 X 10' 2.7 X 10-I
B5 9.5 22.6 2 . 4 ~
105 2.1 x 1013 1.1 x 10-8
B6 -27.8 13.9 9.4 X 106 1.2 X 10' 7.8 X 10-2
cluster 111 -66.7 1.8 1.5 X lo9 1.7 X lo3 8.8 X 105
c1 -34.5 8.3 9.8 X 10' 7.8 X lo7 1.3
B1 c2 8.1 29.3 1.5 X 104 6.7 X 10" 2.2 X 10-8
c3 -25.8 10.0 3.9 X lo7 1.5 X lo9 2.6 X 10-2
c4 -39.3 7.2 1.6 X 10' 1.7 X lo7 9.4
HH c5 -16.9 12.6 1.5 X lo7 1.9 X 10'0 7.9 X lo"
B2 a The site notations A-C are those of Figure 3; AH and E listed for
these sites are computed using large-size surface models while the
vibrational frequencies are obtained with small-size clusters 1-111,
*
respectively,depicted in Figure 4. The value is assigned to that typical
B3 of gas-phase radical recombination reactions.54

B4

B5
HH
I11 x
HH
B6

Figure 4. Small-size clusters used in the calculations of vibrational

HH frequencies. White circles represent carbon atoms and black circles
hydrogen atoms on reacting carbon atoms. Hydrogen atoms saturating
dangling bonds of the lower-level carbon atoms are not shown for clarity.

HH dimer's neighbor. The value of 75.4 kcal/mol, calculated for

HH
Figure 3. Combination of surface sites considered for methyl adsorption:
(a, top) CH3 is added to a radical of the dimer positioned on the left; (b,
middle) CH3 is added to a radical of the bridge site positioned on the left;
(c, bottom) CHI is added to a radical of the lone dihydride carbon unit
positioned in the middle.
B, and cluster I11 to sites C. For comparison, the results obtained
with clusters 1-111 are also listed in Table 1.
The computed energy of CH3 chemisorption to a dimer radical
varies from 65.7 to 75.4 kcal/mol, depending on the nature of the
case A2 representing adsorption of CH3 on the ideal (100)-(2 X
1) surface, is in good agreement with corresponding values
obtained in ASED-MO calculations of Mehandru and Anderson,63
77.9 kcal/mol, and MM3 calculations of Zhu et al.,36 76.1 kcal/
mol, and is somewhat lower than the MM2 result of Harris and
Goodwin,35 80.9 kcal/mol. Similar to the preceding comparison,
our chemisorption energy of 65.7 kcal/mol for site A3 is lower
than the 70.9 kcal/mol reported by Harris and Goodwin35 for the
same type of site. All the chemisorption energies for dimer sites
are markedly smaller than that of a typical C-C bond in
hydrocarbons, largely due to the repulsion among H atoms of the
CH3 group and H atoms of the surface.
Inspection of Table 1 reveals one of the most significant
findings: the absence of potential energy barriers for the addition
of CH3 to all of the considered dimer radical sites, irrespective
of the neighboring site. Such a situation has been implied in a
kinetic analysis35 but without proof. On the MNDO level this
reaction was found23 to possess a sizable barrier, 33 kcal/mol,
and a low chemisorption energy, 30 kcal/mol, results that are
Growth of Diamond (100) Surfaces
due to the overestimation by the MNDO potential of steric
repulsion in the vicinity of van der Waals distances.64 The post-
MNDO methods, AM1 and PM3, correct for this deficiency.64
As a further test, a molecular dynamics simulation was carried
out for theadsorption of CH3 at the A2 dimer site. A freegaseous
CH3radical was placed 3 A above the dimer radical of the (100)
surface, which was preliminarily equilibrated at 1200 K for a
duration of 500 fs. During the MD simulation, the temperature
of the four bottom layers was maintained at 1200K by the method
of Berendsen et al.,47 while the top-layer surface atoms and the
atoms of the incoming methyl radicals were allowed to move
adiabatically. It was found that adsorption takes place even with
the initial kinetic energy of CH3 set to zero. The kinetic energy
of the incoming CH3 and the order of the forming C-C bond
computed during the MD simulation are shown in Figure 5 .
Inspection of Figure 5 shows that the kinetic energy peak of
about 50 kcal/mol corresponds to the creation of the new bond
between the surface radical and CH3. After that, almost all the
excess energy dissipates during the first several tens of femto-
seconds, though full thermal equilibration occurs on a picosecond
time scale. A similar picture was observed for the adsorption of
a superheated gas-phase CH3 radical onto a room-temperature
(100) diamond surface.65 These results show that the rate of
energy transfer for the adsorption of CH3 even at temperatures
as high as 1200 K is much larger than the expected rate of CH3
thermal desorption (101-102 s-l; see, e.g., ref 54), thus indicating
that under the conditionsof diamond CVD the methyl adsorption
f desorption reaction should be in thermal equilibrium with
bulk diamond. The latter consideration underlies the use of
transition-state theory for evaluation of the corresponding rate
coefficients assuming the high-pressure limit.
On the basis of the above results, the rate constant for the
adsorption of CH3 at a dimer radical site, regardless of its neighbor,
was assumed to be 1013cm3 mol-' s-l, typical for barrierless radical
recombinations.54 The rate constants for the reverse direction,
i.e. for CH3 desorption, were calculated from the principle of
detailed balancing. The reaction equilibrium constants were
computed, as described earlier, using vibrational frequencies
obtained for a prototype reaction of CH3 with a small cluster,
C9H13(cluster I in Figure 4), and enthalpy changes from
corresponding large-cluster calculations. Although the environ-
ment of the dimer radical affects the desorption rate, as
demonstrated by the results reported in Table 1, the computed
residence times for the adsorbed CH3 are usually on the order
of the characteristic time of H abstraction, meaning that CH3
adsorbed at dimer sites have sufficient time for "insertion" into
dimers.
Unlike dimer sites, adsorption of CH3 at the bridge (B-type
sites) and dihydride(C-type sites) radical sites encounterspotential
energy barriers (see Table 1). The vibrational frequencies for
the calculation of the rate and equilibrium constants listed in
Table 1 for these sites were obtained using analogous reactions
of CH3 with two small clusters, C10H17 and C ~ H Ishown ~ , as
clusters I1 and 111,respectively, in Figure 4. In these calculations,
the distance between the top-layer atoms was kept at 2.52 A to
mimic the diamond (100) surface structure.
The local environment of the bridge and dihydride sites was
found to be critical. The chemisorption energy varies from -46.8
to 10.9 kcal/mol for the bridge sites and from -39.3 to 8.1 kcal/
mol for the dihydride sites and the potential energy barrier from
2.4 to 24.2 kcal/mol for the bridge sites and from 7.2 to 29.3
kcal/mol for the dihydride sites (Table 1). Of particular interest
in the present study are the void sites (B3 and B4 in Figure 3).
Adsorption of CH3 at these sites must be ineffective for diamond
growth due to the much reduced adsorption rates (and in the case
of site B3 also due to a small equilibrium constant and hence a
short residence time). The reason for this is again the strong
The Journal of Physical Chemistry, Vol. 98, No. 28, 1994 7077
repulsion among H atoms of the CH3 group and the surrounding
surface H atoms.
To explore the repulsion in greater detail, we examined the
barrier to rotation of CH3 adsorbed at site B3 around the C-C
axis. The potential energy as a function of the rotational angle
is shown in Figure 6. As can be seen in this figure, the rotational
barrier was found to be 6.9 kcal/mol, which is significantly higher
than the barrier of 1.8 kcal/mol calculated at the same level of
theory for the relative rotation of methyl groups in a free gaseous
ethane molecule (for comparison, the experimental value of the
latter is 2.9 kcal/mol").
The general mechanistic conclusions we draw from the above
results are as follows. The adsorption of methyl groups at dimer
surface radicals, A-type sites, should be essentially uninhibited
and independent of the nature of the neighboring sites. The
adsorbed CH3 groups are relatively stable, yet their lifetimes are
comparable to and sometimes lower than the time scale of H
abstraction, the latter being the necessary step toward incorpora-
tion of the CH3 into the diamond lattice. In light of this, the
surface reactions discussed below may play a significant role in
determining the fate of the chemisorbed CH3. In contrast to that
at the A sites, CH3 adsorption at the B and C sites is both
kinetically too slow and thermodynamicallyunstable to contribute
significantly to diamond growth.
Migrationof H. Migration of a hydrogen atom between carbon
sites appeared to play an important role in surface rearrangements
during acetylene adsorption onto a diamond (100)-(2 X 1)
surface.16 It is reasonable to anticipate that such H migrations
are rather common in surface chemistry of diamond growth. In
the context of the present investigation, we examined two types
of H migrations. First are the following migrations of H atoms
between carbon sites of the surface itself
H H H H
Heats of formation, potential energy barriers, and rate and
equilibrium constants computed for these reactions are reported
in Table 2. As a point of comparison, the barrier of 7.0 kcal/mol
calculated for reaction 9 is somewhat lower than the 11.2 kcal/
mol obtained for a similar reaction on the MNDO level.23 We
also note that the sum of reactions 7 and 9 is reaction 8, expecting
then A H 7 + A H 9 = A H 0 and K7K9 = Ks. However, the enthalpy
balance is off by 0.8 kcal/mol and the corresponding equilibrium
constants product by about 20%. These deviations are the result
of slight differences in the constraints of surface models used in
the calculations of the individual reactions.
Inspection of these results indicates that the forward and reverse
rates of reactions 7-9 are much larger than the respective per-
site rates of H and CH3 addition reactions, R.Hddand RFZ. This
implies that under the conditions of diamond CVD, these H
migration reactions should be in a state of partial equilibrium,
and which particular configuration prevails is determined by the
corresponding equilibrium constant. On the contrary, due to a
large potential energy barrier, 66.3 kcal/mol, reaction 6 appears
7078 The Journal of Physical Chemistry, Vol. 98, No. 28, 1994
to be very slow and thus insignificant on the time scale of diamond
CVD. The large barrier of this reaction is due to the large
separation between the neighboring dimer carbon atoms that the
H needs to traverse.
The immediate implication of the fast H migrations, reactions
7-9, concerns the discussed above expression r = KtJkfIdd. For
equivalent surface sites, it defines the fraction of surface radical
sites as well as the probability of an individual site to be a radical.
However, the fast H migrations distort the local balance of
reactions 4 and 5. As a result, although still representing the
average fraction of radical sites, r no longer determines the
individual site probability. Based on thevalues of the equilibrium
constants reported in Table 2 for reactions 7-9, the probability
of being a radical decreases from dihydride to bridge to dimer
sites. That is, once an A3 or A5 radical site is formed, it
immediately converts to a less reactive radical site B1 or C1,
respectively; or stated in numerical terms, the rate of CH3
adsorption to an A3 or A5 site is reduced by a factor of 5.5 X
101or 4.4 X 102due to reaction 7 or 8, respectively. This implies
that the adsorptionof CH3occurs with a higher relative frequency
at biradical sites A4 and A6. A similar conclusion was reached
by Harris and Goodwin.35
The second type of H migration reactions considered in the
present study is transfer of H from adsorbed CH3 to the
neighboring surface radical site:
fH3 H /‘tlH2
The computed reaction heats of formation, potential energy
barriers, and rate and equilibrium constants are listed in Table
2. The principal result is that the rates of reactions 10-13 are
much faster than the per-site rates of H abstraction, R:b, and
H addition, RZd,indicating that these reactions will be in a state
of partial equilibrium under the conditions typical of diamond
CVD.
Reaction 12 is of particular interest to the present study. CHJ
adsorbed near a bridge site provides a situation conducive to
filling the void. In fact, the reactant of reaction 12 is the key
intermediate of the “trough” mechanism proposed by Harris and
Goodwin.35 According to their mechanism, abstraction of an H
from the adsorbed CH3 forms a CH2 adradical which then
combineswith the neighboringsurface bridge radical; this is shown
as the left-hand-side reaction sequence in Figure 7. However,
the present results indicate that the rate of the H migration from
the adsorbed CH3 to a neighboring surface radical, reaction 12,
is about 106times faster than the rate of H abstraction. The CH2
adradical formed in this case “inserts” into the dimer and not into
thevoid site, as illustrated by the right-hand-side reaction sequence
in Figure 7. The CH2 “insertion” steps, reactions l a and lb, are
as fast16J4.35as reaction 12, and hence the entire sequence of
reactions between the chemisorbed CH3 site (reactant in Figure
7) and the product (B3 site, the final product of the right-hand-
Skokov et al.
:I: ;
g :
* 0.4
0.2 -
0.0 ;
0 2 ” 6 0 0 8 0 0 1 m
Tim (fs)
Fipure 5. Rtsults of an adiabatic molecular dynamic simulation of CHJ
approaching an A2 site: (top panel) kinetic energy of CH3 in the center-
of-mass coordinate system; (bottom panel) bond order between a
chemisorbedradical and a surfacecarbon, defined as a sum of the squares
of density matrix elements connecting the two carbon atoms.
side reaction sequence in Figure 7) is in a state of partial
equilibrium. At the present level of theory, theoverall equilibrium
constant is about 6 (or 11 using the thermodynamic data of ref
3 3 , showing that only a small part of the chemisorbed CH3
groups will follow the ‘trough” mechanism of Harris and
Goodwin35 and most will lead to the creation of void sites.
The relatively high rates predicted for reactions 10 and 11
mean that the H migration will dominate over the H abstraction
in converting the adsorbed CH3 into a CH2 adradical. In other
words, the incorporation of CH3 adsorbed at a dimer site does
not necessarily require the abstraction of an H atom from CH3
itself, which is much slower than H abstraction from a tertiary
dimer carbon.54
Finally, reaction 13 provides an interesting possibility of filling
a void site, by following a &scission that forms a doubly-bonded
=CH2 group which then adds to a nearby surface radical, as will
bediscussed later in the text. However,theinitial step, adsorption
of CH3 to a C-type radical that forms the reactant of reaction
13, is about 6 orders of magnitude slower than the addition of
CH3 to a dimer radical, at an A-type site, as discussed in the
preceding subsection. Therefore, reaction 13 is also unable to
explain the rate of diamond growth observed experimentally.
Migration and Combination of Surface Radicals. As already
mentioned in the Introduction, in order to overcome the difficulty
of filling the void sites, Zhu et a126 suggested migration of surface
dimers, reaction 2. The key element of their proposal is the
reaction
which is presumed to compete with and thus to prevent the
“insertion” of the chemisorbed CH2 into the dimer, reaction 1,
and thereby to impel the bridging over the void by the CH2. Our
PM3 calculations resulted in a considerable potential energy
barrier, 37 kcal/mol, and consequently the rate of this radical
migration, reaction 2, is several orders of magnitude lower than
therateoftheCH2 “insertion”intodimer, reaction 1. Nonetheless,
the reaction rates of both forward and reverse directions are
sufficiently fast to uphold the state of partial equilibrium. What
Growth of Diamond (100) Surfaces The Journal of Physical Chemistry, Vol. 98, No. 28, 1994 7079
TABLE 2 Enthalpy Changes (AH), Potential Energy Barriers ( E ) , Forward (kf)and Reverse (kr)Rate Constants, and
Equilibrium Constants (I&) for Surface Reaction on a Diamond (100) Surface at 1200 K
small-cluster model
large-cluster model base model
reaction no. AH, kcal/mol E, kcal/mol kf,s-l k,, s-l K, AH, kcal/mol E, kcal/mol in Figure 4
1a' 12.4 15.3 1.6 X 1Olo 8.0 X 1Olo 2.0 X 10-l 6.0 16.0 I
2 7.7 37.0 8.8 X lo5 2.2 X lo7 4.0 X 0. 45.2 VI
6 0. 66.3 1.1 1.1 1. 0. 18.7 I11
7 -9.3 30.1 4.1 x i o 6 7.5 x 104 5.5 x 101 0. 18.7 I11
8 -14.6 23.6 6 . 2 ~107 1.4 ~
105 4 . 4 ~io2 0. 18.7 111
9 -4.5 7.0 6.6 X 1Olo 1.O X 1O'O 6.6 0. 14.9 IIIC
10 -10.4 29.8 4.6 X lo6 6.0 X lo4 7.7 X 10' -6.5 32.8 I
11 -8.8 16.3 1.8 X lo9 1.3 X lo8 1.4 X 10' 9.9 12.3 IV
12 3.9 12.9 7.4 x 109 1.1 x 1011 6.7 x 10-2 9.9 12.3 IV
13 12.1 14.1 4.5 x 109 2.0 x 1012 2.3 x 10-3 9.9 12.3 IV
15 -43.0 0. 8.9 X 10" 2.2 X lo6 4.0 X lo5 -36.0 0.8 IIId
16b 34.1 62.0 8.O 8.8 X lo7 9.1 X 1od 46.3 59.2 I11
17 -13.6 0.7 7.5 X 10" 1.2 X 10" 6.3 -29.4 4.0 VI
18c 24.0 36.3 1.5 x 107 6.5 x 109 2.3 x 10-3 19.8 29.1 V
19 -28.3 3.2 2.9 X 10" 1.1 X lo8 2.6 X lo6 -19.8 9.3 V
20 -13.4 14.9 2.2 X lo9 4.2 X lo8 5.2 -19.8 9.3 V
From ref 16. The units of k, are cm3 mol-' s-l and of K mol cm-3. C The distance between the two top carbon atoms was fixed at 2.7 A. The
distance between the two top carbon atoms was fixed at 2.521. The parameters of this reaction are those calculated for the reverse of reaction 1b.

Figure 7. Comparison of the trough mechanism35 (left-hand-side

8, reactions) with the one initiated by H migration (right-hand-side
t reactions).

TABLE 3 Enthalpy Changes (AH), Potential Energy

Barriers ( E ) , Forward (kf)and Reverse (kr)Rate Constants,
and Equilibrium Constants (Kq)for Reaction l b at 1200 KI
AH, E,
kcal/ kcal/
adjacent sites mol mol kf,s-l k,,s-1 K,
monohydridedimersb -24.0 12.3 6.5 X lo9 1.5 X lo7 4.3 X lo2
bridgingCH2groups 4.5 31.7 1.9 X lo6 6.8 X lo8 2.8 X lP3
bridging CH2 and CH' -6.6 20.5 2.1 X lo8 7.0 X lo8 3.0 X 10-l

"0 30 60 90 120 150 180
Angle (degree)
Figure 6. (Top panel) CH3 adsorbed at a B3 surface site. The white
circle represents a carbon atom of the chemisorbed CH3 group, gray
circles represent surfacecarbon atoms, and black circlestop-layer hydrogen
atoms. Hydrogen atoms saturating dangling bonds on the cluster edges
are not shown for clarity. (Bottom panel) Cluster relativepotential energy
versus the angle of rotation of CH3 around the C-C axis; the maximum
in energy corresponds to the H of CH3 passing through the surface H.
makes this reaction essentially ineffective is its slight endo-
thermicity, 7.7 (PM3, see Table 2) or 6 (MM3, ref 36) kcal/mol,
compared to the moderate exothermicity of reaction lb, -24.0
(PM3, see Table 3) or -28.3 (MM3, ref 35). Thus, with the
reactant configuration of reaction 2 as a starting point, a rough
estimate for the ratio of the fluxes toward the formation of the
The calculations of the vibrational frequencies were performed on
cluster V in Figure 4. Reaction 1b in the present study. The data listed
are from ref 16.
bridge site and toward the product configuration of reaction 2
is Klb/K2, which is equal to 1 X lo4, based on the present level
of theory, or 1 X 105, using the MM3 results.35J6 Considering
also that the lifetime of the dimer radical next to a bridge site
is lowered due to the H migration, as established earlier in this
paper, we must conclude that reaction 2 does not resolve the
problem of filling the void sites during diamond CVD. We note
that theendothemicity of reaction 2 is consistent with (and actually
caused by) the row-zigzag rearrangement of the dimer pattern
studied by us previously.32
To complete the analysis, we also considered the following
combinations of surface radicals,
7080 The Journal of Physical Chemistry, Vol. 98, No. 28, 199‘4
H
H\ +H (16)
Cd cd cd
H H H H
H
‘d& aCd / \
c
cd‘H e H
Cd +d \ ’c \c,/” (17)
Heats of formation, potential energy barriers, and rate and
equilibrium constants computed for reactions 15-17 are reported
in Table 2. Reaction 16 is a possible contributor to the
reconstruction of dihydride surface sites to a monohydride (100)-
(2 X 1) surface dimer structure;23 however, the rate of this reaction
was calculated to be very low, 8 s-l. The present predictions of
62.0 and 59.2 kcal/mol for the potential energy barrier of reaction
16 are somewhat higher than the previous estimate of 49.7 kcal/
mol at the MNDO level.23 Reaction 15 on the other hand, as
expected, was calculated to be very fast, 10I2s-l. Limited by
dehydrogenation of the dihydride surface sites, the formation
rate of a biradical by two consecutive H abstractions is, as
estimated earlier, -3 X 102 s-1. This indicates, by comparison
to the much slower rate of reaction 16, that reaction 15 is a more
likely candidate for participation in the reconstruction. Reaction
17 is another viable possibility for the combination of surface
radicals into dimers: this reaction is kinetically fast and
thermodynamically shifted to the right. Its existence was also
observed in our previous MD simulation^.^^ Reaction 17 may
play an important role in surface migration of CH2 groups, as
discussed next.
Migration of Surface CH,. Invoking additional reactions
introduced above-chemisorption of CHS on different surface
sites, migration of H atom, and migrationof surface radicals-does
not resolve the problem of filling the void sites. Indeed, with a
perfect (100)-(2 X 1) dimer surface as a starting point, CH3 will
be ”inserted” into dimers by reactions 10-12, la, and lb. After
some time, when the surface is covered by dimer and bridge sites,
the rate of CH3 adsorption at dimer sites will start to fall due to
the influence of the H migration, reactions 7 and 8. Finally, the
surface will be covered by bridge sites separated by the voids.
Adsorption of CH3 at the void sites is ineffective due to steric
repulsion, as discussed previously in the text. A possible recovery
from such a situation was suggested by Zhu et to be the
etching (e.g., by the reverse of reaction 1) of undesirable bridge
sites. However, with reaction 2 being ineffectivetocompete with
the formation of bridge sites separated by voids, as discussed in
the preceding subsection, the removal of bridge sites does not
create viable alternatives for filling the voids.
Searching for a possible solution to this problem, we discovered
that migration of CH2, as shown below,
not only is feasible on kinetic and thermodynamic grounds (see
Table 2) but also provides the most likely explanation for the
formation of smooth surfaces observed experimentally. Each of
these reactions is much faster, in both forward and reverse
directions,than the H addition to a surface radical. This indicates
that reactions 18 and 19 should be in a state of partial equilibrium
at theconditions typical of diamond CVD. The overallequilibrium
Skokov et al.
...
Figure 8. Illustration for the growth of a continuous chain of bridge sites.
constant, KlsK19,is equal to about 6, showing that the sequence
of these two reactions is shifted toward a bridge-next-to-bridge
configuration, i.e., toward the formation of a smooth surface. We
smaller than unity, for example K18K19 -
note that even if the overall equilibrium constant happens to be
0.1 (and we do not
expect the accuracy of the present method to produce deviations
larger than 1-2 orders of magnitude), the sequence of reactions
18 and 19 is still capable of filling the void sites, although with
a somewhat reduced efficiency. The only requirement for the
CHI migration is the creation of a biradical at the void site,
which is not formidable in light of the probability for such an
Occurrence discussed earlier in the text.
Another reaction that may contribute to the surface migration
is the addition of chemisorbed CH2 to a dimer radical as shown
below
H H
This reaction is fast in both directions, and its equilibrium at
1200 K is shifted to the right (see Table 2).
Let us now demonstrate that the migration of CH2 is capable
of sustaining the growth of a continuous chain of bridge sites. We
begin with a chain of dimer sites, shown as the initial structure
in Figure 8. Formation of surface radicals, adsorption of gaseous
CH3, migration of H atoms, and “insertion” of chemisorbed CH3
into dimers create bridge sites separated by the voids. A possible
fragment of such an evolving chain is shown as the second structure
in Figure 8. Adsorption of CH3 at one of the carbon atoms of
the void site between the bridges is extremely slow, as established
earlier in this study. After a period of time required for both of
the void H atoms to be abstracted, the CH2 bridge in the center
migrates to the left, following reactions 18 and 19, and the two
surface radicals-one of the newly formed bridge and the other
of the left-behind lone dihydride unit-combine according to
reaction 17. The dimer formed in this manner undergoes the H
abstraction and addition of a gaseous CH3 with the eventual
conversion of this dimer into a bridge. This elementary-reaction
sequence that creates a group of three consecutive bridge sites
from the initial configuration of two bridges separated by a void
can be viewed as a filling-in-the-void overall step. When the
dimer unit located to the right of the chain fragment shown in
Figure 8 converts to a bridge, occurring either simultaneously
with or consequentlyto the previously described sequenceof events,
its CH2 group undergoes a similar migration toward the already
established bridge chain, and so on.
The above discussedprocess can beviewed as surface “diffusion”
of bridge sites, whose rate is limited by the H additions and H
abstractions. The precise interaction among these processes and
the resulting pattern formation shall be the subject of a future
investigation. An immediate conclusion though can be made
regarding the effect of temperature. The surface migration of
CH2 hasa higher activationenergy than H abstraction, and hence
a decrease in reaction temperature should slow down the mobility
of CH2 faster than the activation of surface sites. This predicts
that a decrease in temperature should lead to a stiffer yet reactive
Growth of Diamond (100) Surfaces
Figure 9. Schematic diagram for a configuration undergoing reaction
1bbetween twodihydrideunitsona (100)surface. Whitecirclesrepresent
carbon atoms and black circles hydrogen atoms.
surface, forming an increasing number of lattice defects and
eventually non-diamond carbon, in agreement with experiment.’
In summary, the general implication of the CH2 migration
suggested by the present study is that the reaction mechanism
of diamond (100) growth consists of two principal features:
conversion of dimer sites into bridge sites and surface migration
of the bridge sites toward continuous bridge chains. This
mechanism does not require any particular order of dimer
formation (which may include reactions of gaseous species other
than methyl, like, e.g., acetylene16)but establishes the governing
role of surface diffusion. This conclusion is in harmony with
those drawn from experimental 0bservations.6~In fact, consider-
ing that the fast reactions of H atoms kinetically limit the
migration of CH2 groups to rather small distances, our results
are in remarkable accord with van Enckevort et al.67that “surface
diffusion over a distance far less than ...2 4 nm ...is rate limiting
in { 100) diamond growth”.
Growth of Adjacent Chains of Bridge Sites. The analysis of
surface reactions presented above is applied to the conditions of
a single chain of dimers and bridges on a diamond (100)-(2 X
1) surface. However, during the growth process, as the dimers
are being converted into bridges over the entire surface, one can
no longer assume that reactions take place in isolation-along a
single chain-and the influence of the neighboring-chain bridge
sites must be taken into account.
Of particular interest in the present study is the effect of
hydrogen repulsion exerted on the CH2 group forming a bridge
site, reaction lb, by the CH2 groups of the adjacent bridge sites
as shown in Figure 9. Table 3 presents the results of our
calculations for a case of completely hydrogenated sites, as shown
in Figure 9, and for a case when a hydrogen atom from one of
the adjacent bridging CH2 groups is removed. To complete the
comparison, also listed in Table 3 are the results for an undisturbed
case, computed in our previous studyl6 with adjacent sites being
monohydride dimers.
Inspection of the data presented in Table 3 indicates that with
the adjacent dimers replaced by CH2 bridges the potential energy
barrier of reaction 1b is increased by about 20 kcal/mol and the
reaction rate drops by more than 3 X lo3. Still, the absolute
values of the reaction rates in both forward and reverse directions
are relatively high, larger than the per-site rates of H addition.
What does make the difference for the growth of diamond is the
switch from being a highly exothermic to endothermic step,
manifested in the dramatic decrease, by more than 5 orders of
magnitude, in the equilibrium constant. With such a large change,
the reaction in essenceruns in reverse and thus becomes ineffective
for diamond CVD.
With one of the H atoms removed from the adjacent bridging
CH2 groups, the energy barrier is lowered and, what is more
important, the reaction step becomes exothermicagain. The value
of the equilibrium constant, 0.3, is still lower than unity but not
necessarily formidable: the rate of growth is roughly given as
rR:!KlaKlb, which is equal in this case to 0.1 X 1 X lo3 s-l X
0.2 X 0.3 = 6 s-1. We also found that it does not matter which
H atom of the three CH2 groups involved is removed, as the
decrease in repulsion in all such cases is about the same. The
repulsion is removed essentially completely’when another H is
abstracted from one of the remaining CH2 groups.
The Journal of Physical Chemistry, Vol. 98, No. 28, 1994 7081
While the full impact of the repulsion discussed above on the
growth of diamond must await a detailed stochastic analysis, the
present results are generally consistent with experimental
observations of the decreasing diamond film quality with the
increase in the growth rate. As long as the surface migration of
CH2 is much faster than the adsorption of gaseous CH3, the
aggregation of bridge sites into continuous chains should assure
smooth-surface growth. With the increase in the CH3 addition
rate (e.g., by increasing the gaseous CH3 concentration), adsorbed
CH3 begin to interfere with CHI migration and, as a result, the
growth of the next layer will proceed before all the voids are
completely filled.
Conclusions
The local environment of reactive sites significantly affects
chemisorption of CH3on diamond (100) surfaces. Chemisorption
of CH3 onto bridge and lone-dihydride-unit radicals was found
to be ineffective for diamond growth due to excessive steric
repulsion. Only dimer radical sites are capable of adsorbing
gaseous CH3 radicals with sufficient frequency and keeping them
adsorbed for a sufficient time to become incorporated into the
diamond lattice.
Migrations of H atoms from one surface site to another were
found to be much faster than the H addition and H abstraction
reactions and therefore to provide redistribution of radical sites
on the reacting surface. Thus, due to fast H migrations, the
probability of having a dimer radical near a bridge site or near
a lone dihydride surface unit is decreased by more than 1 or 2
orders of magnitude, respectively. The decreased lifetime of a
dimer radical when it neighbors a bridge site decreases the
adsorption rate of gaseous CH3 at such sites.
Migration of an H atom from chemisorbed CH3 groups to
neighboring surface radicals was also found to be faster than the
H addition and H abstraction reactions. Such H migrations
further decrease the rate of the CH3 incorporation into void sites
as compared to the CH3 “insertion” into dimers. In other words,
the present results do not support the “trough” mechanism
suggested by Harris and G ~ o d w i nto~ explain
~ the growth of
diamond.
A radical migration, reaction 2, proposed by Zhu et as an
alternative mechanism for diamond growth was found to be
ineffective to compete with the CH3 “insertion” into dimers
accompanied by the formation of void sites and thus unlikely to
play a significant role in diamond CVD.
Probably the most important finding of the present study is the
migration of CH2 groups on diamond (100) surfaces. The
migration was found to be feasible on both kinetic and thermo-
dynamic grounds and offers the most likely explanation for the
formation of smooth surfaces observed experimentally. Being
an essentialpart of the diamond growth mechanism, the migration
of CH2 can be viewed as surface “diffusion”of bridge sites, whose
rate is limited by the H addition and H abstraction reactions.
Hydrogen repulsion which is responsible for the reconstruction
of a dihydride (1 X 1) surface was also shown to impede the
“insertion” of CH2 into dimers surrounded by bridge sites. With
all of the involved carbon atoms fully hydrogenated, the CH2
“insertion” reaction is essentially prohibited. It becomes feasible
when at least one of these hydrogen atoms is removed.
Thegeneral implication of the present study is that the reaction
mechanism of diamond (100) growth consists of two principal
features: conversion of dimer sites into bridge sites and surface
migration of the bridge sites toward continuous bridge chains.
The mechanism does not require any particular order of dimer
formation but establishes the governing role of surface diffusion.
The two principal elements identified in the present study, the
conversion of dimers to bridges and the CH2 migration, are not
unique tothegrowth frommethyl radicals andarelikely to govern
the growth of diamond (100) surfaces irrespective of the specific
7082 The Journal of Physical Chemistry, Vol. 98, No. 28, 1994
nature of the gaseous growth species. For instance, the addition
of acetylene to (100) biradicals'6 not only converts dimer sites
into bridge sites but also creates chemisorbed CH2 groups ready
to migrate, according to the mechanism presented here. In this
sense, the CHI migration provides the unifying element for the
growth from different gaseous precursors.
Acknowledgment. The work was supported by the Innovative
Scienceand Technology Program of the Ballistic Missile Defense
Organization via the US. Office of Naval Research, under
Contract No. NO0014-92-5- 1420.
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