Inorganic Materials, Vol. 38, No. 7, 2002, pp. 677–682. Translated from Neorganicheskie Materialy, Vol. 38, No.

7, 2002, pp. 820–825.

Original Russian Text Copyright © 2002 by Golubenko, Kosinova, Titov, Kuznetsov.

Chemical Vapor Deposition of Boron Nitride

in the B–N–H–He–O System
A. N. Golubenko*, M. L. Kosinova**, V. A. Titov**, and F. A. Kuznetsov**
* Novosibirsk State University, ul. Pirogova 2, Novosibirsk, 630090 Russia
** Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 3, Novosibirsk, 630090 Russia
e-mail: marina@che.nsk.su
Received June 21, 2001

Abstract—Thermodynamic analysis of boron nitride (cubic, hexagonal, and wurtzite forms) chemical vapor
deposition in the B–N–H–He–O system was carried out for temperatures from 300 to 2100 K, a total pressure
of 1.33 Pa, residual pressures from 1.33 × 10–5 to 0.133 Pa, and a wide range of He : B3N3H6 ratios. The con-
ditions for the deposition of c-BN, h-BN, or mixtures of BN and B2O3 (solid or liquid) were established. Oxy-
gen impurities are shown to have a significant effect on the temperature stability limits of the condensed phases
involved.

INTRODUCTION shown that c-BN can be deposited at temperatures

The cubic and hexagonal forms of boron nitride find
various applications in modern technology. One
method widely employed to produce BN coatings is
chemical vapor deposition (CVD). Typical precursors
in BN CVD are mixtures of ammonia and volatile
boron compounds, such as B2H6 [1], BF3 [2], BCl3 [3],
and B10H14 [4]. In recent years, a great deal of attention
has been paid to precursors whose molecules contain
both boron and nitrogen atoms, e.g., borazine (B3N3H6)
[5, 6], its derivatives [7, 8], and alkylaminoboranes [9].
A number of earlier works focused on thermody-
namic analysis of BN CVD in the systems B–N–Cl–H
[2], B–N–F–H, B–N–H–F–Si–C–O [2, 10], B–N–O–
C–Cl–H [11], and B–N–Si–H–Cl [12] with the aim of
optimizing CVD conditions—deposition temperature,
total pressure, and vapor-phase composition. Note that
those studies were only concerned with graphite-like
hexagonal boron nitride, h-BN, considered to be the
only thermodynamically stable condensed phase under
standard conditions (298.15 K, 1.013 × 105 Pa). Other
forms of boron nitride—cubic, c-BN, and wurtzite-like,
w-BN—were thought to be stable only at high temper-
atures and pressures. Recent experimental data on the
thermodynamic properties of the cubic and wurtzite
phases [13–16] suggest, however, that c-BN is a stable
phase at low temperatures and atmospheric pressure. In
earlier studies, we used the thermodynamic data for the
cubic, hexagonal, and wurtzite forms to analyze BN
CVD in the systems B–N–H–Cl–He [17] and B–N–H–
He [18, 19] for temperatures from 800 to 2300 K, total
pressures from 1.33 to 1.013 × 105 Pa, and a wide range
of vapor-phase compositions. In this way, we identified
CVD conditions for individual BN polymorphs. It was
below 1804 K. Above this temperature, CVD yields
h-BN. Wurtzite BN was shown to be unstable over the
entire range of CVD conditions studied.
At the same time, Sal’man et al. [20] and Kosinova
et al. [21] were able to produce h-BN films at low dep-
osition temperatures in the B–N–H–He system. The
discrepancy between thermodynamic predictions and
experimental results was tentatively attributed to the
influence of impurities, e.g., oxygen or water vapor,
which might be present in the starting reagents or intro-
duced into the vapor phase in the course of deposition
[22]. Thermodynamic analysis of the B–N–H–Cl–He–O
system [22] indicates that minor amounts of solid or liq-
uid (above 723 K) B2O3 may be codeposited with BN if
the vapor phase contains more than 10–3 mol % O2 .
In this work, we use thermodynamic analysis of
boron nitride CVD in the B–N–H–He system
(B3N3H6 + He) in the presence of trace levels of oxygen
to assess the effect of oxygen impurity on the stability
regions of the condensed phases involved.
THERMODYNAMIC CALCULATIONS
Our purpose was to find the compositions of the
vapor and condensed phases at equilibrium. In calcula-
tions, we minimized the Gibbs energy of the system
using the procedure described elsewhere [17]. We
examined different B3N3H6 + He vapor mixtures with
oxygen impurities at temperatures in the range 300–
2100 K. The conditions considered were typical of the
BN CVD process: total pressure in the system ptotal =
1.33 Pa, residual pressure in the reactor pres = 0.133 Pa
(0.79 mol % nitrogen and 0.21 mol % oxygen). The

0020-1685/02/3807-0677$27.00 © 2002 MAIK “Nauka /Interperiodica”

678 GOLUBENKO et al.
compositions of the starting vapor mixtures were
expressed as the He : B3N3H6 molar ratio R. We took
into account 61 vapor species and 11 condensed
phases: h-BN, c-BN, w-BN, B(cr), B2O3(cr), B2O3(l),
HBO2(cr), HBO2(l), H3BO3(cr), H3BO3(l), and H2O(l).
We supposed that the compositions of the condensed
phases were constant and that the vapor phase obeyed
the ideal-gas law.
As the input thermodynamic information, we used
∆f H°(298 K), S°(298 K), and C °p (T) data for individual
substances. The set of self-consistent thermodynamic
data and the software used were taken from the Elec-
tronic Materials Properties Database [23], which was
configured using, for the most part, data from [24].
RESULTS AND DISCUSSION
The results of thermodynamic analysis are dis-
played in Fig. 1 as a section of the B–N–H–He–O
(B3N3H6 + He + oxygen impurity) phase diagram in
which composition–temperature stability fields are out-
lined for ptotal = 1.33 Pa and pres = 0.133 Pa. As apparent
from these data, the set of condensed phases in equilib-
rium with the vapor phase depends strongly on deposi-
tion conditions, especially on the deposition tempera-
ture Td . Note that there is a very narrow stability field of
h-BN above 1718 K. Single-phase c-BN can be depos-
ited between 1250 and 1718 K. At lower temperatures,
BN is codeposited with liquid (724–1250 K) or solid
(below 724 K) B2O3 . The temperature stability limits of
the condensed phases are seen to depend little on R.
As would be expected, the equilibrium composition
of the vapor phase depends on temperature, total pres-
Td , K
2000
B(cr)
h-BN + B
vapor
c-BN + B h-BN
1500
c-BN
1000 c-BN + B2O3(l) B2O3(l)
500 c-BN + B2O3(cr) B2O3(cr)
0 20 40 60 80 R Taking into account this information, we examined
Fig. 1. Stability fields of condensed phases in CVD from
B3N3H6 + He mixtures at ptotal = 1.33 Pa and pres =
0.133 Pa.
sure, and, to a lesser extent, on R (at small R). Figure 2
shows the partial pressures of vapor species as func-
tions of temperature for R = 0 and 1. Only those vapor
species were included whose partial pressure exceeded
10–7 Pa.
Under the conditions examined, the dominant vapor
species are H2 , N2 , and He (Fig. 2b). Their partial pres-
sures vary little with temperature. Throughout the tem-
perature range studied, one of the major oxygen-con-
taining vapor species is H2O, both in the c-BN + B2O3
and c-BN (T > 1250 K) fields. The concentrations of
other oxygen-containing vapor species (HBO2 , HBO,
B2O3 , B2O2 , and BO) increase sharply with tempera-
ture, attaining the highest levels in the temperature
range of single-phase BN deposition. The vapor phase
also contains trace levels of NH3 (below 700 K) and BO
(above 1200 K).
Our results demonstrate that the films deposited
from the vapor phase containing oxygen impurities
(from 0.38 at. % at R = 0 to 3.5 at. % at R = 100) consist
of BN and B2O3 at temperatures ranging up to 1250 K.
For example, at R = 0, pres = 0.133 Pa, and an oxygen
content of 0.38 at. %, the bulk composition of the
deposit varies insignificantly with temperature (Table 1).
Increasing the He : B3N3H6 ratio in the vapor phase
increases the B2O3 content of the BN + B2O3 deposit
(Table 2).
It follows from our results that the deposition condi-
tions and the purity of the starting reagents are critical
for the preparation of single-phase c-BN. Even small
amounts of oxygen in the starting vapor mixture lead to
codeposition of c-BN and B2O3 . It seems likely that the
presence of liquid or solid hexagonal B2O3 in the
deposit, on the one hand, impedes c-BN nucleation and,
on the other, favors the formation of h-BN.
Assuming that the residual gas in the CVD system is
the major source of oxygen impurity, we analyzed the
reported data on BN low-pressure CVD in different
systems with the aim of assessing the effect of residual
pressure on the composition of the deposit. Unfortu-
nately, the residual pressure and the purity of the
reagents used are rarely specified even in recent publi-
cations (Table 3). As is evident from Table 3, there is no
way to predict unambiguously which polymorph, c-BN
or h-BN, will be deposited at a particular residual pres-
sure in the CVD reactor. At the same time, it can be
seen that deposition at pres ≥ 0.133 Pa and temperatures
of 500–923 K onto Si, Fe, SiO2 , or sapphire substrates
yields, for the most part, h-BN or h-BN + c-BN films.
At low residual pressures (pres < 1.33 × 10–4 Pa), the
CVD process yields either c-BN or c-BN + h-BN films.
BN CVD from borazine at temperatures in the range
300–2100 K, ptotal = 1.33 Pa, and pres from 1.33 × 10–5
to 0.133 Pa. The results are displayed in Fig. 3. It can
be seen that the residual pressure has a significant effect
INORGANIC MATERIALS Vol. 38 No. 7 2002