CHEMICAL VAPOR DEPOSITION (CVD)
AND INFILTRATION (CVI)
Theodore M. Besmann, David P. Stinton, Richard A. Lowden
and Woo Y. Lee
INTRODUCTION
Chemical vapor deposition (CVD) takes
advantage of gas phase reactants to form
desired phases in situ. CVD reactions are not
unlike those described in Part Four, where
ceramic materials are prepared from vapor
phase precursors. The significant difference
is that in CVD the resultant material is in the
form of a coating deposited on a substrate.
Thus, the CVD process takes advantage of
the lowered energies for phase formation
afforded by nucleation and growth on existing
surfaces.
Chemical vapor infiltration (CVI) is simply
CVD on the internal surfaces of a porous pre-
form and has been used to produce a variety
of developmental materials. The most useful
application of CVI is to infiltrate continuous
filament preforms, taking advantage of the
relatively low stress CVD process.
CHEMICAL VAPOR DEPOSITION (CVD)
In CVD, reactive vapor phase precursors flow
over a heated substrate, react, and form a
single- or multi-element coating. One of the
great attractions of CVD is the ability to form
pure, high melting-point materials at rela-
tively low temperatures. For example, TiB2
Carbide, Nitride and Boride Materials Synthesis and Processing. Edited by Alan W. Weimer.
Published in 1997 by Chapman & Hall, London. ISBN 0 412 54060 6.
A. W. Weimer (ed.), Carbide, Nitride and Boride Materials Synthesis and Processing
© Chapman & Hall 1997
22
melts at 3598 K (3325 DC), yet can be produced
at 1300 K (1027 DC) or lower via the reaction
TiCl4 + 2BCl3 + 5H2 -+ TiB2 + 10HCI (22.1)
Another advantage of CVD is its throwing
power, which allows hidden surfaces to be
coated, provided diffusion or convection can
transport reactants to the area. Chemical
vapor deposition has also demonstrated
high material deposition rates, which can
reach tens of micrometers per hour or
greater.
HISTORY OF CVD
Chemical vapor deposition is an old tech-
nology, with the first systematic investigation
being reported in the 1920s (von Arkel
and de Boer, 1925). A patent filed in 1890
by de Lodyguine (1893) on preparing tung-
sten by deposition on carbon lamp filaments
from WCl 6 reduced by hydrogen, however,
may be the first literature reference to the
process. Initially, CVD was simply a tool
for preparing highly pure samples of high
melting temperature materials, particularly
metals. As noted above, preparation tem-
peratures can be substantially below a
material's melting point, thus preventing
548 Chemical vapor deposition and infiltration
contaminating reactions or dissolution of con-
tainer material.
More recently there has been a remarkable
increase in the activity in CVD. Initial applica-
tions were largely related to improving the life
and performance of cutting tools. Closer to the
present the greatest growth has been in the
production of semiconductor devices, a sub-
ject which does not fall under the purview of
this book. Currently, there are over a dozen
suppliers of coating consumables and a half-
dozen suppliers of CVD and physical vapor
deposition (PVD) systems. More than 30
companies also offer coating services. The
majority of today's market for CVD coatings,
however, is found in two specific areas:
aircraft engine components and metal cutting
tool inserts. Other markets, such as auto-
motive parts, are very small in comparison
(Abraham, 1988). A listing of the non-oxide,
non-electronic ceramic coatings produced by
CVD is given in Table 22.1.
SYSTEM CONFIGURATIONS
The configuration of CVD systems is largely
tied to whether the system's use is bench
research, development or production scale.
The issues of reactant depletion (particularly
in larger systems), temperature control and
fluid dynamics in CVD reactors have largely
driven their design. Still, much of CVD reactor
design today is largely empirical, although the
use of fluid flow modeling is becoming more
common.
Cold-wall reactors
Cold-wall CVD reactors are so designated
because the substrate is heated directly, leav-
ing the reactor chamber walls relatively cool
(Figure 22.1). The advantage of such systems
is that there is little or no deposition on the
reactor walls which allows for high precursor
efficiency and low reactant depletion. These
systems usually depend on either resistance
or radio-frequency induction heating. For
resistance heating the substrate can be
heated directly or the substrate holder can be
heated. In a similar manner for induction heat-
ing, the substrate can couple directly with the
radio-frequency field or can be placed on a
holder which can act as the susceptor. An
advantages of resistance heating are that the
power supply can be relatively simple. The
advantages of radio-frequency heating are
that no electrical penetrations into the reactor
are required and there is no concern about the
effect of the possibly corrosive reactant gases
on electrical leads. General problems in CVD
are buoyancy rolls and other thermal con-
vective effects which create differential gas
phase species concentrations that result in
non-uniform coatings. Reduced pressure
often mitigates or eliminates this problem.
Hot-wall reactors
Hot-wall reactors are simpler to construct,
generally only requiring the use of a resis-
tance-heated furnace surrounding a reactor
tube (Figure 22.1). All heated surfaces, how-
ever, provide areas for deposition making
control of gas composition difficult. Obtaining
uniform substrate temperature is easy, pro-
vided the substrate is small or the furnace
can maintain a uniform temperature zone
within which the substrate resides. Three-
zone furnaces are often used for CVD because
it is possible to control the outer zones such
that a uniform temperature profile is main-
tained across the central zone.
Bench-scale reactors
Research and development CVD reactors are
relatively easy to construct, requiring flow
meters, a furnace system and an exhaust
system. Two simple, radio-frequency induc-
tion-heated cold-wall systems, one vertical
and the other horizontal, are illustrated in
Figure 22.2. Buoyancy rolls are more likely in
the vertical configuration with downward
flow.