CVD
CVD
CVD
1.0
INTRODUCTION
400
401
2.0
In CVD, gaseous reactants are admitted into a reactor (see Fig. 7.1).
Near or on a heated substrate surface, a chemical reaction of the following type
occurs:
Gaseous reactants Solid material + Gaseous products
Because of the gas flows as well as the temperature used in CVD, five
important reaction zones are developed during the CVD process (see Fig. 7.2).
The properties of CVD materials are affected by the interacting processes
occurring in these reaction zones. In a CVD process, a main gas flow (the
reaction gas mixture) passes over the substrate/coating surface. For fluid
dynamical reasons, a more or less stagnant boundary layer occurs in the vapor
adjacent to the substrate/coating. During the deposition process, the
gaseous reactants and the gaseous reaction products are transported across
this boundary layer. In reaction zone 1 (see Fig. 7.2) as well as in the main
gas stream, homogeneous reactions in the vapor may occur. These reactions
may lead to an undesirable homogeneous nucleation resulting in a flaky and
non-adherent coating. In some cases however, these reactions, when not
accompanied by homogeneous nucleation, are favorable to the CVD process
(for instance CVD of Al2 O3,[1] of B13C2,[2] and of Si,[3] respectively). The
heterogeneous reactions occur in the phase boundary vapor/coating (zone 2).
These reactions determine, in many systems, the deposition rate and the
properties of the coating.
Relatively high temperatures may be used during CVD. This means that
various solid state reactions (phase transformations, precipitation, recrystallization, grain growth, for example) may occur during the process (the zones
3 - 5). In zone 4, which is a diffusion zone, various intermediate phases may
be formed. The reactions in this zone are important for the adhesion of the
coating to the substrate.
402
3.0
3.1
403
404
405
Thermodynamics
406
0
n ig
g
ni
+
+ ln P + ln
n
RT i
i =1
m
i =0
0
s
ni
RT i
The superscripts g and s refer to the gas phase and the solid phase, respectively.
The value of 0/RT for a specific substance is calculated from
0
H f0,298
G 0 H 298
0
=
+
RT
RT
RT
where:
By minimizing the quantity G/RT (or G) and using mass balance equations
as subsidiary conditions, the equilibrium composition of a system can be
calculated.
The input data in the calculations are the number of moles of the
different reactants, the total pressure, the substrate temperature, the different
substances, and their thermochemical data. From the calculations, various
quantities like the partial pressures of the vapor species, the amounts of the
different substances available for CVD, i.e., the yield, thermodynamic
functions (supersaturation, reaction enthalpies, driving force of different
processes, etc.), are obtained.
407
408
Figure 7.4. Calculated CVD phase diagram for the W - Si system. Reactants WF6,
SiH4, and H2, total pressure 0.1 Torr, H2/WF6 = 39.[9]
409
Adhesion
410
411
economy, etc. In the following, some general comments on the design of CVD
systems are given.
A CVD system is advantageously constructed in three modules:
1. The reaction gas dispensing system.
2. The reactor, including components for defining the gas flows.
3. The exhaust system containing a total pressure controller,
vacuum pump, scrubber and/or reactant recycle system.
3.6
412
413
The Reactor
The process selected and the size, shape, and number of substrates
define the type of reactor and its geometry. Two main reactor types can be
distinguished:
1. In the hot wall reactor (see Fig. 7.7), the reactor tube is
surrounded by a tube furnace. This means that the
substrates and the wall of the reactor have the same
temperature. In addition to the film growth occurring on the
substrates, film growth might thus take place on theinside of
the reactor walls. With thicker films on the reactor walls,
414
2. In the cold wall reactor (Fig. 7.8), the walls of the reactor are
cold and usually no depositionoccurs on the walls, eliminating
the risk of particles breaking loose from the walls. Furthermore,
a low wall-temperature reduces the risk of contaminating
vapor/wall reactions. In the cold wall reactor, the homogenous
reactions in the vapor are suppressed and the importance of
the surface reactions is increased. The steep temperature
gradients near the substrate surface may introduce severe
natural convection resulting in a non-uniform film thickness
and microstructure. However, with the higher flexibility of the
cold wall reactor, high cleanliness, high deposition rates
(yielding high wafer throughput), high cooling rates combined
with the needs of thickness uniformity, automatic wafer
handling and use of increasing wafer diameter, there is
tendency to more frequently use cold wall reactors in the
microelectronics.
415
416
Figure 7.9. Examples of some CVD reactors. (a) and (b) RF heated cold wall
reactors, (c) vertical hot wall reactor, (d) barrel reactor.
417
be chosen with respect to its compatibility with the specific gaseous species.
The polymerization of the oil can easily be followed by measuring its viscosity
at different times. Mechanical pumps also produce back-diffusion of oil
molecules into the system. The back-diffusion can be stopped in a trap
(zeolite trap, liquid nitrogen cold trap) just before the pump. With the current
trend of using lower pressures to create abrupt interfaces and superlattices,
diffusion (to pump hydrogen) and turbo pumps are also utilized. Finally,
external oil filtering systems reduce the wear of the mechanical pumps in
processes where solid particles are formed and transported in the vapor to the
pump.
In a CVD process, more or less toxic, explosive, and corrosive gases
are used/formed. To remove them before exhaust, scrubbers are used. The
scrubber type is appropriate to the CVD process used. Halides can easily be
neutralized in a water scrubber. Carbon monoxide and hydrogen can be burnt
in a flame. Arsine can be removed by simply heating the reactor gas in a
furnace especially arranged for this purpose (i.e., with a high efficiency for
stripping arsenic from the gas stream).
Recycling is frequently used to improve process economy. It becomes
necessary in large scale processes, where expensive reactants are utilized
and the conversion efficiency of the reactants is low. The technique of
recycling varies from process to process. A simple recycling can be achieved
in some processes by selective condensation. It can easily be applied in
systems where the component to be recycled has the highest boiling point.
In the production of boron fibers for instancewhere hydrogen and boron
trichloride are usedthe unconverted boron trichloride is condensed in the exit
stream from the reactor, while the hydrogen and the hydrogen chloride (formed
in the process) are not condensed.
3.9
4.0
The rate and arrangements of the gas flows in a CVD reactor influence
the deposition conditions considerably. In the following, some fundamentals
418
of gas flow dynamics are given. For further details the reader is recommended
textbooks in chemical engineering or other books treating transport processes.
In a gas, different states exist. In the molecular state, the mean free
path of the molecules is much longer than the dimensions of the vessel. In
the viscous state, the mean free path is much shorter than the vessel
dimensions. The viscous state can be divided into two flow regimes. The
laminar flow regime, where the flowing gas layers are parallel, is appropriate
to low gas velocities. At higher velocities, the flow becomes turbulent. The
limit between the laminar and the turbulent flow is defined by the value of
Reynolds number, Re:
where:
Re =
V D
=
=
=
=
At Re < 1100 the flow is laminar, while at Re > 2100 the flow is turbulent. The
range 1100 to 2100 is a mixed flow regime.
The Reynolds number given characterizes the flow in an isothermal
environment. In the non-isothermal environment existing in a cold wall reactor,
natural convection induces a turbulence even at low flow rates. Consider the
situation above a heated surface (Fig. 7.10). At small temperature gradients
dT/dx, the varying density of the gas along the coordinate X is compensated
by the gravitational field and no movement of the gas occurs. At larger
gradients, the gas starts to move and the laminar flow can no longer be
retained. From Fig. 7.10 it can be understood that turbulence at a heated
substrate surface may be obtained at different parts of it. For instance, when
the temperature gradient is perpendicular to the gravitational field turbulence
occurs at smaller temperature gradients than in the antiparallel case.
Different dimensionless quantities are used for identifying conditions of
laminar and turbulent flows at different geometries. For instance, the Rayleigh
number, Ra, and the Grashof number, Gr, are employed.[31] Ra and Gr are
related to each other. Gr multiplied by the Prandtl number (nearly equal to one
for gases) yields Ra.
419
Figure 7.10. Forces at a heated substrate surface. The value, g, the gravitational
force, dT/dx the temperature gradient.
420
In many CVD processe,s the laminar flow region is normally used. High
flow rates (turbulence) usually decrease the conversion efficiency of the
reactants to the coating and very large gas volumes have to be handled. The
flow situation around the object to be coated can be visualized in smoke
experiments where the smoke is generated inside the reactor from, for
instance, titanium tetrachloride and water.
4.1
421
Figure 7.12. Gas flow pattern in a cold wall reactor, where the forced and buoyancedriven convection (a) interact, and (b) counteract, substrate temperature 900 K, Re
= 50.[34]
422
Figure 7.13. Gas flow pattern in a cold wall reactor with a geometry different from
that in Fig. 12.[35]
423
Figure 7.14. Gas flow pattern in a hot wall reactor with a temperature gradient of
6 K cm-1, linear gas flow velocity of 2 cm s-1, and channel height 5 cm, deposition
system Ga-AsCl3, H2.[32]
Boundary Layers
424
425
Figure 7.16. Temperature profile in helium. Linear gas flow velocity: 24.9 cm s-1.[28]
Figure 7.17. Concentration profiles of SiCl4 and HCl in the CVD of silicon from SiCl4
and Hc. Transport distance along the susceptor: 12.5 cm, linear gas flow velocity:
24.9 cm s-1, - - - 1000C, 1140C. [28]
426
the susceptor, the partial pressure of SiCl4 was reduced to about 50% of the
initial value. Sedgwick et al.[29] measured temperature and concentration
profiles in an air-cooled horizontal cold wall reactor using Raman scattering.
They observed a steep temperature gradient near the susceptor. The
temperature profile developed was dependent on the position along the
susceptor.
Figure 7.18. Partial pressure profile of SiCl 4 as a function of the transport distance
along the susceptor at a height of 7 mm above the susceptor.[28]
427
Giling also pointed out the importance of entrance effects, i.e., that it will
take some distance (the entrance length) from the susceptor edge for full
velocity and temperature profiles to develop. According to Schlichting[36] the
entrance length for the development of the full velocity profile is given by the
equation
X = 0.04hRe
where h is the height of the channel and Re is the Reynolds number. Hwang
and Cheng[40] predicted that the thermal entrance length was seven times
longer than the flow entrance length. Giling confirmed this for H2 in his
measurements.
Coltrin et al.[41] have developed a mathematical model of silicon CVD
from silane in a cold wall reactor. The model includes gas phase chemistry
as well as fluid mechanics, and predicts temperature, velocity, and concentration profiles for many vapor species. Figure 7.19 depicts the temperature
contour in a typical calculation. The thickness of the boundary layer is in the
centimeter range and increases with increasing gas transport distance along
the susceptor.
Figure 7.19. Calculated temperature contours for silicon CVD from silane (0.6 Torr)
and helium as a carrier gas (600 Torr). Temperature: 1018 K, gas flow velocity: 15.3
cm s-1.[41]
428
4.3
5.0
429
430
Since the mass transport in the vapor or the surface kinetics usually
controls the deposition rate, the following discussions are limited to just these
two cases. Surface kinetics control is normally desirable and means a
maximum in throwing power or step coverage. Figure 7.21 shows conditions
of complete mass transport control, complete surface kinetics control and
mixed control. In the surface kinetics control, a fast diffusion in the vapor is
combined with a slow surface reaction. For a mass transport control, the
surface kinetics is fast while the mass transport in the vapor is slow.
431
D Pb Ps
R T
D = diffusion coefficient
R = gas constant
T = absolute temperature
= boundary layer thickness
Pb and Ps (see Fig. 7.21)
km (
Ps Peq)
RT
Ps =
km
Peq
D
km + 1
D
Pb +
Km is thus given by
Pb Peq
JM = 1
RT + 1
D km
Pb - P eq is the driving force of the process and /D and 1/km are reaction
resistances. If /D >> 1/km the process is controlled by the mass transport
in the vapor, while surface reaction control is achieved at 1/km << .
432
x
= a
M p
RT
= o T
To
m/ 2
D = Di ,o
Pi
P
T
To
1.75
433
where Di,o is the reference value of the diffusion coefficient andPi is the partial
pressure of species i. The reaction resistance is then
= const P1/ 2
. m/ 2
D
T175
Hence /D increases with increasing pressure and decreasing temperature.
The value of km follows the Arrhenius equation
km = A e
E
a
RT
434
Figure 7.22.
cesses.
435
Figure 7.23. Regions of mass transport and surface kinetics control at different
total pressures (P1<P 2<P3).
Figure 7.24. Influence of gas flow velocity on the control of a CVD process.
436
6.0
REACTION MECHANISMS
437
438
7.0
439
440
Figure 7.27. The Terrace, Ledge, and Kink (TLK) model of a surface.
441
442
443
(a)
(b)
Figure 7.30. The surface of a tungsten filament (a), and preferentially nucleated
boron on ridges of the filament (b).[52]
444
445
9.0
SELECTIVE DEPOSITION
446
Principally there exist several categories of selective deposition systems. In the system described above, the deposition takes place on one
substrate material while no deposition is obtained on the other and areaselective deposition is achieved. However, different phases can also be
deposited simultaneously and selectively on the different materials, resulting
in phase-selective deposition. In analogy to the phase-selective deposition,
films of different microstructures or different chemical compositions may be
deposited on the different substrate materials and hence selectivity in
microstructure or chemical composition is attained.
Selective deposition is an emerging field and there is a great demand
for these processes in many application areas. With the steady reduction of
IC feature sizes there is a need for self-aligned processes. Selective tungsten
for metallization in VLSI and selective GaAs epitaxy for monolithic integration
of optoelectronic devices are well-known examples. Other application areas
may be in micronics, heterogeneous catalysis, engineering of film/substrate
interfaces, and in growth of artificial 2-D and 3-D materials. Since selective
deposition on patterned substrates is based on interfacial chemistry, there are
practically no restrictions in the dimensions of the deposited materials
islands. This opens a fascinating perspective to build up materials with
microstructures without any thermodynamic or kinetics limitations. The
underlying principles of selective deposition are briefly discussed below.
9.1
Area-Selective Growth
447
over the mask. The process is then called ELO (Epitaxial Lateral Overgrowth). For a review of the ELO process, the reader is referred to Ref. 64.
A key point in the SEG is the suppression of the nucleation on the mask
(usually silicon oxide or silicon nitride). As mentioned in Sec. 7, the incubation
time for nucleation varies with the substrate material and the deposition
conditions. In an ideal case, this incubation time is longer than the deposition
time required to prepare the desired structures. However, by using an
alternating growth and etching process, SEG can be attained even for
conditions of short incubation times for nucleation.[65] The growth conditions
are then prevailing for about the incubation time. After the growth cycle, the
process is switched over to etching with, for instance, HCl. A minor etch is
also obtained of the monocrystalline silicon in the SiO2 openings.
The GaAs SEG/ELO is nearly as old as the silicon SEG/ELO. Tausch
and Lapierre reported in 1965 on a GaAs ELO process based on a chloride
vapor transport system.[66] With the development of the purification techniques of metal-organic compounds like trimethyl gallium (TMG) and triethyl
gallium (TEG), CVD as well as MBE, based on the use of these compounds
together with AsH3, are highly attractive for GaAs SEG. MBE and elemental
sources yields monocrystalline growth in etched openings as well as
polycrystalline GaAs on the mask (microstructure-selective deposition).[70]
GaAs SEG has received much attention during the last few years as a
technique for achieving monolithic integration of electronic and optoelectronic
devices.
Growth of GaAs from AsH3 and TMG by MBE or CVD is usually
considered to be a non-equilibrium process. The perfection of the crystals
grown, their morphology, and the correlation between the growth rate and
thermodynamic parameters indicates that near-equilibrium conditions exist at
the interface between the vapor and the solid. Hence thermodynamics can be
utilized to analyze selective growth as well heterogeneous nucleation conditions in GaAs CVD.
According to nucleation theory, a certain supersaturation is needed for
heterogeneous nucleation on the mask. From experimental selectivity data,
the maximum supersaturation for maintaining selectivity can be calculated.
The supersaturation is favorably expressed in terms of chemical potentials.
The influence of temperature on the chemical potential of GaAs (expressed
in elemental chemical potentials of Ga and As2 ) at equilibrium with solid
GaAs is shown in Fig. 7.32. Growth will occur if the chemical potential of
GaAs for the homogeneous equilibrium in the vapor is higher than that for the
heterogeneous equilibrium.
448
Figure 7.32. Chemical potential of GaAs for the heterogeneous equilibrium (full
line), and for two homogeneous equilibria at different total pressures (dashed
lines). H2/AsH3/TMG = 500/10/1.[68]
449
Figure 7.33. Selective growth regime for GaAs. Precursors: Ga(CH3)3, AsH 3.[69]
Substrate-Activated Selective Growth. When a substrate of different materials is exposed to the vapor in a CVD process, the materials
represent areas of different activities or reactivities towards the vapor. One
material may, for instance, act as an effective reducing agent or as a catalyst
of dissociative adsorption of gaseous reactants, which may favor the deposition. The other material may be relatively inert towards the vapor and growth
may be inhibited. The inertness may be increased purposely by using gas
additives which are preferentially adsorbed to one of the materials. Strongly
adsorbed molecules may passivate a substrate surface considerably and
suppress the deposition process completely. A tendency to substrateactivated area-selective growth is frequently seen during the initial growth
stage in CVD on polycrystalline, multi-phase substrates. The different phases
and the different crystallographic orientations of the grains exposed to the
vapor, represent surface areas of different activities/reactivities and initial
growth conditions. Taken to its extreme, this means that the deposition is
inhibited on some substrate areas, while other areas are open for deposition.
Area-selective deposition of refractory metals is of highest interest for
metallization in VLSI and ULSI. Selective deposition of refractory metals for
metallization has been reviewed by several authors (see Refs. 70 - 73). The
450
451
452
The chemical reactions in the first step are usually extremely fast and
a thermodynamically controlled CVD process is obtained. In the second
process step, the deposition process was operated at a low supersaturation
to avoid nucleation on the mask material (SiO2 ). The growth conditions in the
second step are close to those existing in the area-selective epitaxy
discussed above and can be analyzed from thermodynamics. Thermodynamics has been used as a guide for prediction of trends in selectivity and substrate
etching when the deposition conditions are changed. It has also been used
for identification of plausible (and often undesired) side reactions as well as of
gaseous selectivity modifiers, improving selectivity.[9]
Adsorption-Induced Selective Growth. As discussed above, the
heterogeneous nucleation on one of the substrate materials must be
suppressed during a relatively long time in an ideal selective growth
system. The incubation time for nucleation is influenced by many factors:
temperature, substrate reactivity, adsorption, etc. Adsorbed molecules
may reduce the rate of surface reactions and, in extremes, inhibit the
nucleation completely. A concept of strongly adsorbed molecules to one
of the substrate materials was used to achieve area-selective growth of
boron carbide on a patterned substrate exposing areas of titanium and
molybdenum to the vapor.[77] Boron trichloride, ethylene, and hydrogen
were used as reactants and the deposition temperature was 1400 K. The
ethylene molecules (or fragments of them) were preferentially and strongly
adsorbed on molybdenum and no nucleation of boron carbide was
observed. On titanium, however, fast nucleation kinetics was obtained.
The deposition was located only to those substrate areas having titanium.
The boron carbide was amorphous and contained about 21 at% carbon.
This illustrates that adsorbed molecules may act as masks and can be
used to inhibit the deposition on desired substrate areas.
9.2
Phase-Selective Deposition
A new dimension in the field of selective growth is created in phaseselective growth. Phase-selective growth means that several phases are
selectively and simultaneously deposited on desired substrate materials/
areas. This might result in growth of, for instance, a semiconductor together
with an insulator, i.e., selectivity in properties is also obtained. Phaseselective deposition may be achieved in different ways. In this chapter, two
principles of phase-selective growth are discussed: phase-selective deposition attained by differential nucleation behavior and by secondary processes
in or on the growing film, respectively.
453
454
455
11.0 OUTLOOK
CVD offers many advantages in thin film deposition. With the use of new
precursors, the deposition temperature can usually be lowered considerably.
By lowering the total pressure, extremely sharp interfaces with respect to
chemical composition and topography can be obtained. The atmospheric
pressure CVD is attractive in many applications with its high deposition rates
and hence short process times. Since CVD processes are based on
interfacial chemistry, they are sensitive to contamination and load-lock
systems must be used to keep the contamination level low. The selective
deposition opens fascinating prospects for the future, not only for microelectronic applications but also for materials science in general, and for engineering of interfaces and artificial materials.
456
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