.

__
cm Nuclear Instruments and Methods in Physics Research B 116 (1996) 305-321

NOMB
ED E!i
B
EJSEVIER
Beam Interactions
with Materials&Atoms

Silicon carbide: synthesis and processing

W. Wesch
Friedrich-Schiller-UniversitZt Jena, Institutfir Festkiirperphysik, Max-Wien-Platz I, D-07743 Jena, Germany

Abstract
Silicon carbide with its outstanding physical properties is a material of choice for special optoelectronic and electronic
devices working under extreme conditions. Synthesis as well as processing are complicated compared to other materials. The
present paper summarizes some aspects of crystal growth and processing and discusses arising problems.

1. Introduction Refs. [3-91). In the present paper some aspects of Sic

Natural silicon carbide, the mineral Moissanite, was
isolated for the first time by Moissan in 1905 from an iron
meteorite found in Canyon Diabolo, Arizona [ 11. Although
its constituents are abundant and the compound is chemi-
cally and thermally stable, large deposits of Sic have
never been found.
With the development of an industrial method for
producing this hard and stable compound known as car-
borundum by Acheson already in 1892 [2], the large
demand for abrasives could be satisfied. However, a lot of
other applications have been found, as manufacturing of
cheap heating elements with long lifetimes, use of SIC as
coatings for the fuel elements of nuclear reactors and as a
component for producing rocket nozzles [3].
The pronounced tendency of Sic to crystallize into
many different modifications, the so-called polytypes, with
a broad variation of the band gap, in combination with
other outstanding properties - high temperature stability,
high chemical resistivity, radiation hardness - make Sic a
material of choice for device applications. Primary applica-
tion fields of Sic are optoelectronics (blue light emitting
diodes, UV photodiodes), high temperature electronics
(ranging from pn-junction to field effect transistor-based
circuitry), radiation hard electronics (nuclear reactor and
space electronics) and high power/high frequency elec-
tronics (increase of power density and operating tempera-
ture). These promising applications stimulated the efforts
to develop and improve methods of bulk and epitaxial
layer growth since the mid 1950s to produce Sic of high
purity and good crystalline quality. However, the proper-
ties of the material complicate its synthesis as well as its
processing compared to commonly used materials in de-
vice technology.
In the last years several excellent reviews were pub-
lished concerning crystal growth, properties, materials
modification and device fabrication of silicon carbide (e.g.
crystal growth and processing are summarized and the
arising problems are discussed.
2. Structure and properties of silicon carbide
2.1. Crystallographic structure
Silicon carbide, the only stable compound in the sili-
con-carbide system, exhibits a pronounced tendency to
crystallize in a multitude of different modifications called
polytypes [lo]. The building unit of all these polytypes
consists of close packed Si-C tetrahedra. In these elemen-
tary tetrahedra a carbon atom is tetrahedrally surrounded
by four silicon atoms, and in the same way each silicon
atom is surrounded by four carbon atoms (see Fig. la, [4]).
In the silicon carbide crystal the tetrahedra are arranged in
such a way that all atoms lie in parallel planes on the
nodes of regular hexagonal networks. The only difference
between the various polytypes lies in the stacking order of
these elementary tetrahedra. There are two basic stacking
sequences possible: if the projections of silicon atoms in
three successive layers are in three different positions A
(circles), B (squares) and C (triangles), the cubic (zinc
blende) structure is formed (Fig. lb); the hexagonal
(wurtzite) lattice results, if the projection of the atoms. in
the third silicon layer coincides with the position A of the
silicon atoms in the first layer (Fig. lc).
All the different modifications of Sic can be described
in the hexagonal axis system, with three axes a, b and d
having angles of 120 with one another and one c-axis
perpendicular to them. In Fig. lb the axes and the base of
the hexagonal unit cell are indicated. Figs. lb and lc
clearly show that (1120) planes give a correct representa-
tion of the SIC structure, because all relevant atoms lie in

0168-583X/%/$15.00 Copyright 0 1996 Elsevier Science B.V. All rights reserved

PII SO 168-583X(96)00065- 1
306 W. Wed /Nucl. fnstr. and Meth. in Phys.Res. B 116 (1996) 305-321

d.

W
A B C A A B C
zincblende wurtzite
first silicon layer : A
first carbon layer first silicon layer
second silicon layer : B fist carbon layer
third silicon layer : C second silicon layer
n second carbon layer
A third silicon layer

Fig. 1. Elementary Sic-tetrahedron (a) and projection of the Fig. 2. Position of silicon and carbon atoms in (1120) planes of
different positions of the silicon atoms in the zincblende structare the cubic (zinc blende) and hexagonal (wurtzite) structures [4].
(b) (axes system and base of the unit cell are indicated) and in the
wmtzite stmcture (c) [41.

indicated between brackets; Zhdanov [121) or characterize

these planes. Fig. 2 illustrates such representations for the
cubic (zinc blende, left) and hexagonal (wurtzite, right)
structure. In Fig. 3 the positions of the silicon atoms in
(1120) planes for the most common polytypes of silicon
carbide are shown. The bold horizontal lines mark the
completion of a unit cell on the c-axis. As can be seen
from Fig. 3a, the zinc blende structure requires three steps
in the same direction leading to the stacking sequence
ABCABC. According to the nomenclature introduced by
Ramsdell [ll] the cubic lattice is therefore named 3C. A
unit cell of the wurtzite lattice is built up by a sequence of
one step to the right and one step to the left (stacking order
ABAB, Fig. 3b) and is therefore called 2H. In the same
way all other possible polytypes can be characterized, as
illustrated in Figs. 3c and 3d for the hexagonal structures
4H and 6H and in Fig. 3e for the most common modifica-
tion with a rhombohedral unit cell 15R.
Other usual nomenclatures count the steps necessary to
complete one unit cell (the number of steps to the right,
then to the left etc. until the unit cell is completed is
the sequence of layers by their cubic (c) or hexagonal (h)
environment (Wyckoff 1131, Jagodzinski [ 14j) to describe
the various SiC modifications. From the latter notation a
percentage of hexagonality can be derived, i.e.
0%, SO%, 100% hexagonality are assigned to the 3C, 4H
and 2H structures. Table 1 summarizes for some common
polytypes the different nomenclatures being in use.
The principle of stacking identical close packed Si and
C layers along a symmetry axis perpendicular to a hexago-
nal network plane enables, a large number of different
polytypes having cubic, hexagonal or rhombohedral stmc-
ture. More than 250 different polytypes have been reported
until now, among which the most common structures are
3C-Sic or P-Sic, the only polytype with cubic structure,
and the hexagonal polytype 6H.
2.2. Properties
Some properties of silicon carbide are strongly corre-
lated to the polytype. Especially pronounced is the influ-

Table 1
Nomenclature of some polytypes of silicon carbide
Stacking Ramsdell Zhdanov Wyckoff/ 13/ Percentage Chronolo-
order 1111 [I21 Jagodzinski hexagonality gical
[141 [10,15,16]
ABC 3c C 0 P-Sic
AB 2H h 100
ABCB 4H (22) hc 50 a-Sic,
Sic III
ABCACB 6H (33) hcc 33 cu-Sic, Sic II
ABCACB 15R (323232) hcchc 40 cu-Sic, Sic I
CABACA
BCB
 W. Wesch/i?ucl. Instr. and Meth. in Phys. Res. B I16 (1996) 305-321 307

b) 6

@I
Sic
5 L _....- ? vd

a-_--p..,, E
x calculation
s 0 measurement H
h E4
w

C) d)
C
h 2
C C
C C
h h f
ABCABCABC ABCABCABC ABCABCABC
ABCB4H(qtc ABCACR
6H(33),hce 15R(323232),br&
Fig. 3. Position of silicon atoms in (1120) planes of different
polytypes [41.
ence of the polytype on the band structure. All the Sic
polytypes are indirect materials, and indirect transitions
were fiit observed by Choyke and Patrick [17]. It has been
established experimentally that a nearly linear relation
exists between the hexagonality and the energies of the
indirect band gaps (see e.g. Refs. [3,18-201 and references
therein). Fig. 4 shows that this rule is valid up to 50%
hexagonality and does not apply to the 2H structure. This
principal behaviour is meanwhile confirmed by theoretical
calculations of the band structure of different polytypes
(see Refs. [3,21,22] and references therein; cf. experimen-
tal and theoretical results in Fig. 4). They show that the top
of the occupied valence band states for all common poly-
types is situated at the center of the Brillouin zone (P
point; see inset in Fig. 4). For all polytypes besides 2H the
conduction band minima lie along a line joining points L
and M of the Brillouin zone. The indirect band gap
(characterized by transitions r + L-M) linearly varies
with the poiytype reaching values between Es+, = 2.3 eV
(3C) and E,_, = 3.3 eV (4H) [21]. In 2H-SiC the conduc-
tion band minimum lies at a different position (point K)
[ 182 l] leading to the deviation from the linear dependence
of Ega,, on the hexagonal@ (E,, = 3.22 eV>.
3
0 20 40 60 80 100
hexagonahty (%)
Fig. 4. Energies of the indirect band gap Es of various polytypes
as a function of the percentage hexagonal&y [3,21].
Sic is assumed to have a nearly covalent bond charac-
ter with a = 12% ionic contribution [3,4,7,23]. The cova-
lency is a consequence of the nearly perfect tetrahedral
arrangement of the atoms. The ionic contribution manifests
itself in the pronounced reststrahl absorption band at the
wavelength A = 12.6 pm, which is typical for all crystals
having bonds of some polar character. An ionic part is also
deduced from the piezoelectricity and the large piezoelec-
tric coupling constant of SIC [24]. However, the true
nature of the Sic bond is still not completely clear.
The thermal stability of silicon carbide is relatively
high, and it does not melt between atmospheric pressure
and 35 atm 1251. At high temperatures it sublimes and
dissociates into carbon and a silicon-rich vapour. This and
the small solubility of carbon in silicon at lower tempera-
tures (at 1800C only 0.1% carbon can be dissolved in
silicon 126,271) has consequences for the growth of silicon
carbide crystals.
Other important features of Sic are its large hardness
(number 8 in Mohs scale of hardness between diamond
and topaz [4]) and its chemical resistance. Crystalline Sic
can be dissolved by molten oxidizing materials as e.g.
molten Na,O,, a molten Na,CO,-KNO, mixture [4] or
molten KOH [28] and a boiling solution of 50%

Table 2
Comparison of selected semiconductor properties
Si GaAs 6H-Sic 4H-Sic 3C-Sic Diamond
Bandgap[eV] 1.1 1.42 3.0 3.3 2.3 5.5
Melting point 1420 1238 sublimes > 1800 phase
[Cl change
Thermal conductivity 1.5 0.5 4.9 4.9 5.0 20
[W cm- K-1
Electron mobility at lOI cmm3 1100 6OCO 370 800 750 (2200)
[cm* V- s- 1
Hole mobility at 1016cn- 3 420 320 90 115 40 (1600)
[cm* V- s- 1
Breakdown field at lOI7 cmw3 0.6 0.6 3.2 3 4 (10)
[MV cm-]
308 W. Wesch/Nucl. Instr. and Meth. in Phys. Res. B 116 (1996) 30.5-321
K,Fe(CN,) + 50% KOH [29,30], respectively. Further, the
material reacts rapidly with chlorine and Ccl, at 900-
1200C leaving behind a graphite residue 141.
In Table 2 some key properties of Sic are listed in
comparison with those of other technologically relevant
materials (data from Refs. f9,21,31-371). The data show
that SIC, in spite of the low-field carrier mobility disadvan-
tages, because of its high breakdown field, high thermal
conductivity and wide band gap energy seems to be a
candidate for devices operating under extreme conditions,
as high temperature, high power, radiation and, connected
with its chemical stability, in reactive atmosphere.
3. Synthesis of silicon carbide crystals
The preparation of silicon carbide can, on principle, be
done from non-stoichiometric silicon-carbon or silicon-
carbon-metal melts [38-431 and by vapour growth pro-
cesses as chemical vapour deposition (pyrolytic decompo-
sition of silicon and carbon containing gases) or sublima-
tion. Melt growth processes are complicated because of the
small carbon solubility in silicon at temperatures below
2000C as well as its small change with temperature and
the high vapour pressure of silicon (in the order of 0.1
atm) at this temperature [3,26,44]. As consequences, high
process temperatures are necessary and the evaporation of
silicon must be suppressed by a high-pressure inert atmo-
sphere (e.g. argon). The Sic crystals grown by this method
are not adequate for practical applications with respect to
their size, but also to quality and purity. The following
discussion will, therefore, be restricted to some aspects of
vapour growth processes with the emphasis to sublimation
techniques.
3.1. Bulk crystal growth
Till the mid 195Os, SIC was only available from the
industrial Acheson process for producing abrasive mate-
rial. In this process where silicon dioxide and carbon react
to form Sic, crystalline platelets with diameters of several
centimeters with various structures result as a by-product
(for details see the review of Knippenberg 141). Because of
their insufficient and uncontrollable purity they can hardly
be used for device applications, but they are often used as
seed crystals for vapour phase growth and sublimation
processes.
Already in the 1930s a vapour growth process, which
was described for the preparation of pure carbides by van
Arkel and de Boer [45], was applied for the production of
silicon carbide [46,47]. In the van Arkel apparatus silicon
and carbon containing gases (methylchlorosilanes, e.g.
CH,Cl ,SiH, CH $1 ,Si) are pyrolytically decomposed, and
Sic is deposited on heated carbon rods. The deposition
temperature usually lies in the range between 1400 and
16OOC, in several experiments temperatures up to 2400C
Insulation
Porous
Graphite
zfF$ed
Graphite
Atmosphere:
Argon at 200 Pa
Fig. 5. Cross-sectional view of a bulk growth furnace 1481.
were employed. As carrier gas hydrogen is commonly
used. The deposited material is polycrystalline and consists
of small crystal grains (size several hundred microns)
which are stated to be mainly cubic. By adding suitable
gases a definite doping of the Sic is possible (e.g. B,H,
or Al(C,H,), for p-type conductivity and PH, or N, for
n-type doping). The resulting high-purity SIC serves as
basic material to produce 6H-SiC single crystals by the
Lely technique.
A significant breakthrough in bulk Sic growth was
made in 1955 when Lely [48] reported the development of
a sublimation process for growing higher purity single
crystals. Further evolution of this technique resulted in a
configuration, in which a tube of porous graphite is sur-
rounded by a charge of polycrystalline (solid or powder)
Sic. Heating the hollow carbon cylinder to 2500C leads
to sublimation of the material at the hot outer wall and to
diffusion through the porous graphite tube into the inner
part, where it crystallizes on the slightly cooler parts. The
nucleation in this process is uncontrolled, and randomly-
sized, hexagonally-shaped platelets are formed which often
exhibit a layered structure. of various alpha polytypes [8].
Based on the Lely technique, Tairov and Tsvetkov
[49,50] established principles of a modified sublimation
bulk growth process wherein only one large single crystal
of a single polytype is grown. Fig. 5 shows a schematic
representation of the configuration used by Ziegler et al.
[5 l]. As in the Lely process, polycrystalline Sic sublimes
at a temperature of 2400C to form Si, Si,C and Sic,
which diffuse through a porous graphite wall into a cylin-
drical growth cavity. Nucleation occurs on a Sic seed
crystal held at approximately 2200C which is located on
top or bottom of the cavity (see Refs. [8,49-511). The
growth is commonly done in a high-purity argon ambient
at different pressures. The growth rate is in the order of a
few mm/h and increases with increasing temperature,
increasing temperature difference between source and seed,
and decreasing pressure and source-seed distance 152-541.
The method was successfully applied to grow 6H boules
with diameters up to 50 mm on 6H [50,51,55,56] and 4H
boules on 4H [51,53-551. Recently the growth of 6H-SiC
on CVD grown 3C-Sic substrates [57] and the growth of
3C on 6H substrates [58] has been demonstrated. These
 W. Wesch /Nucf. Instr. and Meth. in Phys. Res. 3 116 (1996) 305-321
studies show that the polytype produced can be controlled
by the growth temperature.
Presently only CREE Research in the US is selling 6H-
and 4H-Sic wafers (diameter 1.187 in.) with net doping
densities in the order of several 1017and 10 cmm3. Until
the end of the 1990s upscaling to 2 and 3 in. commercial
wafer sizes and materials with higher purity are expected
191.
Although significant advances have been achieved in
the field of bulk crystal growth during the last years, the
boules contain a variety of defects, as growth spirals
(stepped screw dislocations), subgrain boundaries as well
as micropipes (micron sized voids extending the length of
the boule), the last of which may be associated with
nucleation processes at the seed-boule interface [54].
Among the problems to be solved in this respect the
investigation of the relationships between the occurrence
and concentration of these defects and the kind of polytype
as well as of the effect of the growth parameters (growth
temperature, gas dynamics and total pressure inside the
growth crucible) on the concentration of the defects are of
fundamental interest 1521. Further, efforts have to be ex-
pended to improve the purity of the bulk materials.
3.2. Epitaxial layer growth
At present, chemical vapour deposition (CVD) is the
chiefly used technique to produce epitaxial SiC layers on
Si and Sic substrates, respectively. Typical CVD systems
consist of a horizontal water-cooled quartz tube with an
rf-heated graphite susceptor and a gas supply system (for
details see Refs. [6,59]). As carrier gas hydrogen, purified
by passage through a palladium diffusion cell, is used. The
sources of silicon and carbon are usually silane (3 mole
percent SiH, in H,) and high purity propane (0.3 mole%
C,H, in H,). Additionally, various doping gases can be
introduced. The deposition is carried out by simultaneous
flow of the gases at atmospheric pressure, deposition tem-
peratures range from 1100 to 1600C and are remarkably
lower than those for bulk Sic growth. Before depositing
Sic the substrates are etched with HCl gas at 1500C to
remove the damaged surface layer formed during the
lapping process [6,60].
Because of its availability in well-characterized and
reproducible forms of controlled purity, first of all silicon
was used as a substrate for Sic epitaxy. The results
obtained in various laboratories are described in the review
by Davis et al. [8]. The main problem arising with silicon
as substrate is connected with the formation of defects, as
e.g. microtwins and intrinsic stacking faults (see e.g. Refs.
[61,62]). The generation of these defects is obviously
connected with the mismatches in the coefficients of the
thermal expansion (8%) and the lattice parameters (20%),
and they cannot be sufficiently suppressed also by deposit-
ing a carbon layer and a thick Sic buffer layer [59] or by
deposition on off-axis substrates [61,63].
309
OO-
OFF ANGLE TOWARD [1120] (deg.)
Fig. 6. Growth rate of 3C- and 6H-Sic as a function of the
off-angle of the substrate toward the [ll?O] direction for layer
growth on (Oool) 6H-Sic Si- and C-faces [60].
As an alternative CVD of Sic on Sic substrates is done
which has shown to reduce the concentration of misfit
dislocations and stacking faults drastically [64]. Previous
results obtained in various laboratories showed that on
6H-SiC 3C as well as 6H-Sic layers can be grown in the
temperature region between 1350 and 1550C. 3C-layers
are formed on exactly oriented (OOOl)Si- and (OOOi)C-faces
by two-dimensional nucleation [65-671. The growth in this
case will be controlled by a surface reaction, such as
adsorption of Si species. Recently, the growth of 3C-Sic
on off-axis 6H-SiC with tilt angles less than 1 was
explained to be stimulated by dislocations [68]. However,
the layers grown on the (OOOi)C-faces were relatively
rough and contained a high amount of defects as e.g.
stacking faults and double positioning boundaries (DPBs,
produced as a consequence of nucleation on neighboured
terraces the height of which differs by one monolayer).
Hoinoepitaxial growth of Sic is obtained on off-axis
(0001) 6H-SiC wafers [67,69] by step-controlled epitaxy
[60,70], i.e. the lateral growth proceeds from atomic steps
and no more nucleation is needed.
The influence of the off-angle, the growth temperature
and the C/Si ratio on the growth rate of epilayers on
GH-SiC has been investigated in a systematic study of
Kimoto et al. [60]. Fig. 6 shows the growth rate as a
function of the off-angle of the substrate toward the [ 11201
direction for layer growth on (0001) 6H-SiC Si- and
C-faces (flow rates 0.30 seem for SiH, and 0.20 seem for
C,H,). It can be seen that 6H-SiC can be homoepitaxially
grown on substrates with more than 2 off-angle (open
symbols), whereas at an off-angle 0 heteroepitaxy of
SC-Sic is obtained. On C-faces of well-oriented substrates
(0 off-angle) the growth rate is higher than on Si-faces.
With increasing off-angle the growth rates on both faces
approach each other and reach an almost constant value of
2.5 pm/h for off-angles from 5 to 10.
The influence of the C/Si ratio on the growth was
investigated by varying the C,H, flow rate in the range
310 W. Wesch/Nucl. Ins@. and Meth. in Phys. Res. B 116 (1996) 305-321
from 0.10 to 0.40 seem by keeping the SM, flow rate
fixed at 0.15 and 0.30 seem, respectively. Perfect surfaces
are obtained for C/Si ratios between 1.4 and 2.5. For
C/Si < 1.4 (Si-rich) surfaces with Si droplets are formed,
and for C/Si > 2.5 (C-rich) a wavy or stripe-like surface
morphology occurs. The growth rate is almost constant for
C/Si 2 1.4 and increases proportionally with the flow rate
(Fig. 7), i.e. the supply of SiH, limits the growth. The
remarkable decrease of the growth rate for C/Si < 1.4
may be caused by the lack of C sources. From these results
and an analysis of the gas-phase kinetics in the growth
system it is speculated that the growth proceeds through
the adsorption of Si at atomic steps and its carbonization
by hydrocarbon molecules. This is supported by results of
gas source molecular beam epitaxy (GSMBE) 1711.
The observed small change of the growth rate with the
substrate temperature in the region between 1200 and
1500C (not shown) as well as the only small difference
between C-face and Si-face indicate that the growth pro-
cess on off-angle substrates is mainly controlled by mass
transport and not by surface reactions [60]. In agreement
with that the growth rate increases linearly with the SiH,
flow rate (Fig. 8) indicating that the growth rate is limited
by the supply of Si.
Key problems in Sic layer growth are the definite and
reproducible doping as well as the generation of high-resis-
tivity undoped layers. At the relatively high growth tem-
peratures in the CVD process the resulting layers are
normally n-type (net carrier concentration in the order of
several 1OL6to 10 cme3) due to unintentional incorpora-
tion of nitrogen from the growth system or the reaction
gases. A possible solution of these problems may be the
recently proposed site-competition epitaxy 1721. This
technique is based on the principle of competition between
nitrogen and carbon for the C sites and between aluminum
and silicon for the Si sites of the growing layer which is
consistent with the previous conclusion that nitrogen occu-
pies C sites whereas aluminum atoms occupy Si sites of
the Sic lattice. Thus, by increasing the carbon-source
3 t I I I I
o-
:2c f
01
0
I
1
I
2
t
3
I
4
I
5 low deposition rates at low temperatures [73].
C.&iRATIO
Fig. 7. Dependence of the growth rate on the C/Si ratio at a
growth temperature of 1500C for different SiH, flow rates [60].
b.t 0.5
SiH4 FLOW RATE (seem)
1.0
Fig. 8. SiH, flow rate dependence of growth rate at 1500C bO1.
concentration (or the silicon-source concentration) the N
concentration (or the Al concentration) is decreased by
outcompetition of N by C for the C-sites (or Al by Si for
Si sites). With this method for the ratio Si/C = 0.1 the
most intrinsic Sic reported to date has been grown with an
unintentional dopant concentration of 1 X 1014 cmw3. Fur-
ther, controlled n- and p-type doping has been demon-
strated by variation of the Si/C ratio and of the concentra-
tions of dopant containing gases.
A promising way to produce Sic epitaxial layers seems
to be molecular beam epitaxy (MBE). This technique has a
number of advantages compared to CVD: lower growth
temperatures (Td < llOOT), clean growth ambient (UHV
conditions), in situ control of the growth process, layer-
by-layer deposition, preparation of dopant profiles with
atomic dimensions due to reduced interdiffusion at low
growth temperatures [73]. The first experiments were done
by gas source MBE (GSMBE) using an alternating supply
of disilane (S&H,) and acetylene (C,H,) gas molecular
beams [71,74]. With this method 3C-Sic epilayers were
grown between 850 and 1160C on (07 13) 6H-SiC [75], on
vicinal 6H-SiC (0001) 3C-Sic films were deposited be-
tween 1050 and 1250C [76]. Homoepitaxy of SC-Sic on
SC-Sic substrates by atomic layer epitaxy (ALE) at
1050C has been demonstrated [77], and recently 6H-SiC
was grown for the first time on vicinal 6H-SiC at 1050C
by GSMBE, but with an extremely small growth rate of
5-10 rim/h [78].
Summarizing the results published until now, GSMBE
seems not to be a promising alternative to CVD. This is
mainly connected with the strong adsorption and incorpo-
ration of atomic hydrogen at lower temperature produced
by decomposition of the gas phase reactants which lead to
lattice imperfections. Thus, the growth rate has to be lower
than the desorption rate of hydrogen which leads to very
The problems mentioned may be overcome by solid
source MBE which until now has been used only to a
small extent. In the fit experiments stoichiometric Sic
 W. Wesch/Nucl. Instr. and Meth. in Phys. Res. B 116 (1996) 305-321
Fig. 9. Cross-sectional HRTEM image of Sic grown
source MESE on 4H-Sic (0001) [83,841.
films could be grown epitaxially on (11 I>Si and (OOOllSiC
only at Td > 1100C [79,80]. From the results it was
concluded that the careful control of the flux ratio and the
surface mobility of adatoms play a crucial role in decreas-
ing the growth temperature of Sic [73,81]. In our institute
for the first time stoichiometric SIC films were grown by
solid source MBE on 6H-SiC (0001) substrates at tempera-
tures between 800 and 1000C with an excess Si flux
slightly lower than the limit determined for non-clustering
conditions [73,82]. The growth rate was in the order of 2
nm/min, and the resulting layers consisted of a mixture of
twinned 3C-Sic and o-Sic. Fig. 9 shows as an example a
cross-sectional HRTEM image of a Sic epilayer grown
under Si-stabilized conditions on (0001)4H-Sic [83]. On
the 4H-Sic substrate a layer containing different stacking
sequences is followed by a pure 3C-Sic structure, an
interface with mixed structure and a pure 6H-SiC layer.
The variation of the polytype with proceeding layer growth
is assumed to be connected with small fluctuations in the
adlayer thickness and, consequently, in the surface super-
311
structure which leads to the growth of another polytype
[73,84]. This is supported by results obtained by atomic
layer epitaxy on Si-stabilized (0001) surfaces which have
demonstrated the stabilization of a certain polytype [84]. A
careful control of the Si/C ratio and the Si excess, there-
fore, seems to be a possible way to grow heterostructures
of different polytypes which is the basis for band gap
engineering in Sic.
3.3. Ion beam synthesis
Another approach to produce Sic is high-dose carbon
implantation into silicon in combination with either subse-
quent or in situ annealing. By means of infrared optical
transmission measurements and Rutherford backscattering
spectrometry the formation of Sic microcrystallites in Si
implanted with 10 Cf cm-* and subsequently annealed
at 850C for 20 min was demonstrated for the first time by
Borders et al. [85].
In the following several other groups have shown that
carbon ion implantation with doses > 10 cm-* gener-
ates buried Sic layers of exclusively 3C polytype in
silicon (see Refs. 186-931). From the results published
until now it seems to be clear that annealing temperatures
between = 850 and 900C are necessary to crystallize
room-temperature implanted Si-C layers and to transform
the disordered Si-C bonds into the ordered 3C-Sic struc-
ture [85,87,88,93]. A diminution of the temperature neces-
sary to synthesize Sic from 900 to 800C was reported if
Ar or Ne bubbles as nucleation centres are introduced by
additional ion implantation before annealing, a promotion
of Sic synthesis is also assumed by complete amorphiza-
by solid
tion of the implanted layers 1871. However, other authors
give annealing temperatures of 1000C [89], 1250C [91]
and 1405 [86] to be necessary to achieve crystalline Sic in
silicon. Direct synthesis of Sic in Si by carbon implanta-
tion at 880C was also reported [90], a minimum implanta-
tion temperature of 625C was found to produce epitaxial
3C-crystallites in topotactic relationship with the silicon
matrix [94]. The quality of the resulting Sic layers seems
to be also dependent on the carbon dose implanted. For
example, an overstoichiometric carbon implant (1.2 X 1Onr
cm-) into Si did not result in the formation of a buried
homogeneous layer. It is, therefore, concluded that a lim-
ited C dose for the formation of highly ordered and
homogeneous buried SIC layers is necessary, which also
depends on the orientation of the substrate [92].
Summarizing, depending on the implantation and an-
nealing conditions high dose carbon implantation into sili-
con results in the formation of buried layers either consist-
ing of 3C-Sic microcrystallites surrounded by crystalline
Si grains [85,89], or of a homogeneous distribution of
3C-Sic grains [X6,88] with diameters in the order of = 5
to 15 nm being often severely twinned [88]. This twinning
seems to be the main limiting factor in the fabrication of
312 W. Wesch/Nucl. Instr. and Meth. in Phys. Res. B 116 (1996) 305-321
high-quality Sic by ion-beam synthesis. However, a suc-
cessful application of ion-beam synthesis to produce Sic
demands more systematic work concerning the connection
between the parameters used for the synthesis and the
properties of the resulting layers.
4. Processing of silicon carbide
The fabrication of micro- or optoelectronic devices
requires the modification of the electrical or optical proper-
ties in laterally and vertically defined regions. Important
process steps are the preparation of clean and smooth
surfaces and of certain structures, doping in defined re-
gions as well as the formation of electrical contacts. Be-
cause of the outstanding physical properties of Sic, its
processing is connected with some peculiarities compared
to other semiconductors which will be discussed in the
following.
4.1. Etching and patterning of silicon carbide
Because of the high temperatures and possible reactions
with mask materials wet chemical etching is not an appro-
priate technique in Sic processing (see Section 2.2, [4,28-
301). The preparation of clean and defect-free surfaces as
required for epitaxial growth is commonly done by thermal
oxidation in a dry oxygen atmosphere at 1200C for 1 to 5
h and subsequent removal of the oxidized layer with
hydrofluoric acid @IF) [69,95-971. The thermal oxidation
rate increases with the time and is five to ten times higher
on the (OOOi)C-face of GH-SiC than on the (0001&i-face
(see Fig. 10) [98]. Thus, by estimating the oxide thickness
the polarity of the material can be determined. Further, the
20% faster oxidation rate of 3C-Sic compared to 6H-SiC
allows to distinguish between polytypes [9&l. Defects, as
stacking faults and double positioning boundaries (DPBs)
can be decorated [99].
S-face
0 1 2 3 4 5 6 increase of the etch rate of 6H-SiC compared to the
TIME 00
Fig. 10. Oxide thickness for the Si- and C-face of the (0001) plane
of 6H-Sic at 1180C [98].
Another opportunity to remove surface damage is HCl
etching in flowing Hz (3% HCl in Hz) at temperatures
between 1100 and 1200C [68]. Native oxides are removed
by heating the samples to 15OOC, 10 min in 1 atm flowing
II, 1691.
For Sic patterning plasma-based dry etching in fluori-
nated compounds (CF,, CHFs, CBrF,, SF,, NF, and mix-
tures with 0,) and in combination with lithographic mask-
ing techniques (Au, Al, Cr, indium-tin-oxide (ITO)
masks) is used. The basic mechanisms of this process
consist of a combination of chemical and physical removal
processes. A gas-phase species from a plasma is adsorbed
at the surface to form an adsorbed product molecule (e.g.
SiF,). The following desorption of the product molecule
into the gas phase as well as the removal of the nonreac-
tive residue (e.g. carbon) are supported by interaction with
energetic ions ]lOO,lOl]. Conventional reactive ion etching
(RIE) is commonly done in a radio-frequency (13.56 MHz)
reactor [102,103]. Recently, electron cyclotron resonance
(ECR) systems were used with the advantages of high
plasma density and low ion energy [104]. Compared to
conventional RIE, ECR plasma etching results in higher
etching rates and lower levels of bias [105]. The plasma
etching process is sometimes supported by directing a low
energy ion beam (commonly Ar) to the surface to be
etched (reactive ion-beam etching, RIBE) [106].
It was shown that cubic as well as hexagonal Sic can
be etched by pure fluorinated gases and by mixtures with
oxygen. Generally, in the case of pure plasma the etch
rates are remarkably lower (32 A/min for 6H-SiC in pure
CHFs [107]) than in the case of 0, additive (> 100
W/min are typical for RIE [102,105,107]). Whereas Si
reacts with fluorine and becomes volatile, carbon is sup-
posed to react with oxygen and is changed to volatile CO
or CO,. Consequently, the etch rate is influenced by the
percentage 0, added to the plasma [102,106]. In the case
of conventional RIE a maximum etch rate is obtained
when the percentage 0, was about 67% [102]. The lower
0, concentration of about 40% for maximum etch rate in
RIBE [106] is explained by an increased effectivity of
etching of the nonvolatile residues due to additional sput-
tering with argon ions. Fig. 11 illustrates the dependence
of the etch rate of Sic as a function of the 0, percentage
in CF, gas for RIE and RIBE etching. It can also be seen
that the RIE etch rate for the mask material Cr is small
compared to that of Sic and independent of the 0, con-
tent. The etch rate of Sic depends furthermore on the
rf-power density and the pressure in the reaction chamber.
The linear increase of the etch rate with the rf-power
density (Fig. 12) in the region up to 0.8 W cm-* [102,105]
is attributed to an increased dissociation of CF, and 0,
and therefore an improved reaction with Sic. The faster
3C-polytype with the power density may partly be due to
the lower pressure during the 6H-SiC etching. The etch
rate linearly increases with decreasing pressure as a conse-
 W. Wesch / Nucl. Instr. and Meth. in Phys. Res. B 1 I6 (1996) 305-321 313

i 1 1 .

0 SiC. RIBE
l 3C-Sic , RIE

Fig. 13. Surface of 6H-Sic etched with IT0 mask by rf-RIE in

CF,/O, (a) and CF,/O, /Hz (b) (5: 1: 1) 11051.
n

In the case of ECR plasma etching the etch rate is

Fig. 11.Etch rate of Sic as a function of the 0, mixing ratio in
CF, for RIBE (gas pressure 10e7 atm; Ar sputtering: acceleration
voltage 500 V, current density 0.4 mA/cm* [106] and RIE (gas
pressure 8X 10m4 atm, rf-power 0.5 W/cm; the etch rate for Cr
is also included [ 1021).
quence of the mean free paths of the reactive ions which
obviously leads to an increase of physical sputtering [ 1021.
RIE etching with CHFJO, and CFJO, gas mixtures
resulted in rough surface morphology of 3CSiC
[101,103,108] which was later on also found after etching
of 6H-SiC [105,107]. This micromasking effect is
caused by Al which sputters from the reactor electrode and
redeposits in clusters on the etched surface [ 101,105]. A
suppression of the Al deposition is possible by addition of
a low level (= 10%) H, to the gas mixture. The influence
of H, on the surface morphology of 6H-SiC is illustrated
in Fig. 13 for etching without H, and for a gas mixture of
CFJOJH, in a ratio 5 : 1: 1 [ 1051. The prevention of the
Al residue by H, is believed to be mainly a consequence
of the formation of volatile alane (AiH,). However, it
should be mentioned that H, addition leads to a reduction
in the etch rate, in the example shown in Fig. 12 the
reduction is nearly threefold.
directly proportional to the applied microwave power (Fig.
14) [105]. Two factors are responsible for this behaviour:
higher power leads to a higher density of excited species
reacting with the Sic surface, and higher power is con-
nected with higher ion densities which leads to enhanced
energetic ion bombardment and removal of etch products
adsorbed on the surface. Further, the rate is approximately
proportional to the substrate bias in the range of -20 to
- 150 V (see Fig. 14). The increase of the bias causes an
increase of the energy of ions bombarding the surface, and
therefore an increase in the rate of sputter-induced desorp-
tion of the etch products. However, most noteworthy are
the remarkably higher etch rates of ECR compared to
conventional RIE etching.
Another promising way for Sic patterning is ion-beam
processing, either by using the sputtering effect or the
different chemical resistance of crystalline and amorphous
Sic. Whereas monocrystalline Sic because of the strong
Sic bonds is not attacked by most of the common etchants
at reasonable temperatures, amorphous Sic with its weak
bonds can be etched with a HF/HNO, (1: 1) solution at
temperatures around 50C (the etch rate at 45C has been
reported to be 300 nm min- [ 1091). Based on this selec-
tive chemical etching, it has been recently shown that a
combination of photolithography, ion implantation and wet

6 H-SK?, p=3.3xK5 am l -100 V ,2.6x10-6

atm f
40- l CFJ& (5:l)
0 -21 v ,1.3x10-6
atm /
_ 0 CFdJ02/H2(5:1:1) I
2 3 C-Sic, p=8.4x10d atm ..d r
b /
.$ 30 - AC&l02 (02 : 69.7 36) ./ ..-
/ ./
z . . ...
..
,... /
b ..
P ... ./*-
,.z
d *O / ,..
/
B - /. ,//a
/
s d ,...I ~ __/O
10 - / ./ __--
./ ,. ,_-_d
- .,.y 4__---
/,. _ _--
n &:< I I , I I
"0 0.2 0.4 0.6 0.8
POWER DENSITY (w/cm3 p-WAVE POWER oy)

Fig. 12. Etch rate of 3C- 11021and 6H-SiC [lo51 as a function of Fig. 14. Etch rate of 6H-SiC versus the microwave power for ECR
the rf-power density for CF, /O, and CF, /O, /H, gas mixtures. etching at different levels of substrate bias 11051.
314 W. Wesch /Nucl. Instr. and Meth. in Phys. Res. B I16 (1996) 305-321

chemical etching (HF/HNO, (1: 1) at 65C) can be used Corresponding research concerning Sic has obviously not
to form patterns in Sic [llO]. Trenches with depths down been performed until now.
to 1 pm were produced either by high-dose implantation
of light ions through photoresist masks or by multiple-im- 4.2. Contact formation
plantation of heavier ions through platinum masks.
Ion-beam etching with Ar+ ions with energies between The formation of ohmic as well as of rectifying metal
100 and 500 eV in combination with photoresist masks has contacts is a key problem in device fabrication and a
been used to etch patterns in GaN, AlN and InN [ill]. supposition for measuring the electrical parameters. Espe-

Table 3
Contact resistivity for various Sic-metal combinations
Sub- Contact mate- Process contact Reference
StlTtte lial resistivity @,
[n cm21
n-6H MO magnetron 1x 10-4 [124]
p-6H MO sputtering 2x 10-4
n-6H Ta 1x 10-4
p-6H Ta 7x 10-4
p-6H Ti 3x 10-4

p-6H Al/Ti sputtering; 1.5 x 10-5 b311

1OOOC/Smin (2 X 10 cmw3>
1.7 x 10-3
(I X 1017cme3)

n-6H co e-gun eva- 9.2 X 1O-5 w21

Co/Ti poration; < @c<
Si/Co SOOC/5h, 3 x 10-a
Si/Co/Ti 9cQC/2b
(CoSi, , Tic)

n-6H Ni resistive 2x 1o-4 [1261

evaporation;
1OOOc/3os
3C/n-6H Ni < 1.7 x 10-a
(Si-face)
< 6 x 1O-5
(C-face)
3C/p-6H Al/T1 electron beam (2-3) X 1O-5
evaporation;
95OC/2 min
n-6H TiC epitaxial 1.3 x 10-S [I301
growth

n-6H Ni electron beam < 5 x lo+ tl251

evaporation;
95oC/2 min
(Ni,Si)

3c Al N + implant. 1.4x 1o-5 [132]

Ti Sic; 1.5 x 10-a
evaporation

3c Ti/Ft/Au sputtering 1.14x 1o-4 tl281

W/Pt/Au 1.98 X 1O-4
Ti/TiN/Ft/Au 1.41 x 1o-4

n-3C Tic epitaxial 4.46 x 10-6 < tl291

growth e, <
6.42 X 1O-6
 W. Wesch/Nucl. Instr. and Meth. in Phys. Res. B 116 (1996) 305-321
cially the formation of ohmic contacts is of interest be-
cause high-power high-frequency devices require ohmic
contacts with a specific contact resistivity of less than
1 X low5 fi cm* [112,1131.
The investigation of a large number of metals and
metal alloys on cubic and hexagonal Sic has shown that
most of them (e.g. Pd, Au, Co, Ti, Ag, Tb, Al on 3C-Sic
[ 1141, Pd, Au, Ag, Tb, Er, Mn, Ti, Pt., Hf, Co on 6H-SiC
[115,116]) form Schottky contacts in the as-deposited state.
According to the Schottky-Mott theory ohmic contacts
between metals and semiconductors can be produced if the
work function of the metal is less than that of the semicon-
ductor [ 1171. Thus, metals with work functions exceeding
that of Sic are appropriate for Schottky barrier contacts.
For example, Pt with a work function of 5.65 eV [118]
forms a Schottky contact on 6H-SiC (the work function for
6H-SiC (0001) is reported to be 4.8 eV [119]).
To produce ohmic contacts with low contact resistivity
p, on Sic it has been suggested that the contact material
should contain a transition metal which is capable to form
carbide or silicide compounds with Sic during post-de-
position annealing at temperatures L 700C [ 120,121].
Especially the refractory metal silicides seem to be favoured
for high-temperature device applications because of their
unique thermal stability [ 120,122].
In the last years attempts have been made by several
groups to produce ohmic contacts on Sic using transition
metals (e.g. Ti, Cr, Ni, W, Ta, MO [ 120,123- 1261), transi-
tion metal/Au multilayers (e.g. Cr/Au, Ti/Au, Ta/Au,
W/Au, Ti/Pt/Au, W/Pt/Au, Ti/TiN/Pt/Au,
Ti/TiN/Pt/Au, [123,127,128]), silicides (e.g. TiSi,,
TaSi,, WSi,, CoSi,, [120,122,123]) and carbides (e.g.
Tic, TaC [ 121,129,130]). In most cases post-deposition
annealing was done at temperatures depending on the
contact materials. Table 3 gives selected values of the
specific contact resistivity obtained with various contact
materials and formation procedures. Magnetron sputtering
of MO, Ta or Ti on n- and p-type GH-SIC without post-de-
position treatment results in the formation of ohmic con-
tacts, the contact resistivity, however, reaches only values
in the order of 10e4 n cm* [124]. Contact resistivities
between 3 X 10e3 and 9.2 X low4 fi cm* have been ob-
tained by electron-gun evaporation of Co, Co/Ti, Si/Co
and Si/Co/Ti on n-type 6H-SiC after subsequent anneal-
ing at 5ooC/5 h and 9OOC/2 h, respectively 11221.
These contact materials are believed to form cobalt dicili-
tide (CoSi,) or titanium carbide (TIC). By epitaxial growth
of Tic on n-type 6H-SiC a contact resistivity of 1.3 X lo-
fi cm* was measured, the contacts were thermally stable
up to 13OtYC[ 1301. Resistive evaporation of Ni on n-type
GH-SiC and subsequent annealing at lOOOC/30 s resulted
in a contact resistivity of 2 X lop4 fi cm2. However,
bringing a thin layer of SC-Sic with its lower energy gap
and the lower effective mass compared to 6H-SiC between
n-type 6H-SiC and the metallization improves the contact
resistivity remarkably: for the C-face values < 6 X lo-
315
Q cm* and for the Si-face values < 1.7 x 10ms 0 cm2
were measured [126]. On p-type 6H-SiC with the same
procedure but using an Al/Ti alloy as contact material and
annealing at 95OC/2 min contact resistivities of (2-3) X
lo- fi cm2 are obtained. Similar values of pc were
measured by sputtering of Al/Ti on p-type 6H-SiC and
annealing at lOOOC/5 min [131]. In this study the depen-
dence of pc on the substrate carrier concentration is illus-
trated: the contact resistivity varies between 1.7 X 10e3
&m* for a hole concentration NA= 1 X 1017 cmp3 and
1.5 X lo- a cm2 for NA = 2 X 1019 cm-3.
The best pc values reported until now for n-type
BH-SiC were obtained by electron beam evaporation of Ni
and subsequent formation of Ni,Si with thermal annealing
at 95OC/2 min [ 1251. The specific contact resistivities are
generally < 5 X lop6 a cm2 and stable up to tempera-
tures of 1200C over long periods. A slight variation with
the substrate carrier concentration, the temperature and the
Sic-face was observed. However, the values varied for
several samples produced under the same conditions indi-
cating problems with the reproducibility.
Compared to 6H-Sic, only a few studies exist concern-
ing ohmic contact formation on 3C material. Thermal
evaporation of Ti and W and annealing between 300 and
600C yielded ohmic contacts with p, in the order of 10m3
52 cm*, for sputtered WSi, and TiSi, contact resistivities
around 10v4 CRcm2 were obtained [120]. Sputtering of
Ti/Pt/Au, W/Pt/Au and Ti/TiN/Pt/Au alloys on 3C-
Sic without thermal treatment resulted in values of the
same order of magnitude (1.14 X lop4 fi cm2 for
Ti/Pt/Au), the Ti/TiN/Pt/Au contacts exhibited ther-
mal stability until a temperature of 750C [128]. Recently,
an attempt was made to influence the contact resistivity by
ion-implantation doping of the 3C-Sic surface which is a
method known from silicon technology. Multiple implanta-
tion of 30 and 55 keV Nf implantation was carried out
with ion fluences between 1 X 1014 and 1 X lOI cm-*.
After annealing at 125OC/30 min Al or Ti were deposited
as contact materials. Minimum contact resistivities of 1.4
X lop5 and 1.5 X 10e5 fl cm2 were measured for Al and
Ti contacts, respectively, at the highest substrate doping
concentration of 3 X 102 cmw3 [132]. However, still bet-
ter values of the contact resistivity of n-type 3C-Sic
between f: 4.5 X lop6 and 6.4 X 10m6 M cm2 were re-
ported for epitaxially grown TiC layers [ 1291.
Indeed, the reaction of transition metals to form sili-
tides or carbides or deposition of silicides or carbides
seem to be the most promising way to produce ohmic
contacts on both n- and p-type Sic with low contact
resistivities. The really different values obtained in various
laboratories with equal techniques, however, indicate the
tremendous influence of surface quality and surface treat-
ment on the reproducibility of the results. To what extent
high-level surface doping by ion implantation may be a
way to partly overcome these problems is not yet clear and
needs more work.
316 W. Wesch/Nucl. Instr. and Meth. in Phys. Res. B 116 (1996) 305-321
4.3. Doping
High-purity, undoped SIC with its large energy gap
exhibits insulating properties at normal conditions. How-
ever, although the materials available are normally re-
ported as having n-type character due to unintentional
doping with nitrogen or due to electrically active defects
[133], the application of Sic in semiconductor device
technology requires controlled and selective doping. The
most common dopants are N and P for n-type and B, Al
and Ga for p-type doping (activation energies are given in
Table 4, [971).
Controlled doping of bulk crystals and epitaxial layers
is done in situ by introducing the corresponding species
into the reaction chambers (see e.g. Ref. [8] and references
therein). For a planar technology selective doping in later-
ally and vertically limited regions is demanded which is in
silicon technology carried out by a diffusion process in
combination with suitable masking materials. The selective
doping of SIC by diffusion is complicated and hardly
applicable because of the small diffusion coefficients: the
diffusion coefficients of the usual dopants are in the order
of lo-3 to lo- cm2 s- for the temperature region
1700 to 2400C (see e.g. Ref. [134]). Thus, to achieve
reasonable diffusion rates temperatures in excess of 2OOOC
are necessary for dopant diffusion into SIC. Under these
conditions not only the commonly used masking oxide
layers vaporize, but also Sic decomposes [8,97].
An alternative to overcome these difficulties offers ion
implantation. The advantages of ion implantation - accu-
rate control of dopant distribution and concentration by
energy and dose control - are hampered by the formation
of radiation damage as a consequence of nuclear collisions
of the implanted ions with the target atoms. To produce
electrically active regions the damage has to be removed
e.g. by post implantation heating, but at much lower
temperatures and for much briefer times than necessary for
doping by diffusion. The annealing regime to obtain opti-
mum properties depends on the kind and concentration of
defects produced. Therefore, the investigation of damage
production is a supposition to optimize the process param-
eters for the corresponding material.
The implantation damage in Sic was investigated for
various ions (H+, B+, C+, N+, Al+, Si+, P+, Cr+, Ar+,
Fe+, Gaf, Sbf, Xe+, [135-1471). Depending on the ion
Table 4
Ionization energies of dopant impurities in silicon carbide [97]
Dopant EA WI
3C-Sic 6H-SiC
Al 0.257 0.27
B 0.73 0.39/0.73
N 0.05
e (O.l)?
mass and the implantation temperature, the damage con-
centration increases with the ion fluence, and for a critical
energy density deposited into nuclear processes amorphous
layers are produced. For room temperature implantation
the critical energy density for amorphization was found to
be about 2 X 102 keV cmm3 [135,137] corresponding to
0.2 to 0.25 displacements per atom (dpa) [140].
The damage production is connected with a change of
several material properties. The hardness of Sic increases
to about 10% for ion fluences that do not produce an
amorphous zone. With beginning amorphization the hard-
ness drops, and it is 40% of that of an unimplanted crystal
if an amorphous layer is produced [ 140,148].
Implanted, amorphous Sic is furthermore characterized
by an enhanced chemical reactivity [ 1491. The etching rate
of amorphous Sic in a boiling solution of 50% K,Fe,(CN&
and 50% KOH is 2.5 to 4 times higher than that of the
virgin material. Besides that, the oxidation rate is higher
for amorphous material: amorphous samples exposed to
flowing oxygen for 1 h at 1300C have a 1.7 to 3 times
higher oxide thickness than unimplanted samples. Thus,
amorphization of Sic can be used for selective etching of
the material.
Another consequence of radiation damage is the change
of the near-edge optical properties [ 150,151]. The sub-gap
optical absorption coefficient increases with the ion dose
and reaches values between lo4 and lo5 cm- after
amorphization. This enables the production of patterns
with high optical contrast which can be used as litho-
graphic masks or for permanent storage of data [150,152].
The increase of the near-edge optical absorption is accom-
panied by an increase of the refractive index in this
wavelength region, the relative refractive index change is
in the order of 30% for the amorphous state [151].
For electronic device applications the implant damage
has to be removed to reach substitutional incorporation and
electrical activation of the dopants. In the case of weakly
damaged non-amorphous layers the damage anneals almost
completely in the temperature range of 200 to 1000C
[135,143,153]. The annealing behaviour of amorphous lay-
ers is much more complex and far from being completely
understood. Contradictory to previously reported results
which showed that an epitaxial recrystallization of amor-
phous layers starts only at temperatures above 1450C
[ 136,140,153], we have observed a beginning of epitaxial
E, WI
3C-Sic 6H-Sic
0.15
 W. Wesch/Nucl. Instr. and Meth. in Phys. Rex B 116 (I9961 305-321
recrystallization of amorphous 6H-SiC already at an an-
nealing temperature of 1000C [154]. The process turns
into a crystalline columnar growth and is blocked by a
competing volume crystallization process. Generally, an-
nealing temperatures > 1500C seem to be necessary to
recrystallize amorphous Sic layers. In this temperature
region the annealing time seems to play a role: whereas
rapid thermal annealing (RTA) at 1750C leads to a recrys-
tallized layer with a high concentration of residual damage
[154], a kind of explosive crystallization was reported
[la] for annealing at 1500C/1 h resulting in relatively
defect-free crystalline layers. However, this result has to
be proved by further experiments. It should be mentioned
that at temperatures > 1300C polytype transitions 6H -+
3C have been observed [155] which can disturb a perfect
recrystallization. Other problems connected with the high
annealing temperatures for amorphous layers may arise as
a consequence of stoichiometric deviations 11561, graphiti-
zation of the surface at temperatures 1 1000C [157],
dopant redistribution [158] as well as dopant outdiffusion
[136,159].
One possible way to reduce the annealing temperature
of amorphous layers is ion beam induced epitaxial crystal-
lization (IBIEC) which results in the formation of crys-
talline defective layers [ 160,161]. These are hoped to
anneal at remarkably lower temperatures.
Another opportunity is the suppression of amorphiza-
tion by implanting Sic at elevated temperatures (in situ
recrystallization). It was recently shown by several authors
that implantation temperatures in the range of 750 to
850C prevent the amorphization by B +, Al+ and Ga+
implantation [158,162,163], in the case of N+ a 400C
implant is sufficient to prevent the formation of amorphous
material up to a dose of 1.2 X lOI cm-* 11641.However,
systematic investigations of the influence of the implanta-
tion temperature with respect to an optimization of the
implantation parameters are lacking. Investigations in our
laboratory have shown that at temperatures > 300C Ga+
implantation of 1 X 1016 cm-* does not result in the
formation of an amorphous layer [154]. For both 1 X 10
cm- Ga+ and Sb+ implantation in a narrow range of the
implantation temperature (200-400C) dynamical anneal-
ing during implantation causes a substantial decrease of
damage (Fig. 15) and simultaneously the incorporation of a
large fraction of Sb- and Ga-atoms onto substitutional sites
[ 165,166]. According to these results, the optimum temper-
ature region to obtain minimum defect concentration (-
7%) and maximum substitutional incorporation (85% for
Ga and = 70% for Sb) is 500 to 800C. It should be
mentioned that the annealing effect is limited due to the
formation of new stable defects which can obviously hardly
be removed by post implantation annealing.
In the case of n-type doping with nitrogen it was shown
that an implantation temperature of 400C leads to a sheet
carriei Concentration being more than one order of ma@i-
tude higher than for room temperature implantation if the
317
0.6 ; .....
*. ...., .., \
a x., y 0.62
a L.L,*
.
0.4
annealed at 1500 C, 60 s
T, [Cl
Fig. 15. Relative concentration of displaced atoms npd (de-
termined by RBS-channeling) in the maximum of the damage
distribution for 1 X lOI cm-* Ga+ and SbC implantation and
the fraction of substitutionally incorporated dopautes fi,, versus
the implantation temperature T,. For Sb+ implantation at T, = 350
and 6OOT the effect of subsequent annealing at 1500C/60 s is
depicted 11651.
samples are annealed in the range of 800 to 1200C [ 1671.
The percentage of electrical activation is = 12% in the
case of N+ implantation, for Asi implantation still slighfiy
lower activation was found. In a recent study of the dose
and annealing temperature dependence of electrical activa-
tion of room temperature NW implantation into 6H-SiC
epilayers an electrical activation of about 50% was re-
ported for the dose range = 1Ol3 to = lOI cm- for an
annealing temperature of 1500C [ 1681. In this dose region
the average carrier concentration increases linearly with
the ion fluence. For doses > 1015 cm-* a saturation of the
carrier concentration is observed, which makes the electri-
cal activation ratio decrease down to about = 10% (Fig.
16). The increase of the average carrier concentration with
increasing annealing temperature indicates the influence of
residual defects on the electrical activation.
The electrical activation of p-type doped Sic seems to
be generally lower. For 850C Al+ and B implantation
into n-type 6H- and 3C-Sic only = 1% activation was
measured after a 1400C anneal [ 1631. Poor implant accep-
tor activation seems to be a principal problem for Sic and
may be connected with complexing of the acceptor implant
with Si or C or with vacancies of both species, residing of
acceptor species on non-electrically active interstitial sites,
the presence of stable deep donor type defects, or trapping
of impurities at the dislocations and stacking faults in the
material [8,169,170].
Summarizing, to obtain optimum electrical activation
the damage produced during implantation has to be mini-
mized favouring elevated implantation temperatures. Fur-
ther, short time annealing (RTA) seems to improve the
resulting electrical properties. Generally, systematic work
318 W. Wesch/Nucl. Instr. and Meth. in Phys. Res. B 116 (1996) 305-321
DOSE (cm-*)
Fig. 16. Average carrier concentration for N+ implantation into
6H-Sic annealed at different temperatures versus the ion fluence.
The dotted lines represent 100% and 50% electrical activation
[1681.
has to be done to investigate the connection between
residual defects and the electrical properties to further
optimize the processing parameters.
5. Concluding remarks
Problems of silicon carbide synthesis are the further
reduction of as-grown defects as well as of the uninten-
tional n-type doping occurring during the commonly used
vapour growth processes. These processes allow the growth
of stoichiomehic Sic of a single polytype.
Chemical vapour deposition (CVD) on SIC wafers re-
sults in layers with reduced defect density compared to
epitaxy on Si. Step-controlled epitaxy enables to grow Sic
layers of a certain polytype.
The lower growth temperature of CVD processes com-
pared to sublimation bulk growth reduces the unintentional
doping level. A further significant reduction of uninten-
tional doping is obtained using site-competition epitaxy.
This method also enables accurate intentional doping of
the layers.
A promising way to produce high-purity, undoped as
well as exactly doped Sic layers is solid-source MBE
under Si-stabilized conditions. This method offers also the
opportunity to grow layer sequences consisting of different
polytypes, i.e. the formation of Sic heterostructures be-
comes principally possible. However, research in this field
is still at the beginning.
Ion beam synthesis as another approach to produce Sic
up to now did not give satisfactory results, more work to
optimize the process parameters seems to be necessary.
The processing of SIC is complicated because of some
particular material properties. Wet chemical etching is not
an appropriate method for surface cleaning and patterning.
Thermal oxidation or HCl etching in flowing H, is com-
monly used to remove surface damage. The formation of
patterns is done by plasma-based dry etching processes in
combination with lithography, as reactive ion etching (RIE)
and reactive ion ham etching (RIBE). The highest etch
rates are obtained if RIE is performed in an electron
cyclotron resonance (ECR) system. Combination of ion
beam-induced amorphization and wet chemical etching can
also be used for patterning, but this method is hardly been
systematically investigated. For the future, ion induced
sputtering, with suitable masks or maskless, seems to be a
research field of interest.
With respect to ohmic contact formation, transition
metals forming silicides or carbides give the best results.
However, the reproducibility of the values reported is
poor, and the tremendous role of the surface quality is
obvious. High-level surface doping of the substrate by ion
implantation may bring further success.
Because of the small diffusion coefficients of the
dopants in Sic and the high process temperatures neces-
sary selective doping by diffusion is hardly applicable. Ion
implantation is an alternative, but for doping purposes the
radiation damage occurring during ion bombardment has
to be removed. Hot implantation is the best way to obtain
minimum as-implanted defect concentration and maximum
substitutional dopant incorporation. However, at high doses
stable residual defects are formed which can hardly be
annealed. These residual defects limit the electrical activa-
tion of n-type implants. The activation of p-type implants
seems to be a general problem in SiC processing. Conclud-
ing, with respect to ion beam processing further work
should be directed to the investigation of the connection
between residual defects and the resulting properties as
well as the reduction of these defects in order to optimize
the processing parameters.
Acknowledgement
The author wishes to thank A. Fissel, F. Bechstedt, T.
Bachmann, E. Wendler and A. Heft for helpful discussions
as well as for critical revision of parts of the manuscript.
The technical assistance of U. Bomkessel, U. Barth and C.
Voigt during the preparation of the manuscript is greatly
appreciated. Research in the authors group is supported by
the Deutsche Forschungsgemeinschaft, Sonderforschungs-
bereich 196.
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