MATERIALS

SCIENCE &
ENGINEERING

ELSEVIER Materials Science and Engineering B34 (1995) 83-105

B

Critical review

A critical review of ohmic and rectifying contacts for silicon carbide

Lisa M. Porter, Robert F. Davis
Department of Materials Science and Engineering, North Carolina State University, Raleigh, NC 27695-7907, USA
Received 10 May 1995

Abstract

For more than three decades, SiC has been investigated as a wide band gap semiconductor. This paper reviews ohmic and
rectifying metal contacts on n- and p-type ~- and fl-SiC reported throughout that time period. Electrical characteristics, Schottky
barrier heights (SBHs), thermal stability, and chemical reactions are discussed. Most metals formed very good rectifying contacts
in the as-deposited condition on both n- and p-type 6H-SiC with Schottky barrier heights ~>1 eV. Low ideality factors (n < 1.1)
and high breakdown voltages (> 1100 V) have been displayed in this material. The electrical properties of contacts on 3C-SiC have
been more dependent on the quality of the 3C-SiC films, which have been plagued by higher defect densities than 6H-SiC. In
general, a partial pinning of the Fermi level has been evidenced by positive correlations, which are less than 1 (~0.2-0.6), between
the SBHs and the metal work functions. Ohmic contacts with low contact resistivities (~< 10 -5 f~ cm2), especially important for
high power applications, on any of the SiC polytypes have been exceptionally difficult to achieve. Most of the ohmic contacts have
relied on high doping concentrations in combination with annealing at temperatures between 800 and 1300 °C. Annealed Ni and
A1 have primarily been used in ohmic contact metallizations for n- and p-type SiC, respectively. The tendency of SiC to react with
metals to form carbides and/or silicides at potential device operating temperatures ( ~ 600 °C) can be a problem for potential long
term applications at high temperature. These critical issues are discussed along with future perspectives for research approaches.

Keywords: Silicon carbide; Semiconductors; Ohmic metal contacts; Rectifying metal contacts

I. Introduction actuality, this polytype is only 33% hexagonal. Its

In certain close-packed materials such as SiC, there
exists a one-dimensional type of polymorphism called
polytypism. Polytypes are alike within the closest-
packed planes but differ in the stacking sequence in the
dimension perpendicular to these planes. The stacking
sequence of these closest-packed planes is commonly
described by an ABC notation. In SiC each letter refers
to a bilayer composed of individual layers of Si and C.
A repetitive ABC stacking sequence yields the zinc
blende structure. This is the only cubic SiC polytype
and is referred to as 3C- or fl-SiC, where the 3 refers to
the number of Si/C bilayers in the periodic sequence.
The hexagonal (wurtzite) ( A B A B . . . ) sequence is also
found in SiC. Both can also occur in more complex,
intermixed forms yielding a wider range of ordered,
larger period, hexagonal (H) or rhombohedral (R)
structures of which 6H-SiC is the most common. In
ABCACB stacking sequence consists of two (identical
neighboring) hexagonal bilayers and four (different
neighboring) cubic bilayers. All of these noncubic struc-
tures are known collectively as a-SiC.
The multitude of extreme thermal and electronic
properties of SiC produces numerous and novel combi-
nations of attributes for a semiconductor material for
both optoelectronic and for high-power, -frequency,
-temperature, -speed, and radiation hard microelec-
tronic devices.
The great potential of (6H)-SiC as a semiconductor
in such electronic device applications is challenged by
the difficulty of controlling metal contact properties.
These properties of the metal/SiC interfaces include
uniformity and thickness of the interfacial region, sta-
bility at high temperatures ( ~ 600 °C), and most impor-
tantly, the Schottky barrier height (SBH), or the energy
barrier for electrons traversing the interface.

0921-5107/95/$09.50 © 1995 - - Elsevier Science S.A. All rights reserved

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84 L.M. Porter, R . F Davis / Materials" Science and Engineering B34 (1995) 83 105

Table 1
Selected structural, thermal, and electronic properties of 6H- and 3C-SiC at 300 K

Property 6H-SiC Ref. 3C-SiC Ref.

Band gap Eg = 3.0 eV [31 2.3 eV [3]

Lattice parameter a = 3.08086 A [116] a - 3.08269/k [116]
c= 15.1174 A e = 7.55124/~
Work function ~s = 4.75 + / - 0.10 eV [12] ~s ~ 5.2 eV calculated
(n-type, (0001) surface): from Xs
4.85 + / - 0.10 eV (p-type, value
(0001) surface)
Electron affinity Zs = 3.3 eV calculated Zs - 4.0 eV [12,117]
from [12]
Electron mobility /~n-700cm 2 (Vs) I (at n= [118] /Ln=980cm 2 (Vs) t (at n [119]
1.1 x 1016cm 3) =4.0× 1016cm 3)
Saturated electron vs~,t= 2.0 x 107 cm s i [120] Usat = 2.5 x 107 cm S i [121]
drift velocity
Breakdown E R = 4 x 106Vcm i [122] EB - 3 × 106Vcm i [122]
electric field
Dielectric ~:1(0)= 10.03 [123] ~:(0)= 9.72 [1231
constant c±(0) = 9.66 c(,z) = 6.52
~;11(3c)= 6.70
~:±(oc)= 6.52
Thermal ~rT=4.9Wcm I deg-t [124] aT--4.9Wcm --Ideg ; [124]
conductivity

T h e S c h o t t k y b a r r i e r height d e t e r m i n e s the electrical e m p i r i c a l d e v i a t i o n from the S c h o t t k y - M o t t limit led

b e h a v i o r o f an o h m i c o r S c h o t t k y contact. A n o h m i c
contact, i m p o r t a n t for m a k i n g o u t s i d e c o m m u n i c a t i o n
to a device, is defined as having: (1) a linear a n d
s y m m e t r i c c u r r e n t - v o l t a g e r e l a t i o n s h i p for positive a n d
negative voltages; a n d (2) negligible resistance c o m -
p a r e d with the b u l k o f the device. Therefore, a low
S B H is necessary to create a g o o d o h m i c contact.
H o w e v e r , a large S B H is necessary to create a g o o d
S c h o t t k y , o r rectifying, contact. A rectifying c o n t a c t
allows c u r r e n t to flow for only one sign (positive o r
negative) o f v o l t a g e bias, t h e r e b y b e c o m i n g a c o m p o -
nent o f the active region o f the device.
Because o f the critical i m p o r t a n c e o f the S B H (also
written s y m b o l i c a l l y as ~B), m u c h research has been
d e v o t e d to achieving an u n d e r s t a n d i n g o f the u n d e r l y -
ing p h e n o m e n a , its c o n t r o l , a n d the e x p e r i m e n t a l p r o -
cess routes by which the latter m a y b e achieved. W h e n
two m a t e r i a l s c o m e in contact, the respective F e r m i
levels m u s t align. In 1938 M o t t [1] defined a relation-
ship which is n o w k n o w n as the S c h o t t k y M o t t limit
for an ideal metal s e m i c o n d u c t o r contact. This rela-
t i o n s h i p states t h a t (for an n - t y p e s e m i c o n d u c t o r ) the
b a r r i e r height is equal to the w o r k function o f the
metal, ~M, m i n u s the electron affinity o f the semicon-
d u c t o r , Zs
(1)B = ( ~ M - - X S (1)
This r e l a t i o n s h i p implies t h a t c o n t r o l over the b a r r i e r
height is achieved b y the choice o f metal.
In practice, however, it is c o m m o n l y f o u n d t h a t ~B is
either w e a k l y d e p e n d e n t on o r i n d e p e n d e n t o f ¢~M. This
to the d e v e l o p m e n t o f a t h e o r y b a s e d on surface states
r a t h e r t h a n w o r k function differences [2]. Because the
surface o f a m a t e r i a l is itself an imperfection, surface
states can exist within the energy gap o f the bulk
s e m i c o n d u c t o r . Bardeen f o u n d t h a t the density o f sur-
face states can be so high t h a t they p r e d e t e r m i n e the
b a r r i e r height, such that ~B is c o m p l e t e l y i n d e p e n d e n t
o f q~M- In this case the b a r r i e r height o r the F e r m i level
is said to be ' p i n n e d ' , a n d c o n t r o l over the b a r r i e r
height is lost. Usually the actual r e l a t i o n s h i p between
~B a n d ~ u falls s o m e w h e r e between the S c h o t t k y
M o r t limit a n d the B a r d e e n limit.
In a d d i t i o n to the electronic interactions at an 'inti-
m a t e ' m e t a l - s e m i c o n d u c t o r contact, the chemical a n d
structural interactions m u s t be considered. M o s t b a r r i e r
height m o d e l s d o not address chemical b o n d s at the
interface, yet few interfaces c o n t a i n m a t e r i a l s which are
inert with respect to each other. T h e structure m a y be
i m p o r t a n t in terms o f affecting the n u m b e r o f surface
(interface) states, which in t u r n affects the v a r i a b i l i t y o f
the b a r r i e r height.
2. Important properties of silicon carbide
T a b l e 1 lists some o f the structural, thermal, a n d
electronic p r o p e r t i e s o f c~(6H)-SiC a n d fl(3C)-SiC. T h e
b a n d gaps o f the 6H a n d 3C p o l y t y p e s at r o o m temper-
ature are ~ 3 . 0 a n d ~ 2 . 3 eV, respectively [3]. Different
rating systems for s e m i c o n d u c t o r s , d e p e n d e n t on the
p a r t i c u l a r o p e r a t i n g specifications, have been d e v e l o p e d
 L.M. Porter, R.F. Davis / Materials Science and Engineering B34 (1995) 83-105
as "figures of merit." Johnson's figure of merit [4],
(EBVsat/TC)2 is based on high frequency and high power
operation in discrete devices. Keyes' figure of merit [5],
av(Vs,t/e) 1/2 considers high speed operation in devices in
integrated circuits. Thus, both a high breakdown elec-
tric field, EB, and a high saturated electron drift veloc-
ity, Vsat, are desired for high frequency/power operating
conditions. In the case of SiC, it is the high breakdown
field which gives it a high rating. A high thermal
conductivity, aT, is needed to dissipate heat quickly
from small, closely-spaced devices. The conductivity of
SiC is superior to that of Cu at room temperature.
Baliga's figure of merit [6], (g,t/Eg3) is based on the need
to minimize conduction losses in power field effect
transistors (FETs). Here e is the dielectric constant of
the semiconductor,/z is the electron mobility, and Eg is
the band gap. Baliga later developed a figure of merit
for high frequency applications which accounts for
switching losses [7], (/,tEBZV~°5/(2VBI'5)), where V~ is
the gate drive voltage and VB is the breakdown voltage.
These four figures of merit for a few semiconductors
are normalized with respect to Si in Table 2. The very
high figures of merit for 6H-SiC combined with the
ability to grow boules and films as well as dope the
material both n- and p-type make it a distinguished
wide band gap semiconductor. The reader is referred to
Refs. [8-11] for detailed descriptions of properties and
technological status of SiC and other wide band gap
semiconductors.
Two other properties of the semiconductor which are
important in terms of contacts are work function and
electron affinity. Pelletier et al. [12] measured under
ultra high vacuum conditions the work function of n-
and p-type 6H-SiC as a function of temperature be-
tween 300 and 1600 K, and from these measurements
the electron affinity may be calculated. The n-type
material was doped with N and the p-type material
with A1. Special attention was given to cleaning the
surface so as not to introduce extrinsic surface states
caused by impurities. The normally Si-terminated
(0001) surfaces were heated to T~< 1230°C. Higher
Table 2
Figures of merit calculated for selected semiconductor materials
ratioed to silicon: Johnson's figure of merit (JFM), Keyes' figure of
merit (KFM), Baliga's figure of merit (BFM), and Baliga's high
frequency figure of merit (BHFFM)
Material JFM [115] KFM [115] BFM [7,125] BHFFM [7,125]
Si 1.0 1.0 1.0 1.0
GaAs 7 0.456 13 10
InP 16 0.608 l0 7 nated (0001) surface exhibited a _x/3 × ~/3 LEED pat-
GaN 282 1.76 910 100
6H-SiC 695 5.12 106 13
3C-SiC 1137 5.8 40 12
Diamond 8206 32.2 8574 454
85
temperatures were not used in order to avoid the forma-
tion of excess carbon on the surface as a result of Si
eyaporation. However, heat treatment at those tempera-
tures should still leave a C-rich surface according to [13].
The work function remained constant for each do-
pant type within the temperature range measured. In
addition, the difference in work functions between n-
and p-type samples (4.75 and 4.85 eV, respectively) was
small. These results led to the conclusion that the Fermi
level is pinned at the surface due to intrinsic surface
states. However, if the surfaces were graphite termi-
nated, as is likely for the temperatures used, these
surface states may have been extrinsic in nature rather
than intrinsic.
The electron affinity, which is closely related to the
work function, was also calculated by this group. Using
the method of Frese [14], where Zs = O s - 0.5Eg, the
room temperature electron affinity was calculated to be
3.7eV. However, using the intrinsic work function
value of 4.80 eV and subtracting 1.5 eV, which is half of
the band gap, a value of 3.3 eV is obtained. Because the
3.3 eV value follows from the measured work function
of Pelletier et al., it has been used in the present
research as the electron affinity of 6H-SiC to calculate
predicted Schottky barrier heights. Any error in Zs
simply shifts all of the theoretical barrier heights by the
same amount and, therefore, does not affect the slope
of • B vs. OM. While the room temperature work func-
tion was not measured for 3C-SiC, the room tempera-
ture electron affinity was reported to be 4.0 eV. Using
the method stated above, this would correspond with a
work function of 5.2 eV for intrinsic fl-SiC.
3. Surface chemistry
As the preparation of a clean semiconductor surface
is critically important to the resulting contact proper-
ties, this section briefly reviews the various cleaning
procedures used on SiC, the resulting chemistry and
structure of the surface, and associated problems.
Preparation of a chemically-clean, atomically-ordered
surface has proven to be a nontrivial problem in SiC.
The surface chemistry and structure of single crystals of
the e (6H) polytype were first investigated in 1975 by
van Bommel et al. [13]. The surfaces were monitored
with low energy electron diffraction (LEED) and Auger
electron spectroscopy (AES) after exposure to various
temperatures under ultra high vacuum (UHV) condi-
tions. As a result of low temperature heating (at
250 °C) for an unspecified amount of time, the Si-termi-
tern, while the C-terminated (0001) surface exhibited a
1 x 1 pattern. A 6x/3 × 6x/3, R30 ° pattern began to
develop on the (0001) face during successive 15min
anneals at 800 °C; this became the only pattern after
86 L.M. Porter, R.F. Davis / Materials Science and Engineering B34 (1995) 83 105
heat treatment at 1000 °C. As a result of annealing at
1500 °C the surface exhibited a 1 x 1 graphite phase.
The (000]-) face showed 2 x 2 or 3 x 3 patterns after
800 and 1000 °C. After 1500 °C graphite rings appeared
on this latter face, indicative of polycrystalline graphite.
The surfaces after the 800 °C exposure showed AES
C peaks of the carbide type. After 1000 °C the Si-to-C
ratio decreased, and the C peak changed from carbidic
to graphitic. These two results, along with the develop-
ment of a peak at 20 eV, indicated the formation of
graphite.
The L E E D results at 250 °C were interpreted by van
Bommel et al. as being representative of reconstructed
surfaces with possible submonolayer impurities. The
6x/3, 30 ° pattern was attributed to the SiC substrate
with a monocrystalline graphite top layer, which had
rotated 30 ° with respect to the underlying SiC lattice.
Thus, under the U H V conditions used by these investi-
gators graphite begins to form at the (0001) surface as
low as 800 °C. Graphite formation occurred at lower
temperatures on the (000i) surface. On both faces the
mechanism was reported to consist of the collapse of
three C layers to form one graphite layer due to the
incongruent evaporation of Si. Many orientations are
possible, but apparently only one is favored on the
Si-face.
Following the work of van Bommel, researchers have
experimented with methods to clean the SiC surface
without forming a graphitic surface layer. Kaplan and
Parrill [15] heated fl-SiC (100) and 6H-SiC (0001) and
(000i) samples at progressively higher temperatures,
typically for 3 min, in the presence of a Ga flux to
volatilize the surface oxide. The oxide was reduced at
temperatures as low as 850 °C; however, complete re-
moval was a very slow process below 1050°C. In
addition, temperatures which resulted in complete re-
moval of oxygen also resulted in a decrease of the Si/C
ratio. After annealing at 1185 °C for 3 rain, the Si/C
ratio decreased significantly, and the data indicated the
initial formation of graphite. In fl-SiC C2 x 2 struc-
tures were observed by LEED, which were in agree-
ment with the results of Dayan [16] for comparable
temperatures. The C-face of 6H-SiC displayed 1 x 1
patterns, except after extended heating at 900 °C, when
some areas displayed a x/3 x x/3 reconstruction. The
Si-face displayed a 3 × 3 reconstruction.
The residual, tenacious oxide was thought to be
located in regions of the surface where oxygen can
penetrate well into the surface defects. Therefore, com-
plete oxide removal on rough surfaces should be more
difficult. Although the surface oxide was volatilized by
the Ga, the temperatures required to completely remove
the oxide resulted in the same problem of graphite
termination.
In later work [17] Kaplan heated SiC in the presence
of an elemental Si flux, which removed the surface
oxide as volatilized SiO. Prior to this step and to
loading into the U H V chamber, the samples were
chemically cleaned successively in detergent solution,
trichloroethylene, acetone, and methanol. Some sam-
ples were also dipped in hydrofluoric acid followed by
deionized water, but this treatment did not noticeably
affect the amount of residual oxide. The 6H-SiC (0001)
and fl-SiC (111) surfaces were indistinguishable. Faint
satellite spots appeared with a small amount of oxide
still present. After heat treatment at 850, 950, and
> 1000 °C, the LEED patterns were 3 x 3; (x/3 x x/3),
R30°; and 1 x 1, respectively. The Si surface concentra-
tion decreased with temperature. Parallel electron en-
ergy loss spectroscopy (PEELS) revealed the beginning
of graphite segregation at 950 °C. The 3 x 3 phase was
asserted to correspond with an adsorbed Si bilayer with
a high vacancy concentration. Annealing at 950 °C
depleted the surface Si and caused the surface recon-
struction to change to a x/3 x x/3 phase. Additional
annealing at > 1000 °C resulted in continual depletion
of surface Si, and the development of a corresponding
1 x 1 pattern. The 1 x 1 phase was attributed to a range
of surface chemistries and defect structures. As would
be expected from the above model, with the continued
Si depletion the amount of graphitic C increased. The
initial appearance of the 1 x 1 phase was believed to be
due to the elimination of the Si adlayer resulting in
defects. By comparison, the work of van Bommel ex-
hibited a direct change from x/3 x x/3 to a graphitic
state without first exhibiting a 1 x 1 phase.
In order to more efficiently remove the oxide at low
temperatures, metals which form vapor phase oxides
with more negative free energies than O bound to Si are
worth considering as an extension of the experiments
with Ga and Si. A promising candidate might be A1,
which readily forms vapor phase oxides (A10 and
A120) and which may be easily evaporated from the
surface. Other possible choices are Mg or Ca.
Bozso et al. [18] investigated the Si-terminated (0001)
surface of 6H-SiC crystals using X-ray photoelectron
spectroscopy (XPS) and X-ray and electron excited
Auger spectroscopy. Prior to these analytical studies,
the crystals were dipped into concentrated aqueous HF,
rinsed in distilled H20, and cleaned in acetone and
propyl alcohol. The major residual contaminants left
were fluorine and oxygen. After the chemical clean the
samples were exposed to a combination of low angle
( ~ 80 ° angle of incidence) argon ion sputtering (500 eV)
and high temperature annealing. Fluorine and oxygen
remained after this treatment at 800 °C for 40 min but
were removed at 1000 °C for 2 min. However, Ar was
still present, but was eventually eliminated after pro-
longed heating. An atomically clean surface was
achieved, and preferential removal of Si or C was not
observed. However, possible surface damage due to the
sputtering process was not reported. The resulting state
 L.M. Porter, R.F. Davis / Materials Science and Engineering B34 (1995) 83-105 87

of the surface should be further investigated before this (b) C ls

preparation technique is employed for metal contacts, tf
as defect states can pin the Fermi level. If the annealing
prevents surface damage, this technique may be a viable
solution to the surface cleaning problem.
The Si- and C-faces of a mixture of 6H and 15R
polytypes were investigated after cleaning and disorder- ..........Before 700°Cdesorption f
.," :.:
ing by Ar ion sputtering (similar conditions as above) ..... After 700°0 desorption .~/ ,," ~ ~ ~
.,?'
and subsequent annealing [19]. In agreement with the
previous study [18], the Si/C ratio remained constant. I . . . . I . . . . I . . . . . . "
295 290 285 280
Changes did occur with heat treatment to ~ 1000 °C, Binding Energy (eV)
which caused a decrease in the XPS C (Is) binding
energy. The Si (2p and 2s) binding energies remained Fig. 1. XPS C ls spectra of 6H-SiC (0001) after 10 min in 10% HF
followed by a deionized water rinse. The minor peak attributed to
constant. These results indicated a change in the C hydrocarbons was removed after heating at 700 °C for 15 min in
chemistry. Examination of the peak areas revealed an UHV [21].
increase in the C/Si ratio on the C-face between 630
and 830 °C and a substantial increase on both faces upward band bending of a few tenths of an electron-
above 1030 °C. The C enrichment was much higher on volt was calculated, indicating the presence of surface
the C-face. These results were reaffirmed by the AES states.
analyses. Electron energy loss spectra indicated the Evidence for the absence of surface states in the band
formation of graphite at ~ 900 °C. gap under different conditions has been reported by
While in the latter two studies 500 eV Ar ions were Parrill and Bermudez [22]. Alpha SiC, of unspecified
used in the sputtering process, Andreev et al. [20] polytype and undetermined Si or C termination, was
sputtered oxidized (0001) and (0001) surfaces of 6H-SiC chemically cleaned in acetone, methanol, 30s in concen-
with 640 eV electrons at a flux density of 2 - 5 x 1017 e/ trated aqueous HF, and a final rinse in methanol
(cm 2 s). The sample temperature was between 700 and followed by annealing at 850-950 °C in a Si-flux. All of
1000 °C. Electrons were used instead of ions because of the oxygen was removed, but the surfaces did contain
their low mass and, hence, lower tendency to damage excess Si. The excess Si was removed by annealing for
the SiC surface. Auger analysis showed that this proce- 1-2 min at temperatures ranging from 960 to 1160 °C.
dure resulted in an uncontaminated, stoichiometric sur- The surface showed a 1 x 1 L E E D pattern after anneal-
face. However, it was stated that graphitization ing in the Si flux. Subsequent heating at ,~ 1160 °C gave
occurred when the procedure was continued after the a 3 x 3 reconstruction and no graphite formation ac-
oxide was removed. Although evidence was not given, cording to Auger analysis. Data was collected only
the surface was reported to have been undamaged. from the 1 x 1 surface (Si-rich surface) since 3 x 3
Considering the chemical and microstructural results surfaces were not uniform. The bulk valence band was
along with the experimental process, this cleaning pro- studied by using high energy photons (Mg K~,
cedure may be a viable technique if the equipment is 1253.6eV) for which the photoelectron attenuation
available and the parameters are carefully controlled. length is ~ 7 monolayers in the valence band. The
A chemical and thermal cleaning process [21], which
would be more easily implemented for commercial
devices, was developed in conjunction with the fabrica-
tion and characterization of Schottky contacts on SiC. Ec J
Oxidized 6H-SiC (0001) surfaces were first etched in a EF . . . . . . . . - j
10% H F aqueous solution. Thermal oxidation was
found to be a critical step for leaving a non-C-rich Ev
surface. Hydrocarbons were the main contaminant left
>o
on the surface after the etching step, as shown by the
minor peak component on the high binding energy side
of the C ls XPS peak (Fig. 1). After heating the
samples in a vacuum system (base pressure ~ 1 -
5 x l0 9 Torr) at 700 °C for 15 min, these hydrocar-
J
bons were removed from the surface, while residual O EC is J
and a trace amount of F were still present. As illus-
Fig. 2. Energy band diagram of 6H-SiC showing the relationship
trated in Fig. 2, XPS was also used to determine the between • B and the binding energies measured by XPS. Prior to
amount of band bending before and after deposition of metal deposition, the value of • B was calculated to be 0.40 + 0.1 eV
various metal contacts. After these cleaning steps an [21].
88 L.M. Porter, R.F. Davis' / Materials Science and Engineering B34 (1995) 83 105
surface valence band was investigated using low energy
photons (Zr M-zeta, 151.4 eV) for which the attenua-
tion length is ~2.5 monolayers. The photoemission
results showed no states within the optical band gap;
however, they do suggest that surface states exist below
the valence band edge.
The evidence seems to indicate that certain adatom
terminations (e.g. Si or O) on the (0001) or (0001)
surface of a-SiC result in a reasonably low or the
absence of surface states within the band gap. In the
case of the partial monolayer of oxygen, there appears
to be a sufficient density of surface states to reduce the
index of behavior, defined as the slope of the plot of the
barrier height vs. metal work function, from 1.0 but
which is insufficient to actually completely pin the
Fermi level (shown in later sections). An index of
behavior of 1.0 for a particular semiconductor indicates
that the Fermi level is unpinned, and the Schottky
barrier heights follow the ideal behavior predicted by
the Schottky Mott relationship.
Other work [23] does indicate that there is some
pinning due to intrinsic C vacancies, which vary in
concentration with polytype. The barrier heights of Cr
on m a n y different SiC polytypes were compared with
the theoretically predicted behavior of vacancies on the
surface of a semiconductor. Carbon-terminated surfaces
were prepared by chemical cleaning, which was not
described, and then heated in vacuum at 600 °C for 1 h.
The barrier height correlated well with the degree of
hexagonality for several hexagonal and rhombohedral
polytypes. Although the band gap varies similarly, the
Fermi level did not sit at a constant value of the band
gap, as would occur if this were purely a function of
band gap. As the concentration of vacancies increased,
the barrier height decreased. (The barrier height of
Cr/6H-SiC was 1.1-1.2 eV.) The report claims that
carbon vacancies form a level at the surface in the
upper half of the band gap and that a higher concentra-
tion of carbon vacancies causes a greater shift of Ev
towards E c. Comparing this theory with SBH results
presented later, one might conclude that intrinsic prop-
erties (vacancies) of SiC m a y cause some gap states at
the surface, but the specific details of the surface and its
preparation will be the final factor in determining the
density of surface states and where they are located.
4. Contacts to ~-silicon carbide
4.1. Schottky contacts to or-SiC
4. I. 1. n-type a-SiC
Some of the early investigations of Schottky contacts
on n-type ~(6H)-SiC (summarized in Table 3) were
performed in 1964 by Mead and Spitzer [24]. In this
report barrier heights for metals on SiC and other
elemental G r o u p IV and I I I - V semiconductors were
found to be nearly independent of work function. Al-
though the work functions of Au and A1 differ by
~0.8 eV, their resulting barrier heights on SiC were
1.95 and 2.0 eV, respectively. It was reported that for
most G r o u p IV and III V semiconductors where both
vacuum cleavage and chemical preparation could be
employed, the barrier heights resulting from the two
preparation techniques were the same; however, it was
not specified if both processes were used for SiC. There-
fore, it cannot be concluded whether the results can be
attributed to the surface preparation.
Subsequently, Hagen [25] also found q~B on a-SiC
crystals, comprised of the 6H and 15R polytypes, to be
independent of qbM. The barrier height on n-type sam-
ples was 1.45 eV for Au, Ag, and A1. In addition, q~B
for Au contacts on etched (0001) surfaces was the same
as that on cleaved (IT00) surfaces. The former surfaces
were etched in a molten s o d a - b o r a x mixture, rinsed
with deionized water, treated with an H F solution,
again rinsed with deionized water and kept in methanol
until placed in the vacuum system. It was concluded
that the Fermi level is fixed by surface states at the
middle of the band gap.
Notable results were reported for Au contacts ther-
mally evaporated (base pressure < 10 6 Torr) on n-type
6H-SiC (0001) [26]. The C-terminated surfaces were
cleaned with concentrated HF, etched in molten sodium
peroxide, rinsed in dilute HC1 and deionized water and
then dipped in methanol and dried with N2. The semi-
logarithmic current vs. voltage plot extends over seven
orders of magnitude with an ideality factor of n = 1.07.
The calculated barrier height of 1.45 eV was in agree-
ment with that of Hagen [25] for Au on the Si-termi-
nated (0001) surface.
Platinum, Au, Ag, Ni, Cr, and A1 sputtered on
6H-SiC produced rectifying contacts [27]. Surfaces were
etched in a mixture of potassium hydroxide and sodium
nitrate in ratios ranging from 1:4 to 1:100 at 4 7 7 -
577 °C. However, the carrier type and orientation of
the SiC were not indicated. Depending on the metal
and the surface preparation, the band bending at the
semiconductor surface ranged from 0.6 to 2.5 eV. Alu-
minum evaporated in vacuum (10 ~'Torr) on n-type
SiC was characterized after heat treatment by another
group [28]. The substrates were etched in molten K O H .
The resulting oxide was then etched by dipping in H F
followed by deionized water. Prior to the A1 deposition
Ni was deposited on the back and annealed for 3 min at
1200 °C in an Ar ambient to create an ohmic contact.
After the AI was deposited (vacuum pressure
10 6 Torr) the samples were annealed in an Ar ambient
for 3 min at 660 °C (m.p. of A1), 770 and 900 °C.
Before annealing, the AI contacts showed high leakage
currents. After annealing, the leakage decreased
( ~ 2 × 10 2 A c m 2 at - 5 V ) , and the ideality factor
 L.M. Porter, R.F. Davis / Materials Science and Engineering B34 (1995) 83 105 89

Table 3
R e c t i f y i n g c o n t a c t s o n n - t y p e ~ ( 6 H o r m i x e d ) - S i C . O n l y t h o s e studies w h i c h r e p o r t e d S B H s a r e listed h e r e f o r brevity. T h e s u r f a c e p r e p a r a t i o n s
w h i c h c o n s i s t e d o f a t least a s u r f a c e o x i d e e t c h i n g step a n d a h y d r o c a r b o n r e m o v a l step b y h e a t i n g in h i g h o r u l t r a - h i g h v a c u u m w e r e r e a t e d as
' v e r y g o o d ' . T h o s e w h i c h c o n s i s t e d o f at least a c h e m i c a l c l e a n a n d a s u r f a c e o x i d e e t c h i n g step b u t l a c k e d the c a p a b i l i t y f o r h e a t i n g in h i g h
v a c u u m w e r e r a t e d as ' g o o d ' . T h i s r a t i n g s y s t e m is b a s e d o n a n a l y s e s o f the SiC s u r f a c e b y X P S

Metalliza- Deposition Deposition Deposition Annealing ~ a (eV) SiC Method of Origin of Surface Ref.
tion method temperature pressure (Torr) condition surface qba m e a s . SiC preparation

Au NR NR NR none 1.95 NR C-V NR NR [24]

A1 NR NR NR none 2.0 NR C-V NR NR [24]
Au thermal evap. RT ~10 9 none 1.45 (1i00) C - V , PR NR cleaved in [25]
vac.
Ag thermal evap. RT ~10 9 none 1.45 (1i00) C V, PR NR cleaved in [25]
vac.
AI thermal evap. RT ~ 10 9 none 1.45 (1100) C - V , PR NR cleaved in [25]
vac.
Au thermal evap. NR < I0 6 b.p. none 1.40 (000T) C - V , PR, subl. good [26]
I-V
AI thermal evap. NR 10 - 6 to 900 °C, ~ 1.7 (0001) C-V Acheson good [28]
3 min
Ti e-beam evap. RT 10 io b.p. none 0.84-0.88 (0001) I-V, C-V, seeded sub.; very good [21,30,34]
XPS CVD epi
Ti e-beam evap. RT 10- io b.p. 700 °C, 0.86-1.04 (0001) l-V, C-V seeded sub.; very good [21,30,34]
4 0 - 6 0 min CVD epi
Pd thermal evap. RT 10 to b.p. none 1.60-1.62 (0001) I - V , C V, CVD very good [32]
1.11 (0001) and XPS
Au thermal evap. RT 10 io b.p. none 1.14-1.19 (0001) I-V, C - V , CVD very good [32]
1.37-1.40 (0001) and XPS
Ag thermal evap. RT 10 io b.p. none 1.10 (0001) l - V , C V, CVD very good [32]
0.83-0.92 (0001) and XPS
Mn thermal evap. RT 10 - l ° b.p. none 0.79 0.81 (0001) I - V , C V, CVD very good [32]
and XPS
AI thermal evap. RT 10 lo b.p. none 0.84-0.89 (000I) I V, C - V , CVD very good [32]
0.26-0.30 (0001) and XPS
Mg thermal evap. RT 10 ~o b.p. none 0.33 (0001) I - V and XPS CVD very good . [32]
0.30-0.34 (0001)
Pt sputtered 140 °C NR none 1.04-1.10 NR I V and seeded sub.; NR [441
C-V CVD ept
Ti thermal evap. RT 10 lo b.p. none 1.0-1.03 (000T) 1 V, C - V , seeded sub.; very good [33]
0.73 (0001) and XPS CVD eD
Ti thermal evap. RT 10 1o b.p. 400 °C 0.98 (000I) I V, C V, seeded sub.; very good [33]
0.93 0.97 (0001) and XPS CVD epl
Ni thermal evap. RT 10 ~o b.p. none 1.54 1.68 (000i) I V, C V, seeded sub.; very good [33]
1.24 1.29 (0001) and XPS CVD e D
Ni thermal evap. RT 10 ~o b.p. 400°C, 1.51-1.66 (000i) I V, C - V , seeded sub.; very good [33]
30s 1.23-1.25 (0001) and XPS CVD e D
Ni thermal evap. RT 10 - I ° b.p. 600 °C, 1.16-1.39 (0001) I-V, C-V, seeded sub.; very good [33]
30 s and XPS CVD ep~
AI thermal evap. RT 10 io b.p. none 0.84 0.89 (0001) l - V , C V, seeded sub.; very good [33]
0.26-0.30 (0001) and XPS CVD epi
AI thermal evap. RT 10 ~o b.p. 600 °C, 1.36-1.66 (000T) I V, C - V , seeded sub.; very good [33]
30s 0.82-1.12 (0001) and XPS CVD epi
Au thermal evap. RT NR none 1.4 (000T) I-V Acbeson good [45]
substr.;
CVD epl
Pt e-beam evap. RT 10 ~o b.p. none 1.06 1.33 (0001) I - V and XPS seeded sub.; very good [34,36]
CVD eD
Pt e-beam evap. RT 10 1o b.p. 450 750 °C, 1.15-1.26 (0001) I-V seeded sub.; very good [34,36]
20 min CVD ept
Hf e-beam evap. RT 10 ~o b.p. none 0.97 (0001) I V and C - V seeded sub.; very good [34]
CVD epl
Hf e-beam evap. RT 10 ~o b.p. 700 °C, 1.01-0.86 (0001) l V and C V seeded sub.; very good [34]
20 60 min CVD e D
Co e-beam evap. NR 10 7 none 0.79 (0001) 1-V and C V seeded sub.; good [90,126]
CVD ep~
Co e-beam evap. RT 10 ~o b.p. none 1.06-1.15 (0001) l - V , C V, seeded sub.; very good [35]
and XPS CVD epl
Ni e-beam evap. RT 10 ~o b.p. none 1.14-1.21 (0001) I - V and C V seeded sub.; very good [43]
CVD e D

OB = S c h o t t k y b a r r i e r height; N R = n o t r e p o r t e d ; R T = r o o m t e m p e r a t u r e ; b.p. = b a s e p r e s s u r e ; sub. = s u b s t r a t e ; epi = epilayer; I V = c u r r e n t -

voltage; C V = capacitance voltage; XPS = X-ray photoelectron spectroscopy.
90 L.M. Porter, R.F. Davis / Materials Science and Engineering B34 (1995) 83 105

Fig. 3. High resolution TEM image of as-deposited Ti/6H-SiC. The boxed-in region in the upper part of the image is magnified in the lower part
of the image. The arrow at the interface marks the position of a step in the SiC surface. The misfit dislocations which are marked with lines, did
not extend all the way to the interface. After Ref. [21].

was 2.0-2.3. The built-in voltage was 1.7 V after an-
nealing at 900 °C. It is likely that annealing the SiC at
1200 °C prior to deposition of A1 depleted some of the
surface Si, which in turn may have caused leaky con-
tacts. Reaction of A1 with the excess C very likely
occurred during post-deposition annealing and resulted
in lower leakage currents. The lower temperatures
should not be sufficiently high to activate A1 in SiC and
create a p-type surface layer.
Titanium films deposited by UHV electron beam
evaporation at room temperature onto n-type 6H-SiC
(0001) grew epitaxially and displayed rectifying behav-
ior [21,29 31]. Both Ti ( a = 2 . 9 5 A , c = 4 . 6 8 / k ) and
6H-SiC (a = 3.08 A, c = 15.11 A) have hexagonal crys-
tal structures, corresponding to a - 4 % lattice mis-
match between the close packed planes. Fig. 3 shows a
high resolution T E M image of this nearly ideal inter-
face. The misfit dislocations did not extend to the
interface, and therefore, the Ti film was considered
pseudomorphic. Surfaces were cleaned in a solution of
ethanol/hydrofluoric acid/deionized water (10:1:1) fol-
lowed by a 700 °C thermal desorption in UHV. Analy-
sis of unannealed, thin ( 4 - 1 2 / k ) Ti films by XPS
indicated Ti C bonding at the Ti/SiC interface. The
leakage currents of thicker 1000 ~ ) films were as low
as9xl0 8 A c m 2 a t - 1 0 V , and theideality factors
were between 1.01 and 1.09. The contacts remained
stable after annealing at 700 °C for 1 h, which resulted
in a thin, crystalline TiC layer at the SiC interface and
TisSi 3 in the remainder of the reacted region. Barrier
heights before and after annealing were 0.88 and
1.04 eV, respectively. The change in barrier height is
attributed to the chemical reaction, which created a
new metal/SiC interface.
From the results of I V, C - V , and XPS analyses,
Waldrop et al. [32] have calculated the barrier heights
of Pd, Au, Ag, Tb, Er, Mn, A1, and Mg deposited at
room temperature on the Si- and/or C-faces of n-type
6H-SiC. The metals were deposited in UHV by evapo-
ration from W wire baskets. Prior to the depositions
the substrates were RCA cleaned, oxidized, etched in
HF, and desorbed at 600 °C under UHV conditions. It
was estimated that ~ 1/2 monolayer oxygen remained
on the C-face and ~ 3 / 4 on the Si-face. A relatively
large barrier height variation resulted. With the exclu-
sion of the rare earth elements, in general there was an
increase in q)~ with q~M. This trend is displayed in Fig.
4, where the SBHs calculated from the three techniques
 L.M. Porter, R.F. Davis / Materials Science and Engineering B34 (1995) 83 105
are plotted vs. the work functions of the metals and
compared to the theoretical SBHs according to the
S c h o t t k y - M o t t limit. Three linear fits to the three sets
of data points are also shown. The slopes, S, of these
lines, often referred to as the index of interface behavior,
give a quantitative indication of how closely the system
follows S c h o t t k y - M o t t behavior (i.e. how close S is to
1). As is evident from Fig. 4, the index of interface
behavior may depend on the technique used to measure
the SBHs. In this case S varied from 0.47 to 0.63. These
results give evidence for a partial pinning of the Fermi
level in 6H-SiC. While not shown in the figure, the barrier
heights of the rare earth elements, Er and Tb, ranged
from 1.61 to 2.18 eV calculated from C - V measurements
and 1.04 to 1.41 eV calculated from I - V measurements.
Barrier heights of unannealed and annealed Ni, Ti, and
A1 were later measured by the same group on n-type
6H-SiC [33]. These data points are also included in Fig.
4. X-ray photoelectron spectroscopy analyses indicated
the formation of TiC and TiSi~ in the unannealed Ti/SiC
interface region. No chemical reactions were detected on
the Si-face before or after annealing Ni/SiC at 400 °C.
In addition to the Ti contacts described in a previous
paragraph, Porter et al. [34-36] have also studied the
chemistry and microstructure along with the electrical
properties and SBH's of other metal/SiC systems. The
SBHs calculated from I - V , C - V , and XPS analyses of
Ti, Pt, HI', Co, and Ni contacts are shown in Fig. 5.
The slopes S vary from 0.12 for the data points calcu-
lated from I - V measurements to 0.40 and 0.41 for
those calculated from C - V and XPS measurements,
respectively. While these slopes are somewhat less than
those derived from Waldrop's data, both sets of results
show a significant, positive correlation between SBH
and metal work function and a susceptibility to mea-
surement technique. Differences due to processing
should be minimal since similar cleaning and deposition
procedures and substrate material were used in both
2.5-
-I- theoretical
~-
2.0-
_=z 15-
I •", measured (I-V) I
0 measured (XPS)
0 measured (C-V)
S=l;O..-
.--"
.-
~s=047 <c-v)
~, 1 . 0 - o ~ ~ '~
E
S-0.62 (XPS)
o.5- . - ~ s=o.6s 0-v)
0.0-
Metal Work Function (eV)
Fig. 4. D a t a points of experimentally-determined and
barrier heights on n-type 6H-SiC (000l) vs. work function of the
metal contacts. The experimental data points are from Waldrop et al.
[32,33]. The slopes, S, of the linear fits through each set of data points
are indicated.
91
2.5-
-l.. theoretical I .e
I
Zx measured (I-V) I S=1.0 , ' "
2.0- 0 measured (C-V) .-'"
>A 0 measured (XPS 1 o• •
o
~- 1 . 5 - -• S=0.41
•1- o °
.~_ 1 . 0 - ~ 2 ZX
P_
0.5-
0.0-
I I
3.5 4.0 4.5 510 515 610
Metal Work Function (eV)
Fig. 5. Data points of experimentally-determined and theoretical
barrier heights on n-type 6H-SiC (0001) vs. work function of the
metal contacts. The experimental data points are from Porter et al.
[21,34-36,43]. The slopes, S, of the linear fits through each set of data
points are indicated.
studies. The main difference in the two sets of results
occurs between the calculations based on I - V measure-
ments and XPS. This result is quite interesting consider-
ing that I - V measurements are very dependent on the
homogeneity of the interface [37-41]. The lower slopes
in the former set of data are believed to be partly due
to the particular metals studied. For example, the Pt
contacts yielded a significantly lower SBH calculated
from I - V measurements than that calculated from XPS
analyses, a result attributed to inhomogeneity of the
interface [36].
In this latter study the increase in grain size and grain
orientation with the temperature of the anneal was
accompanied by an increase in the SBH calculated from
I - V measurements. The samples were successively an-
nealed for 20 rain at 450, 550, 650, and 750 °C. No re-
action occurred at temperatures below 750 °C. The first
reaction phases, crystalline PtzSi and an amorphous C
phase, formed after annealing at 750 °C. This interfa-
cial reaction was proposed to reduce any adherence
problems associated with Pt contacts. These contacts
displayed low ideality factors (n < 1.1) and typical leak-
age currents of 5 × 10 - S A c m 2 a n d 2 × 10 8 A c r e -2
at - 1 0 V before and after annealing, respectively.
Cobalt contacts [35] deposited at room temperature
also formed excellent rectifying contacts with ideality
factors and reverse leakage currents similar to the Pt
contacts. However, annealing at 800 °C for 20 min re-
suited in a substantial increase in the leakage currents,
while ohmic-like behavior was displayed after annealing
at 1000 °C for 2 min. Analysis of the latter contacts
revealed that extensive reaction occurred resulting in
the formation of CoSi and graphite. This reaction
resulted in a highly irregular interface, as shown in Fig.
theoretical 6. Nickel, which reacts with SiC at even lower tempera-
ture [42] and is chemically similar to Co, is commonly
used as an ohmic contact to n-type SiC and may also
form a highly irregular interface after annealing.
92 L.M. Porter, R.F. Davis / Materials Science and Engineering B34 (1995) 83 105

single crystalline SiC material of a single polytype was

Fig. 6. High resolution T E M image of Co/6H-SiC interface after
annealing at 1000 °C for 2 min. After Ref. [35].
As stated previously, the contacts studied by Mead and
Spitzer [24] and Hagen [25] showed no correlation
between SBH and metal work function. These results give
strong evidence that the barrier height mechanism in
both studies was due to Fermi level pinning. The fact that
the Fermi level is evidently completely pinned in these
studies as opposed to the more recent studies in which
partial pinning is evident may be due to different surface
preparation and perhaps more importantly the quality of
the substrate material. Prior to about the last 10 years,
very difficult to grow. Therefore, substrate material was
likely a mixture of polytypes.
It should also be noted that both the source of the SiC
material and the surface preparation were similar in the
experiments by Waldrop et al. [32,33] and Porter et al.
[21,34 36,43]. Therefore, comparisons of the results can
more easily be made than in cases where the material and
its preparation differ.
Table 3 summarizes the Schottky barrier heights
calculated for rectifying contacts on n-type 6H-SiC. Most
of these calculations were based on XPS and/or I V and
C - V measurements. Only those studies which reported
the SBHs were included in the table for brevity. In most
cases the surface termination (i.e. Si or C) is indicated in
parentheses next to the calculated SBHs. Most of the
metals on the Si-face had SBHs between approximately
0.8 and 1.25 eV. On the C-face most of the SBHs were
between 1.0 and 1.6 eV. This limited range is most likely
associated with the fact that most transition metals have
work functions within about 0.8 eV of each other. The
first seven contacts listed, which represent the earlier
studies, showed higher SBHs; while in the more recent
studies, A1 and Mg, which have lower work functions,
showed lower SBHs.
Schottky diodes with very high breakdown voltages
and low specific on-resistances have been fabricated with
Pt [44] and Au [45], which is good news for power device
applications. The Pt diodes on the Si-terminated surface
of 6H-SiC yielded breakdown voltages of greater than
400 V. The Au diodes on the C-terminated surface of
6H-SiC yielded breakdown voltages of greater than
1100 V. In addition, the leakage currents of the Au diodes
were very low, 4 . 0 x 10 6 A c m 2 at - 2 0 0 V and
2.1 x 10 3 A cm 2 at - 1100 V. Referring to Table 3, the
higher SBHs of metals on the C-terminated surface may
allow higher breakdown voltages than on the Si-termi-
nated surface.

Table 4
Rectifying contacts on p-type ~(6H or mixed)-SiC. See Table 3 for a description of the rating system for surface preparations

Metallization Deposition Deposition Deposition Anneal q~B (eV) SiC surface Method of Origin of Surface Ref.
method temperature pressure (Torr) condition q~B meas. SiC preparation

A1 thermal evap. RT ~ 10 9 none 1.36, 1.45 (1100) PR, C V NR cleaved in [25]

vac.
Ag thermal evap. RT ~10 9 none 1.15 (1100) PR NR cleaved in [25]
vac,
Au thermal evap. RT ~10 9 none 1.07, 1.37 (1100) PR, C V NR cleaved in [25]
vac,
Au e-beam, evap. RT 10 io b.p. none 1.27 (0001) I V seeded sub.; very good [127]
'~ CVD epi
NiA1 e-beam evap. RT 10 io b.p. none ~ 1.37 (0001) 1 V seeded sub.; very good [43]
C V D epi
Ni e-beam evap. RT 10 to b.p. none ~ 1.36 (0001) I V seeded sub.; very good [43]
C V D epi

q~B=SChottky barrier height; N R = n o t reported; R T - r o o m temperature; b . p . - b a s e pressure; sub. =sublimation; epi=epilayer; I

V = current voltage; C - V - capacitance voltage; PR = photoresponse.
 L.M. Porter, R.F. Davis / Materials Science and Engineering B34 (1995) 83-105
4.1.2. p-type a-SiC
Table 4 summarizes the limited number of Schottky
contacts on p-type a-SiC found in the literature and
their calculated SBHs. These studies were not as exten-
sive as m a n y of those performed for Schottky contacts
on n-type SiC.
Gold and A1 on p-type samples produced SBHs of
0 . 9 - 1 . 2 5 e V and 1.30-1.47eV, respectively [25]. The
higher SBH of A1 compared with Au on p-type material
would be expected considering the lower work function
of the former.
Our measurements on p-type SiC have shown consis-
tent differences from measurements on n-type material.
The SBHs tend to be higher on p-type than on n-type
6H-SiC. While leakage currents for Au, NiA1, and Ni
contacts on p-type 6H-SiC (0001) were comparable
with those on n-type 6H-SiC, the ideality factors were
higher (n ~ 1.1-2.1). These higher ideality factors indi-
cate that thermionic emission is not the dominant
current transport mechanism. Deep level transient
spectroscopy (DLTS) will probably be used to deter-
mine whether recombination at deep levels accounts
for the electrical behavior of the contacts on p-type
material.
4.2. Ohmic contacts to c~-SiC
4.2.1. n-type e - S i C
The earliest work found in the literature on ohmic
contacts to n-type a-SiC was performed in 1970 on Cr
and Cr alloys [46]. The remainder of the work has been
confined within the past few years. In the former case
the main concerns were to form ohmic contacts which
were both ductile and oxidation resistant and had low
resistance. The contacts described were Cr or Cr alloys
(at least 5 wt.%) with Fe, Ni, or Fe and Ni. To form
ohmic contacts the metals were heated to above their
respective melting temperatures (1500-1900 °C). These
high temperatures assured a significant reaction with
the SiC, and very likely created a graded, highly-defec-
tive interface associated with the ohmic behavior. Due
to the processing requirements and the confinements of
size in today's devices, lower processing temperatures
are required.
Although lower annealing temperatures have been
used in the more recent work, in most cases the temper-
atures have been above 900 °C. The exceptions to this
last statement have been in those cases where the SiC
was very heavily doped [47,48]. The two exceptions
listed in Table 5 along with the other ohmic contacts
are the TiN contacts reported by Glass et al. [49,50]
and the TiW contacts reported by Crofton et al. [51]. In
both cases the ohmic behavior is likely associated with
a thin insulating layer. The TiN contacts were de-
posited by ion assisted reactive evaporation and an-
nealed at 600 °C for 30 min. They were found by XPS
93
to contain a thin (5-15 A) layer of silicon nitride at the
interface, creating a metal insulator semiconductor
(MIS) structure. While TiN has a low work function
(favorable for an ohmic contact on n-type material),
ohmic behavior did not occur in the absence of ion
assisted deposition, a process associated with the for-
mation of the S i - N layer. This insulating layer was
critical to the creation of ohmic contacts but not solely
responsible for this behavior, as Pt contacts (high work
function) with a S i - N interlayer resulted in rectifying
characteristics. It was stated that the insulating layer
may act to passivate surface states, resulting in an
electron energy band relationship which behaves ac-
cording to the Schottky Mott limit. Because the insu-
lating layer was so thin, electrons would be able to
tunnel through it.
The Ti W (10:90 wt.%) contacts formed ohmic con-
tacts after annealing at 600 °C for 5 min following
exposure of the SiC surface to an oxygen plasma.
Ohmic behavior did not result without the oxygen
plasma exposure. It is likely that this process step
resulted in the formation of a thin SiO2 layer at the
surface, which may be responsible for the ohmic behav-
ior by forming a MIS structure similar to that for the
TiN contacts.
Annealed Ni has been the most widely used metal for
ohmic contacts to n-type SiC. As shown in Table 5, this
process generally involves annealing at temperatures
above 900 °C. While Crofton et al. reported in an
earlier paper [51] a room temperature contact resistivity
in the mid 10 2 ~-~cm 2 range (5 x 1018 c m - 3 c a r r .
conc.), they were later able to lower this value to less
than 9 x 10 - 6 ~ cm 2 (7 9 x 1018 c m - 3 c a r r . conc.) [52].
The substantial decrease in the calculated contact resis-
tivity was partly attributed by the first author (private
communication) to a combination of the higher carrier
concentration and of the changes in the measurement
technique, the annealing conditions, and the processing
systems.
Comparably low values (1.7-6 x 10 5 ~ c m 2) were
also reported for Ni on 6H-SiC with a 2000/k thick,
highly-doped ( 1 - 3 x 10 I9 c m 3) 3C-SiC interlayer [53].
The authors attribute the low contact resistivity to the
smaller band gap of the 3C polytype. To determine
whether the 3C-SiC layer does in fact reduce the barrier
height at the 6H-SiC surface, the energy band relation-
ship at the interface should be measured.
The lowest values reported to date of contact resistiv-
ities of ~< 1 x 10 6 ~ c m 2 [54] have been achieved for
annealed (1000°C/5min) Ni on very highly doped
(4.5 x 1020 cm 3) n + 6H-SiC (000i). The n + 6H-SiC
films were grown by liquid phase epitaxy (LPE) on
Acheson-grown 6H-SiC substrates. Silicon nitride was
contained in the melt to achieve the notably high N
doping levels. Prior to the annealing step, the contact
resistivities were greater than 1 x 10 4f~ c m 2.
94 L.M. Porter, R.F. Davis / Materials Science and Engineering B34 (1995) 83 105

Table 5
O h m i c c o n t a c t s on n-type c~(6H or mixed)-SiC. See T a b l e 3 f o r a description o f the rating system for surface preparations

Metallization Deposition Deposition Deposition Annealing p , ( f l c m 2) SiC carr. conc. SiC Method Origin of Surface Ref.
method temperature pressure condition (cm 3) surface of p~. SiC preparation
(Torr) mess.

Cr melting 10 3 b.p. melting NR NR NR NR NR [461

(~>2130 °C)
Ni e-beam NR NR 100M °C/20 s 1.7 x 10 4 4.5 × 1017 (0001) T L M seeded sub.; N R [128]
evap. C V D epi
TiN ion-assisted 3 5 0 ° C 10 io b.p. 600°C/30 4 x 10 2 ~1 x 10 ~s (0001) T L M seeded sub. very good [49,50]
e-beam min
evap.
TiW sputtering RT 10 ~' b.p. O2plasma+ 7.8x10 4 4.7x10 ~ (0001) circular seeded sub.: 0 2 plasma [51]
600 °C/5 min TLM C V D epi
Ni e-beam RT 10 6 950°C/5min mid 10 2 4.7 x 10 ~a (0001) four- seeded sub.; good [51]
evap. point C V D epi
Ni C r sputtering RT 10 6 b.p. 9 5 0 ° C / 5 rain 1.8 × 10 ~ 4.7 x 10 ~8 (0001) circular seeded sub.; 02 plasma [51]
(60 40 wt.%) TLM C V D epi
W thermal NR NR 1200 1600°C 5x10 ~ lxl0 4 3x1018 lxl0~,~ (0001) four- Lely varied [59]
evap. I x 10 2 5 × 10 4 1 x 10 J7 I x 10 ~'; (000i) point
TiW sputtering RT 10 6 b.p. 750°C/5min ~ 8 x [0 4 7 8 x I(11~ (0001) circular seeded sub.: good [1291
TLM C V D epi
Ti thermal RT NR none lxl0 2 <2x10 52x 1018 1 × 10 ~° (0001) circular seeded sub. good [47]
evap. TLM
Mo sputtering 10 7 b.p. NR none ~ I x 10 4 > l x 10 I~) (000l) fotlr- seeded sub.: good [48]
point C V D epi
and T L M
Ta sputtering 10 7 b.p. N.R. none ~ 1 x 10 4 > 1 x 10 a~J (0001) four- seeded sub.: good [48]
point C V D epi
and T L M
Ni/3C-SiC resistive NR NR 100M °C/30 s < 1.7 x 10 5 1 2 x 10 as (0001) Cox and Lely very good [53]
evap. < 6 x 10 5 (0001) Strack
Ni e-beam RT 10 (' 950 °C/2 min < 5 × 10 6 7 9 x 1018 (0001) T L M seeded sub.; good [52]
evap. (000i) C V D epi
Ni sputtering NR 10 5 b.p. 1050°C/5 10 3 10 4 9 . 8 x 1017 (0001) T L M seeded sub. good [130]
min
W/Ti/Ni sputtering NR 10 s b.p. 1050°C/5 10 3 10 4 9.8 X 1017 (0001) T L M seeded sub. good [1301
min
Ni thermal NR NR 1000 °C/5 1 x 10 ~' 4.5 x 1020 (0001) contact LPE good [541
evap. min area
Ti-AI thermal NR NR 1000°C/5 < 1 x 10 3 4.5 x 102" (000i) contact LPE good [541
evap. min area

N R = not reported; R T = r o o m temperature: b . p . = base pressure; s u b . = sublimation: epi = epilayer.

4.2.2. p-type e - S i C Table 6 lists a chronology of the various ohmic

It is difficult to form ohmic contacts to p-type mate-
rial by reducing the SBH because o f the large band gap
and work function o f SiC. Aluminum is conventionally
used in pure form or as an alloy to create ohmic
contacts. Annealing the contacts causes A1 to diffuse
into the SiC, resulting in an enhanced p-type carrier
concentration near the surface. A higher carrier concen-
tration corresponds to a narrower depletion region
through which holes can effectively tunnel. However,
the low melting point and the oxidation characteristics
o f AI make processing the contacts difficult. The melt-
ing point can be increased by using A1 alloys (e.g.
A1-Ti [55 57]), but the extremely high thermodynamic
driving force for oxidation o f A1 places strict require-
ments on processing and passivating layers.
contacts to p-type c~-SiC. Boron, which is a deep level
acceptor in SiC, and A1 were used in the earliest
contacts of this type to SiC [58]. The contacts were
made by fusing pellets of A1-Si ( ~ 1:1) or Si with a few
percent B to the SiC. This process required tempera-
tures o f 1700 °C for the A I - S i and from 1700 to above
2000 °C for the Si-B. It was believed that the enhanced
p-type concentration at the SiC surface was formed by
recrystallization from solution rather than diffusion of
A1 into the SiC. While the temperatures required for
these contacts are extremely high, these materials may
be more desirable as interlayers, as Si has a significantly
smaller band gap than SiC.
Hall [58] also investigated W as an ohmic contact
because of its similar thermal expansion coefficient to
 L.M. Porter, R.F. Davis/Materials Science and Engineering B34 (1995) 83-105 95

Table 6
Ohmic contacts to p-type ~(6H or mixed)-SiC. Multi-layered contacts are designated with slashes to separate the distinct layers; layers at the
surface to the interface with SiC proceed from left to right. See Table 3 for a description of the rating system for surface preparations

Metallization Deposition Deposition Deposition Annealing p~ ( ~ cm 2) SiC carr. conc. SiC Method Origin of Surface Ref.
method temperature pressure condition (cm 3) surface of p~ SiC preparation
(Torr) meas.

Al-Si (~1:1) melting NR 1700°C NR NR (0001) -- Lely NR [58]

S i - B (a few melting NR 1700 2000 NR NR (0001) -- Lely NR [58]
%B) °C
W melting NR 1900 °C NR NR (0001) -- Lely NR [58]
Cu-Ti melting I0 5 > 8 8 0 °C NR NR NR -- Carborun- good [131]
(71:29 at.%) d u m Co.
AI-Si melting -- 10 5 900-1000 NR NR NR -- Carborun- good [131]
(88.7:I 1.3 at.%) °C d u m Co.
A1-Ti NR NR NR 950 °C/5 NR NR (0001) -- seeded sub.; good [55]
min LPE epi
AI e-beam RT 10 6 700 °C/10 1.7 x 10 3 1.8 x 1018 (0001) TLM seeded sub.; good [51]
evap. min CVD epi
W / A u W / W / A I sputtering NR NR 1800 2 5 x 10 4 NR (0001) four- Lely varied [59]
°C/120 s and point
(oooT)
AI Ti sputtering RT 10 6 b . p . 1000°C/5 2.9×10 2 1.5)<10 5 5xl0tS 2x1019 (0001) circular seeded sub.; good [57]
min TLM C V D epi
Mo sputtering NR 10 " v b.p. none 2 x 10 4 > l × l019 (0001) four- seeded sub.; good [48]
point CVD epi
and T L M
Ta sputtering NR 10 7 b.p. none 7 x 10 4 > 1 x 1019 {000l) four- seeded sub.; good [48]
point CVD epi
and T L M
Ti sputtering NR 10 7 b.p. none 3 × 10 4 > 1 × l0 ~9 (0001) four- seeded sub.; good [48]
point CVD epi
and T L M
AI sputtering NR l0 5 b.p. 800°C/10 10 2 - 1 0 -~ 8 × 1018 (0001) TLM seeded sub. good [130]
min
W/Pt/At sputtering NR 10 5 b.p. 800 8 5 0 ° C 10 2 - 1 0 3 8 x 1018 (0001) TLM seeded sub. good [130]
/10 min
Ti/AI/C- e-beam NR NR 950 °C/2 2 - 3 x 10 s NR (0001) TLM Lely sub.; very good [53]
SiC evap./ min L P E epi
LPCVD
Pt e-beam RT 10 m b.p. 450 850 NR >1 x 10 Is NR seeded sub.; very good [60]
evap. °C/20 min C V D epi
Ti/AI thermal NR NR 1000 °C/5 NR NR (000i) Acheson good [54]
evap. min sub.; L P E
epi

N R = not reported; R T = r o o m temperature; b . p . = base pressure; s u b . = sublimation; epi = epilayer.

SiC. However, annealing these contacts resulted in even
greater penetration depth than for the Si alloys.
T w o eutectics, C u - T i and A1 Si, were later found to
be ohmic after annealing at > 8 8 0 °C and 9 0 0 - 1 0 0 0 °C,
respectively [13]. These annealing temperatures are
above the eutectic melting points and resulted in pene-
tration o f the contacts in the SiC o f up to 1 pm. Similar
penetration depths occurred for the W/AuW/W/A1 con-
tacts [59]. These extensive chemical interactions would
be devastating in many of today's devices.
As in the case of n-type SiC discussed above, the
need for annealing can be reduced or eliminated by
heavily doping the surface to create a p + layer in
p-type SiC. As-deposited Mo, Ta, and Ti contacts on
p + SiC epitaxial films grown by C V D yielded ohmic
contacts [48]. Contact resistivities measured by
Kuphal's 4-point method were in the 10 -4 ~ c m 2 range,
which was reported to be a conservative value since the
method does not account for nonuniform current densi-
ties.
The patent by Glass et al. [60] is based on the
relationship that the contact resistance decreases with
increasing doping concentration and decreasing SBH.
When tunneling dominates the current transport, as
occurs for high doping concentrations and a finite
barrier, the following proportionality holds
R c oc exp(OB/x/N) (2)
where Rc is the specific contact resistance, OB is the
Schottky barrier height, and N is the carrier concen-
96 L.M. Porter, R.F. Davis Materials' Science and Engineering B34 (1995) 83 105

Table 7
Rectifying contacts on n-type fl-SiC. The deposition and annealing conditions, calculated Schottky barrier heights, and SiC information are listed
for most of the contact metallizations. See Table 3 for a description of the rating system for surface preparations

Metallization Deposition Deposition Deposition Annealing qbB(eV) SiC Method of Origin of Surface Ref.
method temperature pressure condition surface OB means. SiC preparation
(Torr)

Au e-beam NR 10 7 none; to 500 1.2 (100) C V CVD good [62]

evap. °C/1 h
AI thermal RT 10 ¢' b.p. 900°C/3 5 m i n NR (100) CVD good [70]
evap.
Au thermal RT 10 ~' b.p. none 1.2 (100) C V CVD good [70]
evap.
A1 thermal ~RT 10 m b.p. none 1.4 (100) XPS CVD Si-rich [67]
evap.
Pd thermal RT 10 m b.p. none 0.95, 0.92 (100) XPS, C V CVD very good [63]
evap.
Au thermal RT 10 m b.p. none 0.78, 0.87 (100) XPS, C V CVD very good [63]
evap.
Co thermal RT 10 m b.p. none 0.69, 0.73 (100) XPS, C V CVD very good [63]
evap.
Ti thermal RT 10 m b.p. none 0.53 (100) XPS CVD very good [63]
evap.
Ag thermal RT 10 m b.p. none 0.40 (100) XPS CVD very good [63]
evap.
Tb thermal RT 10 m b.p. none 0.35 (100) XPS CVD very good [63]
evap.
AI thermal RT 10 m b.p. none 0.16 (100) XPS CVD very good [63]
evap.
Au thermal RT 10 6 b.p. none vicinal & CVD good [64]
evap. off-axis
(100)
Ni sputtering NR NR none NR carbonization good [71]
of Si

N R = not reported; RT = room temperature; b.p. = base pressure; XPS = X-ray photoelectron spectroscopy; C V = capacitance voltage.

tration [61]. To reduce the SBH on p-type material, a high
work function metal should be used. Although empirical
evidence indicates that there is a partial pinning of the
Fermi level in 6H-SiC, the SBH has some dependence on
metal work function, as shown in Figs. 4 and 5. In this
invention ohmic contacts were fabricated by depositing
Pt on p-type SiC with a p-t- layer at the surface. Both
as-deposited contacts and contacts annealed at tempera-
tures to 850 °C displayed ohmic behavior. Platinum has
several advantageous properties, including its high melt-
ing point and oxidation resistance; however, even its high
work function (5.65 eV) is not enough to eliminate the
SBH on p-type SiC. For this reason the carrier concen-
tration at the SiC surface was increased by ion implan-
tation of A1 (at 10kV, 6 x 1015cm 2 dose or 50kV,
2 x 1015 cm 2 dose; 600 °C substrate) and annealing at
1500 °C prior to metallization.
5. Contacts to fl-silicon carbide
5.1. Schottky contacts to /]-SIC
With the advent of the ability to grow //-SIC thin
films in the 1980s came a thrust of research on metal
contacts to this material. However, large concentra-
tions of stacking faults, associated with the low stack-
ing fault energy of this polytype, as well as twins and
threading dislocations occurring in heteroepitaxial
films have precluded the achievement o f the predicted
electrical properties, both within the semiconductor
substrate and at the metal/SiC interface. Table 7 lists
the rectifying contacts on n-type //-SIC found in the
literature. No rectifying contacts on p-type fl-SiC have
been reported.
Several of these studies have included Au [62 64],
which has a high work function and is nonreactive
with Si and C. Ioannou et al. [62] deposited Au films
on chemically cleaned substrates by electron beam
evaporation at approximately 1 )< l0 7 Tort. The
cleaning procedure, which consisted of degreasing with
solvents and etching in HF, should have removed al-
most all of the O, while some hydrocarbon contamina-
tion could have adsorbed to the samples during their
brief exposure to air while loading in the vacuum
chamber. The as-deposited contacts displayed ideality
factors of 1.5 (linear region > 6 decades) and soft
breakdown at 8 - 1 0 V ( l e a k a g e s 2 . 5 × 10 7 A c r e 2
at 1V). A Schottky barrier height of 1.2 eV was
 L.M. Porter, R.F. Davis /Materials Science and Engineering B34 (1995) 83 105
calculated from C - V measurements. After annealing at
300 °C for 1 h, the ideality factors and SBH decreased
slightly, while the reverse leakage currents increased.
Subsequent annealing at 500 °C for 1.5 h resulted in
further increases in the reverse leakage currents. Ohmic
behavior ensued after annealing at 700 °C for 30 , i n
Auger analyses showed significant diffusion of Si into
the Au film after the latter annealing step. As the
substrates are believed to have been relatively clean, it
is quite likely that the inferior Schottky characteristics
(in comparison to 6H-SiC) and degradation after low
temperature annealing were associated with defects in
the fl-SiC films.
The study of Das et al. [64] gives strong evidence for
the degrading effects of defects on electrical properties
in /7-SIC substrates. Gold films were thermally evapo-
rated onto fl-SiC films grown on both nominal on-axis
(100) and off-axis ([100] oriented 2 ° 4 ° toward [011])
Si. A previous study [65] had shown the presence of
antiphase domain boundaries (APBs) in films grown on
the on-axis (100) substrates. The values of both the
ideality factors and the reverse leakage currents were
greater for the contacts on the on-axis films. In addi-
tion, current transport was determined to be dominated
by space charge limited current rather than thermionic
emission, which has been dominant in many 6H-SiC
contacts [66].
As listed in Table 7, Waldrop and Grant [63] mea-
sured the SBHs of several metals on (100) fl-SiC by
XPS and C - V measurements. The metals were de-
posited at room temperature in UHV after chemical
and thermal cleaning which left ~ 1 monolayer of O as
the only detectable contaminant by XPS. The calcu-
lated and theoretical barrier heights are plotted vs. the
metal work functions in Fig. 7. Both sets of data (XPS
and C V) show a positive correlation between SBH
and metal work function. The slopes, S, of the linear
fits to the two sets of data points were 0.26 and 1.52
1.0- s = 1.o. , #
0.5-
.E
"r 0.0-
E
.'' .Q- theoretical
-0.5-
• ; measured (XPS)
• •-• measured (C-V
-1 . 0 -
2.5 30 315 20 .15 510
Metal Work Function (eV)
Fig. 7. Data points of experimentally-determined and theoretical
barrier heights on n-type 3C-SiC (100) vs. work function of the metal
contacts. The experimental data points are from Waldrop and Grant
[63]. The slopes, S, of the linear fits through each set of data points
are indicated.
97
from XPS and C - V measurements, respectively. Al-
though the slope from the data points calculated from
C - V measurements is very high, the small number of
data points over a small range of work function values
introduces a higher susceptibility to variation. If the
SBH of Tb (@M = 3.0 eV) is neglected, S for the XPS
set of data becomes 0.58, which is more than twice as
high as S for the complete set of data. Thus, it is again
shown that the index of behavior, S, can be very
susceptible to both the particular metal contacts and
the measurement technique. As for 6H-SiC, all results
indicate some positive correlation between SBH and
metal work function.
From XPS analyses Bermudez [67] found an upward
band bending of 1.5 eV at the (100) fl-SiC surface after
annealing in UHV at 1150°C for 2 , i n followed by
exposure to a Si flux, which resulted in a Si rich surface.
The surface states, which are indicated by the band
bending, may have been enhanced by the excess Si;
however, the high degree of covalency of SiC makes it
likely that some surface states are intrinsic to this
material [68]. After depositing 9 A of AI (sample tem-
perature <200 °C), the band bending was reduced by
0.1 eV, yielding a SBH of 1.4 eV. No pronounced inter-
diffusion was detected after "flash annealing" the 9/~
films to 1050 °C. This result suggests that longer an-
nealing times at that temperature are necessary to acti-
vate AI in any p-type SiC polytype for the fabrication
of ohmic contacts from A1 or AI alloys.
5.2. Ohmic' contacts to ~7-SIC
5.2.1. n-type fl-SiC
In addition to 6H-SiC, annealed (900-1250 °C) Ni
has also been commonly used for ohmic contacts to
fl-SiC [69-72]. Steckl and Su [71] employed as-de-
posited and annealed (900 °C for 3 - 5 , i n ) Ni for recti-
fying and ohmic contacts, respectively, in one device.
However, Cho et al. [72] reported Ni to be ohmic on
10mY 10JScm 3 / - S I C in the as-deposited case. The
ohmic behavior in the latter case is likely to be the
(C-V) result of a high concentration of defects in the SiC films
(owing to its high work function, one would not expect
Ni to be ohmic on any n-type SiC polytype); thus, the
substrate quality is very critical to the contact proper-
ties. Daimon et al. [69] and Edmond et al. [70] found
I both annealed Ni and as-deposited AI to be ohmic on
n-type fl-SiC (100) with low carrier concentrations
(5× 1016 l x 10~7cm-3). The latter study reported
high contact resistivities for both contacts, as might be
5!5 expected for the low doping levels in the substrates. The
relatively low work function of A1 probably contributed
to the formation of a low SBH. Annealing the A1 at
900°C for 3 - 5 , i n resulted in rectification. This
change was attributed to the creation of a p - n junction
by diffusion of AI into the SiC.
98 L.M. Porter, R.F. Davis / Materials Science and Engineering B34 (1995) 83 105

Table 8
Ohmic contacts on n-type//-SIC. M u l t i - l a y e r c o n t a c t s a r e l i s t e d in s e q u e n c e (left t o r i g h t ) f r o m t h e t o p m o s t l a y e r to t h e l a y e r in c o n t a c t w i t h t h e
SiC. See Table 3 for a description of the rating system for surace preparations

Metallization Deposition Deposition Deposition Annealing p~ at R T (f~ SiC carr. SiC Method of p~ Origin of Surface Ref.
method temperature pressure condition cm:) cone. surface meas. SiC preparation
(Torr) (cm ~/

Ni NR RT NR 930 °C/3 min NR 6 x 1() [¢' (100) CVD fair [69]

I x 10 Iv
AI NR RT NR as-deposited NR 6 × 10 It' (100) CVD fair [69]
1 x l0 w
Au e-beam NR 10 7 700 ° C / 3 0 m i n NR 5 IO n' (100) NR CVD good [62]
evap. 5 IO w
A1 thermal RT 10 ~' b.p. as-deposited 1.6 x 10 5 I0'" (100) three-contact CVD good [70]
evap. and
extrapolation
Ni thermal RT 10 (' b.p. 1250°C5min 1 . 4 x 10 5 10 ~r' (100) three-contact CVD good [70]
evap. and
extrapolation
Cr thermal RT l0 (' b.p. 1250 °C,5 rain 7.0 x 10 2 5 × 1() 16 (100) three-contact CVD good [7(I]
evap. and
extrapolation
Au Ta (9% 3 thermal RT 10 (' b.p. 1250°C5min 3 . 0 x 10 2 5 × I() I(' (lO0) three-contact CVI) good [70]
at.%) evap. and
extrapolation
TaSi 2 sputtering RT NR 850 °C,'5 rain 2.0 x 10 2 5 x 10 I(, (100) three-contact CVD good [70]
and
extrapolation
Ag MBE RT UHV 1000 °C NR NR (100) CVD sputtered w/ [86]
500 eV A r
ions: no
contaminants
W sputtering RT 10 7 850°C/30min 2 . 4 × 10 i 2 × l0 w (100) contact area CVD sputtered [74]
Ti sputtering RT 10 v b.p. 300 °C/30 90 7.6 9.2 x 10 ~ I() v~ I() ~ (10(/) four-point CVD good [75]
nrin
W sputtering RT 10 7 b.p. as-dep, to 600 1.5 × 10 : 10 ~ I(# s (100) four-point CVD good [75]
°C/10min 2.3 x 10
TiSi: sputtering RT 10 " b.p. 1000°C/10s ~ 1.1 × 10 4 I() ~v I() ~s (100) four-point CVD good [75]
450 °C/390 min
WSi: sputtering RT 10 v b.p. 1000°C'10s+ 3 . 9 x l0 4 I() Iv 1() I~ (100) four-point CVD good [75]
450 °C, 390 min
Mo e-beam NR 10 ~' b.p. as-dep, and 1200 6.2 4.0 × 10 2 1017 10/~ (100) extrapolation CVD NR [72]
evap. °C/6(I min
Ni sputtering NR NR 900 °C/3 5 NR NR NR carboniza- good [71]
rain tion of Si
Au/Pt/Ti sputtering NR l0 v b.p. operated at I.l x 10 4 l0 u' 10 r (100) four-point CVD sputtered [76]
650 °C,,I h
Au/Pt/W sputtering NR 10 7 b.p. operated at 2.0 x 10 4 10 I(' l017 (100) four-point CVD sputtered [76]
65O °@8 h
Au/Pt/TiN/Ti sputtering NR l(I 7 b.p. operated at 1.4 x l0 4 l0 I(' 1017 (100) four-point CVD sputtered [76]
650 °@31 h
Pt/TiW, Ti sputtering NR 10 v b.p. operated at 2.6 x I0 4 1() I~' l0 w (100) four-point CVD sputtered [76]
650 °C/3 h
W sputtenng NR 10 v b.p. as-deposited 10 3 lO 17 IO Is (100) circular T L M CVD good [10(I]
Ta sputtering NR 10 7 b.p. as-dep, to 7 x 10 7 5 × I() I'~ (100) circular T L M CVD fair [77]
1000 °C/I h 4.3 x 10 ~'
Re sputtering NR l(I 7 b . p . as-dep, t o 9 0 0 ° C 1 × 1 0 "* l x 5 × 1 0 v; (100) circular T L M CVD t~fir [771
/30 min I0 s
Pt sputtering NR 10 v b.p. as-dep, to 5 0 0 ° C 6 × 1 0 <~ 1 × 5 × 1() I~ (100) circular T L M CVD fair [77]
/30 rain 10 5

NR = not reported; RT = room temperature; b.p. = base pressure.

 L.M. Porter, R.F. Davis / Materials Science and Engineering B34 (1995) 83-105
Table 8 lists these studies along with several other
ohmic contact metallization schemes. While most of
these contacts were annealed above ~ 8 0 0 °C, there
does not seem to be any simple formula for creating an
ohmic contact to n-type fl-SiC. One of the metals (Ni)
is a silicide former, m a n y (Cr, Ta, W, Ti, Mo) are both
silicide and carbide formers, and some (Ag and Au) are
neither carbide nor silicide formers [73]. In addition, the
work functions of m a n y of the silicides are quite similar
to the pure metals; thus, it is not believed that the
product phases in general have the intrinsic properties
to create an ohmic contact (i.e. as-deposited). While
low work function metals may form relatively low
barrier contacts, the data suggests that the formation of
most of the ohmic contacts to n-type fl-SiC has been
associated with the creation of defects (e.g. vacancies)
after annealing and possibly aided by defects present
within the SiC films.
Gold formed ohmic contacts after annealing at
700 °C for 30 min [62]. Auger analyses showed that the
annealing resulted in Si diffusing into the Au film. In
this case the ohmic behavior is very likely associated
with the creation of Si vacancies rather than the forma-
tion of any new interface compounds.
Many of the studies listed in Table 8 reported contact
resistivities. Edmond et al. [70] reported room tempera-
ture values on lightly doped SiC (5 x 1016 cm 3) to be
between 2.0 x 10 2 f~ c m 2 and 1.6 x 10 i f~ c m 2, with
TaSi2 yielding the lowest value. Some improvement in
the TaSi2 contacts was observed with heating at 400 °C.
Geib et al. [74] estimated contact resistivities of
2.4 x 10 1 and 8.0 x 10 2f~ cm 2 (2 x 1017 cm 3 carrier
conc.) for W contacts at 23 °C and 900 °C, respectively.
In comparison Chaudhry et al. [75] calculated a
contact resistivity of 1.5 x 10 2 f~ cm 2 for as-deposited
W contacts o n 10 j7 t o 1018 cm 3 fl-SiC by the four
point probe method. This value decreased to
6.1 x l 0 - 3 ~ c m 2 after annealing at 300 °C for 30 min.
The contact resistivity of Ti contacts on the same
material decreased significantly from 1.69 ~ cm 2 after
annealing at 300°C for 3 0 m i n to 7.6 x 10 3 ~ c m 2
after 90 min. The decrease in both cases was attributed
to the dissolution of an interfacial oxide layer. Anneal-
ing the Ti contacts at 600 °C for 10 min resulted in a
slight increase to 9.2 x 10 3 ~-~c m 2. The authors stated
that this increase may be due to the formation of a high
resistivity TIC0.6 phase. Recent work [21,31] has shown
that a thin layer (2 3 nm) of TiC1 , forms at the
interface with 6H-SiC after annealing Ti/SiC at 700 °C
for 20 60min. It is possible that the formation of a
thin carbide layer resulted in a slight increase in the
contact resistivity; however, a significant increase due
to the higher resistivity of the carbide is unlikely consid-
ering its thickness. In addition, the much smaller work
function of TiC is more likely to cause a reduction in
the SBH. In fact, one study [76] attributes an observed
99
reduction in the contact resistivity of Ti contacts (an-
nealed at 650 °C for 3 h) to the formation of TiC.
The silicides of these metals (TiSi 2 and WSi2) yielded
lower contact resistivities than the pure metals and
displayed better thermal stability [75]. The lowest re-
ported values for these metallizations were
1.1 x 1 0 - 4 ~ c m 2 for TiSi2 annealed at 450°C for
390rain and 2.0 x 10 4 f ~ c m 2 for WSi 2 annealed at
450 °C for 10 min. A correlation between a high contact
resistivity and an interfacial oxide layer was observed,
emphasizing the importance of surface cleaning and
processing conditions on good contact properties.
Substantially lower contact resistivities were reported
by Chen et al. [77] for Ta, Re, and Pt contacts. In the
latter study the metals were deposited on both uninten-
tionally-doped ( ~ 10 IT cm 3) and N-implanted
(5 X l019 c m - 3 ) n-type (001) fl-SiC. On the unintention-
ally-doped samples the Ta and Re contacts were ohmic
with contact resistivities of 5 x 10 5 f~ cm 2 and
4 x 10 4 ~-~c m 2, respectively, calculated using the T L M
method. The contact resistivity of Ta increased to
1 x 10 - 4 ~ c m 2 after annealing at 500 °C for 30 min;
that for Re decreased to 2.5 x 1 0 - 4 f ~ c m 2. Both of
these contacts became rectifying after annealing 900 °C
for 30 min. The Pt contacts were not ohmic before or
after heat treatment (to 1000 °C) on these samples.
However, all three metals were ohmic in the as-de-
posited condition on the implanted samples. The con-
tact resistivities for as-deposited Ta, Re, and Pt on
these latter samples were 7 x 10 7, l x 10 4, and
6 x 10 - 6 ~ c m 2, respectively. The Pt contacts became
rectifying after annelaing at 900 °C for 30 min. After
annealing at 1000 °C for 1 h, the contact resistivity of
the Ta contacts increased to 4.3 x 10 6 f~ c m 2. These
contacts remained ohmic after heating to 1100 °C for
30 min, but interfacial voids formed, resulting in erratic
I V measurements. The Re contacts were annealed to
900 °C for 30 min, which resulted in a decrease in the
contact resistivity from the as-deposited value to
1 x 10 5 ~ c m 2.
Shor et al. [76] investigated multilevel metallization
schemes based on Ti and W for high temperature
(650 750 °C) operation (see Table 8). This type of
study is very important for extended high temperature
operation of electronic or optoelectronic devices, yet
very little has been published on this subject. The main
concerns include the reactivity and diffusivity between
the contact metallization and the SiC substrate and the
oxidation of the contacts. Prior to the I - V measure-
ments taken at room and elevated temperature, the
contacts were annealed at 650 and 750 °C for various
times. The most promising metallization scheme was
Au/Pt/TiN/Ti, which remained ohmic throughout
operation at 650 °C for 31 h after which it became
rectifying. The reported contact resistivity of the as-
deposited contacts (1016-101Vcm-3carr. conc.) was
100 L.M. Porter, R.F. Davis Materials Science and Engineering B34 (19951 83 105

Table 9
O h m i c c o n t a c t s on p-type/']-SIC. M u l t i - l a y e r c o n t a c t s are listed in sequence (left to right) from the t o p m o s t layer to the layer in contact with the
SiC. All of the /]-SIC (1001 films were grown on Si by CVD. See T a b l e 3 for a description of the r a t i n g system for surface p r e p a r a t i o n s

Metallization Deposition Deposition Deposition Annealing p~. at R T SiC carr. M e t h o d of p~ Surface Ref.
method temperature pressure condition (f~ cm 21 cone. mess. preparation
(Tow) (cm ~)

AI Si NR RT NR 930 °C,'3 min NR I x 10/r' fair [691

(89:11 wrY/o) 4 x 1017
Au Ta-A1 thermal RT 10 (' b.p. 1200°C, ' 4.7 x 10 ~ 1 x 10 u' three-contact good [70]
(91:2:7 at.%) evap. 30 min and
extrapolation
TaSi./AI sputtering/ RT 10 ~' b.p. 1200 °C,' 2.0 x 10 ~ I x 10 ~6 three-contact good [70]
thermal 30 min and
evap. extrapolation
AI thermal RT 10 ~' b.p. 8811°C:3 min 3.1 x 10 2 I × 10 t~' three-contact good [70]
evap. and
extrapolation
Ni e-beam NR 10 (' b.p. as-dep, to 7 0 0 ° C 4.1 x 10 2 ll) ~7 10 ~ extrapolation NR [721
evap. :15min 2.8 x 10 -'

N R = not reported: R T - r o o m t e m p e r a t u r e ; b.p. - base pressure

1.4 x 10 4~'~cm2. This value was reduced by 65%
(4.9 x 10 s fl c m 2) after annealing at 650 °C for 1 h. It
was believed that the TiN layer acted as a good diffu-
sion barrier, thereby improving its thermal stability.
While the authors suggest that a high defect density in
the fl-SiC films may have contributed to a higher
contact resistivity than may be achieved on better qual-
ity material, we believe that these same defects may also
contribute to the actual ohmicity of the as-deposited Ti
and W contacts. The Au/Pt/W contacts also displayed
relatively good thermal stability. Considering the facts
that W has a high melting point and TiN is a good
diffusion barrier, it would be interesting to see if the
thermal stability could be improved by combining both
of these materials in the same metallization scheme.
5.2.2. p-type ~l-SiC
The small number of studies on ohmic contacts on
p-type /l-SiC are listed in Table 9. All but one of the
contact metallizations contains AI. As mentioned in a
previous section, Al is used because it is a p-type
dopant in SiC and therefore can be used to highly dope
the surface of the SiC, narrowing the depletion region
and allowing carriers to tunnel through the barrier.
The contact resistivities of A1 annealed at 880 °C for
3 m i n and TaSi2/A1 and Au Ta AI annealed at
1200°C for 30min were 3.1 x 10 2 2 . 0 x 10 ~, and
4.7 x 10 1 f~ cm 2, respectively on I x 10 ~6 cm 3 /l-SiC.
This high annealing temperature should be enough to
substantially increase the doping level in the substrate;
thus, a higher carrier concentration in the substrate
may not significantly improve the contact characteris-
tics. However, the very high driving force for oxidation
of AI could have resulted in A1 diffusing away from the
interface to react with O. This problem should be
considered with any contact metallization involving A1.
It is believed that the variation in, and sometimes
conflicting, results regarding contacts on fl-SiC may be
attributed to two main causes: (1) differences in crys-
talline quality of the //-SiC films, considering that the
defect densities are much higher than in 6H-SiC; and
(2) differences in the states of the surface prior to metal
deposition. For example, in one study [72] Ni was
ohmic as deposited on p-type (1017 l0 Is cm 3) /]-SIC.
After annealing at 700 °C (15 min?), X-ray diffraction
indicated the formation of Ni2Si, and the contact resis-
tivity decreased from 4.1 × 10 2 to 2.8 × 10 2f~cm 2.
These results indicate that the ohmic behavior was not
caused by the formation of Ni silicide; however, it was
likely associated with a high concentration of defects
near the SiC surface, which probably increased upon
annealing.
6. Discussion
6.1. Suit/hoe states and Fermi level pinning
Throughout this paper the characteristics of many
contacts on n- and p-type c~(6H)- and //-SIC were
reported. Considering the contacts in their unreacted
forms, Figs. 4, 5 and 7 show a positive correlation
between the SBHs and the work functions of the metals
on both ~- and /]-SIC as the Schottky Mott limit
would predict. However, these empirically determined
correlations were significantly less than 1.0, indicating
a partial pinning of the Fermi level attributed to sur-
face states. A partial pinning of the Fermi level in
SiC agrees with the work published by Kurtin et al.
[68].
For many decades it has been known that Fermi level
pinning is more common in covalent materials than in
 L.M. Porter, R.F. Davis / Materials Science and Engineering B34 (1995) 83-I05
ionic materials [78,79]. Pioneering work was performed
by Kurtin et al. [68] who plotted results [80,81] of (I)B
vs. XM, where XM is the electronegativity of the metal,
for several metals on Si, GaSe, and SiO2 substrates ~.
The values of S for Si, GaSe, and SiO2 were ~0.05, 0.6,
and 1.0, respectively. The slopes increased with the
degree of ionicity of the substrate, as defined by the
difference in the electronegativities, AX, of the two
components [82].
A very important trend was revealed in a plot [68] of
S vs. AX, for many semiconductors including the three
above. The plot, which is represented in Fig. 8, shows a
region of low S ( < ~ 0.1) for semiconductors with
A X < 0 . 6 and a region of high S (>0.9) for semicon-
ductors with A X > 0.8 connected by an abrupt transi-
tion region (0.6 < A X < 0 . 8 ) . Carbon and silicon have
electronegativities of 2.55 and 1.90, respectively, which
corresponds to A X = 0.65 for SiC. The data indicates
that Fermi level pinning dominates Schottky barrier
formation in covalent materials, plays a variable role in
materials with a mixture of ionic and covalent bonding
(0.6 < A X < 0 . 8 ) , and does not determine the SBH in
the more ionic materials. According to Fig. 8, SiC is in
the transition between strong Fermi level pinning (sur-
face states) and no Fermi level pinning (no surface
states), which is in good agreement with the empirical
results presented in this paper (e.g. Figs. 4, 5 and 7).
Kolomiets et al. [83] attributed the frequency depen-
dence of the capacitance of SiC on relaxation (filling
time 10 2 - 1 0 6 S ) of surface states. The c u r r e n t -
voltage characteristics of metal/SiC contacts were inde-
pendent of the metal work functions. In addition, very
recent work [84] has also shown direct evidence for the
presence of surface states on 6H-SiC (0001). After
etching for 10 min in 10% H F and annealing at 960 °C
AJN • ZnO A.1203SrTiO
I 0 -- ZnS
0.8 ,o~d] GaS
• CdS
0.6 Se
0.4 SiCfOxI ZnSe
• ~/q s~
CIIFe • ,
0.2 ~e GaA
0.0 I I I I I I I I
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
AX
Fig. 8. Index of interface behavior, S, plotted for various semicon-
ductors as a function of the electronegativity difference in their
elemental components. The index of interface behavior is defined as
the slope in a plot of Schottky barrier height vs. metal work function.
After Ref. [68].
The electronegativity has been shown to have a linear relationship
with the work function (W. Gordy and W.J.O. Thomas, J. Chem.
Phys, 24 (1956) 439-444). However, the work function is dependent
on the crystal plane, whereas electronegativity is an atomic property.
101
in a silane flux, both ultra-violet photoelectron spec-
troscopy (UPS) and XPS analyses indicated that sur-
face states were present within the band gap. These
surface states, however, were removed after hydrogen
plasma exposure yielded a H terminated surface. There-
fore, it is possible to passivate the surface states with H.
If these states could remain passivated after depositing
metal contacts, more control over the SBH, and, hence,
the electrical properties, could be achieved.
6.2. Reactivity of SiC
Extensions of the coavalent vs. ionic theory [68] have
also included heats of formation, AHf, of the semicon-
ductors. Brillson [85] plotted the S values taken from
Mead [79] (and references therein) vs. AHf for a variety
of semiconductors. The plot showed the same type of
transition from covalent to ionic as for S vs. AX.
Covalent semiconductors have low heats of formation
and are less stable against chemical reaction.
It has been shown through many of the studies
discussed in this paper that SiC readily reacts with most
metal contacts. However, the critical reaction tempera-
tures are usually greater than those for Si. These reac-
tions are very important to the resulting electrical
characteristics, especially for operation at elevated tem-
peratures. Even those metals such as Au which do not
form silicides or carbides have shown interdiffusion
with SiC [62], while Ag has evaporated from the SiC
surface at temperatures above 600 °C [86]. This may
mean that diffusion barriers will be a necessary part of
contact metallizations for long term operation at high
temperatures.
Although SiC consists of 50 at.% Si, the reaction
characteristics of SiC with metals can be very different
from the metals with Si. In addition, it is difficult to
predict the reaction products in material systems having
SnO~
three or more components and in the process of attain-
sio5 ing thermodynamic equilibrium, e.g. a metal and SiC
Ga203
chemically bonded at an interface and heated to the
extent that chemical interdiffusion occurs. Thermody-
namic data can yield the equilibrium phase fields; how-
ever, the diffusion path is controlled by the diffusion
coefficients of each component in the pertinent phases.
It is the ratio of the diffusivities which determines the
I I I
1.8 2.0 2.2 2.4 interface compositions, and accordingly the diffusion
path [87].
It is possible that reactions in certain metal/SiC
systems are limited by the dissociation of SiC because
of the strong Si C bond. Evidence in support of this
statement is provided by the initial formation of metal-
rich silicides, for example between SiC and Ni
[42,88,89], Co [35,42,90], and Pd [88,91], which in most
cases were followed by the formation of less metal-rich
silicides. Other metals such as Ti [21,92-95], Mo [96],
Fe [97,98], Nb [99], and W [100] formed both carbides
102 L.M. Porter, R.F. Davis Materials Science and Engineering B34 (1995) 83 105
and silicides after annealing At temperatures between
570 and 1200 °C, the product phases in Ti/SiC were
reported to be TiC [101,102], TisSi3 [103], or both
TiC1 ,. and TisSi3 [21,92 95]. These results were simi-
lar in the Mo/SiC [96] system annealed at 1200 °C for
1 h and W/SiC [100] system annealed at 950 1100 °C
for 60s in which MesSi 3 and Me2C ( M e = m e t a l )
formed. It is immediately apparent that these product
phases are very different than if these same metals
reacted with Si. Not only is the temperature important,
but the thickness of the films and the amount of time
are very important determinants of the resulting phases
in metal/SiC systems.
6.3. Future perspectives
There are still important questions left unanswered
regarding SiC contacts. However, important strides
have been achieved which have provided opportunities
for further research. Because of the nature of SiC, good
Schottky contacts with SBHs of approximately l eV
can be easily fabricated. However, these same proper-
ties make it difficult to form low barrier ohmic contacts.
It is the ability to create ohmic contacts with low
contact resistivities ( ~< 10 6 f~ cm 2) which will be one of
the major challenges facing the SiC community in the
foreseeable future.
Perhaps it would be wise to examine solutions to
similar problems in GaAs. The practical difficulties of
creating good ohmic and/or Schottky contacts to GaAs
has led to recent efforts in barrier height engineering.
The tendency of the Femri level to pin near midgap in
this material led several investigators to try to decrease
the band bending at the surface by using doped inter-
layers of Ge and Si [104 109] and to increase it by
using interlayers of NiA1 and AlAs [109-114].
To decrease the barrier height on GaAs, Chambers
[109] deposited thin semiconductor interlayers of n+Si,
n + G e and GaSe,.As~ , with a smaller band gap and a
favorable band lineup with the substrate. Chambers
and Loebs [108] grew thin epitaxial overlayers of un-
doped and As-doped (n +) Si on n- and p-type GaAs
(001)-(2 x 4) to determine their influence on surface
band bending. X-ray photoelectron spectroscopy (XPS)
measurements indicated that the Fermi level remained
pinned after depositing undoped Si (at ~0.6 eV below
the conduction band for n-GaAs and --~0.5 eV above
the valence band for p-GaAs). However, depositing n
Si onto n-GaAs (p-GaAs) resulted in a significant
reduction (increase) in band bending ( ~ 0 . 3 e V for
n-GaAs and ~0.8 eV for p-GaAs). The authors con-
cluded that the Fermi level was not unpinned, which
would be associated with an elimination of interface
states. Intead, it was believed that the reduction in band
bending could be attributed to charge transfer from the
highly-doped Si interlayer.
Similarly, it would be very desirable to decrease the
band bending at the SiC surface so that low barrier
height contacts could be produced. This might be
achieved by depositing doped semiconducting interlay-
ers with favorable band lineups between the conduction
or valence bands on n-type or p-type SiC, respectively.
A similar but alternate approach is also advocated.
This would involve depositing thin insulating interlay-
ers followed by low (on n-type) or high (on p-type)
work function metals as an extension of the investiga-
tions of TiN [49,50] and TiW [51] contacts discussed in
Section 4.2. In addition to a potentially reduced SBH, a
good diffusion barrier between the metal and the SiC
may be a beneficial result.
Because the long term operation of SiC devices is an
important goal, diffusion barriers are a legitimate con-
sideration. The reactions of SiC with many metals at
potential device operating temperatures ( ~ 6 0 0 °C) can
destroy a device. Therefore, it is important to develop
contacts which are stable at high temperatures. How-
ever, very few studies have reported the thermal stabil-
ity of contacts at elevated temperatures for extended
periods of time. This is another important issue to be
addressed by the SiC community.
As a result of the research which has been performed
for the past few decades, a good understanding of the
limitations of metal contacts to SiC has been gained.
We must now use these achievements as the foundation
for further improvements in contacts if the potential of
SiC devices is to be realized.
7. Conclusions
Schottky and ohmic contacts on n- and p-type ~- and
//-SIC have been reviewed and discussed in terms of
their electrical properties, Schottky barrier heights,
thermal stability, and reaction characteristics.
There is significant evidence for the presence of sur-
face states in SiC. However, if the surface is maintained
relatively clean, the density of surface states is not
sufficiently high to completely pin the Fermi level.
Positive correlations ( g 0 . 2 - 0 . 6 ) between the SBHs on
both ~- and fl-SiC and the work functions of the metals
were displayed, The partial pinning of the Fermi level is
believed to be associated with the percent ionicity of
SiC in agreement with the results of Kurtin et al. [68].
Most metals in the as-deposited condition form very
good rectifying contacts on both n- and p-type 6H-SiC
with SBHs of ~>1 eV. Low leakage currents, low ideal-
ity factors, and high breakdown voltages have been
displayed. The quality of contacts on [i-SiC seems to be
limited by the quality of the /t-SiC films.
On both polytypes it has been difficult to fabricate
ohmic contacts with low contact resistivities. Heavily
doping the surface has shown some success and may be
 L.M. Porter, R.F. Davis / Materials Science and Engineering B34 (1995) 83-I05
a viable technique for many devices. Alternative ap-
proaches using semiconducting or insulating interlayers
should also be investigated to reduce the barrier and,
correspondingly, the contact resistance.
The reactivity of SiC with metals to form silicides
and/or carbides can be a serious problem for long term
operation of devices at high temperatures. These reac-
tions can ultimately destroy a device. For these reasons
diffusion barriers should be investigated for contact
metallizations. There is also a need for testing contacts
for extended operation at high temperatures. These
critical issues must be addressed and transferred to
industry if we are to push the envelope of SiC device
operating conditions and take advantage of the extreme
thermal and electronic properties of SiC.
Acknowledgments
We would like to express our sincere gratitude to J.S.
Bow, M.J. Kim, and R.W. Carpenter of Arizona State
University for contributing the TEM images. We would
like to thank Cree Research, Inc. for providing the
6H-SiC wafers on which the research at N C S U was
based; S. Tanaka for taking valuable time to translate
literature; and M.C. Benjamin, S.W. King, and R.J.
Nemanich for contributing unpublished data regarding
surface states on SiC. We would also like to thank K.
Das, R. Kaplan, J.R. Waldrop, S.A. Chambers, J.
Crofton, and D. Alok for valuable discussions and R.S.
Kern for contributing helpful information. We also
thank many of the authors referenced in this paper for
sending us copies of their publications.
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