Thin Solid Films, 31 (1976) 235-241

© Elsevier Sequoia S.A., Lausanne---Printed in Switzerland 235

STRUCTURE AND MECHANICAL PROPERTIES OF

R.F. SPUTTERED SiC FILMS

KIYOTAKA WASA, TAKESHI NAGAI AND SHIGERU HAYAKAWA

Wireless Research Laboratory, Matsushita Electric Industrial Co. Ltd., Kadoma, Osaka (Japan)
(Received May 6, 1975; accepted June 7, 1975)

Amorphous and polycrystalline SiC films were prepared on glass, sapphire

and silicon substrates by r.f. sputtering of a SiC cathode in argon. From evalua-
tion of their mechanical properties, it was found that the films have a Vickers
hardness of 4000 kg mm-2, similar to bulk SiC, and can be used to make hard
surface coatings due to their high wear resistance. Mixed carbide (Si, B)C films
prepared by r.f. sputtering exhibit a Vickers hardness of 4500 kg mm -2 and
are also usable for hard coatings.

1. INTRODUCTION

Thin films of SiC are of technological interest because of their potential

applications not only in electron devices but also in surface coatings with high
wear resistance. SiC films are obtained by vapor phase reaction 1' 2, evaporation 3,
cathodic sputtering4 or by ion implantation of Si in diamond crystals 5. These
processes differ in the mechanisms of film growth, and thus the resultant films
may also differ in their electrical and structural properties. Among these processes,
cathodic sputtering has the advantage that the SiC films can be deposited onto
various kinds of substrates With little external contamination.
Recently we have deposited SiC films by r.f. sputtering of a SiC cathode.
This paper describes the structure and mechanical properties of r.f. sputtered
SiC films with respect to their application in hard surface coatings.

2. EXPERIMENTAL PROCEDURE

2.1. SiC film deposition

A planar electrode r.f. sputtering set-up with an ultrahigh vacuum oil
diffusion pumped system was used for depositing the SiC films. The electrode
construction is shown in Fig. 1. Two kinds of cathode disks were used for the
sputtering: one was a pressed disk of 0c-SiC (purity 99.8 ~o), the other was of
13-SIC (purity 99.7 ~). These cathode disks were 25 mm in diameter. A 60 mm
diameter disk of aluminum (purity 99.9 ~) was used as anode. The anode disk
was perforated and substrates (pyrex glass, sapphire and silicon) were placed
 236 K. WASA, T. NAGAI, S. HAYAKAWA

behind the anode. The distances from cathode to anode and cathode to sub-
strate were 20 mm and 27 ram, respectively. Sputtering was carried out at 5 x 10 -3
Torr of pure argon. The background pressure before sputtering was
2 x 10 -6 Tort. Typical cathode current densities, cathode potentials and sub-
strate temperatures were 1-2 mA cm -2, - 9 0 0 to - 1 5 0 0 V and 100°-900°C,
respectively. In these sputtering conditions SiC films were deposited on the
substrates at deposition speeds of 0.1-0.7 grn h - 1

2.2. Measurements
The crystallographic structure of the sputtered films was studied by electron
microscopy. Infrared transmission spectra were examined at room temperature.
The mechanical properties were evaluated by measuring microhardness and
wear resistance.

3. RESULTS AND DISCUSSION

3.1. Structure of sputtered SiC films

Semi-transparent films were prepared on the substrates by sputtering
from the m-SiC cathode. Electron microscope analyses suggested that sputtered
films prepared at a substrate temperature below 500°C had an amorphous
structure. Crystalline films were obtained at substrate temperatures above
700°C. An infrared transmission spectrum from sputtered amorphous films
on the (111) plane of a silicon substrate is shown in Fig. 2. The spectrum indicates
that the films are of SiC, since the absorption band with a maximum at about
800 cm 1 corresponds to the lattice vibration of bulk SIC6. Figure 3 shows
an electron diffraction pattern and a surface electron micrograph from
sputtered crystalline films on the (001) plane of a sapphire substrate, prepared
at a substrate temperature of 800cC. The pattern suggests that the sputtered
films are polycrystalline s-SiC with one of the modifications of the hexagonal
phase, which is similar to the results observed with reactively sputtered SiC films 4.
Similar electron diffraction patterns were also obtained for films sputtered onto
(111) silicon substrates.

,._._, /HEATER
SUBSTRATE
HOLDER F::~
""1 I r - - / SUBSTRATE io¢
_ ANOOE

I\/I CA*.O~ I I//I

IV I (s~c) i Iv I zill

IAI I/1 ._,o J

So~ENoio ~oo =ooo ,5oo ,ooo 8OO
I WAVENUMBER (era "l)
Fig. 1. Electrode configuration of the r.f. sputtering system.
Fig. 2. Infrared transmission of a SiC film about 2 lain thick sputtered onto a (111) Si substrate at
440 °C with a deposition speed of 0.25 lam h - i.
R.F. SPUTTERED S i C FILMS 237

I I
0.5 .pm
Fig. 3. Microstructure and electron diffraction pattern of a SiC film about 0.3 ~tm thick sputtered
onto an (001) sapphire substrate at 800°C with a deposition speed of 0.3 pm h -1.

With these sputtering conditions, SiC films of the same crystal phase were
also obtained from the 13-SIC cathode target. The difference in the crystal phase
of the SiC target (0~-phase or [3-phase) hardly affected the crystal phase of the
resultant SiC films. This suggests that, as in ion bombardment of a compound
target 7, the SiC target surface is mostly decomposed into silicon and carbon
atoms during the sputtering process. Most of the sputtered particles are these
silicon and carbon atoms. Sputtered particles with a mean energy of about
10 eV 8 recombine with each other on the substrate and form SiC. The crystal
phase of the sputtered SiC films will be decided chiefly by the substrate tempera-
ture during film growth. The observed s-SiC phase was unstable, since the s-SiC
phase was changed to the I3-SiC phase by annealing the s-SiC films in vacuum
238 K. WASA, T. NAGAI, S. HAYAKAWA

at 1100 °C for 1 h. The sputtering process can quench the s-SiC phase in a way
similar to the effect observed in SiC synthesized by implantation of silicon in
diamond crystals 5.

3.2. Mechanical properties of sputtered SiC films

3.2.1. Hardness
The microhardness of the sputtered SiC films was studied by pressing a
diamond pyramidal indentor, such as is used in the Vickers test, and measuring
the diagonals of the square indentation. A typical scanning electron micrograph
of the indentation for amorphous SiC films sputtered onto sapphire substrates
is shown in Fig. 4 in comparison with those taken from the (001) sapphire

(o)
J f

IO m
Fig. 4. Typical scanning electron micrograph showing the indentation made by a diamond pyramidal
indentor at an indentor load of 50 g: (a) on (001) sapphire; (b) on SiC films about 2.6 gm thick sput-
tered onto an (001) sapphire substrate at 370 °C with a deposition speed of 0.7 gm h-1; (c) on an (001)
SiC single crystal.

substrate and the (001) surface of an s-SiC single crystal. It is seen that the diagonal
of the indentation for the SiC film is smaller than that for the sapphire substrate
and is nearly equal to that for the SiC single crystal. This indicates that the hard-
ness of the SiC film is greater than that of sapphire and nearly equal to that of a
SiC single crystal. Similar results were also observed with the polycrystalline
s-SiC films. Figure 5 shows the Vickers hardness calculated from the diagonal
of the indentation for SiC films sputtered onto the substrate as a function of
indentor load. The surface hardness decreases with an increase in load. At heavy
loads of more than 100 g, the hardness becomes equal to that of the sapphire
substrate (1900 kg mm -z) since the diamond indentor completely penetrates
the SiC film on the sapphire. With light loads of less than 25 g, the surface hardness
tends to 4000 kg mm -z, corresponding to the hardness of the SiC layer. This
value is nearly equal to that of bulk SiC.
3.2.2. Wear resistance
An abrasive wear test was carried out for the sputtered SiC films with the
diamond indentor used in the Vickers test under a load of 25 g with a sliding
speed of 1 mm sec- 1. Figure 6 shows the typical wear scar observed on amorphous
R.F. SPUTTERED S i C FILMS 239

8000

- ooc

--" 2o00 ~----__

I ooo

o
0 50 I00 150 200

LOAD (gr)
Fig. 5. Vickers hardness as a function of indenter load: (a) for a SiC film about 2.6 g m thick sput-
tered onto an (001) sapphire substrate at 370°C with a deposition speed of 0.7 pm h - l ; (b) for an
(001) SiC single crystal.

! I

20 um
Fig. 6. Typical scanning electron micrograph showing the wear scar made by a diamond indentor
at an indentor load of 25 g with a sliding speed of 1 m m see- ' : (a) on a SiC film about 3.6 lxm thick
sputtered onto an (001) sapphire substrate at 370 °C with a deposition speed of 0.7 pm h - 1 ; (b) on an
(001) SiC single crystal.

SiC films on sapphire substrates in comparison with the wear scar observed on
the (001) surface of a SiC single crystal. The size of the wear scar of the sputtered
films is found to be equal to that of the single crystal. A cyclical wear test was
also performed with a diamond stylus of 0.7 mil under a load of 4.0 g with a sliding
speed of 1-4 mm sec-1. Table I compares the wear of sputtered amorphous SiC
films with the wear of pyrex glass and alumina plates (purity 97 ~). The wear of
SiC films is much smaller than that of the pyrex glass and alumina plates. Similar
results were also found for polycrystalline at-SiC films.
3.2.3. Hard surface coatings
Si-C-O layers of 0.05-0.5 ~un thickness made by reactive sputtering from
a SiC target in an oxidizing atmosphere are useful for increasing the adherence
of the SiC films to the substrates. Similarly to SiC films, various kinds of r.f.
sputtered carbide films such as B4C can be used for making hard surface coatings.
However, as the hardness of the coating film increases, so the internal stress
contained in the film increases. This reduces the adherence of the film to the
240 K. W A S A , T. N A G A I , S. H A Y A K A W A

TABLE I
CYCLICAL WEAR TEST OF A SPUTTERED SiC FILM ABOUT 4.7 ~tm THICK FOR VARIOUS SLIDING SPEEDS /)s OF
A 0.7 MIL DIAMOND STYLUS, COMPARED WITH PYREX GLASS AND ALUMINA PLATE

Materials Width o f wear scar ~ (lam)

trs = l m m sec - t Vs = 4 m m see 1

P y r e x glass 5.5 9
A l u m i n a p l a t e ( p u r i t y 97 ~ ) 3.5 7
SiC film*** 1 1

* Sliding d i s t a n c e 100 c m ; l o a d 4.0 g.

** S p u t t e r e d o n t o p y r e x glass at 370 °C w i t h a d e p o s i t i o n speed o f 0.7 ~ m h 1.

substrate. A suitably adherent layer is necessary to make usable surface coatings.

Table II lists the composition and mechanical properties of hard coatings made
by the r.f. sputtering process. The SiC-glass systems are prepared by r.f. sput-
tering from a pressed target of mixed SiC and borosilicate glass powder. The
r.f. sputtered B4C films show very poor adherence. To obtain surface coatings with
high microhardness, mixed layer systems of SiC-B4C are much more useful.
TABLE II
SUMMARY OF THE PROPERTIES OF R.F. SPUTTERED HARD COATING FILMS OF DIFFERENT COMPOSITIONS

Composition Sputtering target* Hv (kg m m - 2 ) Wear resistance** Remarks

SiC P r e s s e d SiC 4000 1

SiC + 1 ~o g l a s s 3800 0.9 Good adherence
SiC + 5 ~o g l a s s M i x t u r e o f SiC + 3300 0.1
b o r o s i l i c a t e glass
SiC + 10 ~ glass 2400 0.03
SiC+25 ~ B4C Mixture of 4500
SiC + B 4 C
B4C Pressed B 4 C 4800 Poor adherence

* S p u t t e r i n g in a r g o n a t 3 0 0 " - 9 0 0 °C.
** R a t i o o f t i m e r e q u i r e d to a given w e a r v o l u m e a g a i n s t a n i r o n p l a t e (S-15C).

4. CONCLUSIONS

The crystallographic structure of SiC films depends on the method of pre-

paration. Table III lists the structure of SiC films for different methods of prepara-
tion. Various kinds of r.f. sputtered carbide films can be used for making hard
coatings. However, hard films are usually associated with poor adherence to the
substrates. A suitably adherent layer is necessary to make hard coatings usable.
These coatings are also appropriate for making high chemical resistance layers.

ACKNOWLEDGMENTS

The authors wish to thank Dr. S. Moil for the electron microscope analysis
and F. Hosomi for the experimental work in the film preparation and measure-
ments.
R.F. SPUTTERED SiC FILMS 241

TABLE III
SUMMARYOF THE PROPERTIESOF SiC FILMSFOR VARIOUSMETHODSOF PREPARATION

Method of Substrate and Deposition speed Structure Ref.

preparation substrate temp. (lain h - 1)
(°c)

Reaction of Si ~ 0.07 13-SIC (sc) 1

acetylene with Si 800-1000
Reaction o f Si 0.1-0.4 13-SIC (sc) 2
methane with Si 1200-1300
Evaporation o f SiC ~0.7 13-SIC (sc) 3
Si in acetylene 1100-1150
Sputtering of Si in Si 0.06 a-SiC (sc) * 4
argon-methane 900-940
Sputtering of Si, sapphire 0.1-0.7 s-SiC (pc) present experiment
SiC in argon 800-900
Ion implantation of Diamond - s-SiC 5
Si in diamond room temp.

2H-type; sc single crystal; pc polycrystalline.

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