ELSEVIER Thin Solid Films 277 (1996) 1-4

Letter

Dielectric constants of Ta20S thin films deposited by r.f. sputtering

Susumu Shibata
LSI Assembly Division, Electronic Devices Group, Oki Electric Industry Co., Ltd., 550-1, Higashiasakawa-cho, Hachoji-shi, Tokyo 193, Japan

Received 9 October 1995; accepted 8 November 1995

Abstract

Thin films of different dielectricconstantswere formeddepending on the sputtering conditions of a Ta-O, ceramicsputteredin an oxygen
and argon gas mixture using a diode d. sputtering apparatus. The dielectric constant was highest at an oxygen percentageof - 20% when
the sputtering power was kept constant. The higher the sputtering power, the higher the dielectricconstant when the oxygen percentage was
kept constant.
Although the thin filmsobtainedwereindicatedto be amorphous by electrondiffraction analysis, they werecrystallizedby heating.Electron
diffractograms of films with a high dielectric constant indicated 0'-TazOs, while those of films with a low dielectric constant indicated
f3-TazOs·

Keywords: Dielectrics; Deposition process; Sputtering; Tantalum

1. Introduction a f3- Ta-O, target in an oxygen and argon gas mixture using a
diode d. sputtering apparatus. The findings are reported in
the following.
Thin films of Ta-O, have been widely investigated as a
potential dielectric material for use in RAM capacitors due
to the oxide's high dielectric constant and chemical stability.
Therefore, the dielectric constant of Ta-O, films is a very 2. Results of experiment
important value, and should be thoroughly investigated for
its relationship to the film formation conditions. A 99.99% pure f3-TazOs target having a diameter of 125
Nakagawa et al., for example, obtained a thin film with x- mm and a thickness of 6 mm was used in an experiment
ray diffractions indicating (200)-oriented Ta-O, thin film for conducted using a diode d. sputtering apparatus. Presputter-
a 450 "C substrate temperature when the Ta target was sput- ing was conducted for 30 min under the deposition conditions
tered in a gas atmosphere of 75% Ar and 25% Oz at 1.0 Pa with the shutter closed. The target was sputtered at a total
[ 1]. Guoping et a1. obtained a (200) -oriented f3- Ta-O, thin pressure of 8 X 10 - 3 Torr and at a substrate temperature of
film having a dielectric constant of 24.5 with a substrate 250 oe.
temperature of more than 450 "C for d.c. magnetron reactive The dielectric constant was determined from the capaci-
sputtering in Oz gas [2]. tance formed by a 2 X 2 mrrr' electrode, fabricated on Corning
Tominaga et a1. obtained a (111) -oriented f3- Ta-O, thin glass 7059. The film thickness ranged from 300 to 400 nm
film on a substrate at 600-700 °C using chemical vapor dep- for the dielectric substance housed in the capacitor. The
osition with metalorganic precursors. The film was amor- capacity was measured using a capacitance bridge at 1 kHz
phous when the substrate temperature was less than 600 "C and the film thickness was measured using a multiple-beam
r3] . Furthermore, Sekido obtained a thin film with a dielec- interferometer.
tric constant of 60 by forming Ta-O, powder into pellets, and The sputtering power was set to 0.40, 0.32, 0.26 or 0.20
then evaporating them with electron bearns. He concluded kW, and the volume percentage of oxygen in the sputtering
that the high dielectric constant was due to the electrons atmosphere gas was set to 0, 5, 10, 19, 31,39,50, and 100%.
trapped in the film causing a lack of oxygen in the film. He The dielectric constant was then obtained for each condition
did not mention anything about the crystal structure [4 ] . (Fig. 1). When the sputtering power was kept constant, the
I made some discoveries on the relationship between sput- dielectric constant showed the highest value at an oxygen
tering conditions and the dielectric constant after sputtering percentage of 19%.

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2 S. Shibata / Thill Solid Films 277 (1996) 1-4

_ _ 0.40kW
----K- 0.32 kW
-0-- 0.26kW
----0- 0.20 kW

20
of 20 40 60 80 100 (%)
Oxygen percentage
Fig. 1. Dielectric constants (at I kHz) under different oxygen percentages
in terms of sputtering gas and sputtering power.

When the oxygen percentage was kept constant, an Fig. 3. Electron diffractogram composed mainly of {3-Ta20; crystals which
increase in the sputtering power gave a higher dielectric con- were produced by heating the films (in 100% 02' 0.4 kW) at I ooooe for
10 min in argon.
stant. The highest value of 41.5 for the dielectric constant
( 19% O2 0.4 kW power) was close to the value of 65 for the
dielectric constant of a- Ta20s which is stable at high Table I
Interplanar spacing d (A) obtained from the oxide film formed in 100% O 2
temperatures. and annealed
The lowest value of 24.1 (100% O2 0.4 kW power) is
close to the value of 24 for the dielectric constant of f3- Ta20s Obtained oxide film Ta205 [5) (low-temperature form)
which is stable at low temperatures. A 50 nm thick thin film
was deposited on a quartz substrate under individual sputter-
c; (A) d (A) hkl

ing conditions. After heating for 10 min at I 000 DC in an 3.895 3.88 001
argon gas flow, the film was peeled off the substrate with a 3.375 3.377 1100
hydrofluoric acid solution to measure its structure using an 3.152 1110
3.179 3.131 141
electron diffractogram. The accelerating potential was 100
3.098 200
kV. The beam spot was 1 11m in diameter, and the camera 2.469 2.449 1111
length was 30 em. Although, all samples were amorphous 2.095 2.105 1180
before heating as indicated by the electron diffractogram 2.035 2.024 340
1.961 1.944 002
(Fig. 2), they tended to assume a crystal structure after
1.820 1.824 142
annealing, showing different electron diffractograms depend- 1.656 1.661 3101
ing on the sputtering conditions.
Fig. 3 shows the electron diffractogram of the thin film
which was obtained by sputtering in 100% oxygen at 0.4 kW
power and annealed. The dielectric constantof the film was
24.1. Table 1 shows the interplanar spacings of the obtained
diffractogram [5]. These interplanar spacings showed good
agreement with that of the f3- Ta20s diffractogram.

Fig. 4. Electron diffractogram of tantalum oxide films which were produced

by heating the film (in 19% O2, 0.4 kW) at 1 000 "C for 10 min in argon.

Fig. 4 shows one of the electron diffractograms for a thin

film having a high dielectric constant after annealing. Table 2
shows the interplanar spacings of the obtained diffractogram
Fig. 2. Electron diffractogram of tantalum oxide films which were obtained [6]. These interplanar spacings are very similar to that for
by r.f. sputtering and are amorphous. a-TA 20 s·
 S. Shibata /Thin Solid Films 277 (1996) 1--4 3

Table 2
Interplanar spacing d (Al obtained from the oxide film formed in 19% O 2
argon and annealed
--- E=41.5 (02:19%)
720nm thick
Obtained oxide film o-Ta-O, (HT) [6] alpha tantalum oxide
...•...£=24.1 (02:10O%)
590nm thick
dobs' (A) d (A) hkl

20 30 40
8.922 8.98 004
6.286 6.Il 006
4.461 4.46 008
3.778 100
-3
3.841 OIl
3.754 101 ·4
3.639 3.621 f03
-5
013
3.457 3.362 015 Fig. 5. Current-voltage characteristics of tantalum oxide capacitors formed
3.049 017 by d. sputtering.
3.006 3.015 107
2.942 2.980 0012
2.794 2.774 109 19%0,
40
2.436 2.459 116
2.438 116
2.286 2.236 Il9
1.856 1.891 35

3. Discussion

Generally, it is said that the electrical conductivity of a-

Ta20S is higher than that of (3- Ta 20 S [7]. To evaluate the
obtained thin films, capacitors were produced by using thin 4 8
films with the dielectric constant of 41.5 and 24.1, respec- Deposition rate

tively. The thicknesses of these films were 720 nm and 590 Fig. 6. Dielectric constants (at I kHz) for various conditions of deposition
nm. Both capacitors were measured and compared for their rates and oxygen percentage in the sputtering gas (argon).

leakage current. The results are shown in Fig. 5. The current

only the atmospheric gas is only effective in the formation of
across the electrode was larger by two orders in the capacitor
a- Ta 20 S, but also the fact that the target itself is (3- Ta205 is
with the dielectric constant of 41. Thus, it can be assumed
one of factors.
from the electrical characteristics that the thin film with higher
While the experiment [4] by Sekido used the electron
dielectric constant has a structure similar to a- Ta20S'
beam deposition, he used {3- Ta205 as the starting material
It is obvious that films with different dielectric constants
and obtained a high dielectric constant. It is an interesting
are formed depending on the sputtering conditions. However,
question whether, in d. sputtering, a- Ta20S is fonned on the
the cause is still unknown. In this experiment, when the oxy-
surface of the target or as a film on the substrate. After a film
gen concentration in the atmospheric gas is constant, the
with dielectric constant of 41.5 was produced, X-ray analysis
higher the sputtering power is, the higher the dielectric con-
was conducted by grinding the surface of the target. Only {3-
stant is. The dielectric constant is shown in Fig. 6 as a function
Ta20S was observed. There was no peak indicating a-Ta205'
of sputtering rate. The oxygen concentration in the atmos-
In addition, when (3- Ta 20 5 was fused by an electron beam
pheric gas is used as a parameter. Also, when the oxygen
and cooled in vacuum, crystals of a- Ta 205 were observed
concentration in the atmosphere is higher, the dielectric con-
with X-ray analysis.
stant becomes higher as the sputtering rate increases. The
ratio of the increase of the dielectric constant to the increase
of the sputtering rate becomes higher. The dielectric constant
in a state where no oxygen is contained is lower than those 4. Conclusion
in the cases where 5% and 10% of oxygen are contained. It
is believed that behavior of oxygen in the atmospheric gas It was made clear that Ta 20 S films demonstrate different
significantly affects the dielectric. dielectric constants depending on the film formation condi-
In the reports in the past, (3- Ta20S was obtained by the tions. However, it is a matter for future experiments to solve
CVD process [3], and (3- Ta20S was obtained by using metal its mechanism. It is necessary to collect more data on the
tantalum as the target and sputtering it in a oxygen gas with relationship between the type of starting materials, film for-
the reactive sputtering [2]. Therefore, it is believed that not mation conditions, and crystal structures.
4 S. Shibata /Thin Solid Films 277 (1996) 1-4

References [3] T. Tominaga, R. Muharnmet, I. Kobayashi and M. Okada , Preparation

of ( II I )-oriented (3-Ta20, thin film by chemical vapor deposition using
rnetalorganic precursors, Jpn. J. Appl. Phys., Part 2. Vol. 31, (5A )
( 1992) L585-L587.
[I] Y. Nakagawa , Y. Gomi and T. Suzuki, Depo sition of Ta 20s thin film [4] Y. Sekido, Characteristics of Ta 20, thin film prepared by electron beam
and applicat ion to SAW devices, lpn. l . App. Phys., 24, Supplement heating method , Trans. 1EICE en, J77-C·1I( I) ( 1994-0 1) 10-15 (in
24-3 (1989 ) 25-27. Japanese) .
[2] C. Guoping, L. Lingzhen, Z. Suixin and Z. Haokang, Structure and [5] A.S.T.M. X-ray Powder Data Card, No. 25-922 .
propert ies of a Ta20s thin film deposited by dc magnetron reactive [6] A.S.T.M. X-ray Powder Data Card, No. 18-1303.
sputtering in a pure O 2 atmosphere, Vacuum, 41 (4-6 ) ( 1990) 1204- [7] A.E. Mchale and H.L. Tuller, Defects and charge transport in stabilized
1206. a -Ta20s. Radiati on Effects, 75 (198 3) 267-281.