JOURNAL OF MATERIALS SCIENCE LETTERS 9 (1990) 1351-1353

Preparation and electrical properties of undoped zinc oxide films

by CVD*
M. F. O G A W A , Y. N A T S U M E , T. H I R A Y A M A
Department of Industrial Chemistry, Tokai University, 1117, Kitakaname, Hiratsuka-shL
Kanagawa 259-12, Japan

H. S A K A T A
Research and Development General Division, Asahi Glass Co., Ltd., 2- 1-2, MarunouchL Chiyoda-ku,
Tokyo 100, Japan

Zinc oxide films have been applied to solar cells,
varistor, and gas sensors [1], being an n-type semicon-
ductor. The films oriented along the e-axis were used
in surface acoustic wave devices [2] due to high piezo-
electricity [3]. Since ZnO thin films are expected for
use in different electronic applications, various film
forming methods have been studied, such as sputtering
[4], ionized-cluster beam deposition [5], spray pyrolysis
[6], and chemical vapour deposition [7, 8]. Kamata
and Matsumoto [9] studied ZnO film formation by a
CVD method, sublimating zinc acetylacetonate in
water vapour atmosphere.
This communication describes the preparation and
electrical properties of ZnO thin films using normal
pressure CVD method under oxygen atmosphere and
oxygen plus water vapour atmosphere. The CVD
apparatus consisted of a horizontal electric furnace.
The reaction chamber was of a mullite tube with an
inside diameter of 30mm where reaction gas flowed
normal to the substrate surface. Gases provided to this
system were dehydrated argon and oxygen. The sub-
strate material was well-cleaned Pyrex glass of
20 x 50 x 3ram in dimensions. Cleaning was car-
their activation energy in electrical conduction were
then investigated.
All the experimental samples were undoped in the
sense that they do not contain any impurity dopants
during the film deposition. The films were charac-
terized by X-ray diffraction and Auger spectroscopy.
Fig. 1 shows X-ray diffractograms for the ZnO film
deposited at substrate temperatures ranging from 500
to 600°C in the case of forming conditions in an
oxygen atmosphere, together with that for ZnO pow-
der as a reference. This and other X-ray data on
these films showed that the films improved highly
their c-axis orientation with increase in deposition
temperature, because the (0 0 2) peak was remarkable.
The c-axis orientation of the film structure was hardly
influenced by the oxygen atmosphere or the oxygen
plus water vapour atmosphere in film forming. This
s
"E
~L
o

ried out successively with water, ion-exchanged water, c

acetone and ethanol in an ultrasonic cleaner for
30 min, respectively, and thereafter drying in an elec-
tric oven. The source material was Bis(2, 4-pentane-
dionato) Zinc, i.e., zinc acetylacetonate. About 0.2 g
of zinc acetylacetonate (Tokyo Kasei, RG) was con-
tained in a glass boat maintained at 160°C and the
/l ° )C I01)

sublimated vapour was transported into the reaction

chamber together with argon gas. At the same time
also oxygen gas was introduced through a separate
part of the reaction chamber. The argon and oxygen
i .ii.
~ J
/
~

•'~ / 600"C
Powder

were used as carrier gas and reaction gas, respectively. /

The flow rate of the former and the latter was 500 and
^ / 5 5/ 0 575
"C °C
10 ml min- l, respectively. The ZnO films were
prepared for 1 h on Pyrex glass substrate for various
substrate temperatures ranging from 500 to 600°C at
an interval of 25 ° C, under the conditions of oxygen O0*C
atmosphere and oxygen plus water vapour atmos-
phere. Thus, 200 to 600nm thick ZnO films were 30 40 50 60 70 BO
CuK a 20(deg)
obtained for 1 h deposition, which were found by
SEM to be highly uniform in surface texture. Figure 1 X-ray diffractionof ZnO films and powder as a reference
Electrical properties of the deposited ZnO films and in an oxygen atmosphere.

*Part of the paper presented at the 1989 International Chemical Congress of Pacific Basin Societies, Honolulu, Hawaii, USA., 17-22
December 1989.

0261-8028/90 $03.00 + .12 © 1990 Chapman and Hall Ltd. ] 351

 . . . . ' ' '
10 0
Surface ,¢ "\~

1.6 nrn I ~ 10-1

Sputter- I/ "~.. u

8.0 nm /~\\',,
Sputter. / / ~"~ lo-Z
o

/~.--~" ~ ~ , , ~ . _ ,

259 261 263 265 267 269

Binding energy (eV)

Figure 2 Zn(L3M45M45)Auger transitions for ZnO films deposited 10-3

in different atmospheres: ( ) oxygen and ( - - - ) oxygen plus
water vapour. Substrate temperature: 550° C. EQ
I I
0 5 10 I
result is the same as that of deposition by the other T -1 x 10 3 (K)
authors [10]. Figure 4 Conductivity against I/T for Z n O films prepared at dif-
Auger spectroscopy measurements were performed ferent substrate temperatures in an oxygen atmosphere: (O) 500,
on the ZnO films to check presence of impurities. (zx) 550 and (El) 600°C.
Fig. 2 shows Zn(L3M45M45 ) Auger transition for the
as-deposited ZnO film, indicating a clear presentation another a minimum value of 2.20 D cm was found for
of ZnO binding energy. Even when the films were a deposition under the oxygen plus water vapour
sputter-etched, the Auger peak position did not atmosphere. At a substrate temperature of 500 ° C, the
change. For the films made in the oxygen atmosphere resistivity was about 50 f~ cm and with increase in the
or oxygen plus water vapour atmosphere, no dif- temperature, it decreased to a minimum resistivity to
ferences were found in binding energy in ZnO and 550°C in the oxygen atmosphere. Further, for a high
metallic zinc. As shown in the figure there were no temperature of 575°C the resistivity again increased.
surface contaminations, as the presence of carbon. This tendency is also shown in the film forming con-
Therefore, it can be admitted that a perfect ZnO bond ditions with oxygen plus water vapour atmospheres.
was formed by this CVD. The resistivities of the as-deposited films are high and
Film resistivity measurements were carried out by this is probably due to the grain boundary effects since
the four-point probe method. The variation of the the films are polycrystalline in structure [11].
resistivity with substrate temperatures is shown in Some samples for various deposition temperatures
Fig. 3. A minimum resistivity (2.44 D cm) was were subjected to obtain activation energy in electrical
obtained for a film deposited at a substrate tem-
perature of 550 ° C under oxygen atmosphere, and for 1o 0

10 2
I
I
I
t
I I0-I
I / T
I /
E
E I /X i

>
.,,.,
io I
t', //
8 IO-2

\,,

10-3 i I
10 0 I I I 5 10
500 550 600
Substratetemperature {Oc) T -1 x l 0 3 (K)
Figure 3 Resistivity of Z n O films as a function of substrate tem- Figure 5 Conductivity against I/T for Z n O films prepared at dif-
perature. ( ) oxygen and ( . . . . ) oxygen plus water vapour ferent substrate temperatures in oxygen plus water vapour atmos-
atmosphere. pheres: (O) 500, (zx) 550 and (El) 600 ° C.

1352
conduction and their temperature dependence of the 2. G. S. KINO and R. S. WAGERS, J. Appl. Phys. 44
electrical conductivity were studied in a temperature (1973) 1480.
3. A. R. HUTSON, Phys. Rev. Lett. 4 (1960) 505.
range from 81 to 264K as shown in Figs 4 and 5.
4. T. MINAM1, H. NANTO and S. TAKATA, Thin Solid
From the linear parts of these curves, the apparent Films 124 (1985) 43.
activation energies E~ in the range 0.03 to 0.09 eV were 5. T. T A K A G I , I. YAMADA, K. MATSUBARA and
obtained for different atmospheric conditions in the H. TAKAOKA, J. Cryst. Growth 45 (1978) 318.
film formation. These data are comparable with those 6. S. MAJOR, A. BANERJEE and K. L. CHOPRA, Thin
Solid Films 108 (1983) 333.
for ZnO films prepared by spray pyrolysis [11]. How-
7. M. S H I M I Z U , T. H O R I I , T. SHIOSAKI and
ever, these curves clearly deviate from the linear A. KAWABATA, ibid. 96 (1982) 149.
relationship for lower temperatures (-%<200K). This 8. J. R. SHEALY, B . J . BALIGA, R . J . FIELD and
suggests that there is a possibility of variable range S. K. G H A N D H I , J. Eleetrochem. Soc. 128 (1981) 558.
hopping occurring [12, 13] of localized electrons in the 9. K. KAMATA and S. MATSUMOTO, Yogyo-Kyokai-shi
89 (1981) 337.
films, since in case of variable range hopping conduc-
10. S. K. G H A N D I and R. J. FIELD, Appl. Phys. Lett. 37
tivity is expected to obey e x p ( - A T -~/("+~)) where A (1980) 449.
and n are a constant and dimensional number in 11. M. N. ISLAM, M. O. HAKIM and H. RAHMAN, J.
conduction, respectively. Further investigations on Mat. Sci. 22 (1987) 1379.
this point are under way. 12. N. F. MOTT, Phil. Mag. 19 (1969) 835.
13. W. BRENIG, G. H. DOHLER and H. HEYSZENAU,
ibid. 27 (1973) 1093.
References
1. S. P I Z Z I N I , N. BUTTA, D. N A R D U C C I and M. PAL- Received 7 March 1990
L A D I N O , J. Electrochem. Soc. 136 (7) (1989) 1945. and accepted 12 June 1990

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