Beruflich Dokumente
Kultur Dokumente
15 FEBRUARY 1998
I. INTRODUCTION
II. EXPERIMENT
Thin-film zinc oxide continues to attract attention because of its low toxicity and its many applications in solar
cell technology1 and as thin-film gas sensors,24 varistors,5,6
and a phosphor for color displays.7,8 A variety of methods
have been reported for the preparation of ZnO thin films. For
example, films have been deposited by thermal evaporation,9
rf-sputtering,3,10 chemical vapor deposition,11 laser ablation,12 and variations on these methods.1316 In addition to
these techniques, spray pyrolysis has received a fair bit of
attention because of its simplicity and consequent economics
as it does not require a high vacuum apparatus. Another advantage of the spray pyrolysis technique is that it can be
adapted easily for production of large-area films, e.g., in the
case of display manufacturing. Previously zinc oxide films
have been prepared from spray solutions of zinc chloride,17,18
zinc acetate,1923 and zinc acetylacetonate.24
Recently, it was reported25 that ZnO films can be deposited by spray pyrolysis in air at relatively low temperatures
from an aqueous solution of Zn~NO3) 2 . The main purpose of
the present work was a comprehensive study of the effects of
pyrolysis temperature on the decomposition of zinc nitrate to
form ZnO films as well as the structural, electrical, and optical properties of the as-deposited and annealed films.
a!
0021-8979/98/83(4)/2104/8/$15.00
2104
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2105
FIG. 2. Relative spray pyrolysis efficiency for growth of ZnO films from
zinc nitrate solution at different pyrolysis temperatures.
In view of these results, the decomposition of zinc nitrate during spray pyrolysis is consistent with the formation
of oxides of nitrogen through some intermediate products
that can be written as follows:
H J
Zn~OH!2
III. RESULTS
A. Film deposition
Zn~NO3!2
Zn2O~NO3!2
Zn~OH!~NO3!
ZnO1yNw Ox 1zO2 .
~1!
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2106
of zinc nitrate to ZnO did not occur readily, and the deposition efficiency remained the same between 180 and 400 C.
perature decreased. The main peak ~002! in diffraction spectra had full width at a half maximum intensity of about 0.008
rad which corresponds to polycrystal dimension d.20 nm,
estimated using the Sherrers formula.30 As a result, x-ray
and SEM data indicated that polycrystal dimensions were in
20100 nm range that has been observed by different authors
for sprayed ZnO.2124
The films were very smooth to the eye and very difficult
to distinguish from the glass substrates. Figure 3 shows an
SEM image of a ZnO film grown at 180 C. Films grown at
higher temperatures had similar images. Very small spots
that can be distinguished are polycrystals with dimensions
about 100 nm or less. In more thorough SEM and atomic
force microscope ~AFM! studies the polycrystallites were reported to be approximately 50 nm in diameter.25 A roughness
of about 10 m m in lateral direction could be seen in Fig. 3.
The same average length of the lateral roughness was obtained by means of Sloan Dektak surface profile measurements. All the films in the study had similar thicknesses of
about 0.3 m m. Vertical roughness of the films was about 0.03
m m. The measured values of the horizontal and vertical
roughness were consistent with the deposition model in
which water droplets containing 0.1 M of Zn~NO3) 2 evaporate and then pyrolyze at the hot substrate. Using this concentration and estimating the size of the droplet gave a 10
m m ZnO disk of 0.01 m m thickness.
Examples of x-ray diffraction patterns of three ZnO
films grown at different temperatures are shown in Fig. 4.
The theoretical pattern for ZnO wurtzite structure (a
53.2495 , c55.2069 ! also is depicted in this figure. It is
evident from the figure that ZnO crystallizes in wurtzite type
structure during pyrolysis. Films grown at critical temperature T c 5180 C has a powder like pattern with no preferred
orientation. The same pattern was observed on the samples
grown at lower than the critical temperature and converted to
ZnO by annealing at 400 C. Films grown at higher than
200 C exhibit predominantly one peak showing a very high
level of orientation along the c-axis perpendicular to the substrate. The degree of orientation decreased slightly as tem-
FIG. 5. Absorption spectra of as-grown and annealed zinc oxide film deposited below the critical temperature.
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FIG. 6. Absorption spectra of ZnO film pyrolyzed at T g 5210 C and annealed under the following conditions: in N2 ~400 C!, in air ~400 C! and in
N2 ~520 C!.
a nh n 5C ~ h n 2E g ! 1/2,
~2!
2107
FIG. 7. Optical band gap of ZnO films measured at a half height of the
maximum absorption as a function of the deposition temperature.
intermediate products if the growth temperature is not sufficiently high. Their presence could cause mechanical strains
and structural distortions, which are known to alter the band
gap and the excitonic effect.
D. Conductivity
FIG. 8. Conductivity of as-deposited ZnO films in daylight in the lab measured either by two-contact and four-point probe methods.
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2108
FIG. 9. Conductivity of as-deposited ZnO films in daylight and in the darkness 8 days after removing the light.
ment did not influence their dark conductivity. Daylight illumination increased the conductivity by about an order of
magnitude for all annealed samples.
E. Photoconductivity relaxation
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2109
FIG. 11. Four exponential transients obtained by sequential subtraction ~starting with the slowest conductivity transient! to give time constants ~a! 1.23
310 4, ~b! 2.223103, ~c! 534, and ~d! 135 s.
IV. DISCUSSION
2 e 0e V i
eN D
1/2
~3!
in which e 0 is the permittivity of free space, e is the dielectric constant ( e 58.59 for ZnO!,34 N D is the concentration of
uncompensated donor impurities, and V i is the band bending.
In the dark, N D does not equal the equilibrium free carrier
concentration because of partial or complete depletion of the
crystallites. However, N D can be estimated from the steady
state photoconductivity at saturation. As discussed above,
saturation of the photoconductivity was confirmed by the
nearly identical values found for illumination in daylight
(I'1 W/m2) and with the arc lamp (I5250 W/m2) 0.073
and 0.1 V 21 cm21, respectively. Saturation of the photoconductivity implies the bands are flat, and the conductivity is
governed by the concentration of donors N D , as discussed
below. Using a carrier mobility m ' 15 cm2/V s,21,25,35 we
get N D < 431016 cm23. The calculated value of W depends
also on the value of V i . The large difference between the
light and dark conductivity indicates this value should be
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2110
eN D r 2
,
6 e 0e
~4!
than the band gap caused the photoconductivity. Electronhole pairs created in the bulk of crystallites mainly recombine via radiative or Shockley-Read-Hall mechanisms. Holes
also can be captured by deep traps at the grain boundaries,
resulting in an increase in number of free electrons which are
unable to recombine with these holes. When the photoconductivity is saturated, the bands are essentially flat, and the
free electron density is equal to the donor density because
hole traps play the role of sensitizing centers36 that prevent
holes from recombining with electrons. After excitation has
ceased, the holes slowly escape from the traps and recombine
with free electrons, and the conductivity slowly decreases as
the electron density drops. Because this process is thermally
activated, deeper levels have slower relaxation rates. The
long relaxation times are consistent with a large density of
deep traps. The shorter relaxation times found for the annealed films is consistent with a decreased density of deep
interface states.
In the case of the annealed films ~Fig. 10!, the multiexponential relaxation indicates discrete levels participated in
the relaxation process. The time required to escape from a
trap at energy E t can be described by the well-known
expression36
t5
E t 2E v
1
exp
,
n
kT
~5!
~6!
s 5e m
(i N i e 2t/ t ,
i
~7!
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sI
(V 21 cm21)
ti
~s!
Ni
~cm23)
Ei
~eV!
1.031024
`a
4.231013
2.0931024
1.233104
8.831013
0.99
1.0331023
2.223103
4.331014
0.94
2.2831023
5.343102
9.631014
0.91
3.831024
1.353102
1.631015
0.87
Structural, optical, conductivity, and relaxation properties of undoped ZnO films deposited by spray pyrolysis at
different temperatures have been studied. The critical temperature for spray pyrolysis of zinc nitrate solutions was
found to be T c 5180 C. The films grown above T c show
strong preferred orientation of polycrystals along the c axis,
while the films grown at T c or below and converted to zinc
oxide by annealing show powder-like non-oriented polycrystalline structure. A slightly larger optical band gap was observed for films grown between 180 and 240 C. Annealing
brought all the samples to the same band gap, 3.30 eV. Photoconductivity showed very slow relaxation kinetics after illumination had been stopped, and the time constant was
about a week for as-grown samples and about 10 h for
samples annealed in nitrogen. Conductivity of as-deposited
films in the daylight and in the darkness could differ by more
than four orders in magnitude. Annealing in nitrogen at
400 C brought all samples to the same conductivity, which
was 1023 V cm21 in daylight and 1024 V cm21 in the dark.
The relaxation had a complicated character, which changed
from a power-law time dependence for as-grown films to a
multiexponential transient for annealed samples. The transients were used to extract information about trap densities
and their energy distribution.
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ACKNOWLEDGMENTS
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