Optical and electrical properties of undoped

ZnO films grown by spray pyrolysis of zinc

nitrate solution
Cite as: Journal of Applied Physics 83, 2104 (1998); https://doi.org/10.1063/1.366944
Submitted: 24 July 1997 • Accepted: 11 November 1997 • Published Online: 23 July 1998

S. A. Studenikin, Nickolay Golego and Michael Cocivera

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© 1998 American Institute of Physics.

JOURNAL OF APPLIED PHYSICS VOLUME 83, NUMBER 4 15 FEBRUARY 1998

Optical and electrical properties of undoped ZnO films grown

by spray pyrolysis of zinc nitrate solution
S. A. Studenikin,a) Nickolay Golego, and Michael Cocivera
Guelph-Waterloo Centre for Graduate Work in Chemistry, University of Guelph,
Guelph, Ontario N1G 2W1, Canada
~Received 24 July 1997; accepted for publication 11 November 1997!
Undoped ZnO films were deposited by spray pyrolysis using aqueous zinc nitrate solution at
different substrate temperatures. The effect of the growth temperature on the structural, optical,
electrical, and relaxation properties has been studied. It was found that there was a critical
temperature T c 5180 °C below which the thermal decomposition to ZnO did not occur or was
incomplete. Films grown above T c showed strong preferred orientation of polycrystals along the
c-axis, while the films grown at T c or below showed a powder-like, non-oriented polycrystalline
structure when they were converted afterwards to zinc oxide by annealing. A slight increase of the
optical band gap was observed for as-prepared films as the substrate temperature was decreased near
the critical temperature. Annealing brought all the samples to the same band gap 3.30 eV measured
at a half height of the maximum absorption. After illumination, the steady-state photoconductivity
decayed very slowly with a time constant of about a week for as-grown samples. The steady-state
photoconductivity in daylight was very close to saturation. Steady-state photoconductivity in the
daylight can be as much as four orders in magnitude larger than the dark value. Annealing in
nitrogen at 400 °C brought all samples to the same conductivity of 10 23 (V cm!21 in daylight and
1024 ~V cm!21 in the dark. The photoconductivity transients were complicated and changed from
a power law to multiexponential time dependence after annealing. The data are discussed on the
basis of model in which hole traps located at the grain boundaries play the major role. © 1998
American Institute of Physics. @S0021-8979~98!04704-5#

I. INTRODUCTION II. EXPERIMENT

Thin-film zinc oxide continues to attract attention be-
cause of its low toxicity and its many applications in solar
cell technology1 and as thin-film gas sensors,2–4 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 abla-
tion,12 and variations on these methods.13–16 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 ad-
vantage 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,19–23 and zinc acetylacetonate.24
Recently, it was reported25 that ZnO films can be depos-
ited 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 op-
tical properties of the as-deposited and annealed films.
a!
Permanent address: Institute of Semiconductor Physics, Siberian Branch of
Russian Academy of Sciences, Novosibirsk 630090, Russia.
The home-made spray pyrolysis apparatus used in this
work and the method were described previously.26,27 In brief,
an ultrasonic nebulizer created an aerosol, which was
sprayed vertically through a 0.9 mm diameter nozzle and
was rastered automatically across a Corning glass substrate
~25350 mm2) mounted on a heating block. Humid air was
used as the carrier gas, and the spray rate of the solution was
2–3 mL/h. Spraying times of 2–4 h provided films with
thicknesses between 0.2 and 0.4 m m. Thicker films can be
obtained in shorter times by increasing the concentration of
the solution. For all studies an aqueous solution of 0.1 M
Zn~NO3) 2 was used. A number of samples were annealed in
a nitrogen ambient at 400 °C in a tube furnace for 1 h before
physical characterization. The heating rate was 20 °C/min
and cooling took 2–3 h.
The samples were weighed before and after the heat
treatment to determine the mass loss. The structural and sur-
face properties of the films before and after annealing were
determined by means of SEM ~Hitachi S570 scanning elec-
tron microscope!, x-ray diffraction ~Siemens D500 x-ray sys-
tem using a 1.5418 Å Cu Ka source!, and a Sloan Dektak
surface profilometer. Optical absorption spectra were re-
corded at room temperature using a Shimadzu UV160U
spectrometer with a blank piece of 7059 glass in the refer-
ence beam. Conductivity of films was measured by means of
two-contact measurements using a Keithley 220 current
source and a Keithley 614 electrometer. For these measure-

0021-8979/98/83(4)/2104/8/$15.00 2104 © 1998 American Institute of Physics

J. Appl. Phys., Vol. 83, No. 4, 15 February 1998
FIG. 1. Percentage decrease in mass relative to the initial mass, caused by
annealing at 400 °C for films grown at different temperatures.
ments the samples were cut in 5310 mm2 rectangles, and
contacts were made with 1–2 mm strips using silver conduc-
tive paint from GC Electronics. Four-point probe measure-
ments gave the same values.
III. RESULTS
A. Film deposition
The thermally induced decomposition of solid bulk zinc
nitrate was observed to start at 350 °C.28 However during
spray pyrolysis the decomposition of zinc nitrate was re-
ported to begin at about 150–170 °C.25,29 This difference
may be due to lower stability of microcrystals relative to
bulk material. To better understand this decomposition pro-
cess during spray pyrolysis, a set of samples were deposited
at temperatures between 130 and 400 °C in steps of 20–
40 °C. A measure of the completeness of the conversion
from the nitrate to the oxide was obtained by measuring the
decrease in the mass of the film after the as-deposited film
had been heated at 400 °C for 1 h in a nitrogen ambient.
Figure 1 shows the percentage decrease in mass relative
to the initial mass for the films grown at various tempera-
tures. Three temperature regions were observed. Below
175 °C, annealing caused a large decrease in the mass, and
the monotonic decrease in the percentage change indicates
conversion to ZnO became more predominant as the sub-
strate temperature was increased. Between 175 °C and
220 °C, the decrease was substantially less, amounting to no
more than about 7%. In this region, the nitrate was almost
completely converted to the oxide during spray pyrolysis. At
250 °C and above, annealing did not cause a decrease in
mass, indicating the conversion was complete at these tem-
peratures. Based on molecular weights, the maximum de-
crease would be 57% for the conversion of pure, anhydrous
solid zinc nitrate film into zinc oxide.
Studenikin, Golego, and Cocivera 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 ni-
trate during spray pyrolysis is consistent with the formation
of oxides of nitrogen through some intermediate products
H J
that can be written as follows:
Zn~OH!2
Zn~NO3!2→ Zn2O~NO3!2 →ZnO1yNw Ox 1zO2 .
Zn~OH!~NO3!
~1!
Consistent with this suggestion are the color changes
observed during heat treatment of samples grown at tempera-
tures lower than 175 °C. Initially after the 400 °C tempera-
ture had been attained the film was white; however, after 20
min the film became dark brown and, subsequently, transpar-
ent with a slight green color. The dark brown color is most
likely N2 O4 gas, which must diffuse out of the film to com-
plete the process. Because it takes at least 20 min for pyroly-
sis of solid bulk zinc nitrate at 400 °C, the process is ex-
pected to take much longer at 250 °C. Furthermore, the
pyrolysis of zinc nitrate films resulted in cloudy ZnO films
whereas films prepared at T>220 °C were clear and trans-
parent. As a result, spray pyrolysis at T>220 °C probably
occurred by way of small aggregates of zinc nitrate.
As indicated in the heat treatment studies above, films
prepared at temperatures of 180 °C or higher lost little or no
mass. Consequently, the stoichiometry and density were very
nearly the same at these temperatures, and it is possible to
compare the relative efficiency of the deposition at each tem-
perature by comparing the ratio film thickness relative to the
number of milliliters of solution sprayed. These data are
shown in Fig. 2. It is seen that the ratio is constant within
10% over temperature range from 180 to 400 °C. Thus the
spray pyrolysis efficiency is very nearly the same for depo-
sition at all temperatures in this range. In summary, there is
a critical temperature T c 5180 °C below which the pyrolysis
2106 J. Appl. Phys., Vol. 83, No. 4, 15 February 1998 Studenikin, Golego, and Cocivera

FIG. 3. SEM image ~20320m 2) of ZnO film grown by spray pyrolysis at FIG. 4. X-ray diffractograms ~Cu Ka, l51.5418 Å! of ZnO films pyrolyzed
180 °C . at different substrate temperatures.

of zinc nitrate to ZnO did not occur readily, and the deposi- perature decreased. The main peak ~002! in diffraction spec-
tion efficiency remained the same between 180 and 400 °C. tra had full width at a half maximum intensity of about 0.008
rad which corresponds to polycrystal dimension d.20 nm,
B. Structural SEM and x-ray study estimated using the Sherrer’s formula.30 As a result, x-ray
and SEM data indicated that polycrystal dimensions were in
The films were very smooth to the eye and very difficult 20–100 nm range that has been observed by different authors
to distinguish from the glass substrates. Figure 3 shows an for sprayed ZnO.21–24
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 C. Optical band gap
about 100 nm or less. In more thorough SEM and atomic Figure 5 illustrates that an as-deposited ZnO film grown
force microscope ~AFM! studies the polycrystallites were re- below the critical temperature ~T c 5180 °C! did not exhibit
ported to be approximately 50 nm in diameter.25 A roughness any absorption in the UV/visible range. An absorption spec-
of about 10 m m in lateral direction could be seen in Fig. 3. trum appeared after this film was annealed at 400 °C, con-
The same average length of the lateral roughness was ob-
tained by means of Sloan Dektak surface profile measure-
ments. 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 evapo-
rate and then pyrolyze at the hot substrate. Using this con-
centration 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 Å, c55.2069 Å! 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 tempera-
ture 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 sub- FIG. 5. Absorption spectra of as-grown and annealed zinc oxide film de-
strate. The degree of orientation decreased slightly as tem- posited below the critical temperature.
J. Appl. Phys., Vol. 83, No. 4, 15 February 1998 Studenikin, Golego, and Cocivera 2107

FIG. 6. Absorption spectra of ZnO film pyrolyzed at T g 5210 °C and an-

nealed under the following conditions: in N2 ~400 °C!, in air ~400 °C! and in FIG. 7. Optical band gap of ZnO films measured at a half height of the
N2 ~520 °C!. maximum absorption as a function of the deposition temperature.

sistent with the conclusion that zinc nitrate films were intermediate products if the growth temperature is not suffi-
formed below 180 °C and subsequently converted to ZnO by ciently high. Their presence could cause mechanical strains
annealing. Figure 6 shows the typical absorption spectrum and structural distortions, which are known to alter the band
for films grown between 180 °C and 360 °C. The distinct gap and the excitonic effect.
absorption edge existed in both as-prepared and annealed
films. Noticeable shifts of the edge were observed after an- D. Conductivity
nealing in nitrogen at 400 °C, even for samples grown at
Figure 8 presents the conductivity of as-deposited films
360 °C. Subsequent annealings in air at 400° and again in
in daylight in the lab measured either by two-contact or four-
nitrogen at 520 °C did not change the absorption.
point probe methods. The difference in time between these
To determine the energy gap, most authors use the
two measurements was more than 1 month, and the good
model for direct interband transitions:
agreement between two sets of measurements indicates the
a n•h n 5C ~ h n 2E g ! 1/2, ~2! films were stable under these conditions. In general, the con-
ductivity of the as-deposited films in daylight decreased as
in which h n is photon energy, n is index of refraction, and a
is the absorption coefficient. In this approximation, ( a nh n ) 2
should be a linear function of h n . This model may not be
suited to wide band gap materials because the optical absorp-
tion band edge is strongly disturbed by a coulombic electron-
hole interaction leading to the excitonic effect. For all of the
films in this study, (ahn n ) 2 was a linear function of energy
over a range of only about 0.05 eV, which is very small
compared to the band gap. Because of the sharpness of the
absorption edge, the photon energy at the half height of the
maximum absorption gave a band gap value very close to the
extrapolated one. Consequently the half height values are
presented in Fig. 7, which shows the optical band gap of
ZnO films as a function of growth temperature, and after
annealing at 400 °C. It is seen in this figure that as-prepared
films grown at or below 220 °C had a slightly bigger band
gap. Annealing at 400 °C brought all films to the same value
~E g 53.30 eV!, except for those films grown below the criti-
cal temperature. The lower values for these films may be
related to their cloudy appearance. An analogous blue shift
of the band edge was observed for ZnO films prepared by
SILAN ~successive ion layer adsorption and reaction!.10 The FIG. 8. Conductivity of as-deposited ZnO films in daylight in the lab mea-
observed shift might be due to the presence of unreacted sured either by two-contact and four-point probe methods.
2108 J. Appl. Phys., Vol. 83, No. 4, 15 February 1998
FIG. 9. Conductivity of as-deposited ZnO films in daylight and in the dark-
ness 8 days after removing the light.
the substrate temperature increased from 180 to 400 °C.
Films grown below T c 5180 °C were dielectric, which sup-
ports conclusions presented above concerning the poor con-
version to ZnO below this temperature.
In daylight the conductivity of the as-grown film was, in
fact, the steady-state photoconductivity, which was very
close to saturation and had a very long relaxation time, of the
order of days. Saturation was tested using an arc lamp to
provide higher intensity, and the steady state photoconduc-
tivity did not increase substantially relative to daylight inten-
sity. For as-deposited samples prepared at various tempera-
tures, Figure 9 illustrates the photoconductivity in daylight
and the dark conductivity at room temperature 8 days after
removing the light. As seen in this figure, the light and dark
conductivities differed by up to four orders of magnitude,
with the lowest dark values around 1028 V 21 cm21. The
magnitude of this change depended on the preparation tem-
perature, with the T c 5180 °C showing the smallest decrease.
As might be expected the rate of relaxation from the steady-
state photoconductivity could be increased by raising the
temperature. Thus, the steady-state photoconductivity of the
as-grown samples decreased to ~2–6!31029 V 21 cm21 in 2
h heated at T5100 °C in the dark. Only the sample grown at
T c 5180 °C did not exhibit a temperature effect over this
range. Relaxation back to the stationary dark values shown
in Fig. 9 took several days. A similar effect was observed
also for another wide band gap material, TiO2 . 31
Annealing at 400 °C in nitrogen brought all the films
~including the dielectric films grown below T c ) to the same
dark conductivity of 1024 V 21 cm21 and about 1.331023
V 21 cm21 in daylight. Consequently, except for the 180 °C
film, the dark conductivity increased for films grown at all
temperatures. In comparison to the as-deposited films, an-
nealed samples had substantially shorter relaxation times,
reaching the equilibrium ‘‘dark’’ state in about 10 h after
illumination was stopped. After annealing, the 100 °C treat-
Studenikin, Golego, and Cocivera
FIG. 10. Photoconductivity relaxation of ZnO film ~T g 5360 °C! annealed 1
hour in nitrogen at 400 °C. Experimental data are fitted with four exponents
by sequential subtraction method.
ment did not influence their dark conductivity. Daylight illu-
mination increased the conductivity by about an order of
magnitude for all annealed samples.
E. Photoconductivity relaxation
These studies employed white light from a Welch Allyn
arc lamp with an intensity of 250 W/m2 at the sample, and
about 0.5% of total power had photon energy h n .E g ~ZnO!.
About one hour was required to reach the steady-state pho-
toconductivity at this intensity. The relaxation rate in the
dark depended on the treatment of the sample, e.g., for an
as-grown sample (T g 5360°) semi-logarithmic and double-
logarithmic plots indicated that the relaxation did not have an
exponential dependence on time. A double-logarithmic plot
indicated the relaxation had two power-law time dependen-
cies with the exponent changing from 20.75 to 21.0 after
103 s of the relaxation. As discussed above, the conductivity
decreased about four orders in magnitude over a period of
days, and the most rapid decrease from 1024 to 10 26
V 21 cm21 occurred in the first 5 h. The stationary dark value
of 231028 V 21 cm21 was reached in about 1 week at room
temperature.
After annealing in nitrogen at 400 °C, the samples re-
laxed more rapidly and took about 10 h to reach the ‘‘dark’’
equilibrium conductivity. An example of the conductivity re-
laxation for annealed sample (T g 5360°) is plotted in Fig.
10. This decay consists of four exponential transients, which
could be separated unambiguously by sequential subtraction
~starting with the slowest conductivity transient! to give time
constants 1.233104, 2.223103, 534 and 135 s ~Fig. 11!. Ex-
cept for the slowest transient, each time constant was ob-
tained by an exponential fit of the D s i data over a range of
two orders of magnitude or more.
J. Appl. Phys., Vol. 83, No. 4, 15 February 1998
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
As presented above, the films are polycrystalline with
grain dimensions lying between 20 and 100 nm. Because
grain boundary states can create depletion layers in grains,
they can cause barriers to carrier transport. This aspect has
been discussed earlier in regard to the dark carrier transport
of polycrystalline ZnO having large grain size ~resulting in a
large barrier!32 and small grain size ~resulting in a small
barrier!.33 Since the size of the barrier is related to the
amount of depletion in the grain, the thickness of the deple-
tion layer will be addressed first. Undoped ZnO films are
known to exhibit n-type conductivity that is usually attrib-
uted to oxygen vacancies in the crystallites. In the crystallite
the depletion width can be estimated according to:
W5 S 2 e 0e V i
eN D D 1/2
~3!
Studenikin, Golego, and Cocivera 2109
in which e 0 is the permittivity of free space, e is the dielec-
tric 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 photocon-
ductivity 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
2110 J. Appl. Phys., Vol. 83, No. 4, 15 February 1998
substantial. However, even a relatively small value of V i
'0.1 eV gives a total depletion width of 100 nm, consider-
ing two interfaces for the grain. Thus, even this small barrier
causes a depletion width that is twice the grain size, and
most likely the grain is fully depleted, especially since the
trap energies are likely to be larger as described below.
Although the grains are probably depleted in the un-
doped films, the prospect of some band bending due to par-
tial surface field screening by the charged impurities should
be considered. For nearly depleted spherical grains with a
uniform impurity distribution that is much larger than the
free carrier concentration, the Poisson equation gives the
band bending V i :
eN D r 2
V i5 , ~4!
6 e 0e
in which r is the radius of the crystallite. For N D <4
310 16 cm23 and r'25 nm, the bend bending is V i ' 10
meV, which is comparable to the thermal energy at room
temperature. Consequently crystallites are fully depleted
with almost flat bands. These results support the conclusion
that the conductivity is completely governed by charging the
grain boundary states. This value of V i is comparable to that
calculated for barrier of thin film ZnO from the temperature
dependence of the mobility.33 Consequently, fully depleted
crystallites are consistent with this mobility study.
The strong dependence of the dark conductivity on the
growth temperature ~Fig. 10! indicates that the density of
uncompensated acceptor states at the grain boundary in-
creased as the pyrolysis temperature increased. These results
are consistent with an increase in Zn vacancies as the films
were grown at higher temperatures in air. The change in
conductivity due to heat treatment in nitrogen at 400 °C de-
pended on the film growth temperature. Consider the high
temperature films, which exhibited an increase in conductiv-
ity after heat treatment. Although bulk diffusion of oxygen is
possible, little oxygen was present in the nitrogen ambient.
Furthermore, incorporation of oxygen in the bulk should re-
sult in a decrease in conductivity rather than an increase
because the decrease in oxygen vacancies ~donors! would
cause a decrease in the free carrier density. An explanation
for the increase in conductivity after annealing could be that
heat treatment removed oxygen from the grain boundary and
caused a decrease in the density of acceptor states at the
grain boundary, resulting in the capture of a smaller number
of bulk electrons by these acceptor states. Support for this
conclusion is that ZnO at 400 °C has a pale green color in-
dicative of an oxygen deficiency.7 In the case of the 180 °C
film, annealing caused a small decrease in the dark conduc-
tivity. The higher conductivity of the film grown at this tem-
perature may be due to passivation of grain boundaries by
gettering of incomplete reaction products at the grain bound-
aries. Annealing brought all samples to the same conductiv-
ity, indicating the same density of grain boundary states.
This grain boundary state model can also be used to
describe the photoconductivity and its transients. The effect
of illumination was to reverse the process described above
by neutralizing negative charge in the surface states. The use
of optical filters confirmed that only photon energy greater
Studenikin, Golego, and Cocivera
than the band gap caused the photoconductivity. Electron-
hole pairs created in the bulk of crystallites mainly recom-
bine 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 photocon-
ductivity 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 an-
nealed films is consistent with a decreased density of deep
interface states.
In the case of the annealed films ~Fig. 10!, the multiex-
ponential 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
1
n
exp S
E t 2E v
kT
, D ~5!
in which (E t 2E v ) is the hole trap energy above the valance
band ~we consider that the main effect is due to captured
holes!, n is the attempt-to-escape frequency, which is usually
accepted to be the lattice vibration frequency ~1013 s21 ). In
the case of fast recombination, hole re-trapping is insignifi-
cant after holes have escaped from the traps, and the excess
free electron density is Dn5SDp t , in which summation
runs over all hole traps. The rate of change of density of
trapped holes in states at energy E t is
dpt pt
52 , ~6!
dt t
in which t is given by Eq. ~5!. Because the samples have
been illuminated for a long time before the light is shut off,
the traps have been filled completely with holes so the free
electron density at saturation can be equated to hole trap
densities, and the trap density N i was obtained by fitting the
experimental s transient curve using
s 5e m (i N i e 2t/ t ,
i ~7!
in which t i is the release time from the trap related to its
energy by Eq. ~5!.
The fitting procedure of the transient for the annealed
sample involved first and exponential fit of the slowest decay
followed by successive subtraction as illustrated in Fig. 11.
This procedure worked unambiguously because of the large
differences in the time constants. Parameters base on these
results ~Table I! were calculated using m 515 cm2/V s. It is
seen from the table that the traps are located about one-third
of the band gap from the valence band as has usually been
observed for sensitizing centers in bulk semiconductors.36
J. Appl. Phys., Vol. 83, No. 4, 15 February 1998 Studenikin, Golego, and Cocivera 2111

TABLE I. Parameters of hole traps in annealed ZnO film ~T g 5360 °C! ACKNOWLEDGMENTS
obtained by fitting the experimental transient curve in Fig. 10 using Eq. ~7!
and the electron mobility m 515 cm2/V s. This work was supported in part by a grant to M.C. from
the Natural Sciences and Engineering Research Council of
sI ti Ni Ei Canada. One of the authors ~S.S.! would like to thank Ser-
(V 21 cm21) ~s! ~cm23) ~eV! guei Grabtchak ~Department of Chemistry! for fruitful re-
1.031024 `a 4.231013 ••• marks during manuscript preparation.

2.0931024 1.233104 8.831013 0.99

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