Thin Solid Films 372 Ž2000.

30᎐36

Zinc oxide films prepared by sol-gel spin-coating

Y. Natsume, H. SakataU
Department of Applied Chemistry, School of Engineering, Tokai Uni¨ ersity, 1117, Kitakaname, Hiratsuka, Kanagawa, 259-1292, Japan

Received 10 August 1999; received in revised form 7 June 2000; accepted 8 June 2000

Abstract

The d.c. electrical conductivity and optical properties of undoped zinc oxide films prepared by the sol-gel process using a
spin-coating technique were investigated. The ZnO films were obtained by 10 cycle spin-coated and dried zinc acetate films
followed by annealing in air at 500᎐575⬚C. The films deposited on the Pyrex glass substrate were polycrystalline and c-axis
oriented. A minimum film resistivity gave 28.2 ⍀ cm at an annealing temperature of 525⬚C. The temperature dependence of the
conductivity indicated electron transport in the conduction band due to thermal excitation of donor electrons for temperatures
from 250 to 300 K. The grain boundary scattering effect due to thermionic emission was confirmed. For temperatures below 250
K nearest-neighbor hopping conduction was dominant in the films. The films were transparent in the visible range above 400 nm
and had sharp ultraviolet absorption edges at 380 nm. The absorption edge analysis revealed that the optical band gap energy for
the films was 3.20᎐3.21 eV and the electronic transition was of the direct transition type. From the Urbach tail analysis the width
of the localized state Ee s 0.07᎐0.08 eV. 䊚 2000 Elsevier Science S.A. All rights reserved.

Keywords: Conductivity; Electrical properties and measurements; Optical properties; Zinc oxide

1. Introduction conduction of ZnO films at temperatures above room-

Because ZnO films are n-type wide-gap semiconduc-
tors with optical transparency in the visible range, ZnO
films have been targeted as a useful material for devel-
opments of electronic and optoelectronic devices such
as: transparent conductors w1᎐3x, solar cell windows
w4,5x, gas-sensors w6x, and surface acoustic wave devices
w7x. For the wide variety of applications, numerous ZnO
film preparation methods have been attempted: r.f. and
magnetron sputtering w1᎐3,8,9x, spray pyrolysis w10᎐13x,
chemical vapor deposition ŽCVD. w14᎐18x, and the sol-
gel process w19x. Recently pulsed laser deposition w20,21x
was reported for ZnO film fabrication. The electrical
U
Corresponding author: Fax: q81-463-50-2012.
E-mail address: skt@keyaki.cc.u-tokai.ac.jp ŽH. Sakata..
temperature has been understood to be thermal excita-
tion of electrons from donor levels originated by de-
fects or impurity atoms.
In polycrystalline ZnO films deposited by CVD w18x,
electronic conduction around room-temperature has
been attributed to band transport involving thermionic
and thermal field emission over grain boundaries in the
films. Zinc oxide films deposited by chemical spray
pyrolysis had resistivities Ž; 10y3 ⍀ cm. w4x. Al-doped
ZnO films formed by sol-gel dip coating gave resistivi-
ties of Ž7᎐10. = 10y4 ⍀ cm w19x. No reports are found
on zinc oxide films prepared by sol-gel spin-coating that
can be made with a simple coating apparatus.
In the present work we report d.c. conductivity,
together with optical properties, of undoped ZnO films
fabricated by the sol-gel process using the spin-coating
method; in this coating, precursor films are formed first

0040-6090r00r$ - see front matter 䊚 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 0 4 0 - 6 0 9 0 Ž 0 0 . 0 1 0 5 6 - 7
 Y. Natsume, H. Sakata r Thin Solid Films 372 (2000) 30᎐36 31

The interfacial characteristics of the ZnO films were

carried out by X-ray photoemission spectroscopy ŽXPS.
ŽShimadzu 850M. using Mg K ␣ radiation from an
X-ray source operated at 8.0 kV, 30 mA. The resolu-
tion energy of the XPS was 1.0 eV. Electrical resistance
measurements at different temperatures were made by
the four-point probe method in the temperature range
of 300᎐92 K using a digital multimeter ŽAdvantest
TR6847.. A constant d.c. was passed through two outer
electrodes and the direct voltage was measured across
the inner electrodes. Each electrode using copper wire,
soldered by indium was accomplished with Ohmic con-
tact. Relative errors in the resistance measurements
are approximately "2%. The optical absorption spec-
tra were measured using a double-beam spectropho-
tometer ŽShimadzu UV-140.. Film thickness was mea-
sured using a surface-profile recording meter ŽSurf-
coder SE30D, Kosaka Co., Tokyo..

Fig. 1. Flow diagram of the sol-gel spin-coating of ZnO films. 3. Results and discussion

at ambient temperature in air and then followed by 3.1. Film structure

subsequent heating for the decomposition and oxida-
tion of the precursor films. Fig. 2 shows X-ray diffractograms for ZnO films
formed by a 10-cycle spin-coating of zinc acetate films
2. Experimental procedure

Reagent grade ŽRG. zinc acetate wZnŽCH3 COO2 . ⭈

2H2 Ox was dissolved in RG methanol and a solution of
0.02 molrl was prepared. As a substrate material we
used a well-polished Pyrex glass plate 20 = 20 = 3 mm
in size. After cleaning the substrate with a neutral
cleaning agent in an ultrasonic bath, it was cleaned
again with ion exchanged distilled water, acetone and
ethanol successively in that bath, and then dried with
hot air, and preserved in a desiccator. Fig. 1 shows the
flow diagram for ZnO films prepared from the sol-gel
process using the spin-coating method.
After setting the substrate on the disk of the spin-
coater, the coating solution Žapprox. 0.2 ml. was
dropped and spin-coated with 3000 rev. miny1 for 20 s
in air. This process made a precursor film on the
substrate. The precursor film specimen was then dried
in air at 80⬚C for 10 min, being kept in an electric oven,
and then annealed in air in an electric furnace at
500᎐575⬚C for 20 min. This heat treatment decom-
posed the precursor film and oxidized it so as to pro-
duce ZnO film. We repeated 10 cycles of this ZnO
film-making process, i.e. the precursor film deposited
by spin-coating was followed by an annealing process.
Finally, a 160᎐230 nm thick multilayered ZnO film was
obtained for measurements.
The characterization of ZnO films by X-ray diffrac- Fig. 2. X-Ray diffractograms of ZnO films prepared by a 10-cycle
tion ŽXRD. ŽRigaku, model 2718. was carried out using spin-coating of zinc acetate films followed by annealing in air at
filtered Cu K ␣ radiation operated at 40 kV, 20 mA. different annealing temperatures.
32 Y. Natsume, H. Sakata r Thin Solid Films 372 (2000) 30᎐36

followed by annealing in air at 500᎐575⬚C Žspin-coating

pyrolysis method.. The XRD pattern clearly showed
the polycrystalline nature of the ZnO film, whose c-axis
was oriented normal to the glass substrate. The Ž002.
peak intensity increased with an increase in the anneal-
ing temperature. However, the full width at half-max-
ima ŽFWHM. of the Ž002. peaks was hardly changed
with increasing film annealing temperature. Hence, the
multiple-coating or piling up of each ZnO film was
considered not to disturb the overall growth of the
films with c-axis orientation. The c-axis orientation was
also reported for ZnO films deposited on oxide glass
substrates by CVD w14,18x, spray pyrolysis w10x, sol-gel-
process w19x and magnetron sputtering w8,9x. Therefore,
the c-axis orientation may be a common phenomenon
in the ZnO film deposition by the chemical process
using organo-zinc compounds.
We investigated the condition of zinc in the present
ZnO film using the Auger signal in XPS spectrum. Fig.
3 exhibits the ZnŽL3 M45 M45 . AES signal in the XPS
spectrum of the ZnO film prepared by the above de-
scribed spin-coating process. The energetic position of Fig. 4. Effect of annealing temperature Ta on the resistivity of ZnO
the XPS signals was revised considering a shift of 6.4 films at room temperature.
eV due to electronic charge caused by the use of the
insulating glass substrate. A major peak for sputter-
etched surfaces was laid at 264.6 eV and a minor at be due to Zn ŽL3 M45 M45 . in zinc oxide and the shoulder
261.2 eV. The major peak at 264.6 eV was thought to peak at 261.2 eV due to Zn ŽL3 M45 M45 . of metallic
zinc w22x seen from the outermost surface of 13.6᎐173.6
nm sputter-etched surfaces. We confirmed that this
shoulder peak was thought to be due to metallic zinc
present, as interstitial atoms, in the lattice of ZnO
crystallites in the film, rather than reduced Zn by Arq
sputter-etching, because the shoulder peak existed from
the outermost surface. Such a shoulder in XPS charac-
terizing interstitial zinc was also found for ZnO films
deposited by CVD w18x. Irrespective of the sputter
etching up to 173.6 nm in depth, no peaks due to
impurities and hydroxyl groups were observed in the
XPS spectra.

3.2. Electrical properties

3.2.1. Effect of ZnO film annealing temperature on

Fig. 3. Depth profiles of XPS of a ZnO film prepared by a 10-cycle
spin-coating of zinc acetate films followed by annealing in air at
550⬚C.
resisti¨ ity
Fig. 4 shows the electrical resistivity of the films
measured at room temperature against the annealing
temperature ŽTa . for ZnO films. The film resistivity
gradually decreased with an increase in Ta up to 525⬚C.
The resistivity then increased when the temperature
changes from 525 up to 575⬚C. Thus, a minimum film
resistivity of 28.2 ⍀ cm was obtained at Ta s 525⬚C.
For Ta higher or lower than 525⬚C, the film resistivity
increased, respectively; this fact was observed for the
ZnO films formed at Ts s 550⬚C by CVD w23x with a
minimum resistivity Ž␳min . of 2.2 ⍀ cm. For spray-de-
posited undoped ZnO film w11x, with ␳min s 12 ⍀ cm at
 Y. Natsume, H. Sakata r Thin Solid Films 372 (2000) 30᎐36 33

the substrate temperature Ts s 360⬚C, and for higher

or lower temperatures than Ts s 360⬚C, resistivity of
the films was increased, respectively. This film resistiv-
ity increase for higher or lower temperatures than
Ts s 360⬚C even after a vacuum heat-treatment at 250⬚C
for 1 h was also reported by Islam et al. w11x.
Hence, we consider this phenomenon as follows. The
film resistivity gradually decreased with increase in
annealing temperature Ta from 23 up to 525⬚C, be-
cause of improvement in the crystallinity of the films
indicated by an intensity increase of the Ž002. reflex in
the XRD pattern ŽFig. 2.. However, the resistivity in-
creased mildly because the decrease of the carrier
concentration might be controlled because of decreas-
ing defects that produce donor levels, as a result,
decomposition and oxidation of the precursor films
became more active, and a better stoichiometry of the
ZnO films was formed above 525⬚C, rather than the
change of the mobility with the annealing temperature.

3.2.2. Electrical conduction mechanism

Fig. 5 presents Arrhenius plots at temperatures
between 300 and 92 K of the d.c. conductivity Ž ␴ . of
ZnO films obtained at different substrate tempera-
tures. It is well-known that non-stoichiometric Zn1q xO
crystal is an n-type semiconductor with carrier elec-
trons excited thermally from donor levels formed by
interstitial zinc atoms w24x. Metallic zinc atoms in the
films were observed in the XPS spectra ŽFig. 3., similar
to the ZnO films w23x deposited by CVD.
According to Hausmann and Teuerle w25x, the con-
duction in In-doped ZnO single crystal at low tempera-
tures below 300 K is classified into three types when
the average spacing between donors r is compared with
the effective Bohr radius aU . Here r and aU are respec-
tively defined as,
r s Ž 4 ␲ Ndr3. y1 r3 ,
aU s 0.53␧ mrmU ,
where Nd is the impurity concentration, m is the mass
of the free electron, mU is the effective mass of the
electron and ␧ is the specific dielectric constant.
Fig. 5. Arrhenius plot of d.c. conductivity ␴ of ZnO films obtained at
different annealing temperatures Ta : Ž`. 500, Ž ⌬ . 525, ŽI. 550, Ž䉫.
575⬚C.
3. For rraU - 2, the high impurity concentration
regime, the metallic conduction takes place be-
cause of overlapping of impurity and conduction
bands.
We discuss the mechanism of conduction of the
present films using these criteria.
3.2.2.1. Electrical conduction at temperatures abo¨ e 250
K. At temperatures lower than room-temperature, and,
in particular, less than 250 K, deviations from the
Ž1. linearities in the conductivity-temperature relationship
became remarkable ŽFig. 5.. Thus, a double-valued
activation energy was observed. For doped semiconduc-
Ž2. tors with low concentration of donors, hopping
transport of carriers is expected between nearest donors
at low temperatures. The conductivity with the two
activation energies ŽFig. 5. for these temperatures can
then be expressed as,

1. For rraU ) 5, impurity concentration is low and
impurity levels are isolated, while the conduction is
explained through a charge transport in the con-
duction band and the nearest neighbor hopping
between isolated donor levels.
2. For 2 - rraU - 5, called the intermediate concen-
tration region, an impurity band is formed by over-
lap of the wave function between donors. There-
fore, a variable-range hopping conduction w26x ap-
pears between localized states in the impurity band.
␴ s ␴1exp Ž yEa1rkT . q ␴2 exp Ž yEa2rkT . , Ž3.
where Ea1 is the activation energy for band conduction
as defined in Eq. Ž3., Ea2 , the activation energy for
nearest neighbor hopping conduction w27x, k, the Boltz-
mann constant and ␴1 and ␴2 , the pre-exponential
factors, respectively.
We assume a linear Arrhenius behavior ŽFig. 5.
above 250᎐300 K to be due to electron transport in the
conduction band expected from the first term of Eq.
34 Y. Natsume, H. Sakata r Thin Solid Films 372 (2000) 30᎐36
Ž3.. Ea1 , obtained from the slopes of the curves in Fig. 5
between 300 and 250 K by means of the best fit
technique, is shown in Table 1, which gives Ea1 s
0.08᎐0.42 eV. These values of Ea1 are similar to those
for the ZnO films deposited by CVD w15,23x. Then
donor levels Ž Ed . generated by the interstitial Zn atoms
and given by Ed s 2 Ea1 lead to Ed s 0.16᎐0.84 eV from
the Ea1 values. As it is described in Section 3.2.2.2, the
conduction is confirmed to be due to transport in the
conduction band because we have aU s 1.53 nm from
Eq. Ž2. and r s 8᎐15 nm ŽTable 1., which gives rraU s
5.3᎐10.1 ŽTable 1. satisfying the condition Ž1..
Next, we discuss the grain boundary effect on the
electron transport in the conduction band as discussed
by Orton and Powell w28x, because the films are c-axis
oriented polycrystalline ŽFig. 2. and involve many grain
boundaries. This effect is examined by evaluation of
the Debye screening length LD given by Eq. 4 in
comparison with the average grain size l.
1r2
LD s Ž ␧␧0 kTre2 Nd . , Ž4.
where ␧ is the specific dielectric constant, ␧0 , the
dielectric constant of vacuum, and Nd , the donor con-
centration. Providing LD is smaller than l r 2, a poten-
tial barrier around each grain boundary is formed due
to band bending. If, however, LD is larger than lr2, the
conduction band becomes flat without the potential
barrier. Then electrons are transported without grain
boundary scattering.
LD for our films was estimated as follows. The elec-
tron concentration was decided to be Nd s 6.40=
1016 ᎐4.54= 1017cmy3 , which was estimated from Eq.
Ž1. using r values illustrated in Table 1. Then with
␧ s 8.5 w29x we have from Eq. Ž4. LD s 0.11᎐5.17 nm.
The mean grain size l estimated for FWHM of XRD
peaks ŽFig. 2. using the Sherrer formula was l s 30᎐40
nm. Thus, LD - lr2, meaning that we have to assume
grain-boundary barrier effects for the present films.
The high-temperature conductivity above 250 K in
Fig. 5 is represented in Fig. 6 as the relationship
Table 1
Activation energy and donor level for ZnO films treated at different annealing temperatures ŽTa .
Annealing Film Activation energy
temperature thickness
Ea1a
Ž⬚C. Žnm. ŽeV.
500 195 0.08
525 215 0.42
550 190 0.12
575 160 0.09
a
For temperatures above 200 K.
b
For temperatures below 200 K.
c
Activation energy for the grain-boundary limited conductivity.
d
Ed s 2 Ea1.
between ␴T1r2 and Ty1. Following Seto w30x, when
carrier transport is caused by thermionic emission over
the grain boundaries, ␴ is given by,
␴ s  e2 1Nr Ž 2 ␲ m) kT . 1r2 4
= exp  y ŽŽ EC y EF . q e␾ . rkT 4 , Ž5.
where EC is the energy of the conduction band mini-
mum, EF the Fermi level, ␾ the grain-boundary poten-
tial barrier and E␴ s Ec y EF q e␾ the activation en-
ergy for the grain boundary limited conductivity. From
Eq. Ž5. we have ␴T1r2 A expŽyE␴rkT .. The results in
Fig. 6 indicating the linear curves confirm thermionic
emission over grain boundaries in these films. E␴ val-
ues obtained from the slopes by best fitting are listed in
Table 1, where E␴rEa1 ; 1 is noticed.
3.2.2.2. Electrical conduction at temperatures below 250
K. Next we discuss the nearest neighbor hopping con-
duction at temperatures below 250 K, which is expected
on the second term of Eq. Ž3.. Ea2 values obtained
from Fig. 5 in the temperature range of 145᎐92 K by
means of the best fitting technique, are listed in Table
1. Assuming the nearest neighbor hopping transport
between the nearest donors, the average spacing r
between the donors is given by,
Ea2 s e2r Ž 4 ␲␧0 ␧ r . Ž6.
From the data of Ea2 ŽTable 1. and with ␧ s 8.5 w29x,
values of r s 8᎐15 nm were estimated as illustrated in
Table 1. We then compare the r values with the
effective Bohr radius aU s 1.53 nm estimated with Eq.
Ž2. using ␧ s 8.5 w29x and mU s 0.3 m w31x. We have
rraU values Ž5.3᎐10.1. listed in Table 1, larger than 5.
This satisfies the condition Ž1.. Thus, it was suggested
that the electron conduction shifted from the band type
at temperatures above 250 K to electronic hopping
between the nearest neighbors Ždonors. at low temper-
atures below 250 K.
The Ty1 r4 dependence of conductivity due to vari-
able-range hopping ŽVRH. w26x was observed below 200
Donor level E␴ c r rraU
ŽeV. Edd ŽeV. Žnm.
Ea2 b
ŽmeV.
10.9 0.16 0.09 15.5 10.1
11.4 0.84 0.39 14.9 9.7
21.0 0.24 0.14 8.1 5.3
12.5 0.18 0.09 13.6 8.9
 Y. Natsume, H. Sakata r Thin Solid Films 372 (2000) 30᎐36 35

Fig. 7. Optical transmittance spectra of ZnO films obtained at dif-

Fig. 6. ␴T1r 2 vs. inverse temperature of ZnO films obtained at ferent annealing temperatures Ta : Ža. 500; Žb. 525; Žc. 550; and Žd.
different annealing temperatures Ta : Ž`. 500⬚C, Ž ⌬ . 525, ŽI. 550, 575⬚C.
Ž䉫. 575⬚C.
Using the ␣ Ž ␻ . data calculated with Eq. Ž7. we
K for ZnO films obtained by CVD w18x. No observation estimated Eopt for wavelengths shorter than 400 nm.
of VRH for the present films may be due to low density For different n values, a good linearity of Eq. Ž8. was
of localized states. observed, n s 1 was found to give the best fit for these
films. Eopt values are listed in Table 2 together with B
3.3. Optical properties values obtained as well.
The Eopt values in Table 2 give Eopt s 3.20᎐3.21 eV,
3.3.1. Absorption edge which are nearly the same as those for ZnO films
Fig. 7 shows optical transmittance spectra in the deposited by CVD w23x Ž3.19᎐3.23 eV., spray pyrolysis
wavelength Ž ␭ . range 300᎐1000 nm for the ZnO films Ž3.26 eV. w10x, and pulsed laser ablation Ž3.26 eV. w20x
formed by the present spin-coating pyrolysis at differ- Ž3.1 eV. w21x. These results along with those for ZnO
ent annealing temperatures. The optical spectra for all films formed by CVD w18x, indicate electronic transi-
samples give the transparency in the visible range above tions of direct type w34x.
␭ s 400 nm. Sharp ultraviolet absorption edges at ap-
proximately ␭ s 380 nm are observed, depending on 3.3.2. Exponential absorption tail
the annealing temperature. The absorption coefficient ␣ Ž ␻ . in the low energy
The absorption coefficient ␣ Ž ␻ . Ž ␻ is angular fre- range follows the well-known exponential law, that is,
quency. is given by the transmittance T and film thick- the Urbach tail w35x expressed by
ness d using the formula,
␣ Ž ␻ . s ␣0 exp Ž ប␻rEe . , Ž9.
␣ Ž ␻ . s 2.303log10 Ž 1rT . rd. Ž7.
where ␣0 is a constant, Ee denotes an energy which is
When ␣ Ž ␻ . exceeds 104 cmy1 , ␣ obeys the relation-
ship w32,33x as, Table 2
Optical parameters of ZnO films
n
␣ Ž ␻ . s B Ž ប␻ y Eopt . rប␻ , Ž8. Annealing Film Eopt Ee B
temperature thickness ŽeV. ŽeV. Ž10 6 cmy1 .
where ប␻ is the photon energy, Eopt the optical band Ž⬚C. Žnm.
gap energy, and B is a constant having a value between
105 and 106 cmy1 w32x. The exponent n takes values of 500
525
195
215
3.21
3.20
0.08
0.08
2.05
1.57
1, 2, 3, 1r2 depending on the types of electronic 550 190 3.20 0.07 1.76
transition in the k-space. 575 160 3.20 0.08 2.17
36 Y. Natsume, H. Sakata r Thin Solid Films 372 (2000) 30᎐36
constant or weakly dependent on temperature and is
often interpreted as the width of the tail of localized
states in the band gap w36x.
Ee values were estimated from the slopes of the
linear relationship ln␣ against ប␻ using Eq. Ž9.. Ee
values, as given in Table 2, which are comparable to
those obtained for undoped ZnO films deposited by
CVD Ž0.08᎐0.10 eV. w23x. Therefore, the present films
have many localized states originated from the donor
levels due to the interstitial Zn atoms. This supports
the nearest neighbor hopping transport in the present
zinc oxide films at low temperatures.
4. Conclusion
Undoped ZnO films were fabricated by the sol-gel
spin-coating method; its d.c. electrical conductivity as
well as its optical properties were investigated. The
160᎐230-nm thick films formed on Pyrex glass substrate
were polycrystalline with c-axis orientation. A mini-
mum d.c. resistivity of 28.2 ⍀ cm was obtained by a
10-cycle spin-coating of zinc acetate film followed by
annealing in air at a temperature of 525⬚C.
From the temperature dependence of d.c. conductiv-
ity, the electron conduction was confirmed to be due to
transport in the conduction band at temperatures above
250 K, where grain boundary scattering was caused by
thermionic emission of electrons over grain boundaries.
Nearest neighbor hopping conduction between donors
was dominant for temperatures below 250 K.
The films were transparent in the wavelength range
of 400᎐1000 nm. The optical band gap energy Eopt was
obtained to be Eopt s 3.20᎐3.21 eV for the films. The
Urbach tail analysis, for the width of the localized
states, gave Ee values from 0.07 to 0.08 eV.
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