Journal of Crystal Growth 192 (1998) 430438

Optical and electrical characteristics of aluminum-doped

ZnO thin lms prepared by solgel technique
A.E. Jime nez-Gonza lez*, Jose A. Soto Urueta, R. Sua rez-Parra
Centro de Investigacio& n en Energ&a, UNAM, Apartado postal 34, 62580 Temixco, Morelos, Mexico
Received 7 August 1997; accepted 20 March 1998
Abstract
Pure and aluminum-doped ZnO thin lms of high quality were prepared by the solgel deposition method. ZnO thin
lms are formed by a three-step decomposition of the chemical complex (Zn(CH
`
COO)
`
) 2H
`
O) to ZnO. The aluminum
doping was achieved by the addition of AlCl
`
) 2H
`
O and Al(NO
`
)
`
) 9H
`
O in the methanol solution of the chemical
complex at an atomic ratio of Al/Zn"10`10`. The lms are transparent (90% optical transmittance) in the near UV,
VIS and near IR ranges. X-ray diraction analysis indicates that the crystallites of both ZnO and ZnO : Al thin lms are
preferentially oriented along the c-axis, [0 0 2] direction of the hexagonal crystal structure. The electrical conductivity of
ZnO thin lms increases with lm thickness, under selected heat treatments and with aluminum doping. The dark
conductivity and photoconductivity values of the lms are in the range 10100 [ cm], which are considered adequate
for certain solar cell and electrochromic applications. Measurements of the activation energy show that pure and
aluminum doped ZnO thin lms have generally one donor level around 50 meV and another at 120 meV below the
conduction band. These results are used to explain the high electrical conductivity of the lms. 1998 Published by
Elsevier Science B.V. All rights reserved.
1. Introduction
ZnO thin lms are technologically important
due to their range of electrical and optical proper-
ties, which make them suitable for a variety of
applications. The optical transmittance of ZnO and
ZnO : Al thin lms in the UV, VIS and NIR ranges
and electrical conductivity are both shown to be
high [1]. Based on this combination of the optical
*Corresponding author. Fax: #52 73 25 00 18.
and electrical properties, these lms have been used
as transparent conductors [13], heat mirrors
[4,5], semiconductor heterojunctions [6,7], lumi-
nescent materials [8], transducers [9,10], etc. Pre-
viously, ZnO thin lms have been prepared by
many techniques such as thermal evaporation [11],
CVD [12], RF-magnetron sputtering [13], spray
pyrolisis [3,14] etc. Pure ZnO thin lms are not
stable against corrosive environments, e.g. adsorp-
tion of O
`
in the lms decreases the electrical
conductivity and also modies the surface mor-
phology. To stabilize the ZnO system against such
changes, doping with dierent elements have been
0022-0248/98/$19.00 1998 Published by Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 0 2 4 8 ( 9 8 ) 0 0 4 2 2 - 9
attempted [8,9,1315]. In this paper we report on
the preparation of high-quality ZnO thin lms by
the solgel deposition process. The solgel deposition
technique is an easy and very cheap method to
prepare metal oxide lms [16], nevertheless, the
preparation of ZnO thin lms by the solgel is al-
most unknown.
In this work we concentrate on the optical prop-
erties (in the near UV, VIS and IR regions) and the
electrical conductivity in the dark and the photo-
conductivity of the ZnO thin lms prepared by this
technique and the modications of the crystalline
and electronic structure introduced by aluminum
doping and annealing processes. Also, we shall see
how the activation energy and band gap measure-
ments help to explain the high dark conductivities
in these lms.
2. Experimental procedure
The electromechanical equipment developed for
the solgel deposition process is reported elsewhere
[17]. The equipment is able to manipulate small
deposition areas (1 cm`) as well as large areas
(1 m`). The deposition rate is varied by varying the
withdrawal velocity of the substrate. A standard
drawing velocity of 40 cm/min was selected for the
present case. Commercial grade glass slides (Corn-
ing, Mexico, 75;25;1 mm) were used for the
deposition. A 14% w/w solution of zinc acetate,
Zn(CH
`
COO)
`
) 2H
`
O, was prepared in pure meth-
anol. The solution was allowed to age for 24 h
before the deposition of the formed zinc complex
on the glass substrate. After the deposition, the
substrate was heated at 50C to evaporate the sol-
vent and at 350C in air to crystallize the zinc oxide
lm. Two cases must be distinguished in the case of
aluminum doping, Al'' or Al`, based on the re-
agents: AlCl
`
) 2H
`
O or Al
`
(NO
`
)
`
) 9H
`
O used for
the doping. In both cases a small quantity of the
aluminum salt was diluted in the deposition solu-
tion, to give an atomic ratio Zn/Al of 1.1;10`
(Al'') and 2.18;10` (Al`) in solution. These are
hereafter referred to as ZnO : AL'' system when
AlCl
`
) 2H
`
O is used, and ZnO : Al` for the case,
when Al
`
(NO
`
)
`
) 9H
`
O is used. The precursors
used in this work were Baker Analyzed Reagents.
A Siemens D-500 X-ray diractometer with Cu
K
?
radiation was used for the crystal structure
determination. A Shimadzu UV-3101/PC Spectro-
photometer was used for the optical characteriza-
tion. Fourier transform infrared spectroscopy
(FTIR) measurements were carried out with a
Nicolet-5SX spectrophotometer. Photoresponse
measurements were obtained using a HP 4140B
picoammeter/DC voltage source and HP 216 PC.
An Oriel solar simulator using a xenon discharge
lamp was used as the light source, which produced
an intensity of 900 W m` at the plane of the
sample. Silver electrodes were painted on the lms
for electrical contact at 5 mm pitch and 5 mm long.
3. Results and discussion
3.1. X-ray diraction analysis
The X-ray diraction analysis (XRD) was used to
investigate the physico-chemical processes involved
in the solgel deposition of ZnO. Fig. 1a shows the
XRD pattern of the Zn-complex deposited on the
glass substrate and dried in air at 50C. At this
temperature, residual chemical solvents will be de-
sorbed without altering the composition of the ad-
sorbed zinc complex. The Zn-complex crystallizes
in a monoclinic structure (JCPDS 14-902) with
a"14.53 A> , b"5.33 A> and c"10.91 A> corre-
sponding to the zinc monoacetate Zn(C
`
H
`
O
`
).
The crystallites are preferentially oriented in [0 0 2]
direction of the monoclinic crystal structure. The
dominant peaks in the pattern are (1 0 0), (2 0 0),
(!1 0 1) and (!3 1 0), which for JCPDS standard
(powder samples) posses relative intensities 8, 100,
20 and 25%, respectively. Heating in air at 100C
for 30 min leaves only the signals at 2"6 and
12.3 for the (1 0 0) and (0 0 2) peaks, respectively.
After annealing at 150C, the only evidence for the
presence of the monoclinic structure of the Zn-
complex is a weak signal at 2"6 for the (1 0 0)
reection. This disappearance of the XRD peaks
coincides with the appearance of well dened XRD
peaks related to the ZnO hexagonal phase (ZnO,
JCPDS 5-0664) with a"3.249 A> and c"5.205 A> .
The diraction pattern is very similar to that
found for ZnO powder, i.e., without preferential
A.E. Jime nez-Gonza lez et al. / Journal of Crystal Growth 192 (1998) 430438 431
Fig. 1. X-ray diraction pattern of pure ZnO thin lms pre-
pared by the solgel method.
orientation of the crystallites. Heating at 300C for
30 min produces preferential orientation of the
ZnO along the c-axis and nally after heating at
450C very strong orientation along [0 0 2] of the
hexagonal crystal structure is noted.
The ZnO lms formed upon annealing at 450C
are very homogeneous and the crystallites are
strongly oriented. ZnO powder (JCPDS 5-0664)
has the relative intensities 100, 56 and 71% respec-
tively for the (1 0 1), (0 0 2) and (1 0 0) reections. In
comparison thin lms processed at 450C (see
Fig. 1e) have relative intensities of 45, 100 and 45%,
respectively for the same reections. Therefore, the
crystallites are very strongly oriented along the
c-axis in the hexagonal structure, i.e., perpendicular
to the plane of the substrate. A very important
result is, that the preferential orientation of the
crystallites is not lost with the annealing, as it
occurs in ZnO lms prepared by other techniques
[18]. Under low doping concentrations of alumi-
num, Al/Zn ratio (10`, the lms have XRD
patterns similar to that found for pure ZnO (Fig. 1).
Visually, the lms show a very homogeneous sur-
face, which is necessary to reduce inelastic scatter-
ing processes at the surface that lead to increased
electrical resistivity, as found in milky ZnO thin
lms [18].
3.2. FTIR results
Fig. 2 shows absorbance spectra in the infrared
region of deposited lms after drying in air at
(a) 23C, (b) 100C and (c) 450C. These spectra
were recorded in the reection mode for (a) and (b),
and in the transmittance mode for (c), in which the
ZnO lm was scrapped o from the glass substrate
and dispersed in a KBr pellet. In curve (a), the
peaks located at 1632 and 1494 cm represent the
asymmetric and symmetric C"O stretching modes
of zinc monoacetate, respectively, whose identica-
tion is in accordance with standard FTIR measure-
ments on this sample (CAS [546-89-4]), [19]. We
can also observe a small signal of the deformation
bands of C"O around 1000 cm. Also, the pres-
ence of (OH) groups is conrmed through the
broad bands around 3350 and 2600 cm. Absorp-
tion peaks in the region between 500 and 850 cm
may not be discussed, because they originate from
the glass substrate. For the case (b), the asymmetric
and symmetric bands of C"O shift to 1653 and
1473 cm accompanied by a decrease in the inten-
sity in the case of the 1653 cm band. The C"O
deformation bands and the broad OH stretching
bands almost disappear, while a narrower OH
stretching band centered at 3570 cm is clearly
formed. These results indicate the decomposition
of zinc monoacetate probably into zinc hydroxide,
as discussed below. At higher temperatures,
150450C, the transformation of zinc monoacetate
continues and the absorbance signals become
weaker and tend to dissapear. Curve (c) shows the
absence of all traces (specially of carbonyl groups)
of zinc monoacetate. The ZnO stretching mode at
452 cm appears in this case. A small signal of
(OH) groups around 3570 cm is observed prob-
ably arising due to contact of the ZnO sample with
432 A.E. Jime nez-Gonza lez et al. / Journal of Crystal Growth 192 (1998) 430438
Fig. 2. FTIR absorbance spectra of as prepared solgel lms at (a) 23C and treated in air at (b) 100C and (c) 450C.
air resulting in adsorption of water vapor. This is in
accordance with reported results on this system [20].
Based on the XRDand FTIR results presented in
Figs. 1 and 2, we can propose for the rst time
a reaction mechanism for the lm deposition of
ZnO by the solgel technique using zinc acetate and
not zinc alkoxide, as precursor material. Here the
precursor material, zinc acetate, is an ester [21] and
the hydrolysis of esters (saponication) leads to the
production of acetic acid (CH
`
COOH) and an al-
cohol (ROH) [22]. We note that the hydrolysis
of the precursor lm is a fundamental step in
the production of materials by the solgel process
[16]. If we consider that water molecules in
Zn(C
`
H
`
O
`
)
`
) 2H
`
O are bonded through oxygen
in the C"O bonding, then we obtain the following
molecular picture projected on a horizontal plane
for zinc acetate in methanol [21]:
(1)
XRD results shown in Fig. 1a, indicate that zinc
acetate Zn(C
`
H
`
O
`
)
`
) 2H
`
O transforms to mono-
acetate Zn(C
`
H
`
O
`
) in methanol, which can result
in a composition from Eq. (1), as follows:
(2)
These compounds will be adsorbed on the glass
substrate during immersion in the solution. Be-
sides, water molecules are incorporated whether
from the solution or from the air to hydrolyze the
lm. After the adsorption the lm dries in the air
and when the lm is heated over 50C methanol
totally evaporates (boiling point of methanol is
45C). The components [CH
`
COO] and H> de-
scribed by the second and third terms in composi-
tion (2) react to give acetic acid (CH
`
COOH),
which evaporates from the lm.
The FTIR results of Fig. 2 conrm the pres-
ence of (OH) groups in the lms annealed at
A.E. Jime nez-Gonza lez et al. / Journal of Crystal Growth 192 (1998) 430438 433
Fig. 3. Optical transmittance spectra of (a) pure ZnO,
(b) ZnO : Al'' and (c) ZnO : Al` thin lms for three dierent
thicknesses. The lms were treated in air at 350C.
temperatures below 150C. This allowed us to sup-
pose the hydrolysis of zinc monoacetate, the rst
component in composition (2) which is present in
the lm annealed at temperatures up to 150C
(Fig. 1), by a process similar to the saponication:
(3)
XRD is unable to identify the zinc hydroxide
phase, probably because it is an amorphous phase.
Finally, at temperatures, over 100C (see Fig. 1)
ZnO will be formed through the chemical reaction
(4)
where oxygen is taken from the air.
3.3. Optical transmittance results
Transparency and homogeneity of pure and alu-
minum-doped ZnO thin lms can be tested
through optical transmittance measurements in the
near UV, VIS and IR regions. Fig. 3 shows the
transmittance spectra in the wavelength range
[2002500 nm] of (a) ZnO, (b) ZnO : Al'' and
(c) ZnO : AL` treated in air at 350C. The optical
transmittance of the lms is high (between 80 and
92%) in the near UV, VIS and IR ranges. The
optical interferences in the transmittance curves in
Fig. 2, can be only observed in very homogeneous
lms, and hence the quality of the present lms are
comparable to those obtained by sophisticated
techniques like RF-magnetron sputtering, CVD,
etc. We can also observe in the inset of Fig. 3 that in
the transmittance curves the threshold of optical
absorption shifts to shorter wavelengths for alumi-
num-doped ZnO thin lms suggesting an increase
in the band gap due to aluminum doping.
3.4. Photoresponse and electrical conductivity
measurements
It is known that pure ZnO is a photosensitive
[14] and n-type semiconductor [13]. Therefore,
ZnO shows a small electrical current under the
inuence of a small voltage (10 V). The dark current
of the lms increases with the lm thickness as
shown in Fig. 4 from 2;10 to 2;10` A when
the lm thickness increases from 350 to 2041 A> .
Also, we can observe in the same gure that the
photocurrent increases from 8;10` to 3;10" A
with the lm thickness. A typical photosensitivity
factor S"(
"'
!
''
)/
''
of 3.24;10" is seen
for a pure ZnO thin lm with thickness 1692 A> ,
photoconductivity
"'
"1.23 [ cm] and
dark conductivity
''
"3.785;10` [ cm].
The photocurrent decay is relatively rapid, in
a time of 18 s the photocurrent decreases by one
tenth of its maximum photocurrent value and in
110 s the photocurrent decreases by one hundredth.
These decay times support the idea that the ZnO
thin lms have only a small concentration of dis-
crete trapping levels (one or probably two) and not
a continuous distribution within the band gap.
Aluminum doping enhances, in general, the elec-
trical conductivity of ZnO lms. Fig. 5 shows the
434 A.E. Jime nez-Gonza lez et al. / Journal of Crystal Growth 192 (1998) 430438
Fig. 4. Photoresponse measurements of pure ZnO thin lms for
dierent thicknesses: (a) 350 A> , (b) 523 A> , (c) 785 A> , (d) 872 A> ,
(e) 1395 A> , (f) 1692 A> and (g) 2041 A> .
Fig. 5. Dependence of the electrical conductivity of ZnO : Al''
thin lms (treated in air at 350C) on the lm thickness.
electrical dark conductivity,
''
, and photocon-
ductivity,
"'
, of the ZnO : Al'' thin lms treated
in air at 350C as a function of the lm thickness.
The dark conductivity increases from 7.05;10'
to 3.17;10` [ cm] when the lm thickness
increases from 302 to 1678 A> and the photoconduc-
tivity increases from 5.17;10` to 6.35 [ cm].
The behavior of the dark conductivity and photo-
conductivity shown in the Fig. 5 is only possible in
aluminum-doped ZnO lms. In pure ZnO, the con-
ductivity values scatter with the lm thickness so
that it is impossible to obtain a good pattern of
behavior with such lms. The increase in electrical
conductivity brought in by the aluminum doping
can be explained as follows: the concentration of
free charge carriers in ZnO increases by the alumi-
num doping because aluminum has one valence
electron more than zinc. We may consider that
aluminum substitutes the zinc atom or it occupies
interstitial sites. In both cases aluminum acts as
a donor. There are two reasons for such arm-
ation: (1) The dierence in electronegativity be-
tween Al (1.61) and Zn (1.65) is very small and
(2) the ionic radii of Al (0.530, 0.675 A> ) are smaller
than the ionic radii of Zn (0.60 and 0.710 A> ) in the
tetrahedral and octahedral congurations [23], re-
spectively. These two reasons favor aluminum
doping.
Dierent annealing processes also inuence the
electrical properties of ZnO to various extents.
Fig. 6 shows the photoresponse signals of (a) ZnO,
(b) ZnO : Al'', (c) ZnO : Al` treated in air at
350C, and annealed in O
`
(P(O
`
)"0.2 mbar) at
400C for 30 min (d) ZnO : Al` and (e) ZnO : Al''
thin lms. The photoresponse curve (a), taken as
reference for the doping cases, presents a dark cur-
rent value of 1.85;10` A and exhibits high
photosensitivity. ZnO : Al'' lms treated in air
at 350C (curve b) have a dark current of
2.15;10' A and a photocurrent of 1.2;10" A,
while ZnO : Al` show a dark current of
6.8;10` A and a photocurrent 4.5;10" A. Fi-
nally, O
`
annealing increases the dark current to
1.1;10` A and
''
and
"'
take values in the
range 10100 [ cm]. These conductivity values
A.E. Jime nez-Gonza lez et al. / Journal of Crystal Growth 192 (1998) 430438 435
Fig. 6. Photoresponse curves of (a) pure ZnO, (b) ZnO : Al` and
(c) ZnO : Al'' treated in air and followed by annealing in O
`
at
400C: (d) ZnO : Al and (e) ZnO : Al''.
Fig. 7. ( h)` versus h curves for the band gap determination
in ZnO, ZnO : Al'', and ZnO : Al` thin lms treated at 400C in
O
`
.
are adequate for application of the lms as trans-
parent conductors in certain solar cell structures
and electrochromic devices. Summarizing, alumi-
num doping enhances the dark current of ZnO by
up to ve orders of magnitude and the photocur-
rent by more than one order.
3.5. Band gap determination
Fig. 7 shows the ( h)` versus h curves of pure
ZnO, ZnO : Al'' and ZnO : Al` treated in O
`
at
400C, where represents the absorption coe-
cient and h photon energy. We observe that pure
ZnO, ZnO : Al` and ZnO : Al'' have a band gap of
3.29, 3.30 and 3.31 eV, respectively. These values
are smaller than E

of 3.35 eV found for bulk cry-

stalline ZnO [24]. In general, we observe that alu-
minum doping increases the band gap of ZnO by
a maximum of two hundredths of an eV. Apparent-
ly it is not a signicant increase in the band gap, but
it must slightly reduce the photoconductivity, as
experimentally found. In spite of the small increase
in the band gap in aluminum doped ZnO lms, its
dark conductivity increases because the conduction
electrons obtained by ionization of the introduced
donor levels dominate the electrical transport.
3.6. Activation energy measurements
It is known that to activate the electrical con-
ductivity in a n-type semiconductor, it is necessary
to ionize the donor levels with at least a minimum
energy equal to the energy dierence E
'
!E
'
,
where E
'
represents the valence band minimum
and E
'
the donor levels. In the case of ZnO lms,
which presents deeper levels (traps), E
'
, below the
conduction band E
'
, Major et al. [25] found that
the electrical conductivity depends on the free car-
rier concentration, n, in the conduction band, in the
following form:
n"N
'
exp[!(E
'
!E
'
)/k], (5)
where N
'
is a function of the doping level, the
density of states in the conduction band, the trap
density and the grain size; k is the Boltzmann con-
stant and the absolute temperature. If the
436 A.E. Jime nez-Gonza lez et al. / Journal of Crystal Growth 192 (1998) 430438
Fig. 8. Log (I) versus 1000/ [K] of pure (a) ZnO,
(b) ZnO : Al and (c) ZnO : Al'' treated in O
`
at 400C.
temperature-activated mobility is not the dominant
process [26] by the experiment, we can use Eq. (5)
to calculate the activation energy of the electrical
conductivity. Fig. 8 shows the log (I) versus 1000/
curves for (a) pure ZnO, (b) ZnO : Al` and
(c) ZnO : Al'' thin lms in the temperature range
[50350C]. We can separate the range in which
the log(I) versus 1000/ curve has a linear behav-
ior. In this range, the activation energy for the
conductivity is proportional to the (negative) slope.
In this way, pure ZnO (curve a) presents an acti-
vation energy of 53 meV in the 1000/ range
(2.153.25 [1/K]) and another activation energy of
152 meV in the 1000/ range (1.91.12 [1/K]). For
the case of ZnO : Al`, we determine an activation
energy of 54.7 meV in the 1000/ range (3.202.60
[1/K]) and another of 210 meVin the 1000/range
(2.222.0 [1/K]). Above 1000/"1.9 K an in-
exion point is found. Due to the limited capability
of the equipment, it was not possible to investigate
this temperature range completely. Finally, in the
case of ZnO : Al'', an activation energy of 26 meV
was measured in the 1000/ range of (3.162.26
[1/K]) and another of 260 meVin the 1000/range
(2.051.69 [1/K]). Basically, the electron concentra-
tion in the ZnO lms increases by the aluminum
doping and the trapping levels with activation en-
ergy under 55 meV contribute to the electrical con-
ductivity with a very low energy cost. That is one of
the reasons for the improvement of dark conductiv-
ity improvement found in aluminum doped ZnO
lms, shown in Figs. 5 and 6.
4. Conclusions
In this paper we have shown that it is possible to
grow ZnO and ZnO : Al thin lms possessing good
optical, electrical and structural properties by the
solgel technique. For the rst time we proposed
a reaction mechanism based on experimental re-
sults for the solgel deposition of ZnO using zinc
acetate; Zn(CH
`
COO)
`
) 2H
`
O, which transforms
rst into zinc monoacetate, whose hydrolysis pro-
duces Zn(OH)
`
which converts to ZnO under an-
nealing.
Aluminum doping enhances the dark conductiv-
ity of ZnO thin lms treated in air at 350C by four
orders of magnitude and the photoconductivity
by more than an order. After heating in O
`
, dark
conductivity and photoconductivity between 10
and 100 [ cm], were obtained in aluminum-
doped ZnO. These values are in the range of con-
ductivity for transparent conductor applications of
the ZnO lms. Through measurements of the ac-
tivation energy for the conductivity, it was possible
to determine that donor levels are located at
53, 54.7 and 26 meV under the conduction band
for pure ZnO, ZnO : Al` and ZnO : Al'' thin
lms, respectively. The last system shows, in
fact, the highest dark conductivity and photocon-
ductivity. A deeper donor level is located at 152,
210 and 260 meV for pure ZnO, ZnO : Al` and
ZnO : Al'', respectively, which are not ionized at
room temperature.
A.E. Jime nez-Gonza lez et al. / Journal of Crystal Growth 192 (1998) 430438 437
Acknowledgements
The authors are grateful to Dr. P.K. Nair for the
revision of this manuscript, to Leticia Ban os from
IIM-UNAM for the XRD-spectra, to Jose Saniger
from CI-UNAM for FTIR-Spectra and to CON-
ACYT, Me xico, for nancial support (Project Nr.
0192P-E).
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