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Thin Solid Films 516 (2008) 1391 – 1395

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ZnO thin films prepared by a single step sol–gel process

Shane O'Brien a , L.H.K. Koh a , Gabriel M. Crean a,b,⁎
a
Tyndall National Institute, Cork, Ireland
b
Department of Microelectronic Engineering, University College Cork, Ireland

Available online 5 April 2007

Abstract

ZnO thin films were prepared on fused silica from a single spin-coating deposition of a sol–gel prepared with anhydrous zinc acetate [Zn
(C2H3O2)2], monoethanolamine [H2NC2H4OH ] and isopropanol. Crystallization annealing was performed over the range 500 to 650 °C. X-ray
analysis showed that thin films were preferentially orientated along the [002] c-axis direction of the crystal. The films had a transparency of greater
than 85% in the visible region for sol–gels with a zinc content of up to 0.7 M and exhibited absorption edges at ∼ 378 nm. The optical band-gap
energy was evaluated to be 3.298–3.306 eV. Photoluminescence showed a strong emission centered at ca. 380 nm along with a broad yellow-
orange emission centered at ca. 610 nm. Single step sol–gel thin film deposition in the film thickness range from 80 nm to 350 nm was
demonstrated. The effect of sol–gel zinc concentration, film thickness and crystallization temperature on film microstructure, morphology and
optical transparency is detailed. A process window for single spin coating deposition of c-axis oriented ZnO discussed.
© 2007 Published by Elsevier B.V.

Keywords: Zinc oxide; Sol–gel

1. Introduction
ZnO thin films now attract significant attention due to their
wide range of electrical and optical properties. They have
potential application in electronics, optoelectronics and infor-
mation technology devices including displays, solar cells and
sensors [1,2].
Several thin-film deposition techniques have been used to
produce pure ZnO films, including sputtering [3], molecular
beam epitaxy [4], metal-organic chemical vapour deposition
[5], pulsed laser deposition [6], spray pyrolysis [7] and the sol–
gel process [8,9]. The sol–gel method has distinct potential
advantages over these other techniques due to its lower
crystallization temperature, ability to tune microstructure via
sol–gel chemistry, conformal deposition ability, compositional
control and large surface area coating capability [10,11].
The deposition of pure and doped ZnO thin films by the sol–
gel process has already been reported [12–15]. However, to-
date, multiple deposition steps have been generally necessary to
⁎ Corresponding author. Tyndall National Institute, Cork, Ireland. Tel.: +353
21 4904572.
E-mail address: gcrean@tyndall.ie (G.M. Crean).
0040-6090/$ - see front matter © 2007 Published by Elsevier B.V.
doi:10.1016/j.tsf.2007.03.160
produce thin films of the required film thickness for specific
technological applications. Typical multi-step deposition pro-
cesses that have been demonstrated include the use of five
sequential depositions to achieve 100 nm [16] and seven
sequential depositions to achieve 300 nm [17].
A single-step sol–gel process to deposit ZnO thin films in the
hundreds of nanometer range is of considerable interest from
both process cost-of-ownership and film quality aspects. A
decrease in the number of coating applications would reduce
both application and drying steps required and the number of
interfaces within the resultant thin film which can contribute to
reduced optical transparency.
In this study, a novel sol–gel process is investigated for
deposition of c-axis orientated ZnO thin films with thicknesses
up to 350 nm in a single spin-coating step. The use of anhydrous
zinc acetate, which avoids the introduction of large amounts of
water to the sol–gel, enabling control over reactions taking
place within the sol–gel is described. In addition, the use of
isopropyl alcohol (IPA), as a low boiling point solvent in place
of 2-methoxyethanol (B.P. = 125 °C) to facilitate efficient
solvent removal and drying from thick films in order to avoid
the occurrence of cracking during the crystallization annealing
stage of processing is detailed. The effect of process deposition
1392 S. O'Brien et al. / Thin Solid Films 516 (2008) 1391–1395
parameters, such as the zinc concentration of the sol–gel and
furnace annealing temperature, on ZnO film microstructure,
morphology and optical transparency was also examined.
2. Experimental
The ZnO sol–gel was prepared was as follows: zinc acetate
(M= 183.46, Zn(C2H3O2)2, 99.99% chemical purity) was first
dissolved in isopropanol ((CH3)2CHOH) at room temperature.
Then monoethanolammine (M= 61.08, H2NCH2CH2OH, MEA,
AR) was added as a sol stabilizer [17]. The molar ratio of MEA to
zinc acetate was maintained at 1.0 and the final concentration of the
zinc acetate was varied between 0.3 to 1.3 mol/L. The resulting
mixture was then stirred at 50 °C for 1 h to form a clear and
transparent homogeneous mixture and upon cooling was syringe
filtered using a 0.45 μm, Acrodisc Versapor® filter to remove any
foreign particulates and aged for 24 h at room temperature. ZnO
thin films were prepared by spin coating the aged solution onto UV
fused silica (Spectrosil 2000) glass at rotation speeds of 2000 rpm
for a duration of 30 s. To facilitate film thickness measurements, a
section of the substrate was covered by adhesive tape which was
subsequently peeled off after the spin-coating process [12]. The
substrates were then dried on a hotplate at 60 °C for 1 h. On cooling,
the samples were placed in a furnace for crystallization annealing at
a heating rate of 5 °C/min to a final temperature of 650 °C. Samples
was maintained at this temperature for 1 h before being air-cooled to
room temperature. Fig. 1 shows a schematic of the sol preparation
process.
The degree of crystallinity and crystalline orientation of the
ZnO thin films was measured using a Phillips (PW3719) X'pert
Fig. 1. Process flow chart showing the procedure for preparing the sol–gel and
thin films.
Fig. 2. The X-ray diffraction patterns of ZnO films prepared by a single coating
process at different zinc concentrations. All films were spin-coated at 2000 rpm,
dried at 60 °C and post annealed at 650 °C.
materials research X-ray diffractometer (XRD) with a Cu Kα
radiation, and a scanning range of 2θ set between 25° and 50°.
The average ZnO thin film particle size was calculated from the
measured XRD peak height at FWHM data using the Lotgering
formula and Scherrer's equation respectively [20]. Optical
transmittance spectra were recorded using a Shimadzu (UV-
2401 PC) UV–VIS recording spectrophotometer over the
wavelength range between 200 and 800 nm. The surface
morphology of the films was evaluated using a Philips
(XL30TMP) scanning electron microscope (SEM). Thin film
thickness was measured using a TENCOR (Alpha-Step 500)
surface profilometer. The optical band-gap energy was
estimated from optical transmittance and wavelength data,
using an extrapolation of the linear portion of α2 versus hν
where α is the absorption coefficient and hν, the photon energy.
The optical absorption edge was determined using a first
derivative method was used to acquire the wavelength value
required for calculation of the optical bandgap [18].
Photoluminescence (PL) spectra of the ZnO films on fused
silica substrates were recorded using an in house optical system.
Samples were optically pumped with an Innova Enterprise II
argon (Coherent) ion laser and the emitted light collected using
a Triax 190 0.19 m monochromator (Jobin-Yvon). PL spectra
were acquired by directing the 350 nm excitation light onto the
ZnO films at an angle of 27° to the plane of the sample, and
collecting the resulting luminescence at an angle of 63 degrees.
Table 1
Degree of preferred orientation, crystallite size and film thickness with respect to
the zinc concentration of the sol–gel
Zn concentration Preferred Degree of (002) Crystallite Film thickness
(M) orientation orientation size (nm) (nm)
0.3 (002) 0.96 288 84
0.6 (002) 0.62 385 185
0.7 (002) 0.50 315 188
1.3 (101) 0.22 348 437
 S. O'Brien et al. / Thin Solid Films 516 (2008) 1391–1395 1393

Fig. 3. SEM micrographs of ZnO films prepared with a) 0.3 M, b) 0.6 M c) 0.7 M and d) 1.3 M zinc concentrations respectively.

All spectra were recorded with an excitation power of 15 mW at
an integration time of 1 s using a R928 PMT (Hamamatsu).
3. Results and discussion
Fig. 2 shows X-ray diffraction patterns of ZnO thin films
deposited on Spectrosil by spin-coating at 2000 rpm, hotplate
drying at 60 °C and annealed in air at 650 °C as a function of Zn
sol–gel content. It was observed that all the deposited films were
polycrystalline with a hexagonal wurtzite structure [19]. (100),
(002) and (101) XRD peaks were observed, along with low
intensity (110) diffraction in most cases. The degree of c-axis
orientation of the ZnO thin films was strongly dependant on the
initial zinc concentration of the sol–gel, as shown in Table 1. It is
observed that samples were preferentially oriented in the c-axis, or
(002) plane, for sol–gel zinc concentrations between 0.3 and 0.7 M,
with a degree of c-axis orientation of 0.96 obtained from the 0.3 M
sol–gel, decreasing to a degree of c-axis orientation of 0.5 for the
0.7 M sol–gel. An increase of zinc concentration to 1.3 M resulted
in a film preferentially oriented in the (101) plane. The average ZnO
thin film particle sizes are presented in Table 1. The calculated
values of the crystallite sizes ranged between 289 and 386 nm. It
was observed that crystallite size increased with increasing sol–gel

Fig. 4. Optical Transmittance spectra of the ZnO thin films at (a) 0.3; (b) 0.6; Fig. 5. First derivative (dT / dλ) plot of the transmittance spectra of the ZnO thin
(c) 0.7; and (d) 1.3 M Zn concentrations respectively. films, as a function of Zn concentration.
1394 S. O'Brien et al. / Thin Solid Films 516 (2008) 1391–1395
zinc concentration. This trend is consistent with the SEM
micrograph analysis presented in Fig. 3a–d, where the ZnO grain
size is clearly seen to increase with increasing Zn concentration.
The ZnO thin film thickness measurement data are also presented in
Table 1. It was observed that increasing the zinc concentration of
prepared sol–gels resulted in an increase in film thickness from
84 nm (0.3 M Zn sol–gel) to 437 nm (1.3 M Zn sol–gel).
The optical transmittance spectra of the sol–gel deposited ZnO
thin films in the UV–visble wavelength range (200–800 nm) are
presented in Fig. 4, with the first derivative of these spectra
presented in Fig. 5. The bandgap of the fabricated ZnO thin films
calculated from this optical data were 3.306 eVand 3.298 eV for the
0.3/0.6 M and 0.7/1.3 M samples respectively, consistent with
published values of the ZnO electronic transition bandgap data [21].
From Fig. 5, the absorption wavelength values that correspond to
the peaks for the 0.3/0.6 M and 0.7/1.3 M Zn concentration were
375 nm and 376 nm respectively. It should be noted that this
absorption is close to that of crystalline [22] (Table 2).
It is observed that the optical transmittance of the films was
80–92% over the visible wavelength range from 400 nm to
800 nm for the lower ZnO (0.3 to 0.7 M) concentration sols. In the
case of the 1.3 M Zn sol–gel, the optical transmittance was 57–
84% over the same wavelength range. The transmittance of the
films increases with the percentage of c-axis orientation,
consistant with a reduction in light dispersion in grain boundaries
[23] as the film microstructure becomes more c-axis oriented.
PL spectra of the ZnO films shows a strong emission centred at
ca. 380 nm, due to free-exciton emission [24,25] are presented in
Fig. 6. The samples also show a strong and broad yellow-orange
emission, with a peak centred at ca. 610 nm and a shoulder at ca.
730 nm. It is known that pure ZnO can show green and/or orange
visible luminescence depending on the growth temperature and
availability of oxygen during sample preparation. The green
emission results from the recombination of electrons with holes
trapped in singly ionized oxygen vacancies and is commonly seen
in ZnO materials synthesized under oxygen-deficient conditions
[24]. The orange emission is less commonly reported and its origin,
although not fully understood, seems to involve the presence of
interstitial oxygen ions. Orange PL has also been seen in ZnO
grown electrochemically [26], hydrothermally [27], by pulsed laser
deposition [28] and spray pyrolysis [29]. The strong orange PL and
complete absence of green emission from the ZnO samples
measured is consistent with the above assignments. Regardless of
the exact origin of the orange emission, the large ratio of orange PL
intensity to band-edge PL intensity, particularly for the 1.3 M
sample, indicates that the as-grown sol–gel films are rich in atomic
Table 2
% Transmittance range and optical bandgap of the films fabricated from sol–
gels containing a range of zinc concentrations.
Zn concentration (M) % Transmittance Bandgap (eV)
0.3 87–92 3.306
0.6 87–92 3.306
0.7 80–89 3.298
1.3 57–84 3.298
Fig. 6. PL spectra of the ZnO thin films as a function of initial Zn concentration
of prepared sol–gel.
defects. Further work is in progress to determine the influence of
sol–gel film preparation parameters on this PL emission.
4. Conclusion
Zinc oxide thin films were fabricated from sol–gels prepared
with 0.3–1.3 M zinc acetate concentrations. Thin film thicknesses
were found to depend on sol–gel zinc concentration and ranged
from 84 to 437 nm. Crack-free films were obtained in all cases.
XRD analysis showed that all samples had a hexagonal wurtzite
structure. Within the zinc concentration range 0.3–0.7 M samples
were preferentially c-axis oriented. Increasing the zinc concen-
tration of the sol–gel above 0.7 M was observed to result in films
that were not preferentially c-axis oriented. The % transmittance
of films was 80–92% over the wavelength range 400–800 nm for
the lower ZnO (0.3 to 0.7 M) concentration sols. In the case of the
1.3 M Zn sol–gel, the optical transmittance was 57–84% over the
same wavelength range. These % transmittance values were
significantly influenced by the microstructure of the films. PL
spectra of the ZnO films showed a strong emission centered at ca.
380 nm and also a strong and broad yellow-orange emission, with
a peak centered at ca. 610 nm and a shoulder at ca. 730 nm. These
results suggest that a single step sol–gel ZnO process can
fabricate films with good crystallinity and optical transparency
properties.
Acknowledgements
This work was supported by the Irish Government, Depart-
ment of Education and Science, through the Higher Education
Authority Programme for Research in Third Level Institutions,
Project Eco-Electronics. The authors thank the Photonic
Nanostructures Group for their assistance in Scanning Electron
Microscopy and Dr. Hugh Doyle of the Nanotechnology Group,
Tyndall National Institute, for his assistance in PL measurement.
References
[1] S. Bandyopadhyay, G.K. Paul, S.K. Sen, Sol. Energy Mater. Sol. Cells 71
(2002) 103.
[2] Y. Natsume, H. Sakata, Thin Solid Films 372 (2000) 30.
[3] P. Nunes, D. Costa, E. Fortunato, R. Martins, Vacuum 64 (2002) 293.
 S. O'Brien et al. / Thin Solid Films 516 (2008) 1391–1395
[4] D.C. Look, D.C. Reynolds, C.W. Litton, R.L. Jones, D.B. Eason, G.
Gantwell, Appl. Phys. Lett. 81 (10) (2002) 1830.
[5] K. Tominaga, T. Takao, A. Fukushima, T. Moriga, I. Nakabayashi, Vacuum
66 (2002) 505.
[6] N. Naghavi, C. Marcel, L. Dupont, A. Rougier, J.B. Leriche, C. Guery,
J. Mater. Chem. 10 (2000) 2315.
[7] M. Krunks, E. Mellikov, Thin Solid Films 270 (1995) 33.
[8] T. Shuler, M.A. Aegerter, Thin Solid Films 351 (1999) 125.
[9] Y. Natsume, H. Sakata, Mater. Chem. Phys. 78 (2002) 170.
[10] E.J. Luna-Arredondo, A. Maldonado, R. Asomoza, D.R. Acosta, M.A.
Melendez-Lira, M. de la L. Olvera, Thin Solid Films 490 (2005) 132.
[11] N.R.S. Farley, C.R. Staddon, L.X. Zhao, K.W. Edmunds, B.L. Gallagher,
D.H. Gregory, J. Mater. Chem. 14 (2004) 1087.
[12] N. Viart, M. Richard-Plouet, D. Muller, G. Pourroy, Thin Solid Films 437
(2003) 1.
[13] A.E. J.-Gonzalez, J.-A. S.-Urueta, R. S.-Parra, J. Cryst. Growth 192 (1998)
430.
[14] L.J. Mandalapu, F.X. Xiu, Z. Yang, D.T. Zhao, J.L. Liu, Appl. Phys. Lett.
88 (2006) 112108.
[15] M. Ohyama, H. Kozuka, T. Yoko, Thin Solid Films 306 (1997) 78.
[16] C.Y. Zhang, X.M. Li, X. Zhang, W.D. Yu, J.L. Zhao, J. Cryst. Growth 290
(2006) 67.
1395
[17] H. Li, J. Wang, H. Liu, H. Zhang, X. Li, J. Cryst. Growth 275 (2005) e943.
[18] F.K. Lotgering, J. Inorg. Nucl. Chem. 9 (1959) 113.
[19] R.E. Marotti, D.N. Guerra, C. Bello, G. Machado, E.A. Dalchiele, Sol.
Energy Mater. Sol. Cells 82 (2004) 85.
[20] Joint Committee on Powder Diffraction Standards, Powder diffraction file,
International Center for Diffraction Data, Swarthmore, PA, Card, 1988, 36.
[21] J.-H. Lee, K.-H. Ko, B.-O. Park, J. Cryst. Growth 247 (2003) 119.
[22] S.M. Sze, Physics of Semiconductor Devices, Wiley, New York, 1981.
[23] Y.S. Kim, W.P. Tai, S.J. Shu, Thin Solid Films 491 (2005) 153.
[24] J.C. Johnson, H. Yan, P. Yang, R.J. Saykally, J. Phys. Chem., B 107 (2003)
8816.
[25] L.E. Greene, M. Law, J. Goldberger, F. Kim, J.C. Johnson, Y. Zhang, R.C.
Saykally, P. Yang, Angew. Chem., Int. Ed. Engl. 42 (2003) 3031.
[26] M.J. Zheng, L.D. Zhang, G.H. Li, W.Z. Shen, Chem. Phys. Lett 363 (2002)
123.
[27] T. Sekiguchi, S. Miyashita, K. Obara, T. Shishido, N.J. Sakagami, Cryst.
Growth 214/ 215 (2000) 72.
[28] X.L. Wu, G.G. Siu, C.L. Fu, H.C. Ong, Appl. Phys. Lett. 78 (2001) 2285.
[29] S.A. Studenikin, N. Golego, M.J. Cocivera, Appl. Phys. 84 (1998) 2287.