Study of the structure, optical properties, surface

morphology and topology of ZnO thin lms grown by

solgel on silicon substrates
J G Quiones-Galvn1, H Tototzintle-Huitle2, L A Hernndez-Hernndez3,
J S Arias-Cern4, F de Moure-Flores5, A Hernndez-Hernndez6,
E Campos-Gonzlez4, A Guilln-Cervantes4, Orlando Zelaya-Angel4 and
J J Araiza2
1
Departamento de Fsica, Instituto Nacional de Investigaciones Nucleares, Apartado postal
18-1027, Mxico D. F., C. P. 11801, Mxico
2
Unidad Acadmica de Fsica, UAZ, Zacatecas 98060, Mxico
3
Escuela Superior de Fsica y Matemticas del IPN, Mxico D. F. 07738, Mxico
4
Departamento de Fsica, CINVESTAV-IPN, Apdo. Postal 14-740 Mxico, D. F. 07360,
Mxico
5
Facultad de Qumica, Materiales, Universidad Autnoma de Quertaro, Quertaro, 76010,
Mxico
6
Escuela Superior de Apan, Universidad Autnoma del Estado de Hidalgo, Calle Ejido de,
Chimalpa Tlalayote s/n Colonia Chimalpa, Apan Hidalgo, Mxico
E-mail: erk_183@hotmail.com

Received 9 June 2014, revised 15 August 2014

Accepted for publication 27 August 2014
Published 25 September 2014
Materials Research Express 1 (2014) 036404
doi:10.1088/2053-1591/1/3/036404

Abstract
Polycrystalline visible light photoluminescent zinc oxide (ZnO) thin lms have
been grown on silicon substrates by the dip immersion solgel technique at low
sintering temperature. The optical properties of the lms were analyzed by
UVvis spectroscopy. The structural properties were measured with x-ray dif-
fraction. The results show that the lms are polycrystalline and have hexagonal
wurtzite structure. The estimated band gap of the samples by UVvis absorption
spectroscopy is in good agreement with the value measured by UVvis reec-
tance spectroscopy and is near 3.2 eV. The surface topography was observed
with atomic force microscopy. The morphology of the samples was analyzed by
scanning electron microscopy. Energy dispersive x-ray spectroscopy was used to
make chemical composition measurements, the results indicate that the sample is
stoichiometric. The photoluminescence (PL) spectroscopy shows a strong band
in the bluegreen region of the spectrum, which makes these lms interesting to
optoelectronic applications.

Keywords: ZnO, sol-gel, optoelectronic, band gap

Materials Research Express 1 (2014) 036404

2053-1591/14/036404+09$33.00 2014 IOP Publishing Ltd
Mater. Res. Express 1 (2014) 036404 J G Quiones-Galvn et al

1. Introduction

Because of its wide direct band gap (Eg = 3.3 eV) [1, 2] ZnO has potential applications in
optoelectronics. It has been used in light emission devices. ZnO thin lms are of interest for
blue and ultraviolet optical devices such as light emission and laser diodes [3]. ZnO has a high
transmittance in the visible region; because of this property it has been used as a window
material for solar cells [4]. ZnO crystallizes in hexagonal wurtzite and cubic zincblende
structures. The wurtzite structure is the most stable phase at ambient conditions.
Several physical vapor deposition techniques have been used to obtain ZnO thin lms such
as sputtering [5, 6], pulsed laser deposition [4, 79] and cathodic arc evaporation [10, 11]. ZnO
has also been obtained by chemical methods such as solgel [1219] and spray
pyrolysis [20, 21].
In the present paper ZnO thin lms have been deposited on silicon substrates using the dip
immersion solgel technique. This is a simple chemical deposition technique that allows the
deposition of a variety of materials; it has been specially designed for the deposition of metallic
oxides. Some of the principal advantages of the solgel technique among other deposition
techniques are: good homogeneity, ease of composition control, low processing temperature,
large area coatings, low equipment cost and good optical properties on the obtained lms.
Besides, it is a low cost process.
The solution used to obtain ZnO thin lms in this work is based on zinc acetate dihydrate
(Zn(O2CCH3)2(H2O)2) dissolved in methanol, no solution stabilizers were used, there is not
much work on solgel deposited ZnO using the solution described in the present paper.
Generally deposition of thin lms using zinc acetate as a precursor requires the use of stabilizer
agents, a chelating agent, or the use of some substance to avoid precipitates [13, 22, 23]. Due to
its low boiling point (65 C) methanol used as a solvent improves the quality of the lms [24].
The lms obtained in the present work are polycrystalline in the hexagonal wurtzite structure.
ZnO lms have a strong bluegreen photoluminescence (PL) band. The optoelectronic
properties of the lms where analyzed and compared using different optical characterization
methods. The principal contribution of the present paper is the use of a simple, stable and highly
transparent solgel solution to obtain good quality photoluminescent ZnO thin lms.

2. Experimental

The precursor solution for the thin lms deposition was prepared dissolving zinc acetate
dihydrate (Zn(O2CCH3)2(H2O)2) in methanol. Once the components were mixed, the solution
was magnetically stirred at room temperature for 24 h. A highly transparent, stable and
homogeneous solution was obtained.
For the deposition of the ZnO lms silicon substrates were used. The substrates were
degreased rinsing them in different solvents. After the Si substrates were clean, ve immersions
were done of the substrate into the solution; a thermal treatment in air was applied after each
immersion in order to evaporate residues. The sintering temperature was 180 C for 10 min.
Finally, the lm was thermally annealed at 500 C in air for 3 h. The lms thickness is estimated
to be 350 nm.
The samples were structurally characterized by x-ray diffraction (XRD) in a Siemens
D5000 diffractometer using the Cu-K line at grazing angle. The surface topography studies

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Mater. Res. Express 1 (2014) 036404 J G Quiones-Galvn et al

Figure 1. XRD pattern of ZnO thin lm grown on silicon substrate.

were performed by atomic force microscopy (AFM) using a Thermo Microscope Autoprobe CP
Research AP-2001 in contact mode. The surface morphology images were taken with a eld
emission scanning electron microscope Jeol model JSM-7401F. Atomic concentration
measurements of the samples were carried out with an 1100/1110 EDX system from Noran
Instruments installed in the Jeol microscope. A lm was grown on glass in order to measure the
UVvis transmittance and absorbance spectra in a UVvis Perkin Elmer Lambda 25
spectrophotometer. Reectance measurements were done in the same equipment for the
sample grown on silicon. The room temperature PL emission spectrum was obtained using the
325 nm line of a He:Cd laser using a 1403-SPEX monochromator and an RCA-C31034
photomultiplier as a detector.

3. Results and discussion

The XRD pattern of the sample is presented in gure 1. Seven peaks located at 31.72, 34.42,
36.18, 47.48, 56.54, 62.82 and 67.88 corresponding to the (100), (002), (101), (102),
(110), (103) and (200) planes of the hexagonal wurtzite structure can be observed, the sample
has a slightly preferential orientation in the (101) direction. From the XRD data the lattice
parameters were calculated. Using the plane spacing equation for the hexagonal system [25]:

1 4 h 2 + hk + k 2 l2
= + (1)
d2 3 a2 c2

Where d is the plane spacing, a and c are the lattice parameters, h, k, l are the Miller indices.
The lattice spacing was calculated using the Bragg relation = 2d sin, where = 1.54 is the
x-ray wavelength.
Taking into account the plane (100), the interplanar distance gives a value of d = 2.82 ,
thus, solving equation (1) for the lattice parameter gives a = 3.25 . For the plane (002)
d = 2.60 and solving equation (1) for c the lattice parameter gives c = 5.20 . The calculated
values for the lattice parameter from XRD data are in good agreement with the reported values
in the literature for the hexagonal wurtzite structure of ZnO [16].

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Mater. Res. Express 1 (2014) 036404 J G Quiones-Galvn et al

a)
PL b)
0818S005.HDF

120.0
186.9
93.4 80.0
0.0
20 40.0
20
15 0.0
15
10
m 10
m
5 5 0 5 10 15 20 m
0 0

Figure 2. 3D atomic force micrograph (a) and plan view image (b) of ZnO thin lm
grown on silicon substrate.

For the mean crystallite size the Scherrer formula [26] was used. This relation is given by:
0.9
t= (2)
B cos B
Where = 1.54 is the x-ray wavelength, t is the crystal diameter, B is the full width at half
maximum (FWHM) and B is the Bragg diffraction angle. The mean crystal size of the sample
is 16 nm.
In gure 1 three peaks located at 28.5, 32.6 and 50.7 can be observed; these peaks may
be assigned to zinc acetate (ZnAc) according to diffraction pdf card # 010089, indicating that
the precursor was not completely dissolved and residues of it remain in the obtained lms.
The topography of the surface was observed with atomic force microscopy. Figure 2
shows the 3D AFM image (gure 2(a)) and the plan view image (gure 2(b)) of the sample
surface. In gure 2(b) can be seen circular shape large grains with sizes ranging between 500
and 700 nm. The large grain sizes can be associated to the annealing temperature. According to
the AFM results, the root mean square (rms) roughness is 1.72 nm. Despite the low rms
roughness value, the surface morphology of the ZnO lm cannot be considered as smooth
because the height of the top and bottom is approximately 100 nm. The white lines at the edge
of the micrographs are generated by the noise; they are not related to the morphology of the
sample.
The surface morphology of the sample was observed with SEM. Figure 3 shows the
scanning electron micrograph of the sample. A dense chain-like structure can be observed along
with small random shape grains with sizes ranging between 10 and 20 nm distributed among the
surface of the sample, the chainlike behavior indicates the agglomeration of grains due to the
annealing temperature. These structures are interesting for gas sensing applications [27].
According to EDS measurements the lm is stoichiometric with atomic compositions of
48.56% of Zn and 51.44% of O.
A ZnO sample was grown on a commercial microscope glass slide substrate under the
same deposition conditions and annealing process in order to perform the transmittance and
absorbance UVvis spectroscopy measurements.

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Mater. Res. Express 1 (2014) 036404 J G Quiones-Galvn et al

Figure 3. Scanning electron micrograph of ZnO thin lm grown on silicon substrate.

Figure 4. UVvis transmittance spectrum of ZnO thin lm grown on glass substrate.

In gure 4 the transmittance spectrum of the sample is shown. The sample is transparent in
the visible region with a transmission of 85%. The absorption edge can be observed near
385 nm (3.2 eV), which corresponds to the value of the excitonic transition in ZnO [2].
An estimation of the band gap (Eg) of the sample was made from the UVvis absorption
spectrum of the sample also known as optical density (OD). Figure 5 presents the OD spectrum
of the ZnO thin lms grown on glass substrate, the inset exhibits (OD h)2 versus h, where
h is the photon energy. The band gap determination is made by an extrapolation of the linear
part of the curve intercepting the h axis [28].
The estimated band gap gives a value of Eg = 3.21 eV. This value is in agreement with the
reported values for ZnO [2, 29].
The crystalline quality of the lms deposited on Si is slightly better than that of the sample
grown on glass; for practical purposes the optical properties of both lms are the same, thus the
estimation of the bandgap from the measurements of the lm grown on glass is a good
approximation of the value for the lm grown on Si.

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Mater. Res. Express 1 (2014) 036404 J G Quiones-Galvn et al

Figure 5. Optical density spectrum of ZnO thin lm grown on glass substrate. The inset
exhibits the band gap determination of the sample.

Figure 6. PL and UVvis Reectance spectra of the ZnO thin lm grown on silicon
substrate by solgel.

In gure 6 the UVvis reectance spectrum and the PL spectrum of the ZnO sample are
shown. In the reectance spectrum a peak centered at 3.25 eV can be observed, this signal is
associated to the band-to-band transition.
The PL spectrum has three peaks at 2.33, 2.54, and 3.19 eV, as shown in gure 6. The
broad band in the bluegreen region is characteristic of ZnO. This band can be resolved into
two components, showed in gure 6, one component centered in the green region (2.33 eV) of
the spectrum and another one centered in the blue region (2.54 eV). The origin of the green
emission component has been explained by defects associated transitions, there are different
possibilities for the related defects associated to this transition; it can be associated to oxygen
antisites (OZn) [7], oxygen interstitials (Oi), oxygen vacancies (Vo) and zinc interstitials (Zni)

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Mater. Res. Express 1 (2014) 036404 J G Quiones-Galvn et al

[21]. However, the emission mechanism in the lms is probably associated to the oxygen
related defects due to the lms grew with small oxygen excess.
For the emission band in the blue region of the spectrum there are some reports in the
literature that explain its origin [21, 24]. The mechanism of emission of the blue band has been
associated with zinc vacancies (VZn) and zinc interstitials (Zni) [30].
Another band centered in 3.19 eV can be observed in the PL spectrum; as can be seen, this
band corresponds to the value of the band gap estimated by UVvis absorption spectroscopy,
thus this band is associated to the near edge transition. It is important to notice the energy
difference of 60 meV between the value of the band gap and the band observed in the
reectance spectrum. An energy difference of 63 meV has been reported [29] between the near
edge transition observed in PL and the band gap measured by reectance spectroscopy.
The emission lines involving phonons in PL and excitonic emission can be expressed as
[29]:
Em = E0 m LO + E (3)

Where Em is the energy position of the PL spectral peaks, E0 is the exciton energy at K = 0, m is
an integer, and mLO 72 meV is the LO phonon energy and E = 2K2/2 M is the kinetic
energy of free excitons in the crystal. At room temperature E 12.5 meV [20]; thus there is an
expected shift of the PL near edge emission equal to mLO E = 60 meV, which is exactly
the energy shift observed in the experimental data obtained in the present work. Thus, the shift
in the PL maximum corresponding to the near edge transition is attributed to the emission of
1LO phonon replica of the free exciton.

4. Conclusions

Polycrystalline ZnO thin lms have been grown on silicon substrates by a simple and novel
solgel dip coating process dissolving zinc acetate in methanol; a stable and highly transparent
solution was obtained, after a month of aging the solution did not change at all. Thus, using this
solution, good quality solgel thin lms can be obtained in a simple process different from the
existing reports. The results show a photoluminescent lm in the bluegreen region of the
spectrum, and this result makes the lm interesting for optoelectronic applications. Besides, the
results obtained from optical measurements gives a value of the band gap that is in agreement
with published reports. It was concluded that the near edge PL emission is dominated by the
free exciton LO phonon replicas.

Acknowledgements

We acknowledge Marcela Guerrero, Ana Bertha Soto and Rogelio Fragoso from CINVESTAV-
IPN for their technical support. Cyntia I Ziga Romero and Dr Omar Jimnez Sandoval from
CINVESTAV-IPN unidad Quertaro are also acknowledged. This work was partially supported
by Project SEP-CONACyT-105723 and PIFI-UAZ-2011, and PIFI-UAZ 2012-2013.

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