JOURNAL OF SCIENCE OF HNUE DOI: 10.18173/2354-1059.

2016-0040
Mathematical and Physical Sci., 2016, Vol. 61, No. 7, pp. 122-127
This paper is available online at http://stdb.hnue.edu.vn

STRUCTURAL, OPTICAL AND ELECTRICAL PROPERTIES OF UNDOPED

AND Al DOPED-ZnO FILMS FOR USE IN PHOTOVOLTAIC DEVICES

Nguyen Dinh Lam, Tran Thi Mui, Le Thuy Trang, Pham Van Vinh,
Vuong Van Cuong and Nguyen Van Hung
Faculty of Physics, Hanoi National University of Education

Abstract. ZnO films are deposited on glass substrates using a sol-gel spin coating method.
To investigate the influence of Al doping concentration on structural, optical and electrical
characteristics of films, Al doping concentrations are varied from 0% to 5%. The surface
morphology, structure and optical transmittance characteristics of the films are studied
using scanning electron microscopy, an X-ray diffractometer and a UV-Vis-NIR system,
respectively. All the peaks shown in the XRD patterns are sharp and narrow, and they
closely matched that of the hexagonal wurtzite ZnO structure. Average transmittance of the
films in the visible region exceeds 95%, with the highest average transmittance obtained
by 1% Al-doped film. Furthermore, the optical bandgaps of the films are determined by
Tauc’s law and they show a tendency to increase with the incorporation of Al content. The
I-V plots of 1% Al-doped ZnO film were carried out in the dark and under illumination. The
film shows good photoconductivity response. The results suggest a potential application of
Al-doped ZnO films for different optoelectronic and photovoltaic devices.
Keywords: ZnO film, sol-gel spin coating, Al-doped, photovoltaic.

1. Introduction
Zinc oxide (ZnO) films can be employed in thin film solar cells, transistors, sensors and
other optoelectronic devices because of its wide band gap (3.37 eV) and large exciton binding
energy (60 meV) [1-3]. The optical transmittance and electrical conductivity of ZnO films can be
improved by adding dopants such as aluminum (Al), tin (Sn), and indium (In) [4-6]. ZnO films
can be fabricated using growth techniques such as molecular beam epitaxy (MBE), metal-organic
chemical vapor deposition (MOCVD) and high vacuum sputtering [7-9]. Using these techniques,
high quality ZnO film can be obtained. However, the total cost to manufacture ZnO film will be
high because of the need for sophisticated, high cost equipment. However, the sol-gel spin coating
technique is simple and it’s not difficult to fabricate ZnO films. Furthermore, the sol-gel spin
coating technique also has good composition controllability and it’s easy to coat a desired shape or
area [10, 11]. For these reasons, the sol-gel spin coating technique is usually utilized to fabricate

Received March 31, 2016. Accepted July 25, 2016.

Contact Nguyen Dinh Lam, e-mail address: [email protected]

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ZnO films. In this work, Al-doped ZnO films were deposited on glass substrates. The Al doping
concentration varied from 0% to 5%. The influence of the Al content on the structural, optical,
and electrical characteristics of ZnO films was investigated in detail.

2. Content
2.1. Experimental details
Using zinc acetate dehydrate (Zn(CH3 COO)2 .2H2 O) as a precursor, isopropanol (IPA) as a
solvent and diethanolamine (DEA) as a stabilizer, ZnO films were prepared. Appropriate amounts
of aluminum (Al) doping were achieved by adding aluminum nitrate to the precursor solutions
with Al/Zn molar ratios of 0.0, 0.5, 1, 1.5, 2, 2.5, 3 and 5%. The solutions were stirred at room
temperature for 2 hours to obtain homogeneous solutions. The obtained solutions were deposited
on glass substrates using a spin coating system. Before film deposition, all contaminates were
removed from the glass substrates by an NaOH solution, methanol and deionized water. The
solutions were dropped onto glass substrates and spun at 3000 rpm for 30 s for all films. After
deposition, the obtained films were dried at 150 ◦ C for 20 minutes in an oven to evaporate the
solvent and remove organic residuals. The procedures from coating to drying were repeated five
times to get a desire thickness of ZnO films. After the coating procedure, the films were annealed
at 500 ◦ C for 1 h in air using an electric furnace.
The structure, surface morphology, optical spectra and I-V curves were determined using
a D5000 X-Ray Diffractometer with Cu.Kα radiation (λ = 1.5406 Å), a Scanning Electron
Microscope (SEM), an UV-VIS-NIR spectrophotometer in the wavelength range of 300 - 800 nm
at room temperature, and a Keithley 2000 multimeter, respectively. For electrical measurements,
silver paste was used to create ohmic contact. A mercury lamp was used to evaluate the
photoconductivity response of the fabricated sample.

2.2. Results and discussion

The structures of the ZnO films were characterized using a X-ray Diffractometer as shown
in Figure 1. All of the peaks shown in the X-ray diffraction patterns (XRD) are sharp and
narrow peaks and closely match that of the hexagonal wurtzite ZnO structure. Diffraction peaks
related impurity phases were not observed in the XRD patterns. A small variation of interplaner
spacing (dhkl) of Al doped-ZnO from that of ZnO is also observed which implies that aluminum
incorporates into ZnO crystal lattice. This means that doping would induce a distorted crystal
lattice manifested by the displacement of lattice indices. Moreover, the study of peak intensity
also indicates that the ZnO films tend to orient along the c-axis when Al doping concentration
0.9λ
increases. The crystallite size of the films is calculated using Scherrer’s formula d = βcosθ [14],
where d is the crystallite size, λ is the X-ray wavelength (1.54 Å), β is the full width at half
maximum (FWHM) and θ is the diffraction angle. The calculation indicates that average grain size
is slightly reduced with the increase in Al-doping amount which might be due to the substitution
of smaller Al atoms at the Zn sites in the lattice of ZnO [12, 13].

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 N. D. Lam, T. T. Mui, L. T. Trang, P. V. Vinh, V. V. Cuong and N. V. Hung

Figure 1. XRD patterns of fabricated ZnO films

Figure 2 shows SEM images of fabricated ZnO thin films on glass substrates with different
Al doping amount. The surface morphology of the films is strongly dependent on the Al doping
concentration. The fabricated films are formed by many round nanoparticles. The particle size is
bigger when the doping concentration of aluminum increases. Therefore, the surface of the films
is rougher when the Al doping concentration increases.

Figure 2. SEM images of ZnO films

Figure 3 (a) shows the optical transmittance spectra of the films in the wavelength range
of 300 - 800 nm at room temperature. As seen in Figure 3 (b), the average transmittance of the
films in the visible region is higher than 95%. And, the highest average transmittance was obtained

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when the Al doping concentration is 1%. Furthermore, the absorption edges of the doped thin films
exhibit a blue shift. For estimating the band gap energy (Eg) of the fabricated films, the (αhν)2
= β(hν - Eg )m relationship is utilized [14] where, α is the absorption coefficient, β is a constant
and hν is the photo energy. The ZnO is a direct band gap semiconductor so m is chosen as 12 [14].
The absorption coefficient α of the films is calculated from the transmittance spectra using the
equation α = 1/t ln(1/T), where t is the thickness of film and T is the transmittance [14]. The band
gap energy Eg is determined by extrapolating the linear region of (αhν)2 versus the photo energy
in the Figure 3 (c) and depicted in Figure 3 (d). The optical band gap energy is enlarged from 3.21
to 3.31 eV when Al doping concentration is increased from 0% to 5%. The enlargement in the
optical band gap energy can be attributed to the Burstein-Moss effect [15].

Figure 3. (a) Optical transmittance spectra of the ZnO films,

(b) Average transmittance of the films vs. Al doping concentration,
(c) The plots of (αhν)2 vs. photon energy of the ZnO films,
(d) Optical band gap energy of the films vs. Al doping concentration

The measured dark and illuminated I-V characteristics of the 1% Al doped-ZnO thin film
are shown in Figure 4. The I-V curves show ohmic and quasi-liner behavior in the dark and under
illumination. The current at a given voltage for the film in the dark is lower than that when under
illumination. Therefore, the film shows good photoconductivity response. The influence of light
on the electrical characteristics of the film indicates that fabricated ZnO films can be utilized as a
photovoltaic material.

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 N. D. Lam, T. T. Mui, L. T. Trang, P. V. Vinh, V. V. Cuong and N. V. Hung

Figure 4. I-V plots of 1% Al doped-ZnO thin film in the dark and under illumination

3. Conclusion
Undoped and Al-doped ZnO thin films were successfully deposited on glass substrates
using the sol–gel spin coating method. The structural, optical, and electrical characteristics of
these films were investigated. The XRD results show that all films crystallize as a hexagonal
wurtzite structure having a preferential orientation along the c-axis as the Al doping concentration
increases. The average transmittance of all films is over 95% in the visible range and 1% of
the Al doped-ZnO film show the highest value. Al doping has an influence on the energy
band structure of ZnO which is illustrated by a change in the optical band gap energy. The
measured I-V characteristics of the 1% Al doped-ZnO thin film indicate that the film has good
photoconductivity response. These results show the potential use of Al-doped ZnO thin film for
different optoelectronic and photovoltaic devices.
Acknowledgments: This research was funded by Vietnam National Foundation for Science
and Technology Development (NAFOSTED), Grant number 103.99-2014.60.

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