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Physics Procedia 32 (2012) 687 – 695

18th International Vacuum Conference (IVC-18)

Effects of oxygen flux on the aluminum doped zinc oxide thin

films by direct current magnetron sputtering
L. N. Lia, Y. Zhaob, X. L. Chenb, J. Sunb, X. D. Zhangb,a*
a
Tianjin Economic-Technological Development Aera Polytechnic, Electronic Information College, Tianjin300457, China
b
Institute of photo-electronic thin film devices and technique of Nankai University, Key Laboratory of photo-electronic thin film
devices and technique of Tianjin, Key Laboratory of Optoelectronic Information Science and Technology, Chinese Ministry of
Education, Tianjin. 300071. China

Abstract

Aluminum doped zinc oxide (AZO) thin films were prepared by direct current (DC) magnetron sputtering with pure
argon gas on glass substrates, usually showed relatively low transmission in our experiments. It was unfavorable for
AZO as front electrode for silicon thin film solar cells. In order to increase the transmission of AZO thin films, we
tried to add oxygen gas into vacuum chamber during sputtering processes. The microstructures, optical and electrical
properties of AZO films were investigated. During the process of sputtering, the O2 flow rate indicated a greater
negative impact on the electrical properties of AZO thin films than the improvement of optical properties. Raman
peak related to zinc interstitial atoms (560cm-1) was observed in the AZO thin films grown with different O2 flow
rates. With the increasing of O2 flow rate, intensity of Raman peak at 560cm-1 decreased. When the O2 flow rate
increased, more O atoms involved in the process of reactive sputtering, and O and Zn interstitial atoms combined to
Zn-O bond, which reduced the Zn interstitial atoms. The transmission between 400 nm and 1100 nm was enhanced
by the increase of O2 flow rate. The average transmissions of AZO thin films were more than 90% in the visible and
near-infrared range and the resistivity of these films increased acutely.

©2012
© 2011Published
Published by Elsevier
by Elsevier Ltd. Selection
B.V. Selection and/or
and/or peer peer-review
review under responsibility
under responsibility of [name
of Chinese Vacuum organizer]
Society (CVS).

Keywords: zincoxide; O2 flow rate; magnetron sputtering; solar cell

1. Introduction

Silicon thin film solar cells in the p-i-n (superstrate) structure require transparent conductive oxide
(TCO) films as their front electrodes, which combine low series resistance and high transparency in the

* Corresponding author. Tel.: 022-60662816; fax: 022-60662345.

E-mail address: llnnankai@yeah.net

1875-3892 © 2012 Published by Elsevier B.V. Selection and/or peer review under responsibility of Chinese Vacuum Society (CVS).
doi:10.1016/j.phpro.2012.03.619
688 L.N. Li et al. / Physics Procedia 32 (2012) 687 – 695

visible (400-800 nm) and near-infrared (800-1100nm) range [1]. ZnO receives growing attention as a
TCO for silicon based thin film solar cells because it combines excellent transparencies, electrical
properties and high durability against hydrogen plasmas. Moreover, industrial applications need cost
effective deposition techniques like magnetron sputter of aluminum doped zinc oxide thin films.
In some case, when AZO thin films were prepared by pure argon gas with ceramic target, they had
relatively low transmission. In order to improve the optical property of AZO thin films, many
experiments have been done such as substrate temperature, post-deposition annealing, hydrogen flux rate,
and so on [2]. This paper addressed the electrical and optical properties of AZO films prepared using
direct current (DC) magnetron sputtering with various O2 flow rates on general floating glass. We
investigated the influence of O2 flow rates on the AZO thin films properties. The role of the O2 flow rates
as one decisive process parameter was studied for AZO thin films on the optical and electrical properties.

2. Experimental details

In this experiment, AZO films were deposited by direct current magnetron sputtering system. These
thin films were grown on general float glass substrates at 200 ć using a high purity ZnO ceramic target
with 2wt. % Al2O3. Before deposition, the glass substrates were ultrasonically cleaned in acetone, ethanol,
and de-ionized water sequentially. Immediately after cleaned, the glass substrates were loaded into the
chamber followed by evacuation. The target to substrate distance was fixed at 45 mm and the flow of pure
Ar gas was set at 45 sccm as a constant. The base pressure of the sputtering chamber was below 2.4×10-
4
Pa, and the working pressure was kept constant at 1.5 mTorr. During the sputtering, the sputtering power
of direct current source was kept at 0.5A. A series of AZO films were deposited with different O2 flow
rates, the thickness of these films were 1­m, more or less.
Transmission at normal incidence in the UV, visible, near-IR and IR regions was measured on Cary
5000 double beam spectrophotometer at room temperature. From the Hall measurements, the type of
conduction, Hall mobility and carrier concentrations were determined. The Hall measurements were made
with Accent HL5500 Hall System. The structural properties were determined with Xƍ Pert PRO X-ray
diffract meter. The thicknesses of these films were measured by Dektak 150 step meter. The atomic ratio
of Zn, Al and O was tested by ThermoFisher K-alpha X-ray photoelectron spectroscopy.

3. Results and discussion

3. l. Structural properties
Fig. 1 shows the X-ray diffraction spectra of ZnO: Al films deposited on general float glass substrates
at the same deposition conditions. During the deposition, the O2 flow rate was kept at 0, 0.5, 1.0, 1.5 and
2.0 sccm, respectively. X-Ray diffraction analysis indicated that the deposited films were polycrystalline,
hexagonal wurtzite structure. In these AZO thin films, only ZnO phase was detected from the X-ray
pattern, which implies that aluminum replaced zinc substitution in the lattice. From the X-ray patterns, it
can be seen that the AZO films exhibit a (002) preferred orientation. With increasing O2 flow rates the
locations of the measured diffraction peaks do not change significantly, and they become more intense.
This means that the crystallization of the resulted films was improved and the position of (002) peak
become larger with elevating O2 flow rate. The (002) peak position and intensity of AZO films deposited
at various O2 flow rates conditions were showed in Fig. 2. The larger diffraction angles shift to a
significant of compressive stress with increase of O2 flow rate [3]. During the sputtering process, vacuum
which leaded to oxygen gas, some oxygen molecules were ionized oxygen ions. Oxygen ions with high-
energy bombarded glass substrate lead to the increasing of compressive stress of AZO thin films. In
addition, this leads to a lower oxygen vacancies presence in the film grown from ceramic target.
 L.N. Li et al. / Physics Procedia 32 (2012) 687 – 695 689

Fig.1.X-ray diffraction spectra of AZO films deposited on glass substrate with different O2 flow rates

Fig.2. (002) peak position and intensity of ZnO: Al films as a function of O2 flow rates
690 L.N. Li et al. / Physics Procedia 32 (2012) 687 – 695

Figure 3 shows Raman spectra of AZO thin films on generally float glass substrate with various O2
4
flow rates. As one knows that ZnO has wurtzite symmetry with c6X or 6 mm symmetry. There are four
atoms per unit cell leading to 12 phonon branches, 9 optical, and 3 acoustic [4]. In this experiment,
Raman peak related to zinc interstitial atoms (560cm-1)[5] was observed between 200 cm-1 and 700 cm-1
in the AZO thin films grown with different O2 flow rates. With the increasing of O2 flow rate, intensity of
Raman peak at 560cm-1 decreased. When the O2 flow rate increased, more O atoms involved in the
process of reactive sputtering, O and Zn interstitial atoms combine to Zn-O bond, resulted in Zn
interstitial atom reduced. This phenomenon of the existence metallic Zn in AZO thin films achieved by
sputtering method has never been observed by XRD analysis. This may be due to the limited content of
interstitial Zn noticed in AZO thin films, which is beyond the sensitivity of XRD analysis. Zn atoms may
be segregated around grain boundaries [6, 7].

Fig.3. Raman spectra of AZO films with different O2 flow rates

3.2. Chemical state

Fig. 4 showed XPS data of Zn 2p3/2 in AZO thin films with different O2 flow rates. AZO thin film
sputtered in pure argon gas exhibited a little asymmetry, which was related to the presence of excess zinc
in the AZO thin film [8]. Then, AZO thin film prepared with 2.0 sccm oxygen gas displayed high
symmetry, indicating that zinc atom was combined to oxide with oxygen atom.
Fig. 5 was XPS spectrum of Al 2p3/2 information in AZO thin films sputtered in both pure argon
atmosphere and 2.0 sccm oxygen gas. The line shown asymmetry feature with a boarder FWHM, it
contained a multi-state Al, possibly. The low binding energy peak at 72.9f0.15eV is corresponded to
metallic Al. The relative intensity of metallic Al characteristic peak of AZO thin film sputtering in pure
argon atmosphere was stronger than prepared in induced 2.0 sccm oxygen gas into vacuum during
sputtering process. It was indicated that part of Al element exists in AZO film as metallic state, it may be
as interstitial atom and provide electron to electrically active, principally segregated around grain
boundary. When addition oxygen gas was introduced into vacuum during sputtering process, more
 L.N. Li et al. / Physics Procedia 32 (2012) 687 – 695 691

metallic Al atom combined with oxygen to oxide and become electrically inactive. Therefore, the
intensity of high binding energy of Al 2p3/2 loaded at 74.3f0.15eV attributed to Al3+ was higher in AZO
thin film which was sputtered with 2.0 sccm oxygen gas.
Fig. 6 was XPS data of O 1s spectrum in AZO thin films sputtered in pure argon atmosphere and 2.0
sccm oxygen gas, respectively. The typical chart was fitted by two peaks, centered at 531.25f0.15eV
and 530.15f0.15eV, respectively. The composition of O 1s peak at 530.15f0.15eV is related to O2- ions
with Zn2+ ion array in hexagonal wurtzite structure, encircled by Zn(or the substitution of Al) atoms with
their full complement of nearest-neighbor O2- ions[9,10,11]. It means that, the intensity of this
composition is the standard of the amount of oxygen atoms, which were surrounded with metallic Zn
atoms in a fully oxidized stoichiometric. The peak, centered at 531.25f0.20eV attributed to O2- ions in
the oxygen deficient regions within the lattice of ZnO [12]. So, the intensity of this composition
connected to the changes in the concentration of oxygen vacancies, in part. The total O 1s content
presented small change with different O2 flow rates. The binding energy of Al2O3 was smaller than ZnO,
it demonstrated oxygen atom combined with Al atom relatively easier, compare with Zn atom. Therefore,
with O2 flow rate increasing, the peak relate to oxygen vacancies increased, and more oxygen existed in
AZO thin films and electrically inactive.

Fig. 4. XPS data of Zn 2p3/2 in AZO thin films with different O2 flow rates
692 L.N. Li et al. / Physics Procedia 32 (2012) 687 – 695

Fig. 5. XPS data of Al 2p3/2 in AZO thin films with different O2 flow rates

Fig. 6. XPS data of O 1s in AZO thin films with different O2 flow rates

3. 3. Electrical properties
In AZO thin films, interstitial atom, aluminum substitute zinc in the lattice and oxygen vacancy, all of
these provide the carriers to the conductive properties of AZO thin films. Fig. 7 showed the O2 flow rate
dependence of the resistivity ȡ, carrier concentration n and hall mobility ȝ of AZO thin films on general
float glass substrates.
The resistivity increased from 6.138×10-4ȍ·cm to 6.427×10-2ȍ·cm with increasing of O2 flow rate,
and carrier concentration changed from 1.213×1021cm-3 to 6.033×1019cm-3 and hall mobility decreased
from 8.38 cm2·V-1·s-1 to 1.61 cm2·V-1·s-1 monotonically. This observation can be interpreted as follows:
with O2 flow rate increases, it leads to more O atoms involved in the process of reactive sputtering,
oxygen atom combined to metal oxide with metal, Zn interstitial atoms decreased, as shown in Raman
test result (fig.3). Consequently, the interstitial Zn atom, which was combined with oxygen to oxide loss
electrically active, could not provide the electrons to conductivity. Furthermore, metallic Al atoms were
combined with oxygen atoms to oxides, at the same time. The Al atom with electrically active decreased,
we can also observed the phenomenon in XPS test pattern (fig.4-fig.7). Then, the carrier concentration
decreased attributed to oxygen atom and metal atoms combine to metal oxide. And moreover, there were
 L.N. Li et al. / Physics Procedia 32 (2012) 687 – 695 693

more oxygen vacancies in AZO lattice as center of impurity scattering, as result, the Hall mobility
decreased.

Fig.7. Resistivity ȡ, Carrier concentration n and Hall mobility ȝ as a function of O2 flow rates

3. 4. Optical properties
Fig.8 showed the transmittance vs. wavelength and optical band gap of AZO thin films with O2 flow
rates at 0, 0.5, 1.0, 1.5 and 2.0 sccm, respectively. All AZO films showed average more than 90% optical
transmission in the visible range, and the thicknesses of films were 1­m, more or less. This was
important for applications such as transparent conductive films and solar cell windows. The transmission
was increased with in increasing O2 gas flow rate, when the wavelength was above in the near-infrared
and infrared range. The sharp absorption edges were observed in all of the thin films. This means that
AZO thin films deposited on glass substrates by sputtering are of high optical quality.
As a direct band gap semiconductor, the absorption coefficient Į is proportional to –lnT. Therefore, we
made a plot of [Įh(h®)]2 against the photon energy h®. The sharp absorption edge can be accurately
determined for the high quality thin film by a linear fit. The band gap energies (Eg) of the thin films were
calculated by fitting the sharp absorption edges and shown in fig. 8. It is found that band gap energies of
AZO thin films decreased monotonously with increasing O2 gas flow rates, from 3.74eV to 3.35eV. All of
them were larger than the band gap of ZnO in bulk at 300K. The optical absorption edge shifts with the
carrier concentration n could attribute to the Burstein-Moss effect [13].
694 L.N. Li et al. / Physics Procedia 32 (2012) 687 – 695

Fig.8. Transmittance vs. wavelength of AZO thin films and optical band gap of AZO thin films with various O2 flow rates.

4. Conclusion

Aluminum doped zinc oxide thin films were prepared by direct current magnetron sputtering with
various O2 flow rates on general floating glass. High purity ceramic ZnO: Al2O3 target and O2 gas were
used as source materials. The O2 flow rate gave far greater negative impact on the electrical properties of
AZO thin films than the improvement of optical properties. The optical and electrical properties,
microstructure information of AZO films were investigated. In this experiment, it was observed Raman
peak related to zinc interstitial atoms (560cm-1) in the AZO thin films grown with different O2 flow rates.
With the increasing of O2 flow rate, intensity of Raman peak at 560cm-1 decreased. When the O2 flow rate
increased more O atoms involved in the process of reactive sputtering, O and metallic interstitial atoms
combine to metal oxide, resulted in metallic interstitial atom reduced, conductance of AZO thin films
decreased acutely. The transmission between 400 nm and 1100 nm was enhanced by the increase of O2
flow rate. The average transmissions of AZO thin films were more than 90% in the visible and near-
infrared range.

Acknowledgements

This work is supported by National Basic Research Program of China (Grant No.2006CB202602,
No.2006CB202603), Project of Hi-Tech Research and Development Program of China (2009AA050602),
and International Cooperation Project between China-Greece Government (2006DFA62390,
2009DFA62580), China Tianjin Applied Basic Research Projects & Cutting-edge Technology Research
Plan (No. 09JCYBJC06900), Nankai University science & technology Innovation project and TEDA
Polytechnic technology service & Innovation project.
 L.N. Li et al. / Physics Procedia 32 (2012) 687 – 695 695

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