Bull. Mater. Sci., Vol. 33, No. 2, April 2010, pp. 119–122. © Indian Academy of Sciences.
Properties of Nb-doped ZnO transparent conductive thin films deposited
by rf magnetron sputtering using a high quality ceramic target
J W XU, H WANG, M H JIANG* and X Y LIU
Guangxi Key Laboratory of Information Materials, Guilin University of Electronic Technology,
Guilin 541004, China
MS received 2 January 2009; revised 25 March 2009
Abstract. Nb-doped ZnO films with (002) orientation have been grown on glass substrates by rf magnetron
sputtering followed by vacuum annealing at 400°C for 3 h. The microstructures and surface figures of the Nb-
doped ZnO films were investigated with X-ray diffraction (XRD) and scanning electron microscopy (SEM),
respectively. And its optical and electrical properties were measured at room temperature using a four-point
probe technique and 756-type spectrophotometer, respectively. X-ray diffraction (XRD) revealed that the
films are highly textured along the c axis and perpendicular to the surface of the substrate. After annealing at
400°C for 180 min under vacuum, transmittance of about 90% in visible region for Nb doped ZnO films was
confirmed by the optical transmission spectra, and the low resistivity of 5⋅47 × 10–3 Ω·cm was obtained.
Keywords. ZnO films; Nb-doped; magnetron sputtering; optical and electrical properties.
1. Introduction on, has been attempted by many groups, resulting in
high-quality, highly conductive n-type ZnO films (Cao
Transparent conducting oxides (TCOs) have found appli- et al 2004; Özgü et al 2005). Recently, n-type ZnO films
cations in several optoelectronic devices such as light doped with other elements such as rare earth, W, Zr and
emitting diodes (LEDs), solar cells, and flat panels as so on has been prepared by different methods (Swanepoel
well as flexible displays (Srikant and Clarke 1998; Cui et 1983; Sarkar et al 1991; Fujimura et al 1993). To our
al 2005; Hsieh et al 2007). Indium tin oxide (ITO) is the knowledge, there is no report for single Nb doped ZnO
most commonly used TCO for these applications because films. In this paper, we report Nb-doped ZnO films
of its high transmittance in the visible region and a resis- grown on glass substrates at room temperature by rf
tivity close to 1⋅0 × 10–4 Ω⋅cm (Paraguay et al 1999). magnetron sputtering and post vacuum annealing process.
However, high cost and scarce resources of In limit its
usage in these devices. This has led researchers to
explore alternative materials for the TCO applications. 2. Experimental
Some of the TCOs which have shown transmittance and
resistivity values close to those of ITO are ZnO : Al, 2.1 Preparation of ceramic targets
ZnO : Ga, F : SnO2, Nb : TiO2 and so on. Among these,
ZnO is the most favourable material because of its benign The raw materials were the commercially available ZnO
nature, relatively low cost, good stability in hydrogen and Nb2O5 (99⋅95% in purity). Mechanical mixed powders,
plasma process, and non-toxicity (Paraguay et al 1999; as the raw materials, were treated by die pressing and
Joseph et al 2001). After doping, ZnO as a semiconductor normal pressing, and then sintered at 1300°C for 4 h in
will become conductive. Therefore, there is a consider- air. The following compositions were chosen: 98%
able interest in understanding the electrical and transport ZnO + 2% Nb2O5 (wt%). The linear shrinkage ratios of
properties of doped ZnO films, which is critical for fur- the sintered targets reached about 22% and the relative
ther improvement of TCOs characteristics. density was about 95%.
Most of the careful doping studies have been per-
formed by the kinds of techniques in order to improve the 2.2 Preparation of thin films
performance of ZnO films (Srikant et al 1995; Tang et al
1998; Paraguay et al 1999; Minami et al 2001; Dang et al
Room temperature deposition of high quality transparent
2007; Saito et al 2007). Doping with Al, Ga, In and so
conductive thin films is an advantage to industrial pro-
duction. Nb-doped ZnO thin films were deposited on
*Author for correspondence (jmhsir@[Link]) glass substrates using the ratio frequency (rf) magnetron
119
120 J W Xu et al
sputtering technique. The glass substrates were tho- The results of these doped thin films are in good agree-
roughly cleaned ultrasonically using ethanol absolute, ment with those reported in PDF for ZnO (PDF75-576,
acetone and distilled water as solvents and then dried a = 0⋅324270 nm, c = 0⋅519480 nm), and the peaks corre-
prior to be loaded into deposition chamber. Sputtering spond to a hexagonal wurtzite structure. Only the (002)
was carried out at room temperature with a target– peaks are observed in the XRD patterns, which show that
substrate distance of 67 mm and a sputtering gas pressure the films are highly textured along the c-axis and perpen-
of 1⋅6 Pa. The chamber was evacuated to a base pressure dicular to the surface of the substrate.
of 8 × 10–5 Pa. A sputter-etch of 15 min was used to
remove the target surface contamination. Finally, argon
gas was introduced, and the gas pressure was adjusted.
The substrate temperature was at room temperature. The
sputtering power was 110 W. In order to produce more
oxygen vacancies, oxygen was not used during the depo-
sition. The samples were annealed at 400°C for 3 h under
vacuum (~ 10–1 Pa). The thickness of the films was about
500 nm.
Crystallographic and phase structures of the as-grown
Nb-doped ZnO films were determined by X-ray diffrac-
tion (XRD) (D8-Advance) with CuKα radiation. The
scanning electron microscope (SEM) (JSM-5610LV) was
used to investigate the surface morphology and measure
the thickness of the films. Optical measurements (absorp-
tion and transmission) were made for photon wavelengths
ranging from 300–900 nm, using a spectrophotometer
(UV-756). During the spectrum testing, as a contrast the
absorption spectrum of the bare substrate was already
eliminated. The electrical resistivity was measured using
a four-point probe technique (RTS-8) at room tempera-
ture.
3. Results and discussion
3.1 Structural studies
Figure 1 shows the X-ray diffraction (XRD) patterns of
the Nb-doped ZnO films prepared at room temperature.
Figure 2. SEM micrographs of Nb-doped ZnO thin films: (a)
deposited at room temperature; (b) annealed at 400°C for 3 h
Figure 1. XRD diffraction patterns of Nb-doped ZnO thin films. under vacuum and (c) the cross-section of the thin film (a).
Properties of Nb-doped ZnO transparent conductive thin films 121
The Nb-doped films obtained exhibited smooth, uni- bandgap semiconductor, the optical bandgap, Eg, can be
form, and dense surface morphology, as shown in figure determined by the following equation (Sarkar et al 1991)
2. In order to calculate the particle size, g, of the Nb-
α = A(hν – Eg)1/2, (2)
doped films we have used the Scherrer formula
(Moustaghfir et al 2003) where A is a constant dependent on the electron–hole
mobility, α the absorption coefficient, as a function of the
0.94λ
g= , (1) photon energy, hν. α is given by the formula (Swanepoel
B cos θ B 1983)
where λ, θB and B are the X-ray wavelength (1⋅54056 Å), α = (ln 100/T)/d, (3)
Bragg diffraction angle and line width at half maximum.
where T is the optical transmittance, d the film thickness.
The crystallite size is in the range 15–20 nm.
The values of the optical energy gap (Eg) is determined
by extrapolating the linear portion of the curves to α = 0.
3.2 Photoelectric properties By comparing with pure ZnO (the optical bandgap
≈ 3⋅37 eV), a shift from 3⋅37–3⋅20 and 3⋅30 eV for the
The transmission spectra of the doped ZnO thin films films deposited and annealed, respectively was observed.
(with glass substrate) prepared at room temperature is This is similar to the report of Kim and Park (2002) who
shown in figure 3. In the visible region, all films perform observed the bandgap shift from 3⋅25–3⋅13 eV for Co
high average transmittances that are more than 90% at doped ZnO film (8% doping concentration), and of Lin et
wavelengths above 500 nm. The transmission curve for al (2008) who observed the bandgap shift from 3⋅58–
the bare substrate is also shown in figure 3. Evidently, the 3⋅45 eV for Gd doped ZAO film (1 wt.% Gd doping con-
absorption edge of the bare substrate is away from that of centration). There seems to be an increase in refractive
the film, and the absorption edge of the film is within the index on annealing as seen by the appearance of fringes
light-admitting range of the bare substrate. In the visible in figure 3. It is attributed to the amplitude of the oscilla-
region, the film annealed shows the average transmittance tions obtained in the envelope of the film at 400°C
of the order of 90%, while the film as-deposited was of annealing temperature corresponding to good-quality
the order of 95%. It illustrates that the annealing reduces film, seen from figure 1.
the optical properties. It is caused by diffusing of Nb5+ The doped ZnO film shows transition from insulator to
into the ZnO layer to partially substitute Zn2+ sites at high metallic behaviour. The low resistivity value of 5⋅47 ×
annealing temperature and forming of an impurity energy 10–3 Ω⋅cm for the Nb-doped ZnO thin film was obtained
level. So a part of visible light is absorbed by exciting the by an annealing process of 400°C for 3 h. But before
electrons of the impurity level into conduction band. annealing, the Nb-doped ZnO film exhibits an insulating
Figure 4 shows plot of α2 as a function of photon property. This indicates that an optimal annealing process
energy against hν of the Nb doped films. As a direct will improve the electrical conductivity by increasing
2
Figure 3. Optical transmission spectra of Nb-doped ZnO thin Figure 4. Plots of (αhν) against hν for Nb doped ZnO thin
films. films.
122 J W Xu et al
the oxygen defects and reducing the grain boundary Laboratory of Information Materials for supporting this
scattering (Lin et al 2008). This result is similar to the research under the 200807LX121 and 0710908-09-Z
argument of Han (2002). For further improvement of grants, respectively.
properties of the Nb-doped ZnO thin film, increasing
sputtering powder and substrate temperature were useful
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