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Workfunction tuning of zinc oxide films by argon sputtering and oxygen plasma: an experimental and computational study

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 2012 J. Phys. D: Appl. Phys. 45 065301 (http://iopscience.iop.org/0022-3727/45/6/065301) View the table of contents for this issue, or go to the journal homepage for more

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IOP PUBLISHING J. Phys. D: Appl. Phys. 45 (2012) 065301 (7pp)

JOURNAL OF PHYSICS D: APPLIED PHYSICS doi:10.1088/0022-3727/45/6/065301

Workfunction tuning of zinc oxide lms by argon sputtering and oxygen plasma: an experimental and computational study
Fang-Ling Kuo, Yun Li, Marvin Solomon, Jincheng Du and Nigel D Shepherd
Department of Materials Science and Engineering, University of North Texas, Denton, TX 76203, USA

Received 30 July 2011, in nal form 20 November 2011 Published 27 January 2012 Online at stacks.iop.org/JPhysD/45/065301 Abstract Zinc oxide (ZnO) lms were grown by radio frequency magnetron sputter deposition and the changes to its surface composition and workfunction induced by argon sputter cleaning and oxygen plasma treatments were characterized using x-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy and density functional theory modelling. Compared with a workfunction of 3.74 eV for the as-deposited ZnO lms, a workfunction of 3.95 eV was obtained after Ar sputter cleaning and 4.21 eV after exposure to oxygen plasma. The data indicate that oxygen plasma treatment leads to a more negative ZnO surface. The dipole induced by this charge redistribution reinforces the original surface dipole, which results in an increase in the surface dipole moment and an increase in workfunction. The reverse is true for hydrocarbon contamination of ZnO surfaces. Excellent qualitative agreement between the experimental results and computational modelling was obtained. The results suggest that specic surface functionalization may be a viable method of controlling the workfunction of ZnO for use as the transparent conducting oxide in optoelectronic applications such as solar cells and organic light-emitting diodes. (Some gures may appear in colour only in the online journal)

1. Introduction
Zinc oxide (ZnO) thin lms are being widely investigated for a variety of optoelectronic applications including the channel layer in transparent thin-lm transistors [1, 2], the active material in light-emitting diodes (LEDs) [3, 4], and transparent conducting oxide (TCO) electrodes [5, 6] in organic lightemitting diodes (OLEDs) and solar cells. The standard TCO material used in OLEDs and solar cells is indium tin oxide (ITO). However, given the Earths reserve of indium which is only approximately 6000 ton [7], and when it is considered that solar cells must to be deployed on a Terawatt scale to have a noticeable impact on energy needs [8], then the need for TCOs constituted from Earth-abundant elements becomes obvious. In this regard, the potential use of ZnO as a TCO is an attractive proposition and understanding its surface properties is therefore critical. More specically, it is expected that the ability to tune the workfunction of TCO ZnO lms will facilitate control of the charge outcoupling efciency in solar
0022-3727/12/065301+07$33.00

cells, and control of the charge (hole) injection efciency in the case of OLEDs. The wurtzite crystal structure of ZnO is the most thermodynamically stable variant under atmospheric conditions, and is therefore the most common. It exists with non-polar (1 0 1 1) surface termination, with polar (0 0 0 1) O-termination, and with polar (0 0 0 1) Zn-terminated surfaces [9], which results in termination-dependent chemical reactivity [10]. Exposure of ZnO lms to normal atmospheric conditions leads to surface contamination by adventitious hydrocarbon and hydroxyl species [5, 11], and the presence of these chemisorbed and physisorbed groups typically leads to changes in the electronic properties of the surface such as its workfunction and sheet resistance. Treatments to remove surface contamination such as UVozone, Ar sputtering and oxygen plasma have been reported to themselves induce additional, sometimes unpredictable changes to the electrical properties [5, 10, 11]. However, the specic mechanisms that are responsible for the changes in surface electrical properties remain highly debated.
1
2012 IOP Publishing Ltd Printed in the UK & the USA

J. Phys. D: Appl. Phys. 45 (2012) 065301

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Here, x-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) were used to investigate changes to the workfunction and chemical composition of RF magnetron sputtered ZnO thin lms, induced by Ar sputtering and oxygen plasma treatment. To develop deeper insights into the mechanisms involved, rst-principle calculations based on density functional theory (DFT) were performed to model the effects of hydrocarbon contamination, and oxygen enrichment and deciency on the workfunction of ZnO surfaces. Excellent agreement between the experimental data and the computational results was obtained.

charging. An Oriel MS257 spectrophotometer was used to measure the transmittance of the lms over the 2001000 nm spectral range. The incident light beam was normal to the sample.

3. Computational method
DFT calculations were performed using the Vienna Abinitio Simulation Package (VASP) with standard generalized gradient approximation (GGA) exchange and correlation functionals with the Perdew, Burke and Enzenhofer (PBE) parametrization. Cleaved surfaces were prepared based on fully relaxed super cells, each with eight layers of Zn, eight layers of O, and a 15 thick vacuum above the cleaved surface. In order to mimic the bulk structure beneath the surface, the atoms of the bottommost two layers were xed while the upper layers were allowed to be fully relaxed until the forces acting on each atom were smaller than 0.01 eV 1 . Due to the difference in cell sizes of the simulated surfaces, reciprocal space K point sampling for integrations was performed on 4 2 1 grids for neutral surfaces (e.g. (1010)) and on 4 4 1 grids for polarized surfaces (e.g. (0 0 0 1)). We used methyl groups as a surface carbon source to investigate the effect of hydrocarbon contamination. The methyl groups were attached to part or all of the surface oxygen atoms on the relaxed surfaces, and subsequently geometry optimization was performed. In order to understand workfunction changes associated with non-stoichiometric surface effects that could result from the Ar or oxygen plasma treatments described above, oxygen or zinc atoms were gradually removed from the surface to represent an oxygen or zinc decient surface.

2. Experiment
ZnO thin lms were deposited onto 2974 Corning glass by RF magnetron sputtering using a 99.99% purity ZnO target and a circular, 2 inch magnetron. The target to substrate separation was 6 cm. Prior to opening the substrate shutter for deposition, the surface of the ZnO target was cleaned by exposure to the plasma for 10 min. The deposition pressure was maintained at 2.66 Pa of argon and the substrate temperature was 100 C. The thickness and electrical properties of the deposited lms were determined with a Veeco Dektak 150 stylus prolometer and an Ecopia HMS 5000 Hall measurement system, respectively. As table 1 shows, deposition at 4.44 W cm2 produced the best combination of electrical conductivity and optical transparency in our laboratory [2]. This deposition power was therefore used for all of the ZnO lms in this study. With the aforementioned deposition conditions a thickness of 300 nm was obtained after 90 min. X-ray diffraction (XRD) was performed using the 1.540 56 Cu K1 line of a Rigaku Ultima III system. A PHI 5000 Versaprobe instrument was used for XPS and UPS characterization. The workfunction of the ZnO surfaces was determined by UPS using He-I 21.22 eV UV light, and their chemical composition was measured by XPS using monochromatic 1486.6 eV Al K radiation. ZnO specimens were deposited onto 1 inch square glass substrates, which were then cleaved into three nominally identical samples for the surface modication experiment. Of the three samples, one was used as a control, i.e. was not subjected to any surface treatment. A second sample was exposed to an oxygen plasma (60 W) for 5 min, which is the typical treatment used in our laboratory for enhancing hole injection from ITO anodes in OLEDs [12, 13]. After oxygen treatment the sample is immediately loaded into the XPS/UPS system for analysis. This process requires 60 to 90 s. The surface of the third sample was subjected to in situ Ar sputter cleaning (2 kV, 2 A) for 5 min in the XPS/UPS system, which is sufcient to eliminate adventitious carbon and hydrocarbons. For the UPS measurements the samples were biased at 9 V dc in order to clearly observe the secondary electron cutoff, and a pure gold specimen was used as a reference to calibrate the workfunction of the spectrometer. The workfunction of the gold specimen was determined to be 4.91 eV. The spectrometer workfunction was 8.7 eV. Metallic clamps that are integrated with the UPS sample holder facilitated electrical contact between the ZnO lms and the body of the spectrometer, and thus eliminated 2

4. Results and discussion

4.1. Experimental The electrical properties and transparency of ZnO lms deposited with different sputtering powers at 100 C are presented in table 1. The lms were all n-type, and as table 1 shows, the lms deposited at 4.44 W cm2 possessed the best combination of electrical and optical properties. Specically, the typical conductivity, mobility and transparency of ZnO lms grown at 4.44 W cm2 were 20.3 1 cm1 , 35.2 cm2 V1 s1 and 80%, respectively. The lms are polycrystalline (wurtzite crystal structure) and exhibit strong (0 0 0 2) texturing as the XRD spectrum in gure 1 shows. Figure 2 is representative of the results obtained from UPS measurements of the control and plasma treated ZnO lms. The workfunction was determined according to = h E, where E is the energy difference between the secondary electron cutoff and the spectrometer workfunction. As is shown in gure 2, the secondary electron cutoff shifted to lower energies with surface treatments. Using the formalism described above, the workfunction of the ZnO control was measured to be 3.74 eV. After exposure to Ar sputtering the workfunction increased to 3.95 eV, and after the oxygen plasma treatment it increased to 4.21 eV. These increases are signicant in the context of interfacial barriers for charge injection or outcoupling.

J. Phys. D: Appl. Phys. 45 (2012) 065301

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Table 1. Electrical conductivity and optical transparency for ZnO lms deposited at different sputtering powers. Power (W cm2 ) 4.44 5.92 7.40 8.88 Carrier concentration (cm3 ) 3.6E + 18 1.7E + 18 2.9E + 18 1.4E + 18 Mobility (cm2 V1 s1 ) 35.2 10.2 26.8 6.3 Conductivity ( 1 cm1 ) 20.3 2.8 12.4 1.4 Transparency (%) 80 80 80 80

34.2(0002)
Sputtered ZnO at 4.44 W/cm2 , 100C

31.3(1010)

20

30

40

50
2 []

60

70

80

90

Figure 1. X-ray diffraction spectrum of ZnO sputter deposited at 100 C. The peaks are labelled with their 2 angles and orientations (in brackets).
2.5x10
7

2.1x10

2.0x10

1.5x10

1.4x10
C/S

1.0x10

5.0x10

7.0x10

0.0 8.8 8.0 7.2 Binding Energy [eV] 6.4

0.0
ZnO without any treatment ZnO with Ar sputtering clean for 5 min ZnO with Oxygen plasma for 5 min

15

10

-5

-10

Binding Energy [eV]

Figure 2. UPS spectra of the ZnO lms without any treatment (blue), after Ar sputter cleaning for 5 min (black), and after oxygen plasma treatment for 5 min (red). The inset is an expanded view of the secondary electron cutoff.

Typical results of the XPS analysis of the control and treated lms are presented in gures 3(a)(c). As gure 3(a) shows, a strong C 1s signal is observed in the as-prepared ZnO lms, which is essentially eliminated after exposure to the oxygen plasma. A carbon signal was not detected after 3

argon sputtering, which was performed in situ. We ascribe the small carbon signal detected in the oxygen plasma treated sample to atmospheric contamination during transfer of the specimen from the oxygen plasma reactor to the XPS/UPS system. The data indicate that both treatments are effective for carbon removal from ZnO surfaces. The strongest carbon peak at 284.8 eV 0.1 eV in the as-deposited/control sample has been allocated to CH or CC bonding, and the weaker peak at 288.8 0.1 eV to C=O or COO groups [14]. Figure 3(b) shows typical XPS O 1s spectra for the investigated samples. The asymmetry in the O 1s peaks is a clear indication that more than one oxygen species is present on the surface. All three of the ZnO samples being compared exhibited a strong signal at 530.2 0.1 eV, which is due to ZnO bonding [9, 14]. A small shoulder due to loosely bound oxygen on the surface of the samples is observed at 532.0 0.1 eV [15] for the as-deposited (control) and oxygen plasma treated samples, but this feature disappears after Ar sputtering cleaning. Yoon and Cho [16] have also shown that Ar sputtering is effective in removing physisorbed oxygen from ZnO surfaces. Analysis of Zn for the control and Ar treated samples shows the core Zn 2p3/2 line at 1021.9 0.1 eV is highly symmetric (gure 3(c)), which is an indication that Zn was present only in the Zn2+ oxidized state. However, the Zn 2p3/2 peak of the sample treated with the oxygen plasma exhibited a shift to a higher binding energy by 0.3 eV. The shift to higher binding energy indicates increased oxidation of Zn, which means that its environment becomes more electronegative with oxygen plasma treatment. We shall return to the signicance of this shift in the section where the computational results of the oxygen plasma treatment are discussed. Metallic Zn which has a binding energy of 1021.5 eV was not detected in any of the samples. A summary of the UPS and XPS results is presented in table 2. The data indicate that both Ar sputtering and oxygen plasma surface treatments increase the workfunction of ZnO lms, with the latter being more effective. The XPS results suggest that in addition to removing carbon, Ar sputtering may also be removing some oxygen as the Zn/O ratio indicates. We hypothesize that the increased workfunction in this case is primarily linked to the removal of carbon contamination, and ascribe the workfunction increase observed with oxygen plasma treatment primarily to oxygenation of the ZnO surface. As such, the observed workfunction increases appear to be related to chemical and physical changes associated with both carbon removal and oxygenation, with the latter process being more effective for increasing the workfunction as table 2 shows. To better understand the mechanisms involved, such as

Intensity [a.u.]

c/s

J. Phys. D: Appl. Phys. 45 (2012) 065301

C without treatment C with oxygen plasma C with Ar sputtering

F-L Kuo et al

Table 2. Summary of the workfunctions, Zn/O ratios, and compositions for the ZnO samples determined by XPS and UPS.
C1s

Workfunction ZnO as deposited ZnO with Ar sputtering ZnO with oxygen plasma 3.74 eV 3.95 eV 4.21 eV

Zn/O ratio (Zn/O/C) 1.05 (39.4/37.2/23.4) 1.19 (54.1/45.2/0.6) 1.02 (47.5/46.7/5.8)

Intensity [a.u.]

295

293

290 288 285 283 Binding Energy [eV]

O1s

280

278

O without any treatment O with oxygen plasma O with Ar sputtering

544 542 540 538 536 534 532 530 528 526 524 522 Binding Energy [eV]
Zn for ZnO without any treatment Zn for Zno with oxygen plasma Zn for ZnO with Ar sputtering

Zn 2p3/2

1035 1033 1030 1028 1025 1023 1020 1018 1015

Binding Energy [eV]

Figure 3. (a) C 1s, (b) O 1s and (c) Zn 2p3/2 XPS spectra for the as-deposited control (blue), oxygen plasma treated (red), and Ar sputter cleaned (black) ZnO samples.

changes induced by the plasma treatments to the charge state of the ZnO surfaces, DFT modelling of carbon removal and oxygenation was performed. 4.2. Computational After full geometry optimization of the model structures as previously described in the simulation method, the 4

workfunction was determined from the electrostatic potentials of the surfaces with respect to a vacuum layer. Figure 4(a) shows the surface slab and electrostatic potential along the z-axis. As it shows, the vacuum potential (Ev ) was taken to be at the half way point of the vacuum slab because at this position the inuence from the adjacent cell was minimized. The workfunction (Wf ) was calculated as the energy difference between the Fermi energy (Ef ) of the surface slab and the vacuum potential (Ev ): Wf = Ev Ef . This method has been widely used in the literature for calculating workfunctions from periodic rst-principles calculations [1719]. In addition to the standard DFT GGA exchange and correlation functional (with PBE parametrization), we have also studied the DFT+U [20, 21] method that usually leads to better description of the bandgaps and other properties compared with standard DFT [22, 23], and has been used to improve the description of systems with strongly localized d electrons as in zinc. Based on the tuning of zinc 3d energy states to experimental values in wurtzite ZnO [24], we chose a Coulomb parameter (U) of 9 in the ZnO calculations. We found that DFT+U had limited effect on the workfunctions of both the polar and neutral surfaces compared with standard DFT GGA, with the difference being less than 0.1 eV. Thus all of the reported surface energy and workfunction values are from the standard GGA PBE [25] functional. Among the three non-polar surfaces studied, the (1 0 1 0) surface had the lowest energy and workfunction, as shown in table 3. Specically, the workfunction of the (1 0 1 0) surface was 4.9 eV. The workfunction of polar O-terminated (0 0 0 1) surface was found to be 4.8 eV, which is lower than the value for non-polar surfaces. In contrast, the surface energy of the polar (0 0 0 1) surface was found to be higher than that of the non polar (1 0 1 0) surfaces. The lowest energy surfaces namely, the non-polar (1 0 1 0) and polar (0 0 0 1) surfaces were then used to study how carbon contamination and non-stoichiometry affected workfunction values. As mentioned earlier, carbon contamination was simulated by adding methyl groups to the fully relaxed surfaces, whereas non-stoichiometry was simulated by adding/removing oxygen from the surface. Figure 4(b) shows the four oxygen surface sites that are available on the non-polar (1 0 1 0) surface in the simulation super cell for bonding to methyl groups. There are four similar sites on the polar (0 0 0 1) surface where methyl groups can bond to oxygen. We gradually increased the number of methyl groups from one to four. This was intended to simulate a gradual increase in surface coverage with carbon. The workfunction was calculated as described above. The calculated workfunction as a function of surface methyl coverage is shown for the (1 0 1 0) surface in gure 5(a) and surface in gure 5(b). In both cases, increasing for the (0 0 0 1)

Intensity [a.u.]

Intensity [a.u.]

J. Phys. D: Appl. Phys. 45 (2012) 065301

F-L Kuo et al

Figure 4. (a) Method of calculating the workfunction shown here for the (1 0 1 0) surface, (b) schematic showing four available O atoms on the surface (1 0 1 0) plane. Table 3. Workfunction and surface energy of ZnO surfaces from DFT calculations. Surface Work function (eV) Surface Energy(eV 2 )
a b c

(0 0 0 1)a 5.1 0.190

(0 0 0 1)b 4.8 0.180

(1 0 1 0)c 4.9 0.124

(0 1 1 0)c 4.9 0.124

(2 1 2 0)c 5.2 0.125

(2 1 2 2)c 5.6 0.240

Polarized surface, Zn terminated. Polarized surface, O terminated. Non-polarized surface.

the surface methyl coverage initially led to a decrease in workfunction compared with the pristine ZnO surface. For the (1 0 1 0) surface, the workfunction decrease saturated at coverage values higher than 0.03(#/2 ). For the polar (0 0 0 1) surface, the largest workfunction decrease was obtained at a coverage of 0.082(#/2 ). The increase in workfunction observed at coverage higher than 0.082(#/2 ) for this surface is due to the fact that at very high coverage (close to monolayer), there is a steric effect between the methyl groups. As a result, one of the methyl groups could no longer bond to the surface oxygen with regular OC lengths (i.e. for a full monolayer coverage of methyl groups on the (0 0 0 1) surface, one methyl group was pushed above the average plane due to a large repulsion from the other methyl groups leading to a large distortion). This strained conguration led to higher surface energy and consequently higher workfunction. In summary, the simulation results clearly indicate that pristine surfaces are characterized by a higher workfunction compared with carbon (methyl) contaminated ones. Increasing the concentration of surface methyl coverage decreased the workfunction until the coverage was very high where repulsion among the absorbed species led to increased surface energies. These results are in excellent agreement with the experimental ndings: removal 5

of surface carbon contamination from the ZnO surface using plasma cleaning increases its workfunction as the UPS data show. The non-polar (1 0 1 0) surface which exhibited the lowest surface energy was used to model the effect of oxygen plasma treatment. We considered the two most likely scenarios that could result from oxygen plasma treatment taking into account that deviations from stoichiometry are normal in as-grown ZnO lms [2, 6], and, the vapour pressure differences between Zn and O. Namely, (1) removal of oxygen resulting in an oxygen decient, zinc-rich surface (ZnO(1x) ) and (2) addition of oxygen creating an oxygen enriched surface (ZnO(1+x) ) i.e. oxygenation. Figure 6 shows the workfunction as a function of composition for both types of surfaces. The zinc rich (ZnO(1x) ) surface was created by generating oxygen vacancies on the surface. It was found that the workfunction decreased with increasing levels of oxygen deciency as gure 6(a) shows. On the other hand, the work function increased with increasing levels of oxygen excess (gure 6(b)). Both types of surfaces suggest that the surface workfunction increases with increasing oxygen to zinc ratio. These ndings are consistent with the UPS and XPS data. Specically, the UPS data show that a chemical shift of the Zn peak to higher

J. Phys. D: Appl. Phys. 45 (2012) 065301

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Figure 5. DFT calculated workfunction variation with methyl group coverage for (a) non-polar (1 0 1 0) and (b) polar O terminated (0 0 0 1) surface.

Figure 7. Charge density difference plots for methyl absorbed on ZnO (a) (1 0 1 0) surface (b) (0 0 0 1) surface. Red is hydrogen; green is carbon; turquoise is oxygen; blue is zinc. Red contour is electron excess; green contour is electron deciency.

Figure 6. DFT calculated workfunction variation with Zn : O ratio of the rst two surface layers (a) ZnO(1x) and (b) ZnO(1+x) . 1 : 1 is the stoichiometric value.

binding energies (see gure 3(c)) is induced by oxygen plasma treatments, which indicates an increase in electronegativity of the Zn environment. This suggests that the surface of the ZnO becomes more negative. The dipole formed from this charge redistribution is pointing in the direction of the original surface dipole, leading to an increase in the surface dipole moment and an increase in workfunction. This is consistent with the prediction that electronegative absorbates would in general increase the workfunction of a surface [26]. No peak shifts of the XPS Zn signal were observed in the Ar sputter cleaned samples, wherein the main effect was hydrocarbon removal. Therefore, charge density calculations of carbon-contaminated surfaces were performed to understand charge transfer between the absorbate and the surface, and to elucidate the change in induced surface dipole moment. The charge difference density was obtained by doing three single point energy calculations based on the nal optimized geometry of the ZnO surface with absorbate. The rst calculation was performed using the surface with absorbate, the second one was of the absorbate only and the third was of the ZnO surface only. The charge difference density was then calculated by subtracting the charge density of the surface only and the absorbate only from the total charge density of the ZnO with absorbate. Figure 7 shows the charge difference density plots of the surface oxygen layer with methyl groups for both non-polar (1 0 1 0) and surfaces. For both surfaces, it is clear that the polar (0 0 0 1) oxygen atoms that bond to CH3 groups show electron density 6

J. Phys. D: Appl. Phys. 45 (2012) 065301

F-L Kuo et al

increases, while the volume around the carbon atom shows that the electron density decreases. This indicates electron transfer from the absorbate to the surface. This transfer of electrons from the absorbate to the ZnO surface leads to an excess of negative charge on the inside and positive charge on the outside of the surface. The dipole thus formed is pointing outwards and opposite the direction of the original surface dipole leading to a change (decrease) of surface dipole moment, which in turn leads to a decrease in workfunction. This is consistent with the prediction that electronegative absorbates would in general increase the workfunction of a surface, whereas electropositive absorbates, as is the case here, lead to a decrease in workfunction [26].

5. Conclusion
ZnO thin lms were prepared by RF magnetron sputtering and exhibited an as-deposited workfunction of 3.74 eV. After subjection to low-energy Ar sputter cleaning and oxygen plasma treatment, the workfunctions increased to 3.95 eV and 4.21 eV, respectively. These changes are signicant from the standpoint of carrier injection or outcoupling in device applications. The experimental and computational results indicate that oxygen plasma treatments result in an electronegative surface and an associated dipole moment that reinforces the original surface dipole moment. This leads to a workfunction increase. The opposite is true for hydrocarbon coverage of ZnO surfaces. In this case the dipole formed is pointing opposite the direction of the original surface dipole leading to a decrease in surface dipole moment, which in turn leads to a decrease in workfunction.

Acknowledgments
This work was supported by National Science Foundation grant No. 1051502.

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