• Proceedings of the Korean Vacuum Society Conference
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• 2010.08a
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• pp.145-145
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• 2010

In this paper, we report that the effects of hydrogen doping on the electrical and optical properties of typical transparent conducting oxide films such as ZnO and $SnO_2$ prepared by magnetron sputtering. Recently, density functional theory (DFT) calculations have shown strong evidence that hydrogen acts as a source of n-type conductivity in ZnO. In this work, the beneficial effect of hydrogen incorporation on Ga-doped ZnO thin films was demonstrated. It was found that hydrogen doping results a noticeable improvement of the conductivity mainly due to the increases in carrier concentration. Extent of the improvement was found to be quite dependent on the deposition temperature. A low resistivity of $4.0{\times}10^{-4}\;{\Omega}{\cdot}cm$ was obtained for the film grown at $160^{\circ}C$ with $H_2$ 10% in sputtering gas. However, the beneficial effect of hydrogen doping was not observed for the films deposited at $270^{\circ}C$. Variations of the electrical transport properties upon vacuum annealing showed that the difference is attributed to the thermal stability of interstitial hydrogen atoms in the films. Theoretical calculations also suggested that hydrogen forms a shallow-donor state in $SnO_2$, even though no experimental determination has yet been performed. We prepared undoped $SnO_2$ thin films by RF magnetron sputtering under various hydrogen contents in sputtering ambient and then exposed them to H-plasma. Our results clearly showed that the hydrogen incorporation in $SnO_2$ leads to the increase in carrier concentration. Our experimental observation supports the fact that hydrogen acting as a shallow donor seems to be a general feature of the TCOs.

• Journal of the Korean Chemical Society
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• v.39 no.3
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• pp.163-175
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• 1995

Metal free phthalocyanine($H_2Pc$) partially doped with iodine, $H_2Pc(I)x$, has been made to improve photosensitizing efficiency of ZnO/$H_2Pc$. The content of iodine dopant level(x) for $H_2Pc(I)x$ upon $H_2Pc$ polymorphs was characterized as ${\chi}-H_2Pc(I)_{0.92}$ and ${\beta}-H_2Pc(I)_{0.96}$ by elemental analysis. Characterization of iodine-oxidized $H_2Pc$ were investigated by TGA (thermogravimetric analysis), UV-Vis, FT-IR, Raman and ESR (electron spin resonance) spectrum, and the adsorption properties of $H_2Pc(I)x$ on ZnO were characterized by means of Raman and ESR studies. TGA for $H_2Pc(I)x$ showed a complete loss of iodine at approximately 265$^{\circ}C$ and the Raman spectrum of $H_2Pc(I)x$ and ZnO/$H_2Pc(I)x$ at 514.5 nm showed characteristic $I_3^-$ patterns in the frequency region 90∼550 $cm^{-1}$. ZnO/$H_2Pc(I)x$ exhibited a very intense and narrow ESR signal at $g=2.0025{\pm}0.0005$ compared to $H_2Pc$/ZnO. Iodine doped ZnO/$H_2Pc(I)x$ showed a better photosensitivity compared to iodine undoped ZnO/$H_2Pc$. That is, the surface photovoltage of ${\chi}-H_2Pc(I)_{0.92}$/ZnO was approximately 31 times greater than that of ZnO/${\chi}-H_2Pc$ and ZnO/${\beta}-H_2Pc(I)_{0.96}$ was 5 times more efficient than ZnO/${\beta}-H_2Pc$ at 670 nm. And the dependence of photosensitizing effect upon $H_2Pc$ polymorphs was exhibited that the surface photovoltage of ZnO/${\chi}-H_2Pc(I)_{0.92}$ was approximately 5 times greater than ZnO/${\beta}-H_2Pc(I)_{0.96}$ at 670 nm. Therefore Iodine doping of H_2Pc$ resulted in increase in photoconductivity of $H_2Pc$ and photovoltaic effect of ZnO/$H_2Pc$ in the visible region.

• Korean Journal of Materials Research
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• v.11 no.10
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• pp.889-894
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• 2001

2wt% $Al_2O_3-doped$ ZnO (AZO) thin films were deposited on sapphire (0001) single crystal substrate by parellel type rf magnetron sputtering at 55$0^{\circ}C$. The as-grown AZO thin films was polycrystalline and showed only broad deep defect-level photoluminescence (PL). In order to examine the change of PL property, AZO thin films were annealed in $N_2$ (N-AZO) and $H_2$ (H-AZO) at the temperature of $600^{\circ}C$~$1000^{\circ}C$ through rapid thermal annealing. After annealed at $800^{\circ}C$, N-AZO shows near band edge emission (NBE) with very small deep-level emission, and then N-AZO annealed at $900^{\circ}C$ shows only sharp NBE with 219 meV FWHM. In Comparison with N-AZO, H-AZO exhibits very interesting PL features. After $600^{\circ}C$ annealing, deep defect-level emission was quire quenched and NBE around 382 nm (3.2 eV) was observed, which can be explained by the $H_2$passivation effect. At elevated temperature, two interesting peaks corresponding to violet (406 nm, 3.05 eV) and blue (436 nm, 2.84 eV) emission was firstly observed in AZO thin films. Moreover, peculiar PL peak around 694 nm (1.78 eV) is also firstly observed in all the H-AZO thin films and this is believed good evidence of hydrogenation of AZO. Based on defect-level scheme calculated by using the full potential linear muffin-tin orbital (FP-LMTO), the emission 3.2 eV, 3.05 eV, 3.84 eV and 1.78 eV of H-AZO are substantially deginated as exciton emission, transition from conduction band maximum to $V_{ Zn},$ from $Zn_i$, to valence band maximum $(V_{BM})$ and from $V_{o} to V_BM}$, respectively.

• Bulletin of the Korean Chemical Society
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• v.31 no.1
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• pp.112-115
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• 2010

Transparent conducting undoped and Al impurity doped ZnO films were deposited on glass substrate by spin coat technique using 24 days aged ZnO precursor solution with solution of ethanol and diethanolamine. The films were characterized by UV-Visible spectroscopy, X-ray diffraction (XRD), scanning electron microscope (SEM), electrical resistivity ($\rho$), carrier concentration (n), and hall mobility ($\mu$) measurements. XRD data show that the deposited film shows polycrystalline nature with hexagonal wurtzite structure with preferential orientation along (002) crystal plane. The SEM images show that surface morphology, porosity and grain sizes are affected by doping concentration. The Al doped samples show high transmittance and better resistivity. With increasing Al concentration only mild change in optical band gap is observed. Optical properties are not affected by aging of parent solution. A lowest resistivity ($8.5 \times 10^{-2}$ ohm cm) is observed at 2 atomic percent (at.%) Al. With further increase in Al concentration, the resistivity started to increase significantly. The decrease resistivity with increasing Al concentration can be attributed to increase in both carrier concentration and hall mobility.