• Korean Journal of Materials Research
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• v.21 no.10
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• pp.550-555
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• 2011

A high-quality CIGS film with a selenization process needs to be developed for low-cost and large-scale production. In this study, we used $Cu_2In_3$, CuGa and $Cu_2Se$ sputter targets for the deposition of a precursor. The precursor deposited by sputtering was selenized in Se vapor. The precursor layer deposited by the co-sputtering of $Cu_2In_3$, CuGa and $Cu_2Se$ showed a uniform distribution of Cu, In, Ga, and Se throughout the layer with Cu, In, CuIn, CuGa and $Cu_2Se$ phases. After selenization at $550^{\circ}C$ for 30 min, the CIGS film showed a double-layer microstructure with a large-grained top layer and a small-grained bottom layer. In the AES depth profile, In was found to have accumulated near the surface while Cu had accumulated in the middle of the CIGS film. By adding a Cu-In-Ga interlayer between the co-sputtered precursor layer and the Mo film and adding a thin $Cu_2Se$ layer onto the co-sputtered precursor layer, large CIGS grains throughout the film were produced. However, the Cu accumulated in the middle of CIGS film in this case as well. By supplying In, Ga and Se to the CIGS film, a uniform distribution of Cu, In, Ga and Se was achieved in the middle of the CIGS film.

• Journal of the Korean Vacuum Society
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• v.3 no.3
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• pp.346-354
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• 1994

삼원화합물 반도체 CuAlSe2 및 CuGaSe2 단결정의 solid solution 인 CuAl1-xGaxSe2 및 cobalt를 2.0 mol% 첨가한 CuAl1-xGaxSe2 : Co2+ 단결정을 iodine을 수송물질로 사용한 화학수송법으로 성장시켰 다. source material로는 CuAl1-xGaxSe2 의 화학조성비에서 Se를 3.0mol% 과잉으로 첨가하여 합성한 ingot를 사용하였으며 불순물이 첨가된 CuAl1-xGaxSe2:Co2+ 단결정성장시에는 source ma-terial 에 cobalt 분말을 2.0mol% 첨가하였다. X-선 회절무늬로부터 성장된 단결정들이 chalcopyrite 결정구조를 하고 있음을 확인하였으며 격자상수를 구하였다. 광흡수 spectra 측정으로부터 성장된 단결정에서 나타 는 cobalt 불순물에 의한 광흡수 peak가 Td 대칭점에위치한 Co2+ 이온의 에너지 준위들간 전자전이에 의해 나타남을 규명하였다.

• Korean Journal of Materials Research
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• v.5 no.8
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• pp.988-996
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• 1995

CuInSe$_2$this films as a light absorber layer were fabricated by vacuum evaporation using In$_2$Se$_3$and Cu$_2$Se precursors and their properties were analyzed. Indium selenide films of 0.5${\mu}{\textrm}{m}$ thickness were first deposited by vacuum evaporation of In$_2$Se$_3$ on a Corning 7059 glass substrate. The films deposited at suscepor temperature of 40$0^{\circ}C$ showed a flat surface morphology with densely Packed grain structure. CuInSe$_2$films directly formed by evaporating Cu$_2$Se on the predeposited In$_2$Se$_2$films also showed a very flat surface when the susceptor temperature was $700^{\circ}C$. Cu$_2$Se, a second phase in the CuInSe$_2$film, was removed by evaporating additional In$_2$Se$_3$on the CuInSe$_2$film at $700^{\circ}C$. The grain size of 1.2${\mu}{\textrm}{m}$ thick CuInSe$_2$, film was about 2${\mu}{\textrm}{m}$ and the film had a (112) preferred orientation. As the amount of deposited In$_2$Se$_3$increased, the electrical resistivity of CuInSe$_2$films increased because of the decrease of hole concentration. But the optical band gap was almost constant at the value of 1.04eV, The CuInSe$_2$film grown on a Mo/glass substrate had a similar smooth microstructure compared to that on a glass substrate. A solar cell with ZnO/CdS/CuInSe$_2$/Mo structure may be realized based on the above CuInSe$_2$films.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2007.06a
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• pp.152-153
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• 2007

$CuInSe_2$ single crystal thin film was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the hot wall epitaxy (HWE) system. After the as-grown $CuInSe_2$ single crystal thin films was annealed in Cu-, Se-, and In-atmospheres, the origin of point defects of $CuInSe_2$ single crystal thin films has been investigated by the photoluminescence(PL) at 10 K. The native defects of $V_{Cu}$, $V_{Se}$, $Cu_{lnt}$, and $Se_{lnt}$ obtained by PL measurements were classified as a donors or acceptors type. And we concluded that the heat-treatment in the Cu-atmosphere converted $CuInSe_2$ single crystal thin films to an optical n-type. Also, we confirmed that In in $CuInSe_2$/GaAs did not form the native defects because In in $CuInSe_2$ single crystal thin films existed in the form of stable bonds.

• Proceedings of the Materials Research Society of Korea Conference
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• 2003.11a
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• pp.154-154
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• 2003

A stoichiometric mixture of evaporating materials for CuGaSe2 single crystal thin films was prepared from horizontal electric furnace. Using extrapolation method of X-ray diffraction patterns for the polycrystal CuGaSe2, it was found tetragonal structure whose lattice constant at and co were 5.615 ${\AA}$ and 11.025 ${\AA}$, respectively. To obtain the single crystal thin films, CuGaSe2 mixed crystal was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the hot wall epitaxy (MWE) system. The source and substrate temperatures were Slot and 450$^{\circ}C$, respectively. The crystalline structure of the single crystal thin films was investigated by the photoluminescence and double crystal X-ray diffraction (UXD). The carrier density and mobility of CuGaSe2 single crystal thin films measured with Hall effect by van der Pauw method are 5.0l${\times}$10$\^$17/ cm$\^$-3/ and 245 $\textrm{cm}^2$/V$.$s at 293K, respectively. The temperature dependence of the energy band gap of the CuGaSe2 obtained from the absorption spectra was well described by the Varshni's relation, Eg(T) = 1.7998 eV - (8.7489${\times}$10$\^$-4/ eV/K)T$^2$/(T + 335 K. After the as-grown CuGaSe2 single crystal thin films was annealed in Cu-, Se-, and Ca-atmospheres, the origin of point defects of CuGaSe2 single crystal thin films has been investigated by the photoluminescence(PL) at 10 K The native defects of V$\_$CU/, V$\_$Se/, Cu$\_$int/, and Se$\_$int/ obtained by PL measurements were classified as a donors or accepters type. And we concluded that the heat-treatment in the Cu-atmosphere converted CuGaSe2 single crystal thin films to an optical n-type. Also, we confirmed that Ga in CuGaSe2/GaAs did not form the native defects because Ga in CuGaSe2 single crystal thin films existed in the form of stable bonds.

• Journal of the Korean institute of surface engineering
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• v.48 no.4
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• pp.169-173
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• 2015

$CuInSe_2$ thin films which have been widely used for thin solar cells as a light absorber were prepared by hydrazine solution processing, and their microstructural properties were investigated. Hydrazine $CuInSe_2$ precursor solutions were prepared by dissolving $Cu_2S$, S, $In_2Se_3$ and Se powder in hydrazine solvent. Multilayer $CuInSe_2$ chalcopyrite phase thin films were prepared by repeating spin-coating process using the precursor solution. Unfortunately, the presence of the interfaces between each $CuInSe_2$ layer formed by multi-layer coating impeded grain growth across the interface. Here, by doing simple interface engineering to solve the limited grain growth issue, the large grained (${\sim}1{\mu}m$) $CuInSe_2$ thin films were obtained.

• Electrical & Electronic Materials
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• v.8 no.3
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• pp.298-305
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• 1995

Copper-indium diselenide, $CuInSe_2$, thin films have been fabricated by selenizing Cu/In stacked layers with different sputtered Cu/(Cu+ln) mole ratios at 450.deg. C for 1hr on alumina substrates. The selenium source was selenium vapor. Microstructure, crystallization, and composition of the selenized $CuInSe_2$ films were examined by using scanning electron microscope, X-ray diffraction, Auger electron spectroscopy, and secondary ion mass spectrometry. Electrical resistivity and hall effects were also measured to investigate the electrical properties. As the sputtered Cu/(Cu+In) mole ratio of In/Cu layer increased, the amounts of void and CuSe phase in the selenized films increased but the composition of $CuInSe_2$ phase was the same regardless of the sputtered mole ratio. Comparing the electrical properties of $CuInSe_2$ thin film before and after the chemical etching, it was seen that the electrical resistivity, carrier concentration, and carrier mobility of the selenized films were affected by the amount of CuSe phase which seemed to increase primarily the hole concentration of the selenized films.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.134-137
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• 2009

Commercially available elemental powders of Cu, Zn, Sn and Se were employed for crystallizing a stannite-type $Cu_2ZnSnSe_4$ compound by means of solid state reaction. $Cu_2ZnSnSe_4$ reaction chemistry was also modeled based on differential-thermal analysis and X-ray powder diffraction results. It was observed that Se tends to react preferably with Cu to form CuSe and $CuSe_2$ phases at low reaction temperature. The formation of $Cu_5Zn_8$ intermetallic phase was found to be the intermediate reaction path for the binary ZnSe formation. A solid state reaction at $320^{\circ}C$ reacted elemental powderst obinary selenides of CuSe, ZnSe and SnSe completely. The crystallization of $Cu_2ZnSnSe_4$ was was detected to begin at $300^{\circ}C$ and its weight fraction increased with an increase of reaction temperature, which most probably formed from the reaction between $Cu_2SnSe_3$ and ZnSe.

• Journal of the Korean Vacuum Society
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• v.3 no.2
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• pp.227-233
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• 1994

CuAlGeSe4 및 CuAlGeSe4 ; Co2+ 결정을 고순도의 성분원소로부터 합성하고 서냉법으로 결정을 성장시켰다. 이들결정은 chalcopyrite 결정구조를 갖고 있으며 직접전이형 energy gap 구조를 갖고 286K에서 energy gap은 CuAlGeSe4 결정의 경우는 2.394eV이며 CuAlGeSe4 ; Co2+ 결정의 경우는 2.302 eV로 주어졌다. CuAlGeSe4 : Co2+ 결정에서 cobalt에 의한 불순물 광흡수 peak들은 12243, 7002, 3890 cm-1에서 나타났으며 이 peak들은 CuAlGeSe4 : Co2+ 결정의 Td symmetry site에 위치한 Co2+ ion의 energy 준위사이의 전자전이에 의한 optical absorption임을 규명했다.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.11a
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• pp.100-101
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• 2008

To obtain the single crystal thin films, $CuGaSe_2$ mixed crystal was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the hot wall epitaxy (HWE) system. The source and substrate temperatures were $610^{\circ}C$ and $450^{\circ}C$, respectively. After the as-grown $CuGaSe_2$ single crystal thin films was annealed in Cu-, Se-, and Ga-atmospheres, the origin of point defects of $CuGaSe_2$ single crystal thin films has been investigated by the photoluminescence(PL) at 10 K. The native defects of $V_{CU}$, $V_{Se}$, $Cu_{int}$, and $Se_{int}$ obtained by PL measurements were classified as a donors or acceptors type. And we concluded that the heat-treatment in the Cu-atmosphere converted $CuGaSe_2$ single crystal thin films to an optical n-type. Also, we confirmed that Ga in $CuGaSe_2$/GaAs did not form the native defects because Ga in $CuGaSe_2$ single crystal thin films existed in the form of stable bonds.