• 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.

• 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.

• 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.

• 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 Ceramic Society
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• v.35 no.8
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• pp.871-877
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• 1998

$CuInSe_2$ thin films have been formed by two-step method in which Cu-In alloy layer was first deposited and then it was selenized. Cu-In alloy layers were deposited by co-sputtering method at ambient tem-perature. XRD analysis showed that both of $Cu_{11}In_{9}$ and CuIn$_2$ phases were formed from these films. $Cu_{11}In_{9}$ peak intensity was increased increased with varying the composition from In-rich to Cu-rich. The metallic layers were selenized either in low pressure of 10 mTorr or in atmospheric pressure(AP) Less compounds of Cu-Se and In-Se were observed during the early stage of selenization and also $CuInSe_2$ thin films selenized in vacuum showed lower roughness larger grain size and better crystallinity than those in AP.

• 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.

• Korean Journal of Materials Research
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• v.23 no.3
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• pp.183-189
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• 2013

$Cu_2ZnSn(S,Se)_4$ material is receiving an increased amount of attention for solar cell applications as an absorber layer because it consists of inexpensive and abundant materials (Zn and Sn) instead of the expensive and rare materials (In and Ga) in $Cu(In,Ga)Se_2$ solar cells. We were able to achieve a cell conversion efficiency to 4.7% by the selenization of a stacked metal precursor with the Cu/(Zn + Sn)/Mo/glass structure. However, the selenization of the metal precursor results in large voids at the absorber/Mo interface because metals diffuse out through the top CZTSe layer. To avoid the voids at the absorber/Mo interface, binary selenide compounds of ZnSe and $SnSe_2$ were employed as a precursor instead of Zn and Sn metals. It was found that the precursor with Cu/$SnSe_2$/ZnSe stack provided a uniform film with larger grains compared to that with $Cu_2Se/SnSe_2$/ZnSe stack. Also, voids were not observed at the $Cu_2ZnSnSe_4$/Mo interface. A severe loss of Sn was observed after a high-temperature annealing process, suggesting that selenization in this case should be performed in a closed system with a uniform temperature in a $SnSe_2$ environment. However, in the experiments, Cu top-layer stack had more of an effect on reducing Sn loss compared to $Cu_2Se$ top-layer stack.

• Journal of the Korean Vacuum Society
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• v.3 no.2
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• pp.203-206
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• 1994

동시증착법으로 성장한 CuIn3Se5 박막의 구조 및 광학적 특성을 XRD, SEM 광투과 및 광반사 측정으로부터 조사하였다. XRD 측정에 의하면 CuIn3Se5 는 정열된 Cu 빈자리와 Cuqls자리에 in으로 대 치되는 defect chalcopyrite 구조임이 확인디었다. 또한 광흡수 측정으로부터 CuIn3Se5 는 금지대내에서 직접 전이에 의한 광흡수 특성을 보여주며 이때 에너지띠 간격은 1.27ev 이었다. CuIn3Se5 박막에 대한 연구결과들은 CuInSe2 의 결과들과 비교하여 논의하였다.