• 한국재료학회지
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• 제21권10호
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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.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2008년도 추계학술대회 논문집 Vol.21
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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.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2003년도 추계학술발표강연 및 논문개요집
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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.

• 마이크로전자및패키징학회지
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• 제29권2호
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• pp.73-79
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• 2022

본 연구에서는 최근 저온접합 소재로 각광받고 있는 Ga과 대표적인 전극 물질인 Cu와의 반응연구를 실시하여 저온 솔더링 적용시 필요한 정보들을 확인하고자 하였다. 80-200℃ 온도범위에서 Ga과 Cu/Au 기판을 반응시켜 계면반응 및 금속간화합물(IMC) 성장을 관찰하고 분석하였다. 반응계면에서 성장하는 주요한 IMC는 CuGa₂ 상이었으며 그 상부에는 작은 입자크기를 가지는 AuGa₂ IMC 그리고 하부에는 얇은 띠 형상의 Cu₉Ga₄ IMC가 형성되었다. CuGa₂ 입자들은 scallop 형상을 보이며 Cu₆Sn₅ 성장의 경우와 비슷하게 반응시간이 증가함에 따라서 큰 형상변화없이 입자 크기가 증가하였다. CuGa₂ 성장기구를 분석한 결과 120-200℃ 온도범위에서 시간지수는 약 3.0으로 산출되었고, 활성화에너지는 17.7 kJ/mol로 측정되었다.

• Current Photovoltaic Research
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• 제1권1호
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• pp.38-43
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• 2013

$Cu(In,Ga)_3Se_5$ is a candidate material for the top cell of $Cu(In,Ga)Se_2$ tandem cells. This phase is often found at the surface of the $Cu(In,Ga)Se_2$ film during $Cu(In,Ga)Se_2$ cell fabrication, and plays a positive role in $Cu(In,Ga)Se_2$ cell performance. However, the exact properties of the $Cu(In,Ga)_3Se_5$ film have not been extensively studied yet. In this work, $Cu(In,Ga)_3Se_5$ films were fabricated on Mo-coated soda-lime glass substrates by a three-stage co-evaporation process. The Cu content in the film was controlled by varying the deposition time of each stage. X-ray diffraction and Raman spectroscopy analyses showed that, even though the stoichiometric Cu/(In+Ga) ratio is 0.25, $Cu(In,Ga)_3Se_5$ is easily formed in a wide range of Cu content as long as the Cu/(In+Ga) ratio is held below 0.5. The optical band gap of $Cu_{0.3}(In_{0.65}Ga_{0.35})_3Se_5$ composition was found to be 1.35eV. As the Cu/(In+Ga) ratio was decreased further below 0.5, the grain size became smaller and the band gap increased. Unlike the $Cu(In,Ga)Se_2$ solar cell, an external supply of Na with $Na_2S$ deposition further increased the cell efficiency of the $Cu(In,Ga)_3Se_5$ solar cell, indicating that more Na is necessary, in addition to the Na supply from the soda lime glass, to suppress deep level defects in the $Cu(In,Ga)_3Se_5$ film. The cell efficiency of $CdS/Cu(In,Ga)_3Se_5$ was improved from 8.8 to 11.2% by incorporating Na with $Na_2S$ deposition on the CIGS film. The fill factor was significantly improved by the Na incorporation, due to a decrease of deep-level defects.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
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• pp.314.2-314.2
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• 2013

CIGS 박막의 물성은 조성에 크게 영향을 받으며, 특히 박막 내 Cu/(In+Ga) 비는 매우 중요한 변수로서 태양전지 특성에 영향을 주게 된다. Cu(In1-xGax)Se2 박막의 전하농도 및 반도체로의 성격을 가장 명확하게 결정하는 조성비는 Cu/(In+Ga) 비이다. 태양전지와 같은 소자로 작용하기 위해서는 Cu/(In+Ga) 비가 1보다 작아야 한다. 고효율의 태양전지는 Cu/(In+Ga)조성이 0.85~0.95로 slightly Cu-poor가 되어야 만들어진다. 본 연구에서는 Cu조성에 따른 CIGS 박막의 구조적, 전기적 특성과 CIGS 태양전지 효율 특성에 관하여 연구하였다. 미세구조 분석결과 Cu 조성이 증가함에 따라 큰 결정립을 가지며 결정립의 성장이 고르게 되어 접합 형성을 좋게 하는 경향을 보였다. X선 회절 분석결과, Cu 함유량 비율이 증가하면서 <112>의 우선배향성에서 <220/204>으로 변화하였다. 그러나, Cu/(In+Ga) 비율이 1이상이 첨가됨에 따라 우선배향은 다시 <112>로 변화함을 알 수 있었다. EDX 분석결과 Ga/(In+Ga) 0.31, Cu/(In+Ga) 0.86의 비율일 때, Carrier density $1.49{\times}1016$ cm-3을 나타내었다. CIGS의 태양전지의 효율 측정결과 Voc=596mV, Jsc=37.84mA/cm2, FF=72.96%로 ${\eta}$=16.47%를 달성하였다.

• 한국재료학회지
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• 제20권8호
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• pp.434-438
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• 2010

The selenization process has been a promising method for low-cost and large-scale production of high quality CIGS film. However, there is the problem that most Ga in the CIGS film segregates near the Mo back contact. So the solar cell behaves like a $CuInSe_2$ and lacks the increased open-circuit voltage. In this study we investigated the Ga distribution in CIGS films by using the $Ga_2Se_3$ layer. The $Ga_2Se_3$ layer was applied on the Cu-In-Ga metal layer to increase Ga content at the surface of CIGS films and to restrict Ga diffusion to the CIGS/Mo interface with Ga and Se bonding. The layer made by thermal evaporation was showed to an amorphous $Ga_2Se_3$ layer in the result of AES depth profile, XPS and XRD measurement. As the thickness of $Ga_2Se_3$ layer increased, a small-grained CIGS film was developed and phase seperation was showed using SEM and XRD respectively. Ga distributions in CIGS films were investigated by means of AES depth profile. As a result, the [Ga]/[In+Ga] ratio was 0.2 at the surface and 0.5 near the CIGS/Mo interface when the $Ga_2Se_3$ thickness was 220 nm, suggesting that the $Ga_2Se_3$ layer on the top of metal layer is one of the possible methods for Ga redistribution and open circuit voltage increase.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2003년도 하계학술대회 논문집 Vol.4 No.1
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• pp.352-356
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• 2003

A stoichiometric mixture of evaporating materials for $CuGaSe_2$ single crystal am films was prepared from horizontal electric furnace. Using extrapolation method of X-ray diffraction patterns for the polycrystal $CuGaSe_2$, it was found tetragonal structure whose lattice constant $a_0$ and $c_0$ were $5.615\;{\AA}\;and\;11.025\;{\AA}$, respectively. 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, The crystalline structure of the single crystal thin films was investigated by the photoluminescence and double crystal X-ray diffraction (DCXD). The carrier density and mobility of $CuGaSe_2$ single crystal thin films measured with Hall effect by van der Pauw method are $9.24{\times}10^{16}\;cm^{-3}$ and $295\;cm^2/V{\cdot}s$ at 293 K, respectively. The temperature dependence of the energy band gap of the $CuGaSe_2$ obtained from the absorption spectra was well described by the Varshni's relation, $E_g(T)\;:\;1.7998\;eV\;-\;(8.7489\;{\times}\;10^{-4}\;eV/K)T^2(T\;+\;335\;K)$. 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 accepters 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.

• 한국태양에너지학회 논문집
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• 제23권2호
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• pp.59-70
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• 2003

A stoichiometric mixture of evaporating materials for $CuGaSe_2$ single crystal thin films was prepared from horizontal electric furnace. Using extrapolation method of X-ray diffraction patterns for the polycrystal $CuGaSe_2$, it was found tetragonal structure whose lattice constant $a_0$ and $c_0$ were $5.615{\AA}$ and $11.025{\AA}$, respectively. 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. The crystalline structure of the single crystal thin films was investigated by the photoluminescence and double crystal X-ray diffraction (DCXD). The carrier density and mobility of $CuGaSe_2$ single crystal thin films measured with Hall effect by van der Pauw method are $5.01\times10^{17}cm^{-3}$ and $245cm^2/V{\cdot}s$ at 293K. respectively. The temperature dependence of the energy band gap of the $CuGaSe_2$ obtained from the absorption spectra was well described by the Varshni's relation, $E_g$(T)=1.7998 eV-($8.7489\times10^{-4}$ eV/K)$T^2$/(T+335K). 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.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2008년도 추계학술대회 논문집 Vol.21
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• pp.279-280
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• 2008

For the manufacture of the $CuGaS_2$, Cu, Ga and S were vapor-deposited in the named order. Among them, Cu and Ga were vapor-deposited by using the Evaporation method in consideration of their adhesive force to the substrate so that the composition of Cu and Ga might be 1 : 1, while the surface temperature having an effect on the quality of the thin film was changed from R.T.[$^{\circ}C$] to 150$[^{\circ}C]$ at intervals of 50$[^{\circ}C]$. As a result, at 400$[^{\circ}C]$ of the Annealing temperature, their chemical composition was measured in the proportion of 1 : 1 : 2. It could be known from this experimental result that it is the optimum condition to conduct Annealing on the $CuGaS_2$ thin film under a vacuum when the $CuGaS_2$ thin film as an optical absorption layer material for a solar cell is manufactured.