• Proceedings of the Korean Vacuum Society Conference
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• 2011.02a
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• pp.404-405
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• 2011

Cu(InGa)$Se_2$ (CIGS) 박막 태양전지의 저가 및 대면적화를 위한 양산화 공정인 two-step process (sputter/selenization) 공정에서는 sputtering으로 형성한 metal precursor stack을 $H_2$ Se gas를 이용하여 selenization하는 공정을 주로 이용한다. 하지만 이러한 selenization 공정은 유독한 $H_2$ Se gas를 이용해야 한다는 점과 긴 시간 동안 열처리를 해야 하는 단점을 가지고 있다. 이에 metal precursor stack 위에 Se 막을 우선 증착하고, Rapid Thermal Process (RTP)를 이용하여 selenization하는 방법이 현재 많은 관심을 끌고 있다. 본 논문에서는 sputtering 이후 RTP를 이용한 CIGS 흡수층 제작에 대한 선행연구의 일환으로 co-evaporator 장비를 이용하여 다양한 구조의 precursor를 제작하고 RTP 조건에 따른 selenization 효과를 연구하였다. Co-evaporator를 이용하여 CIGS, CIG/Se, CuGa/In/Se, In/CuGa/Se 4가지 구조의 precursor stack을 Mo coated soda lime glass 위에 제작하였다. 이때 amorphous 상태의 precursor stack을 만들기 위하여 기판에 열은 가하여 주지 않았으며, 각각의 stack 구조에서 가지고 있는 Cu, In, Ga, Se의 총량을 동일하게 유지하기 위하여 각 stack의 증착 시간을 동일하게 유지하였다. Selenization을 위한 RTP 조건은 550, $600^{\circ}C$ 각각에 대하여 1, 5, 10분으로 split을 진행하였다. Precursor stack의 증착 후 관찰한 XRD 결과는 비정질 상태를 잘 나타내었으며, SEM 결과 CIGS precursor stack을 제외한 나머지 구조의 stack에서는 In 박막의 surface roughness로 인하여 박막의 평탄화가 좋지 않음을 확인하였다. CIGS precursor stack의 경우, RTP 온도와 시간 split와 상관없이 결정화가 잘 이루어졌으나 grain의 성장이 부족하였다. 이에 비하여 CIG/Se, CuGa/In/Se, In/CuGa/Se 구조의 precursor stack의 경우, $550^{\circ}C$ 열처리에서는 InSe의 결정상이 관찰 되었으며 $600^{\circ}C$, 5분 이상 열처리에서 CIGS 결정상이 관찰되었다. 이러한 결과는 Se이 metal 원소들과 함께 있는 CIGS 구조에 비하여 metal precursor stack 위에 Se을 증착한 stack 구조들의 경우는 CIGS 결정을 형성하기 위해 Se이 metal 층들로 확산되어 반응을 하여야 하므로 상대적으로 많은 열에너지가 필요한 것으로 이해할 수 있으며, RTP를 이용한 selenization 공정으로 CIGS 박막 태양전지의 흡수층 형성이 가능함을 확인하였다.

• Current Photovoltaic Research
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• v.3 no.1
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• pp.16-20
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• 2015

Ag addition in chalcopyrite materials is known to lead beneficial changes in aspects of structural and electronic properties. In this work, the effects of Ag alloying of $Cu(In,Ga)Se_2$-based solar cells has been investigated. Wide bandgap $(Ag,Cu)(In_{1-x},Ga_x)Se_2$ (x = 0.75~0.8) films have been deposited using a three-stage co-evaporation with various Ag/(Ag+Cu) ratios. With Ag alloying the $(Ag,Cu)(In_{1-x},Ga_x)Se_2$ (x~0.8) films were found to have greater grainsize and film thickness. Device were also fabricated with the $(Ag,Cu)(In_{1-x},Ga_x)Se_2$ (x~0.8) films and their J-V and quantum efficiency measurements were carried out. The highest-efficiency $(Ag,Cu)(In_{1-x},Ga_x)Se_2$ solar cell with Eg > 1.5 eV had an efficiency of 12.2% with device parameters $V_{OC}=0.810V$, $J_{SC}=21.7mA/cm^2$, and FF = 69.0%.

• Solar Energy
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• v.20 no.2
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• pp.43-54
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• 2000

We prepared and characterized $Cu(In_{1-x}Ga_x)Se_2$(CIGS) films using a elemental co-evaporation method for absorbing layer of high efficiency thin film solar cells. The CIGS films deposited on a soda-lime glass exhibited low resistivity because of higher carrier concentration. Na was accumulated at the CIGS surface and the 0 and Se were also accumulated at the surface, suggesting that oxidation is a driving force of Na accumulation. The structure of CIGS film was modified or a secondary phase was formed in the Cu-poor CIGS bulk films probably due to the incorporation of Na into Cu vacancy sites. As the Ga/(In+Ga) ratio increased, the diffraction peaks of $Cu(In_{1-x}Ga_x)Se_2$ films were shifted to larger angle and splitted, and the grain size of $Cu_{0.91}(In_{1-x}Ga_x)Se_2$ films became smaller. All $Cu_{0.91}(In_{1-x}Ga_x)Se_2$ films showed the p-type conductivity regardless of the Ga/(In+Ga) ratio. Ag/n-ZnO/i-ZnO/CdS/$Cu_{0.91}(In_{0.7}Ga_{0.3})Se_2$/Mo solar cells were fabricated. The currently best efficiency in this study was 14.48% for $0.18cm^2$ area ($V_{oc}=581.5mV,\;J_{sc}=34.88mA$, F.F=0.714).

• Korean Journal of Materials Research
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• v.20 no.12
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• pp.661-668
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• 2010

Cu(In,Ga)$Se_2$(CIGS) photovoltaic thin films were electrodeposited on Mo/glass substrates with an aqueous solution containing 2 mM $CuCl_2$, 8 mM $InCl_3$, 20 mM $GaCl_3$ and 8mM $H_2SeO_3$ at the electrodeposition potential of -0.6 to -1.0 V(SCE) and pH of 1.8. The best chemical composition of $Cu_{1.05}In_{0.8}Ga_{0.13}Se_2$ was found to be achieved at -0.7 V(SCE). The precursor Cu-In-Ga-Se films were annealed for crystallization to chalcopyrite structure at temperatures of 100-$500^{\circ}C$ under Ar gas atmosphere. The chemical compositions, microstructures, surface morphologies, and crystallographic structures of the annealed films were analyzed by EPMA, FE-SEM, AFM, and XRD, respectively. The precursor Cu-In-Ga-Se grains were grown sparsely on the Mo-back contact and also had very rough surfaces. However, after annealing treatment beginning at $200^{\circ}C$, the empty spaces between grains were removed and the grains showed well developed columnar shapes with smooth surfaces. The precursor Cu-In-Ga-Se films were also annealed at the temperature of $500^{\circ}C$ for 60 min under Se gas atmosphere to suppress the Se volatilization. The Se amount on the CIGS film after selenization annealing increased above the Se amount of the electrodeposited state and the $MoSe_2$ phase occurred, resulting from the diffusion of Se through the CIGS film and interaction with Mo back electrode. However, the selenization-annealed films showed higher crystallinity values than did the films annealed under Ar atmosphere with a chemical composition closer to that of the electrodeposited state.

• Journal of Surface Science and Engineering
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• v.37 no.4
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• pp.191-195
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• 2004

Gallium or sulphur additions in $CuInSe_2$ were prepared using RF magnetron sputtering and pulsed laser deposition respectively. All of the observed thin films shows a chalcopyrite structure with the S and Ga addition increases the favourable (112) peak. The optical absorption coefficients were slightly decreased. The energy band gap of films could be shifted from 1.04 to 1.68 eV by adjusting the mole ratio of S/(S+Se) and Ga/(In+Ga). It is possible to obtain the optimum energy band gap by adding S or Ga solute at a certain ratio in favour of Se and In respectively. It is also necessary to control the ratio of Ga and S additions and to retain a certain portion of In and Se to provide better properties of thin films.

• 한국신재생에너지학회:학술대회논문집
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• 2011.11a
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• pp.47.1-47.1
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• 2011

We report on a direct measurement of two-dimensional chemical and electrical distribution on the surface of photovoltaic Cu(In,Ga)$Se_2$ thin-films using a nano-scale spectroscopic and electrical characterization, respectively. The Raman measurement reveals non-uniformed surface phonon vibration which comes from different compositional distribution and defects in the nature of polycrystalline thin-films. On the other hand, potential analysis by scanning Kelvin probe force microscopy shows a higher surface potential or a small work function on grain boundaries of the thin-films than on the grain surfaces. This demonstrates the grain boundary is positively charged and local built-in potential exist on grain boundary, which improve electron-hole separation on grain boundary. Local electrical transport measurements with scanning probe microscopy on the thin-films indicates that as external bias is increases, local current is started to flow from grain boundary and saturated over 0.3 V external bias. This accounts for carrier behavior in the vicinity of grain boundary with regard to defect states. We suggest that electron-hole separation at the grain boundary as well as chemical and electrical distribution of polycrystalline Cu(In,Ga)$Se_2$ thin-films.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2003.07a
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• pp.331-334
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• 2003

Photovoltaics is considered as one of the most promising new energy technology, because its energy source is omni present, pollution-free and inexhaustive. It is agreed that these solar cells must be thin film type because thin film process is cost-efficive in the fact that it uses much less raw materials and can be continuous. The defect chalcopyrite material $CuIn_3Se_5$ has been identified as playing an essential role in efficient photovoltaic action in $CuInSe_2$-based devicesm It has been reported to be of n-type conductivity, forming a p-n junction with its p-type counterpart $CuInSe_2$. Because the most efficient cells consist of the $Cu(In,Ga)Se_2$ quarternary, knowledge of some physical properties of the Ga-containing defect chalcopyrite $Cu(In,Ga)_3Se_5$ may help us better understand the junction phenomena in such devices.

• Proceedings of the KIEE Conference
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• 1998.07d
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• pp.1264-1267
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• 1998

$Cu(In_xGa_{1-x})Se_2$ thin films were prepared and characterized with various Ga contents. As the Ga content increased, the grain size of CIGS film became smaller. The 2 $\theta$ values in XRD patterns were shifted to larger values and the overlapped peaks were splitted. The energy bandgap increased from 1.04 to 1.67 eV and the resistivity decreased. The solar cell fabricated with ZnO/CdS/$Cu(In_{0.7}Ga_{0.3})Se_2/Mo$ structure yielded an efficeincy of 14.48% with an acitive area of 0.18 $cm^2$. The efficiency decreased with further increase of Ga content.

• 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.

• 한국신재생에너지학회:학술대회논문집
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• 2006.06a
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• pp.210-213
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• 2006

나노입자를 이용하여 치밀한 $Cu(In,\;Ga)Se_2$ 태양전지용 광흡수층을 제조하기 위해 먼저, 콜로이달 방법으로 합성된 20nm이하의 CIGS 나노입자를 저가의 스프레이 법을 이용하여 CIGS 막을 제조하였다. 제조된 CIGS막을 two-zone RTP (rapid temperature Process) 방법으로 Se 분위기 안에서 열처리를 행하였다. 입자의 치밀화를 위해 기판의 온도, Se 증발온도와 수송가스의 유량을 조절하여 CIGS 입자성장을 행하였다. 그러나, Se의 증발온도가 높을수록 CIGS와 MO 박막 사이에서 $MoSe_2$ 층이 형성되었다. 형성된 $MoSe_2$층의 부피 팽창으로 인해 하부의 유리기판과 Mo층 사이에서 peeling off 현상이 발생했다. 이러한 Peeling off현상을 억제하면서 CIGS 나노입자 성장을 하기 위해, Se 공급을 빨리 할 수 있도록 Se의 증기압을 높였으며, 최적조건에서 급속 열처리 공정을 통해 CIGS 나노입자 성장과 치밀화를 위한 소결거동을 관찰하였다.