• Proceedings of the Korean Vacuum Society Conference
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• 2010.02a
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• pp.24-24
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• 2010

Chalcopyrite $Cu(In,Ga)Se_2$ (CIGS) 화합물 반도체는 고효율 박막태양전지의 광 흡수층으로 사용되는 물질 중 가장 우수한 효율 (19.9%, NREL 2008)을 보유하고 있다. CIGS는 직접천이형 에너지밴드갭 (direct bandgap)을 가지고 있고, 광흡수계수가 $1{\times}10^5\;cm^{-1}$로서 반도체 중 서 가장 흡수율이 높은 재료에 속하여 두께 $1{\sim}2\;{\mu}m$의 박막으로도 고효율의 태양전지 제조가 가능하고, 또한 장기적으로 전기광학적 안정성이 매우 우수한 특성을 지니고 있다. 현재 고효율 CIGS 셀생성을 위해 널리 사용되고 있는 CIGS 흡수층 성장공정은 "co-evaporation(동시증발법)"과 2-step 공정이라 불리는 "sputter-selenization(스퍼터-셀렌화)" 방법이다. 동시증발법은 개별원소 Cu, In, Ga, Se 들을 고진공 분위기에서 고온 ($550{\sim}600^{\circ}C$)기판위에 증착하는 방법으로 소면적에서 가장 좋은 효율(~20%)을 보이는 공정이다. 하지만, 고온, 고진공 공정조건과 대면적 증착시 온도 및 조성 불균일 등의 문제점 등으로 상용화에 어려움이 있다. 스퍼터-셀렌화 공정은 1단계에서 스퍼터링 방식으로 CuGaIn 전구체를 증착하고, 2단계에서 고온($550{\sim}600^{\circ}C$)하에 $H_2Se$ 혹은 Se vapor와 반응시켜 CIGS를 생성한다. 일본의 Showa Shell와 Honda Soltec 등에 의해 이미 상업화 되었듯이, 저비용 대면적으로 상업화 가능성이 높은 공정으로 평가되고 있다. 하지만, 2단계에서 사용되는 $H_2Se$ 및 Se vapor의 유독성, 기상 Se과 금속전구체 간의 느린 셀렌화 반응속도, 셀렌화반응 후 생성된 CIGS 박막 두께방향으로의 Ga 불균일분포, 생성된 CIGS/Mo 계면 접착력 저하등의 문제점들이 해결되어야만 상업화에 성공할 수 있을 것이다. 본 Tutorial에서는 CIGS 물질의 열역학 상평형과 반응메카니즘에 대해 설명하고, 다양한 생성 공정들을 소개할 것이다.

• Proceedings of the Materials Research Society of Korea Conference
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• 2005.05a
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• pp.80-80
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• 2005

• Journal of the Korean Solar Energy Society
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• v.25 no.4
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• pp.1-11
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• 2005

The stoichiometric mixture of evaporating materials for the $CuInSe_2$ single crystal thin film was prepared from horizontal furnace. Using extrapolation method of X-ray diffraction patterns for the polycrystal $CuInSe_2$, it was found tetragonal structure whose lattice constant $a_0$ and $c_0$ were $5.783\;{\AA}$ and $11.621\;{\AA}$, respectively. To obtain the $CuInSe_2$ single crystal thin film, $CuInSe_2$ mixed crystal was deposited on throughly etched GaAs(100) by the HWE(Hot Wall Epitaxy) system. The source and substrate temperature were $620^{\circ}C$ and $410^{\circ}C$ respectively. The crystalline structure of $CuInSe_2$ single crystal thin film was investigated by the double crystal X-ray diffraction(DCXD). Hall effect on this sample was measured by the method of Van der Pauw and studied on carrier density and mobility depending on temperature. From Hall data, the mobility was likely to be decreased by impurity scattering in the temperature range 30 K to 100 K and by lattice scattering in the temperature range 100 K to 293 K. The temperature dependence of the energy band gap of the $CuInSe_2$ obtained from the absorption spectra was well described by the Varshni's relation, $E_g(T)=1.1851\;eV-(8.99{\times}10^{-4}\;eV/K)T^2/(T+153\;K)$. The open-circuit voltage, short current density, fill factor, and conversion efficiency of $n-CdS/p-CuGaSe_2$ heterojunction solar cells under $80\;mW/cm^2$ illumination were found to be 0.51V, $29.3\;mA/cm^2$, 0.76 and 14.3 %, respectively.

• 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 Korean Vacuum Society Conference
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• 2010.08a
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• pp.319-319
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• 2010

칼코젠계 태양전지의 광흡수층으로 사용되는 CuInSe2은 직접천이형 반도체로 광흡수계수가 $1{\times}105cm-1$로 매우 높고, 전기광학적 안정성이 우수하여 실리콘 결정질 태양전지를 대체할 고효율 태양전지로 각광받고 있다. 광흡수층의 밴드갭 에너지가 증가하면 태양전지의 개방전압(Voc)이 증가하여 광변환 효율을 향상시킬 수 있으므로, CuInSe2에서 In의 일부를 Ga으로 치환하여 에너지 밴드갭의 변화를 주는 연구가 많이 진행되고 있다. 그러나 화합물내의 Ga 조성비가 증가하면 단락전류(Jsc), 충진률(fill factor)이 낮아져 태양전지 효율을 저하시키게 되므로 CIGS 박막의 적절한 화합물 조성비를 갖도록 최적조건을 확립하는 것이 매우 중요하다. 본 실험에서는 광흡수층 형성을 위해 Sputtering법으로 금속 전구체를 증착하고, 고온에서 셀렌화 열처리를 수행하는 Sequential process(2단계 증착법)를 이용하였다. soda-lime glass 기판에 Back contact으로 Mo를 증착하고, 1단계로 CuIn0.7Ga0.3 조성비의 타겟을 이용하여 Sputtering법으로 $0.5{\sim}2{\mu}m$ 두께의 CIG 전구체를 증착하였다. 2단계로 CIG 전구체의 셀렌화열처리를 통하여 CIGS 화합물 구조의 박막을 형성시켰다. 이때 형성된 CIGS 화합물 박막의 두께는 동일하게 함으로써, 열처리온도에 의한 박막의 구조변화를 비교하였다. 증착된 CIGS 박막은 고온 엑스선회절분석을 통해 증착 두께와 온도 변화에 따른 CIGS 층의 구조 변화를 확인하고, 동일한 증착조건으로 Buffer layer, Window layer, Grid 전극을 형성하여 태양전지셀 특성을 평가함으로써 CIGS 태양전지 광흡수층의 결정구조에 따른 광변환 효율을 비교하였다.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.12 no.4
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• pp.202-209
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• 2002

The stochiometric mix of evaporating materials for the $CuInSe_2$single crystal thin films was prepared from horizontal furnace. To obtain the single crystal thin films, $CuInSe_2$compound crystal was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the Hot Wall Epitaxy (HWE) system. The source and substrate temperature were $620^{\circ}C$ and $410^{\circ}C$, respectively. The crystalline structure of single crystal thin films was investigated by the photoluminescence and double crystal X-ray diffraction (DCXD). The carrier density and mobility of $CuInSe_2$single crystal thin films measured from Hall effect by van der Pauw method. From the photocurrent spectrum by illumination of perpendicular light on the c-axis of the $CuInSe_2$single crystal thin film, we have found that the values of spin orbit splitting $\Delta$So and the crystal field splitting $\Delta$Cr. From the photoluminescence measurement on $CuInSe_2$single crystal thin film, we observed free exciton ($E_x$) existing only high quality crystal and neutral bound exciton ($A^{\circ}$, X) having very strong peak intensity. Then, the full-width-at-half-maximum (FWHM) and binding energy of neutral donor bound exciton were 7 meV and 5.9 meV, respectivity. By haynes rule, an activation energy of impurity was 59 meV.

• 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.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.02a
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• pp.370-370
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• 2011

I-III-IV2족의 Cu(In,Ga)Se2 (CIGS) 박막 태양전지는 3단계(three-stage) 동시증발공정을 통하여 약 19.9%의 최고의 효율을 보유하고 있다. 3단계 공정에 있어 IV2족 Se의 증발 속도 또는 증착압력은 우선 배향성 제어 및 표면 미세구조 영향 등에 큰 영향을 미치는 것으로 알려져 있다. 본 연구에서는 CIGS 박막 합성을 위한 3단계 공정에서 각 단계별 Se 분압의 변화를 주어, 각 공정 단계에서 Se 분압의 변화가 CIGS 박막의 미세구조 및 셀 효율에 미치는 영향을 분석하였다. 3단계 공정에서 Cu, In, Ga 분압은 고정시키고, Se 분압의 크기 순서대로 1, 2, 3으로 변화시켜 CIGS 박막을 제조하였다. 이 박막의 미세구조, 특히, 우선 배향성, 표면의 기공, 결정성을 제어 하기 위하여 3단계 공정에서 1st stage 이후 Se 분압을 증가시키는 방법($3{\rightarrow}1$, $2{\rightarrow}1$)과 1st stage 이 후 Se 분압을 감소시키는 방법($1{\rightarrow}3$, $1{\rightarrow}2$)을 적용하여 비교하였다. 그 결과 3단계에서 1st stage 이후 Se 분압을 증가시킴으로써 (220)/(204)의 우선 배향성을 촉진시키며, 결정성을 개선하였고, 1st stage 이후 Se 분압을 감소시킴으로써 CIGS 박막 표면의 기공을 제거하고, 결정성을 향상시켰다. 이렇게 1st stage이 후 Se 분압을 증가시킴으로써 (220)/(204)의 우선 배향성의 촉진과 결정성 개선은 단락 전류(Jsc)를 증가시켰으며, 1st stage 이후 Se 분압을 감소시킴으로써 CIGS 박막 표면의 기공을 제거와 결정성 개선은 개방전압(Voc)의 증가효과를 가져왔다.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.19-22
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• 2009

A non-vacuum process for fabrication of $CuIn_xGa_{1-x}Se_2$ (CIGS) absorber layer from the corresponing Cu, In, Ga solution precursors was described. Cu, In, Ga precursor solution was prepared by a room temperature colloidal route by reacting the starting materials $Cu(NO_3)_2$, $InCl_3$, $Ga(NO_3)$ and methanol. The Cu, In, Ga precursor solution was mixed with ethylcellulose as organic binder material for the rheology of the mixture to be adjusted for the doctor blade method. After depositing the mixture of Cu, In, Ga solution with binder on Mo/glass substrate, the samples were preheated on the hot plate in air to evaporate remaining solvents and to burn the organic binder material. Subsequently, the resultant CIG/Mo/glass sample was selenized in Se evaporation in order to get a solar cell applicable dense CIGS absorber layer. The CIGS absorber layer selenized at $530^{\circ}C$ substrate temperature for 1h with various metal organic ratio.

• Laser Solutions
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• v.17 no.4
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• pp.7-13
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• 2014

In this work, the application of laser induced breakdown spectroscopy (LIBS) for the composition analysis of thin $Cu(In,Ga)Se_2$ (CIGS) solar cell films ($1-2{\mu}m$ thickness) is reported. For the ablation of CIGS films, femtosecond (fs) laser (wavelength = 343nm, pulse width = 500fs) and nanosecond (ns) laser (wavelength = 266nm, pulse width = 5ns) were used under atmospheric environment. The emission spectra were detected with an intensified charge coupled device (ICCD) spectrometer and multichannel CCD spectrometer for fs-LIBS and ns-LIBS, respectively. The calibration curves for fs-LIBS and ns-LIBS intensity ratios of Ga/Cu, In/Cu, and Ga/In were generated with respect to the concentration ratios measured by inductively coupled plasma optical emission spectrometry (ICP-OES).