• Proceedings of the KIEE Conference
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• 2000.07c
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• pp.1625-1627
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• 2000

Cu(InGa)$Se_2$(CIGS) thin film absorbers with various Cu/(In+Ga) atomic ratios were prepared by a three-stage process using a co-evaporation appartus. The effect of Na on the structural and electrical properties of CIGS films were studied and their effects on the CIGS/Mo thin film solar cells were investigated. Soda-lime glass and Corning glass were used as substrates to compare the effect of Na diffusion into CIGS film. The resistivity of CIGS films was not changed in the Cu-poor lesion due to diffusion of Na from soda-lime glass but was mainly determined by the surface resistivity controlled by excess Na.

• New & Renewable Energy
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• v.1 no.2 s.2
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• pp.6-10
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• 2005

[ $CulnSe2$ ]계 화합물은 직접천이형 반도체로 광흡수계수가 매우 높아 박막형 태양전지 제조에 매우 유리하다. 또한 화학적으로 안정하며 Ga, Al 등을 첨가하면 에너지 금지대폭을 조절할 수 있어 Wide Bandgap 태양전지 및 탠덤구조 태양전지를 제조하기에도 용이하다. CIS 물질에서 In을 $20-30\%$ 정도 치환한 $Cu(In,\;Ga)Se_2(CIGS)$ 태양전지의 경우 19.5%의 세계 최고 효율을 보고하고 있으며 이는 다결정 실리콘 태양전지의 효율과 비슷한 수준이다. 본 연구에서는 동시 질공증발법을 이용하여 증착한 CIGS 박막 및 $CuGaSe_2(CGS)$ 박막을 이용하여 태양전지를 제조하였다. 공정의 재현성 및 결정립계가 큰 광흡수층 제조를 위하여 실시간 기판 온도 모니터링 시스템을 도입하였으며 버퍼층으로는 용액성장한 CdS 박막을 사용하였다. SLG/MO/CIGS(CGS)/CdS/ZnO/Al 구조의 태양전지를 제조하여 면적 $0.5cm^2$에서 각각 $17\%(CIGS)$와 $7\%(CGS)$의 효율을 얻었다.

• 한국태양에너지학회:학술대회논문집
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• 2012.03a
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• pp.149-152
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• 2012

$Cu(In,Ga)Se_2$ (CIGS) is one of the most promising photovoltaic materials because of large conversion efficiency which has been achieved with an optimum Ga/(In+Ga) composition in $CuIn_{1-x}Ga_xSe_2$ (X~0.3). The Ga/(In+Ga) content is important to determine band gap, solar cell performances and carrier behaviors at grain boundary (GB). Effects of Ga/(In+Ga) content on physical properties of the CIGS layers have been extensively studied. In previous research, it is reported that GB is not recombination center of CIGS thin-film solar cells. However, GB recombination and electron-hole pair behavior studies are still lacking, especially influence of with different X on CIGS thin-films. We obtained the GB surface potential, local current and I-V characteristic of different X (00.7 while X~0.3 showed higher potential than 100 mV on GBs. Higher potential on GBs appears positive band bending. It can decrease recombination loss because of carrier separation. Therefore, we suggest recombination and electron-hole behaviors at GBs depending on composition of X.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.85.2-85.2
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• 2010

$Cu_2ZnSnSe_4$ (CZTSe) is one of candidate to alternate $Cu(In,Ga)Se_2$ as solar absorber material for solar cell. The expensive elements of In and Ga are replaced by Zn and Sn, respectively to lower the material cost. In this study we fabricated CZTSe thin film by selenization of single precursor layer consisted metallic constituent. Precursor compositions ratio were selected to have Cu-poor and Zn-rich content and prepared by RF magnetron sputtering. Thermal processing was applied to introduce selenium into as-deposited films at temperatures ranging from 350 to 500 for time up to 120 minutes. Single precursor films showed amorphous structure and consist of individual elements of Cu, Zn, and Sn. It was confirmed by XRD analysis that synthesis of CZTSe compound is occurred from lower temperature process, although concurrently additional phases such as binary cooper selenides are also existed. The quality of CZTSe crystal was improved as temperature increased. We also investigated the optical and electrical properties of as-selenized CZTSe as well.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2005.11a
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• pp.111-112
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• 2005

To obtain the single crystal thin films, $CuInSe_2$, mixed crystal was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the hot wail epitaxy (HWE) system. The source and substrate temperatures were 620$^{\circ}C$ and 410$^{\circ}C$, 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 mobilily of $CuInSe_2$ single crystal thin films measured with Hall effect by van der Pauw method are $9.62\times10^{16}$ $cm^{-3}$ and $296cm^2/V{\cdot}s$ at 293 K, respectively. The temperature dependence of the energy band gap of the CulnSe$_2$ obtained from the absorption spectra was well described by the Varshni's relation E$_g$(T) = 1.1851 eV - ($8.99\times10^{-4}$ ev/K)T$_2$/(T + 153K). 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 nat ive 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 $CuInSe_2$ 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 Crystal Growth and Crystal Technology
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• v.14 no.6
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• pp.244-252
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• 2004

A stoichiometric mixture of evaporating materials for $CuInSe_2$ single crystal thin films was prepared from horizontal electric furnace. To obtain the single crystal thin films, $_CuInSe2$ 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 $620^{\circ}C$ and $410^{\circ}C$, 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 $CuInSe_2$ single crystal thin films measured with Hall effect by van der Pauw method are $9.62\times10^{16}/\textrm{cm}^3$, 296 $\textrm{cm}^2$/Vㆍs at 293 K, respectively. 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 -($8.99\times10^{-4} eV/K)T^2$(T + 153 K). The crystal field and the spin-orbit splitting energies for the valence band of the CuInSe$_2$ have been estimated to be 0.0087 eV and 0.2329 eV at 10 K, respectively, by means of the photocurrent spectra and the Hopfield quasicubic model. These results indicate that the splitting of the Δso definitely exists in the $\Gamma$6 states of the valence band of the $CuInSe_2$. The three photocurrent peaks observed at 10 K are ascribed to the $A_1-, B_1$-와 $C_1$-exciton peaks for n = 1.

• 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.

• 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).

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2002.05c
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• pp.63-66
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• 2002

Bi-layer Mo films were deposited on sodalime glass substrates using DC magnetron sputtering. As the gas pressure and power density, the resistivity varied from $1.5{\times}10^{-5}$ to $4.97{\times}10^{-4}{\Omega}{\cdot}cm$. Furthermore, stress direction yielded compressive-to-tensile transition stress curves. The microstructure of the compressive stress films which had poor adhesion consists of tightly packed columns, but of the tensile-stressed films had less dense structure. Under all gas pressure conditions, Mo films exhibited distinctly increasing optical reflection with decreasing gas pressure. The expansion of (110) peak width with the gas pressure meant the worse crystalline growth. Also, The highest efficiency was 15.2% on 0.2 $cm^2$. The fill factor, open circuit voltage and short circuit current were 63 %, 570 m V and 42.6 $mA/cm^2$ respectively.

• Proceedings of the Materials Research Society of Korea Conference
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• 2011.05a
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• pp.42.1-42.1
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• 2011

높은 광흡수 계수를 갖는Cu(In,Ga) $Se_2$ (CIGS) 화합물 박막 소재는 고효율 태양전지 양산을 위해 가장 전도유망한 재료이나 상대적으로 매장량이 적은 In 및 Ga을 사용한다는 소재적 한계가 있다. $Cu_2ZnSnSe_4$ (CZTSe) 혹은 $Cu_2ZnSnS_4$(CZTS)와 같은 Cu-Zn-Sn-Se계 화합물 반도체는 CIGS 내 희소원소인 In과 Ga이 범용원소인 Zn 및 Sn으로 대체된 소재로써 미래형 저가 태양전지 개발을 위해 활발히 연구되고 있는데, 그 화합물 조합에 따라 0.8 eV부터 1.5 eV까지의 에너지 밴드갭을 갖는 것으로 알려져 있다. 스퍼터링법에 기반한 2단계 공정에 의해 3.2%의 CZTSe 및 6.7%의 CZTS 태양전지 효율 달성이 보고된 바 있으며, 최근 비진공 방식을 이용하여 제조된 $Cu_2ZnSn(S,Se)_4$ (CZTSSe) 태양전지가 9.6%의 변환효율을 생산하여 세계 최고기록을 갱신한 바 있다. 반면, 동시진공증발법에 의한 Cu-Zn-Sn-Se계 연구는 박막 조성 조절이 상대적으로 용이하다는 장점에도 불구하고, 상대적으로 공개된 연구결과의 양이 적으며 그 효율에 대한 보고는 특히 미미하다. 본 연구에서는 동시진공증발법에 의한 CZTSe 박막 연구 결과를 바탕으로 Sn 손실을 최소화하기 위한 진공증발 공정을 최적화하였으며, 이를 통해 CZTSe 박막 태양전지를 제조하고 그 특성분석을 통해 5% 이상의 변환효율을 달성하였다.