• Current Photovoltaic Research
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• v.7 no.4
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• pp.103-110
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• 2019

Cu(In,Ga)₃Se₅ (β-CIGS) has a band gap of 1.35 eV, which is an optimum value for high solar-energy conversion efficiency. The effects of Cu and Ga content on the cell performance were investigated previously. However, the effect of Se content on the cell performance is not well understood yet. In this work, β-CIGS films were fabricated by three-stage co-evaporation of elemental sources with various Se fluxes at the third stage instead of at all stages. The average composition of five samples was Cu_1.05(In_0.59,Ga_0.41)3Se_y, where the stoichiometric y value is 5.03 and the stoichiometric Se/metal (Se/M) ratio is 1.24. We varied the Se/metal ratio in a range from 1.18 to 1.28. We found that the best efficiency was achieved when the Se/M ratio was 1.24, which is exactly the stoichiometric value where the CIGS grains on the CIGS surface were tightly connected and faceted. With the optimum Se/M ratio, we were able to enhance the cell efficiency of a β-CIGS solar cell from 9.6% to 12.0% by employing a Na₂S post deposition treatment. Our results indicate that Na₂S post deposition treatment is very effective to enhance the cell efficiency to a level on par with that in α-CIGS cell.

• 한국신재생에너지학회:학술대회논문집
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• 2009.11a
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• pp.400-400
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• 2009

Despite the success of Cu(In,Ga)$Se_2$ (CIGS) based PV technology now emerging in several industrial initiatives, concerns about the cost of In and Ga are often expressed. It is believed that the cost of those elements will eventually limit the cost reduction of this technology. One candidate to replace CIGS is $Cu_2ZnSnSe_4$ (CZTSe), fabricated by co-evaporation technique. Co-evaporation technique will be one of the best methods to control film composition. This type of absorber derives from the $CuInSe^2$ chalcopyrite structure by substituting half of the indium atoms with zinc and other half with tin. Energy bandgap of this material has been reported to range from 0.8eV for selenide to 1.5eV for the sulfide and large coefficient in the order of $10^{14}cm^{-1}$, which means large possibility of commercial production of the most suitable absorber by using the CZTSe film. In this work, Effects of substrate temperature of $Cu_2ZnSnSe_4$ absorber layer on the performance of thin films solar cells were investigated. We reported on some of the absorber properties and device results.

• Current Photovoltaic Research
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• v.3 no.1
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• pp.21-26
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• 2015

High efficiency $Cu(In,Ga)Se_2$ solar cells are generally prepared above $500^{\circ}C$. Lowering the process temperature can allow wider selection of substrate material and process window. In this paper, the three-stage co-evaporation process widely used to grow CIGS thin film at high temperature was modified to reduce the maximum substrate temperature. Below $400^{\circ}C$ the CIGS films show poor crystal growth and lower solar cell performance, in spite of external Na doping by NaF. As a new approach, Cu source instead of Cu with Se in the second stage was applied on the $(In,Ga)_2Se_3$ precursor at $400^{\circ}C$ and achieved a better crystal growth. The distribution of Ga in the films produce by new method were investigated and solar cells were fabricated using these films.

• 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.

• 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.

• 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.

• 한국신재생에너지학회:학술대회논문집
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• 2005.06a
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• pp.109-112
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• 2005

Cu계$I-III-VI_2$화합물은 직접천이형 반도체로 광흡수계수가 매우 높아 박막형 태양전지 제조에 매우 유리하다 또한 화학적으로 안정하며 Ga, A1등을 첨가하면 에너지 금지대폭을 조절할 수 있어 Wide Bandgap 태양전지 및 탠덤구조 태양전지를 제조하기에도 용이하다. $CuInSe_2(CIS)$ 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 진공증발법을 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/Al구조의 태양전지를 제조하여 면적 $0.5cm^2$에서 각각 $15\%$(CIGS)와 $7\%(CGS)$의 효율을 얻었다.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.14 no.6
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• pp.445-454
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• 2001

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$_2$ mixed crystal was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the Hot Wall Epitaxy(HWE) system. The source and substrate temperature were 62$0^{\circ}C$ and 41$0^{\circ}C$, 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 fby van der Pauw method are 9.62x10$^{16}$ cm$^{-3}$ , 296$\textrm{cm}^2$/V.s at 293 K, respectively. 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 he values of spin orbit splitting ΔSo and the crystal field splitting ΔCr were 6.1 meV and 175.2 meV at 10K, respectively. From the photoluminescence measurement on CuInSe$_2$ single crystal thin film we observed free excition (Ex) existing only high quality crystal and neutral bound exiciton (D$^{\circ}$,X) having very strong peak intensity. Then, the full-width-at-half-maximum(FWHM) and binding energy of neutral donor bound excition were 7meV and 5.9meV, respectivity. by Haynes rule, an activation energy of impurity was 50 meV.

• 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 Materials Research Society of Korea Conference
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• 2003.03a
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• pp.83-83
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• 2003

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$_2$ mixed crystal was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the Hot Wall Epitaxy (HWE) system. The source and substrate temperature were 62$0^{\circ}C$ and 41$0^{\circ}C$, 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 are 9.62$\times$10$^{16}$ cm$^{-3}$ , 296 $\textrm{cm}^2$/V.s at 293 K, respectively 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 ΔSo and the crystal field splitting ΔCr were 6.1 meV and 175.2 meV at 10 K, respectively. From the photoluminescence measurement on CuInSe$_2$ single crystal thin film, we observed free excition (Ex) existing only high quality crystal and neutral bound exiciton (D$^{\circ}$,X) having very strong peak intensity. Then, the full-width-at -half-maximum(FWHM) and binding energy of neutral donor bound excition were 7 meV and 5.9 meV, respectivity. By Haynes rule, an activation energy of impurity was 59 meV.