• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2002.07b
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• pp.869-873
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• 2002

$Cu_2ZnSnS_4$ (CZTS) thin film is one of the candidate materials for the solar cell. It has an excellent optical absorption coefficient as well as appropriate 1.4~1.5eV band gap. The purpose of this study is replacing a half of high-cost Indium(In) atoms with low-cost Zinc(Zn) atoms and the other half with low-cost Tin(Sn) atoms in the lattice of CIS. In annealing process of thin films deposited with mixture target, the thin films were appeared the peeling. The resistivity was decreased. Thin films were deposited on ITO glass substrates using a compound target which were made by $CU_2S$, ZnS, $SnS_2$ powder were sintered in the atmosphere of Al at room temperature by rf magnetron sputtering We investigated potentialities of a low-cost material for the solar cell by measuring of thin film composition, the structure and optical properties. We could get an appropriate $Cu_2ZnSnS_4$ composition A (112) preferred orientation was appeared without annealing temperature as shown in the diffraction peaks of the CIS cells and was available for photovoltaic thin film materials. The band gap increased from 1.4 to 1.7eV as the composition ratio of Zn/Sn.. The optical absorption coefficient of the thin film was above $10^4cm^{-1}$.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.86.1-86.1
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• 2010

Cu2ZnSnSe4는 CIS 태양전지의 In 대체 물질계로 주목을 받고 있는 저가형 태양전지 재료로 장차 차세대 태양전지 재료로 응용이 기대되고 있다. 그러나 에너지 밴드갭이 0.9~1.1eV로 다소 낮아 태양전지 광흡수층 재료로 사용하기 위해서는 wide band gab화 처리가 필요하다. 본 연구에서는 CZTSe에 S를 첨가하여 에너지 밴드갭을 확장하고자 하며, S의 첨가가 CZTSe 박막의 특성에 미치는 영향에 대하여 조사하였다. 실험의 편의성을 도모하고자 펄스레이저 법을 사용하여 증착하였다. 박막 조성 제어에는 Cu, Zn, Sn, Se, S 분말을 볼밀로 분쇄, 혼합하여 균질 혼합상 프리커서를 제조하고 이를 Cold Isostatic Press(CIP) 성형하여 Source target을 사용하였다. Pulsed YAG-Laser를 사용하여 soda lime glass상에 증착하고 조성, 구조, 조직을 관찰하고 에너지 밴드갭, 광흡수계수, 면저항, 전하밀도 등 특성을 조사하였다.

• Journal of the Korean institute of surface engineering
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• v.35 no.1
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• pp.39-46
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• 2002

$Cu_2$$ZnSnS_4$(CZTS) thin film is one of the candidate materials for the solar cell. It has an excellent optical absorption coefficient as well as appropriate 1.4~1.5eV band gap. The purpose of this study is replacing a half of high-cost Indium(In) atoms with low-cost Zinc(Zn) atoms and the other half with low-cost Tin(Sn) atoms in the lattice of CIS. Thin films were deposited on ITO glass substrates using a compact target which were made by $Cu_2$S, ZnS, SnS$_2$ powder at room temperature by rf magnetron sputtering and were annealed in the atmosphere of Ar and $S_2$(g). We investigated potentialities of a low-cost material for the solar cell by measuring of thin film composition, the structure and optical properties. We could get an appropriate $Cu_2$$ZnSnS_4$ composition. Structure was coarsened with increasing temperature and (112), (200), (220), (312) planes appeared to conform to all the reflection Kesterite structure. A (112) preferred orientation was advanced with increasing the annealing temperature as shown in the diffraction peaks of the CIS cells and was available for photovoltaic thin film materials. The band gap increased from 1.51 to 1.8eV as the annealing temperature increased. The optical absorption coefficient of the thin film was about $10^4$$cm^{-1}$.

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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• pp.407.2-407.2
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• 2016

Cu2ZnSnS4 (CZTS) 박막은 낮은 가격과 유리한 특성을 가지므로서 차세대 박막 태양전지에서 이상적인 흡수층 물질 중 하나로 여겨지고 있다. 우리는 CZTS 박막 태양전지를 합성하는 데 있어서 Zn와 ZnS를 전구체에 사용하여 이에 따른 특성 차이를 연구하였다. 열처리 한 박막은 Zn와 ZnS를 사용하였을 때 특성 차이를 조사하기 위하여 여러 분석을 진행하였다. CZTS 박막의 미세구조와 조성 분포, 전기적 특성을 살펴보았다. Zn를 사용한 CZTS 박막은 큰 입자크기와 더 적은 영역에서 Zn가 집중되어 있는 층을 가진다. CZTS와 Mo 경계인 이 영역에 ZnS 2차상이 존재함을 의미하며 Zn 타겟을 사용하였을 때 더 낮은 Zn 조성을 가지는 것을 확인하였고 이는 결과적으로 접합 특성의 향상을 가져온다. 제작 된 CZTS 태양 전지 소자에서 이러한 이유로 Zn를 사용하였을 때 5.06%로 ZnS를 사용하였을 때에 비하여 더 높은 효율을 얻을 수 있었다.

• Current Applied Physics
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• v.18 no.12
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• pp.1571-1576
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• 2018

Recent study shows that the main reason for limiting CZTS device performance lies in the low open circuit voltage, and crucial factor that could affect the $V_{oc}$ is secondary phases like ZnS existing in absorber layer and its interfaces. In this work, the $Cu_2ZnSnS_4$ thin film solar cells were prepared by sputtering CuSn and CuZn alloy targets. Through tuning the Zn/Sn ratios of the CZTS thin films, the crystal structure, morphology, chemical composition and phase purity of CZTS thin films were characterized by X-Ray Diffraction (XRD), scanning electron microscopy (SEM) equipped with an energy dispersive spectrometer (EDS) and Raman spectroscopy. The statistics data show that the CZTS solar cell with a ratio of Zn/Sn = 1.2 have the best power convention efficiency of 5.07%. After HCl etching process, the CZTS thin film solar cell with the highest efficiency 5.41% was obtained, which demonstrated that CZTS film solar cells with high efficiency could be developed by sputtering CuSn and CuZn alloy targets.

• Current Photovoltaic Research
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• v.2 no.4
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• pp.177-181
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• 2014

$Cu_2ZnSn(S_xSe_{1-x})_4$ (CZTSSe) absorber thin films were prepared on Mo coated soda lime glass substrates by sulfo-selenization of sputtered stacked Zn-Sn-Cu precursor thin films. The Zn-Sn-Cu precursor thin films were sulfo-selenized inside a graphite box containing S and Se powder using rapid thermal processing furnace at $540^{\circ}C$ in Ar atmosphere with pre-treatment at $300^{\circ}C$. The effect of different S/Se ratio on the structural, compositional, morphological and electrical properties of the CZTSSe thin films were studied using XRD (X-ray diffraction), XRF (X-ray fluorescence analysis), FE-SEM (field-emission scanning electron microscopy), respectively. The XRD, FE-SEM, XRF results indicated that the properties of sulfo-selenized CZTSSe thin films were strongly related to the S/Se composition ratio. In particular, the CZTS thin film solar cells with S/(S+Se)=0.25 shows best conversion efficiency of 4.6% ($V_{oc}$ : 348 mV, $J_{sc}$ : $26.71mA/cm^2$, FF : 50%, and active area : $0.31cm^2$). Further detailed analysis and discussion for effect of S/Se composition ratio on the properties CZTSSe thin films will be discussed.

• Journal of the Korean institute of surface engineering
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• v.44 no.5
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• pp.185-189
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• 2011

$Cu_2ZnSnSe_4$ thin films for solar absorber application were prepared by pulsed laser deposition of a synthesized $Cu_2ZnSnSe_4$ compound target. The film's composition revealed that the deposited films possess an identical composition with the target material. Further film compositional control toward a stoichiometric composition was performed by optimizing substrate temperature, deposition time and target rotational speed. At the optimum condition, X-ray diffraction patterns of films showed that the films demonstrated polycrystalline stannite single phase with a high degree of (112) preferred orientation. The absorption coefficient of $Cu_2ZnSnSe_4$ thin films were above 104 cm.1 with a band gap of 1.45 eV. At an optimum condition, films were identified as a p type semiconductor characteristic with a resistivity as low as $10^{-1}{\Omega}cm$ and a carrier concentration in the order of $10^{17}cm^{-3}$.

• 한국신재생에너지학회:학술대회논문집
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• 2007.11a
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• pp.305-305
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• 2007

• 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.

• Current Photovoltaic Research
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• v.5 no.1
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• pp.20-24
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• 2017

Recently, three-dimensional (3D) light harvesting structures are highly attracted because of their high light harvesting capacity and charge collection efficiencies. In this study, we have fabricated $Cu_2ZnSn(S_xSe_{1-x})_4$ based 3D thin film solar cells on PR patterned Molybdenum (Mo) substrates using photolithography technique. Specifically, Mo patterns were deposited on PR patterned Mo substrates by sputtering and the thin Cu-Zn-Sn stacked layer was deposited over this Mo patterns by sputtering technique. The stacked Zn-Sn-Cu precursor thin films were sulfo-selenized to form CZTSSe pattern. Finally, CZTSSe absorbers were coated with thin CdS layer using chemical bath deposition and ZnO window layer was deposited over CZTSSe/CdS using DC sputtering technique. Fabricated 3-D solar cells were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF) analysis, Field-emission scanning electron microscopy (FE-SEM) to study their structural, compositional and morphological properties, respectively. The 3% efficiency is achieved for this kind of solar cell. Further efforts will be carried out to improve the performance of solar cell through various optimizations.