• 한국재료학회지
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• 제23권3호
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• pp.183-189
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• 2013

$Cu_2ZnSn(S,Se)_4$ material is receiving an increased amount of attention for solar cell applications as an absorber layer because it consists of inexpensive and abundant materials (Zn and Sn) instead of the expensive and rare materials (In and Ga) in $Cu(In,Ga)Se_2$ solar cells. We were able to achieve a cell conversion efficiency to 4.7% by the selenization of a stacked metal precursor with the Cu/(Zn + Sn)/Mo/glass structure. However, the selenization of the metal precursor results in large voids at the absorber/Mo interface because metals diffuse out through the top CZTSe layer. To avoid the voids at the absorber/Mo interface, binary selenide compounds of ZnSe and $SnSe_2$ were employed as a precursor instead of Zn and Sn metals. It was found that the precursor with Cu/$SnSe_2$/ZnSe stack provided a uniform film with larger grains compared to that with $Cu_2Se/SnSe_2$/ZnSe stack. Also, voids were not observed at the $Cu_2ZnSnSe_4$/Mo interface. A severe loss of Sn was observed after a high-temperature annealing process, suggesting that selenization in this case should be performed in a closed system with a uniform temperature in a $SnSe_2$ environment. However, in the experiments, Cu top-layer stack had more of an effect on reducing Sn loss compared to $Cu_2Se$ top-layer stack.

• Current Photovoltaic Research
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• 제10권2호
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• pp.39-48
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• 2022

A Se-containing Cu/SnSe₂/ZnSe precursor was employed to introduce S to the precursor to form Cu₂ZnSn(S,Se)₄ (CZTSSe) film. The morphology of CZTSSe films strongly varied with two different pre-annealing environments: S and N₂. The CZTSSe film with S pre-annealing showed a dense morphology with a smooth surface, while that with N₂ pre-annealing showed a porous film with a plate-shaped grains on the surface. CuS and Cu₂Sn(S,Se)₃ phases formed during the S pre-annealing stage, while SnSe and Cu₂SnSe₃ phases formed during the N₂ pre-annealing stage. The SnSe phase formed during N₂ pre-annealing generated SnS₂ phase that had plate shape and severely aggravated the morphology of CZTSSe film. The power conversion efficiency of the CZTSSe solar cell with S pre-annealing was low (1.9%) due to existence of Zn(S.Se) layer between CZTSSe and Mo substrate. The results indicated that S pre-annealing of the precursor was a promising method to achieve a good morphology for large area application.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2015년도 제49회 하계 정기학술대회 초록집
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• pp.86.2-86.2
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• 2015

Cu2ZnSn(S,Se)4 thin film solar cells have been fabricated using sputtered Cu/Sn/Zn metallic precursors on Mo coated sodalime glass substrate without using a toxic H2Se and H2S atmosphere. Cu/Sn/Zn metallic precursors with various thicknesses were prepared using DC magnetron sputtering process at room temperature. As-deposited metallic precursors were sulfo-selenized inside a graphite box containing S and Se pellets using rapid thermal processing furnace at various sulfur to selenium (S/Se) compositional ratio. Thin film solar cells were fabricated after sulfo-selenization process using a 65 nm CdS buffer, a 40 nm intrinsic ZnO, a 400 nm Al doped ZnO, and Al/Ni top metal contact. Effects of sulfur to selenium (S/Se) compositional ratio on the microstructure, crystallinity, electrical properties, and cell efficiencies have been studied using X-ray diffraction, Raman spectroscopy, field emission scanning electron microscope, I-V measurement system, solar simulator, quantum efficiency measurement system, and time resolved photoluminescence spectrometer. Our fabricated Cu2ZnSn(S,Se)4 thin film solar cell shows the best conversion efficiency of 9.24 % (Voc : 454.6 mV, Jsc : 32.14 mA/cm2, FF : 63.29 %, and active area : 0.433 cm2), which is the highest efficiency among Cu2ZnSn(S,Se)4 thin film solar cells prepared using sputter deposited metallic precursors and without using a toxic H2Se gas. Details about other experimental results will be discussed during the presentation.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2007년도 추계학술대회 논문집
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• pp.270-273
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• 2007

In this report, Indium-free and Indium-reduced thin film materials for solar absorber were studied in order to search alternative materials for thin film solar cell. The films of $Cu_2ZnSnSe_4$ and $Cu_2ZnSnSe_2$ were deposited using mixed binary chalcogenides powders. From the film bulk analysis result, it is observed that Cu concentration is a function of substrate temperature as well as CuSe mole ratio in the target. Under optimized conditions, $Cu_2ZnSnSe_4$ and $Cu_2ZnSnSe_2$ thin films grow with strong (112), (220/204) and (312/116) reflections. Films are found to exhibit a high absorption coefficient of $10^4$ $cm^{-1}$. $Cu_2ZnSnSe_4$ film shows a 1.5 eV band gap. On the other side, an increasing of optical band gap from 1.0 eV to 1.25 eV ($CuInSnSe_2$) is found to be proportional with an increasing of Zn concentration. All films have a p-type semiconductor characteristic with a carrier concentration in the order of $10^{14}$ $cm^{-3}$, a mobility about $10^1$ $cm^{2{\cdot}-1.}S^{-1}$ and a resistivity at the range of $10^2-10^6$ ${\Omega}{\cdot}m$.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2010년도 춘계학술대회 초록집
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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.

• Current Photovoltaic Research
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• 제2권4호
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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.

• Current Photovoltaic Research
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• 제3권3호
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• pp.75-79
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• 2015

Recently, $Cu_2ZnSn(S_xSe_{1-x})_4$ (CZTSSe) has been received a tremendous attraction as light absorber material in thin film solar cells (TFSCs), because of its earth abundance, inexpensive and non-toxic constituents and versatile material characteristics. Kesterite CZTSSe thin films were synthesized by sulfo-selenization of sputtered Cu/Sn/Zn stacked metallic precursors. The sulfo-selenization of Cu/Sn/Zn stacked metallic precursor thin films has been carried out in a graphite box using rapid thermal annealing (RTA) technique. Annealing process was done under sulfur and selenium vapor pressure using Ar gas at $520^{\circ}C$ for 10 min. The effect of tuning Se/(S+Se) precursor composition ratio on the properties of CZTSSe films has been investigated. The XRD, Raman, FE-SEM and XRF results indicate that the properties of sulfo-selenized CZTSSe thin films strongly depends on the Se/(S+Se) composition ratio. In particular, the CZTSSe TFSCs with Se/(S+Se) = 0.37 exhibits the best power conversion efficiency of 4.83% with $V_{oc}$ of 467 mV, $J_{sc}$ of $18.962mA/cm^2$ and FF of 54%. The systematic changes observed with increasing Se/(S+Se) ratio have been discussed in detail.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2010년도 춘계학술대회 초록집
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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.

• 한국표면공학회지
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• 제44권5호
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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 $10^{17}cm^{-3}$.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2011년도 춘계학술발표대회
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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.