• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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• pp.98.2-98.2
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• 2012

Thin film solar cells are growing up in the market due to their high efficiency and low cost. Especially CdTe and $CuInGaSe_2$ based solar cells are leading the other cells, but due to the limited percentage of the elements present in our earth's crust like Tellurium, Indium and Gallium, the price of the solar cells will increase rapidly. Copper Zinc Tin Sulfide (CZTS) and Copper Zinc Tin Selenide (CZTSe) semiconductor (having a kesterite crystal structure) are getting attention for its solar cell application as the absorber layer. CZTS and CZTSe have almost the same crystal structure with more environmentally friendly elements. Various authors have reported growth and characterization of CZTSe films and solar cells with efficiencies about 3.2% to 8.9%. In this study, a novel method to prepare CZTSe has been proposed based on selenization of stacked Copper Selenide ($Cu_2Se$), Tin Selenide ($SnSe_2$) and Zinc Selenide (Zinc Selenide) in six possible stacking combinations. Depositions were carried out through RF magnetron sputtering. Selenization of all the samples was performed in Close Space Sublimation (CSS) in vacuum at different temperatures for three minutes. Characterization of each sample has been performed in Field Emission SEM, XRD, Raman spectroscopy, EDS and Auger. In this study, the properties and results of $Cu_2ZnSnSe_4$ thin films grown by selenization will be presented.

• Korean Journal of Materials Research
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• v.34 no.10
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• pp.515-521
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• 2024

Solar energy has been recognized as an alternative energy source that can help address fuel depletion and climate change issues. As a renewable energy alternative to fossil fuels, it is an eco-friendly and unlimited energy source. Among solar cells, thin film Cu₂ZnSn(S,Se)₄ (CZTSSe) is currently being actively studied as an alternative to heavily commercialized Cu(In,Ga)Se₂ (CIGS) thin film solar cells, which rely upon costly and scarce indium and gallium. Currently, the highest efficiency achieved by CZTSSe cells is 14.9 %, lower than the CIGS record of 23.35 %. When applied to devices, CZTSSe thin films perform poorly compared to other materials due to problems including lattice defects, conduction band offset, secondary phase information, and narrow stable phase regions, so improving their performance is essential. Research into ways of improving performance by doping with Germanium and Cadmium is underway. Specifically, Ge can be doped into CZTSSe, replacing Sn to reduce pinholes and bulk recombination. Additionally, partially replacing Zn with Cd can facilitate grain growth and suppress secondary phase formation. In this study, we analyzed the device's performance after doping Ge into CZTSSe thin film using evaporation, and doping Cd using chemical bath deposition. The Ge doped thin film showed a larger bandgap than the undoped reference thin film, achieving the highest Voc of 494 mV in the device. The Cd doped thin film showed a smaller bandgap than the undoped reference thin film, with the highest J_sc of 36.9 mA/cm². As a result, the thin film solar cells achieved a power conversion efficiency of 10.84 %, representing a 20 % improvement in power conversion efficiency compared to the undoped reference device.

• Korean Journal of Materials Research
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• v.31 no.11
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• pp.619-625
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• 2021

Cu₂ZnSn(S,Se)₄ (CZTSSe) based thin-film solar cells have attracted growing attention because of their earth-abundant and non-toxic elements. However, because of their large open-circuit voltage (V_oc)-deficit, CZTSSe solar cells exhibit poor device performance compared to well-established Cu(In,Ga)(S,Se)₂ (CIGS) and CdTe based solar cells. One of the main causes of this large V_oc-deficit is poor absorber properties for example, high band tailing properties, defects, secondary phases, carrier recombination, etc. In particular, the fabrication of absorbers using physical methods results in poor surface morphology, such as pin-holes and voids. To overcome this problem and form large and homogeneous CZTSSe grains, CZTSSe based absorber layers are prepared by a sputtering technique with different RTA conditions. The temperature is varied from 510 ℃ to 540 ℃ during the rapid thermal annealing (RTA) process. Further, CZTSSe thin films are examined with X-ray diffraction, X-ray fluorescence, Raman spectroscopy, IPCE, Energy dispersive spectroscopy and Scanning electron microscopy techniques. The present work shows that Cu-based secondary phase formation can be suppressed in the CZTSSe absorber layer at an optimum RTA condition.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.08a
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• pp.25-25
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• 2010

Cu(In, Ga)$Se_2$ (CIGS), $CuInS_2$ (CIS) 등의 Se, S계 화합물 박막 소재를 활용한 태양전지는 높은 광흡수 계수, 상대적으로 높은 효율, 화학적 안정성, 도시적인 미관 등으로 인하여 최근 부각되고 있다. 하지만 CIGS, CIS 등의 Se, S계 박막 소재는 상대적으로 매장량이 적은(희유 원소) In, Ga을 사용하고 있는 약점이 있으며 특히 In의 경우는 LCD Display에 사용되는 ITO 필름으로 인해 가격이 상승하고 있다. 따라서 결정질 실리콘 태양전지의 경험에서와 같이 생산량의 급증에서 기인하는 소재 부족 문제를 미연에 방지하고 안정적인 성장을 이루기 위해서는 희유 원소인 In과 Ga을 저가 범용원소로 대체 하는 기술을 추가적으로 개발해야 한다. $Cu_2ZnSnS_4$ (CZTS) 박막 태양전지는 Se, S계 태양전지에서 III 족 원소인 In, Ga을 II-IV 원소인 Zn와 Sn으로 대체하는 기술로 기존의 CIGS계 태양전지가 보유하고 있는 장점을 유지하면서 저가 태양전지를 구현할 수 있는 대체 물질로 최근 많은 관심을 받고 있다. CZTS 박막 태양전지 관련 세계 기술동향 조사에 따르면, 최근 2008년에 일본 Nagaoka 대학의 Katagiri 그룹에서 스퍼터를 이용하여 제조한 CZTS 박막 태양전지의 최고 효율이 6.77%가 됨을 보고하였고, 2010년 초에는 IBM에서 스핀코팅법을 이용하여 제조한 CZT(S, Se) 박막 태양전지의 효율을 9.66%까지 올릴 수 있음을 Advanced Materials에 보고하였다. 본 발표에서는 우선 CZTS 박막태양전지 제조 및 특성 분석 관련 개요 및 세계 기술 개발 동향 분석 결과를 설명할 것이다. 또한 본 실험실, 에너지 기술 연구원 및 KIST, 영남대 등 국내에서 진행되고 있는 CZTS 관련 기술 개발 현황에 대하여 설명할 것이다.

• Korean Journal of Materials Research
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• v.29 no.9
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• pp.553-558
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• 2019

$Cu_2ZnSn(S,Se)_4(CZTSSe)$ thin film solar cells areone of the most promising candidates for photovoltaic devices due to their earth-abundant composition, high absorption coefficient and appropriate band gap. The sputtering process is the main challenge to achieving high efficiency of CZTSSe solar cells for industrialization. In this study, we fabricated CZTSSe absorbers on Mo coated soda lime glass using different pressures during the annealing process. As an environmental strategy, the annealing process is performed with S and Se powder, without any toxic $H_2Se$ and/or $H_2S$ gases. Because CZTSSe thin films have a very narrow stable phase region, it is important to control the condition of the annealing process to achieve high efficiency of the solar cell. To identify the effect of process pressure during the sulfo-selenization, we experiment with varying initial pressure from 600 Torr to 800 Torr. We fabricate a CZTSSe thin film solar cell with 8.24 % efficiency, with 435 mV for open circuit voltage($V_{OC}$) and $36.98mA/cm^2$ for short circuit current density($J_{SC}$), under a highest process pressure of 800 Torr.

• Korean Journal of Materials Research
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• v.23 no.11
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• pp.613-619
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• 2013

$Cu_2ZnSn(S_x,Se_{1-x})_4$ (CZTSSe) thin films were prepared by sulfurization of evaporated precursor thin films. Precursor was prepared using evaporation method at room temperature. The sulfurization was carried out in a graphite box with S powder at different temperatures. The temperatures were varied in a four step process from $520^{\circ}C$ to $580^{\circ}C$. The effects of the sulfurization temperature on the micro-structural, morphological, and compositional properties of the CZTSSe thin films were investigated using X-ray diffraction (XRD), Raman spectra, field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). The XRD and Raman results showed that the sulfurized thin films had a single kesterite crystal CZTSSe. From the FE-SEM and TEM results, the $Mo(S_x,Se_{1-x})_2$ (MoSSe) interfacial layers of the sulfurized CZTS thin films were observed and their thickness was seen to increase with increasing sulfurization temperature. The microstructures of the CZTSSe thin films were strongly related to the sulfurization temperatures. The voids in the CZTSSe thin films increased with the increasing sulfurization temperature.

• Korean Journal of Materials Research
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• v.30 no.6
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• pp.285-291
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• 2020

Recent advances in technology using ultra-thin noble metal film in oxide/metal/oxide structures have attracted attention because this material is a promising alternative to meet the needs of transparent conduction electrodes (TCE). AZO/Ag/AZO multilayer films are prepared by magnetron sputtering for Cu₂ZnSn(S,Se)₄ (CZTSSe) of kesterite solar cells. It is shown that the electrical and optical properties of the AZO/Ag/AZO multilayer films can be improved by the very low resistivity and surface plasmon effects due to the deposition of different thicknesses of Ag layer between oxide layers fixed at AZO 30 nm. The AZO/Ag/AZO multilayer films of Ag 15 nm show high mobility of 26.4 ㎠/Vs and low resistivity and sheet resistance of 3.58^⁎10^-5 Ωcm and 5.0 Ω/sq. Also, the AZO/Ag (15 nm)/AZO multilayer film shows relatively high transmittance of more than 65 % in the visible region. Through this, we fabricated CZTSSe thin film solar cells with 7.51 % efficiency by improving the short-circuit current density and fill factor to 27.7 mV/㎠ and 62 %, respectively.

• Korean Journal of Materials Research
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• v.22 no.5
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• pp.259-273
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• 2012

Chalcogenide-based semiconductors, such as $CuInSe_2$, $CuGaSe_2$, Cu(In,Ga)$Se_2$ (CIGS), and CdTe have attracted considerable interest as efficient materials in thin film solar cells (TFSCs). Currently, CIGS and CdTe TFSCs have demonstrated the highest power conversion efficiency (PCE) of over 11% in module production. However, commercialized CIGS and CdTe TFSCs have some limitations due to the scarcity of In, Ga, and Te and the environmental issues associated with Cd and Se. Recently, kesterite CZTS, which is one of the In- and Ga- free absorber materials, has been attracted considerable attention as a new candidate for use as an absorber material in thin film solar cells. The CZTS-based absorber material has outstanding characteristics such as band gap energy of 1.0 eV to 1.5 eV, high absorption coefficient on the order of $10^4cm^{-1}$, and high theoretical conversion efficiency of 32.2% in thin film solar cells. Despite these promising characteristics, research into CZTS-based thin film solar cells is still incomprehensive and related reports are quite few compared to those for CIGS thin film solar cells, which show high efficiency of over 20%. The recent development of kesterite-based CZTS thin film solar cells is summarized in this work. The new challenges for enhanced performance in CZTS thin films are examined and prospective issues are addressed as well.

• Korean Journal of Materials Research
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• v.32 no.11
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• pp.481-488
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• 2022

The Cu₂ZnSn(S_xSe_1-x)₄ (CZTSSe) absorbers are promising thin film solar cells (TFSCs) materials, to replace existing Cu(In,Ga)Se₂ (CIGS) and CdTe photovoltaic technology. However, the best reported efficiency for a CZTSSe device, of 13.6 %, is still too low for commercial use. Recently, partially replacing the Zn²⁺ element with a Cd²⁺element has attracting attention as one of the promising strategies for improving the photovoltaic characteristics of the CZTSSe TFSCs. Cd²⁺ elements are known to improve the grain size of the CZTSSe absorber thin films and improve optoelectronic properties by suppressing potential defects, causing short-circuit current (J_sc) loss. In this study, the structural, compositional, and morphological characteristics of CZTSSe and CZCTSSe thin films were investigated using X-ray diffraction (XRD), X-ray fluorescence spectrometer (XRF), and Field-emission scanning electron microscopy (FE-SEM), respectively. The FE-SEM images revealed that the grain size improved with increasing Cd²⁺ alloying in the CZTSSe thin films. Moreover, there was a slight decrease in small grain distribution as well as voids near the CZTSSe/Mo interface after Cd²⁺ alloying. The solar cells prepared using the most promising CZTSSe absorber thin films with Cd²⁺ alloying (8 min. 30 sec.) exhibited a power conversion efficiency (PCE) of 9.33 %, J_sc of 34.0 mA/cm², and fill factor (FF) of 62.7 %, respectively.

• Current Photovoltaic Research
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• v.11 no.3
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• pp.67-74
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• 2023

The earth-abundant element-based Cu₂ZnSn(S,Se)₄ (CZTSSe) thin film solar cells (TFSCs) have attracted greater attention in the photovoltaic (PV) community due to their rapid development in device power conversion efficiency (PCE) >13%. In the present work, we demonstrated the fine-tuning of the bandgap in the CZTSSe TFSCs by altering the sulfur (S) to the selenium (Se) chalcogenide ratio. To achieve this, the CZTSSe absorber layers are fabricated with different S/(S+Se) ratios from 0.02 to 0.08 of their weight percentage. Further compositional, morphological, and optoelectronic properties are studied using various characterization techniques. It is observed that the change in the S/(S+Se) ratios has minimal impact on the overall Cu/(Zn+Sn) composition ratio. In contrast, the S and Se content within the CZTSSe absorber layer gets altered with a change in the S/(S+Se) ratio. It also influences the overall absorber quality and gets worse at higher S/(S+Se). Furthermore, the device performance evaluated for similar CZTSSe TFSCs showed a linear increase and decrease in the open circuit voltage (V_oc) and short circuit current density (J_sc) of the device with an increasing S/(S+Se) ratio. The external quantum efficiency (EQE) measured also exhibited a linear blue shift in absorption edge, increasing the bandgap from 1.056 eV to 1.228 eV, respectively.