• Bulletin of the Korean Chemical Society
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• 제35권8호
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• pp.2331-2334
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• 2014

$Cu_2SnSe_3$ (CTSe) and $Cu_2ZnSnSe_4$ (CZTSe) nanoparticles were synthesized by sonochemical reactions under multibubble sonoluminescence (MBSL) conditions. First, $Cu_2SnSe_3$ nanoparticles were synthesized by the sonochemical method with an 85% yield, using CuCl, $SnCl_2$, and Se. Second, ZnSe was coated on the CTSe nanoparticles by the same method. Then, they were transformed into CZTSe nanoparticles of 5-7 nm diameters by heating them at $500^{\circ}C$ for 1 h. The ratios between Zn and Sn could be controlled from 1 to 3.75 by adjusting the relative concentrations of CTSe and ZnSe. With relatively lower Zn:Sn ratios (0.75-1.26), there are mostly CZTSe nanoparticles but they are believed to include very small amount of CTS and ZnSe particles. The prepared nanoparticles show different band gaps from 1.36 to 1.47 eV depending on the Zn/Sn ratios. In this sonochemical method without using any toxic or high temperature solvents, the specific stoichiometric element Zn/Sn ratios in CZTSe were controllable on demand and their experimental results were always reproducible in separate syntheses. The CZTSe nanoparticles were investigated by using X-ray diffractometer, a UV-Vis spectrophotometer, scanning electron microscope, Raman spectroscopy, and a high resolution-transmission electron microscope.

• 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.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2009년도 춘계학술대회 논문집
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• pp.130-133
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• 2009

$Cu_2ZnSnSe_4$(CZTSe) is one of the promising materials for the solar cell due to its abundant availability in the nature. In this study, we report the fabrication of CZTSe thin film by Pulsed Laser Deposition(PLD) method using quaternary compound target on sodalime glass substrate. The quaternary CZTSe compound target was synthesized by solid state reaction method using elemental powders of Cu, Zn, Sn and Se. Powders were milled in high purity ethanol using zirconia ball with mixed size of 1 and 3 mm at the same proportions for 72 hours milling time. The structural, chemical and mechanical properties of the synthesized CZTSe powders were investigated prior to the deposition process. The CZTSe compound powder, and $500^{\circ}C$ of sintering temperature shows the best properties for PLD target. Results show that the as-deposited CZTSe thin films with the precursors by PLD have a composition near-stoichiometric.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2009년도 춘계학술대회 논문집
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• pp.85-87
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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. Effects of substrate temperature of $Cu_2ZnSnSe_4$ absorber layer on the performance of thin films solar cells were investigated. As substrate temperature increased, the grain size of $Cu_2ZnSnSe_4$ films increased presumably. At a optimal condition of substrate temperature is $320^{\circ}C$, the solar cell shows a conversion efficiency of 1.79% with $V_{OC}$ of 0.213V, JSC of $16.91mA/cm^2$ and FF of 49.7%.

• 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.

• 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.

• 한국태양에너지학회:학술대회논문집
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• 한국태양에너지학회 2012년도 춘계학술발표대회 논문집
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• pp.400-403
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• 2012

$Cu_2ZnSnSe_4$(CZTSe) is emerged as a promising material for thin-film solar cells because of non-toxic, inexpensive and earth abundant more than $Cu(In,Ga)Se_2$ materials. For fabricating compound semiconductor thin-film solar cells, CdS is widely used for a buffer layer which fabricated by a chemical bath deposition method (CBD). Through the experiment, we controlled deposition temperature and mol ratio of solution conditions to find the proper grain 크기 and exact composition. The optimum CdS layers were characterized in terms of surface morphology by using a scanning electron microscope (SEM) and atomic force microscope (AFM). The optimized CdS layer process was applied on CZTSe thin-films. The thickness of buffer layer related with device performance of solar cells which controlled by deposition time. Local surface potential of CdS/CZTSe thin-films was investigated by Kelvin probe force microscopy (KPFM). From these results, we can deduce local electric properties with different thickness of buffer layer on CZTSe thin-films. Therefore, we investigated the effect of CdS buffer layer thickness on the CZTSe thin-films for decreasing device losses. From this study, we can suggest buffer layer thickness which contributes to efficiencies and device performance of CZTSe thin-film solar cells.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2012년도 춘계학술발표대회
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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.

• Current Photovoltaic Research
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• 제3권3호
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• pp.97-100
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• 2015

The kesterite $Cu_2ZnSnSe_4$ (CZTSe) thin film solar cells were synthesized by selenization of sputtered Cu/Sn/Zn metallic precursors on Mo coated soda lime glass substrate in Ar atmosphere. Cu/Sn/Zn metallic precursors were deposited by DC magnetron sputtering process with 30 W power at room temperature. As-deposited metallic precursors were placed in a graphite box with Se pellets and selenized using rapid thermal processing furnace at various temperature ($480^{\circ}C{\sim}560^{\circ}C$) without using a toxic $H_2Se$ gas. Effects of Selenization temperature on the morphological, crystallinity, electrical properties and cell efficiency were investigated by field emission scanning electron microscope (FE-SEM) and X-ray diffraction (XRD), J-V measurement system and solar simulator. Further details about effects of selenization temperature on CZTSe thin films will be discussed.

• 한국분말재료학회지
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• 제18권3호
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• pp.256-261
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• 2011

In order to make a $Cu_2ZnSnSe_4$ (CZTSe) sputtering target sintered for solar cell application, synthesis of CZTSe compound by solid state reaction of Cu, Zn, Sn and Se mixed powders and effects of ball milling condition on sinterability such as ball size, combination of ball size, ball milling time and sintering temperature, was investigated. As a result of this research, sintering at $500^{\circ}C$ after ball milling using mixed balls of 1 mm and 3 mm for 72 hours was the optimum condition to synthesis near stoichiometric composition of $Cu_2ZnSnSe_4$ and to prepare sintered pellet with high density relatively.