• Current Photovoltaic Research
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• v.9 no.3
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• pp.84-95
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• 2021

The power conversion efficiency of Cu₂ZnSnSe₄ (CZTSe) solar cells depends on the absorber layer thickness; however, changes in the characteristics of the cells with varying absorber layer thickness are unclear. In this study, we investigated the changes in the characteristics of CZTSe solar cells for varying absorber layer thickness. Five absorber thicknesses were employed: CZTSe1 2.78 ㎛, CZTSe2 1.01 ㎛, CZTSe3 0.55 ㎛, CZTSe4 0.29 ㎛, and CZTSe5 0.15-0.23 ㎛. The efficiency of the CZTSe solar cells decreased as the absorber thickness decreased, resulting in power conversion efficiencies of 10.45% (CZTSe1), 8.67% (CZTSe2), 7.14% (CZTSe3), 3.44% (CZTSe4), and 1.54% (CZTSe5). As the thickness of the CZTSe absorber layer decreased, the electron-hole recombination at the grain boundaries and the absorber-back-contact interface increased. This caused an increase in the current loss, owing to light loss in the long-wavelength region. In addition, as the thickness of the CZTSe absorber layer decreased, more ZnSe was produced, and the resulting defects and defect clusters led to an open-circuit voltage loss.

• Proceedings of the Korean Vacuum Society Conference
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• 2014.02a
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• pp.398.1-398.1
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• 2014

The $Cu_2ZnSnSe_4$ (CZTSe) thin films solar cell is one of the next generation candidates for photovoltaic materials as the absorber of thin film solar cells because it has optimal bandgap (Eg=1.0eV) and high absorption coefficient of $10^4cm^{-1}$ in the visible length region. More importantly, CZTSe consists of abundant and non-toxic elements, so researches on CZTSe thin film solar cells have been increasing significantly in recent years. CZTSe thin film has very similar structure and properties with the CIGS thin film by substituting In with Zn and Ga with Sn. In this study, As-deposited CZTSe thin films have been deposited onto soda lime glass (SLG) substrates at different deposition condition using Pulsed Laser Deposition (PLD) technique without post-annealing process. The effects of deposition conditions (deposition time, deposition temperature) onto the structural, compositional and optical properties of CZTSe thin films have been investigated, without experiencing selenization process. The XRD pattern shows that quaternary CZTSe films with a stannite single phase. The existence of (112), (204), (312), (008), (316) peaks indicates all films grew and crystallized as a stannite-type structure, which is in a good agreement with the diffraction pattern of CZTSe single crystal. All the films were observed to be polycrystalline in nature with a high (112) predominant orientation at $2{\theta}{\sim}26.8^{\circ}$. The carrier concentration, mobility, resistivity and optical band gap of CZTSe thin films depending on the deposition conditions. Average energy band gap of the CZTSe thin films is about 1.3 eV.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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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.

• Advances in nano research
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• v.5 no.3
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• pp.203-214
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• 2017

In this study we present the reaction mechanism of $Cu_2ZnSnSe_4$ (CZTSe) nanoparticles synthesized by microwave-assisted chemical synthesis. We performed reactions every 10 minutes in order to identify different phases during quaternary CZTSe formation. The powder samples were analyzed by x-ray diffraction (XRD), Raman spectroscopy, energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The results showed that in the first minutes copper phases are predominant, then copper and tin secondary phases react to form ternary phase. The quaternary phase is formed at 50 minutes while ternary and secondary phases are consumed. At 60 minutes pure quaternary CZTSe phase is present. After 60 minutes the quaternary phase decomposes in the previous ternary and secondary phases, which indicates that 60 minutes is ideal reaction time. The EDS analysis of pure quaternary nanocrystals (CZTSe) showed stoichiometric relations similar to the reported research in the literature, which falls in the range of Cu/(Zn+Sn): 0.8-1.0, Zn/Sn: 1.0-1.20. In conclusion, the evolution pathway of CZTSe synthesized by this novel method is similar to other synthesis methods reported before. Nanoparticles synthesized in this study present desirable properties in order to use them in solar cell and photoelectrochemical cell applications.

• 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.

• 한국태양에너지학회:학술대회논문집
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• 2012.03a
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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.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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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.

• 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.

• Bulletin of the Korean Chemical Society
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• v.35 no.7
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• pp.1985-1988
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• 2014

$Cu_2ZnSnSe_4$ (CZTSe) thin films were synthesized on transparent conducting oxide glass substrates via a simple, non-toxic, and low-cost process using a precursor solution paste. A three-step heating process (oxidation, sulfurization, and selenization) was employed to synthesize a CZTSe thin film as an absorber layer for use in thin-film solar cells. In particular, we focused on the effects of sulfurization conditions on CZTSe film formation. We found that sulfurization at $400^{\circ}C$ involves the formation of secondary phases such as $CuSe_2$ and $Cu_2SnSe_3$, but they gradually disappeared when the temperature was increased. The formed CZTSe thin films showed homogenous and good crystallinity with grain sizes of approximately 600 nm. A solar cell device was tentatively fabricated and showed a power conversion efficiency of 2.2% on an active area of 0.44 $cm^2$ with an open circuit voltage of 365 mV, a short current density of 20.6 $mA/cm^2$, and a fill factor of 28.7%.

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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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.