• 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.

• ETRI Journal
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• v.38 no.2
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• pp.265-271
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• 2016

We analyzed the interface characteristics of Zn-based thin-film buffer layers formed by a sulfur thermal cracker on a $Cu(In,Ga)Se_2$ (CIGS) light-absorber layer. The analyzed Zn-based thin-film buffer layers are processed by a proposed method comprising two processes - Zn-sputtering and cracker-sulfurization. The processed buffer layers are then suitable to be used in the fabrication of highly efficient CIGS solar cells. Among the various Zn-based film thicknesses, an 8 nm-thick Zn-based film shows the highest power conversion efficiency for a solar cell. The band alignment of the buffer/CIGS was investigated by measuring the band-gap energies and valence band levels across the depth direction. The conduction band difference between the near surface and interface in the buffer layer enables an efficient electron transport across the junction. We found the origin of the energy band structure by observing the chemical states. The fabricated buffer/CIGS layers have a structurally and chemically distinct interface with little elemental inter-diffusion.

• Proceedings of the Korean Vacuum Society Conference
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• 2014.02a
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• pp.356.1-356.1
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• 2014

The Isolation of few-layered transition metal dichalcogenides has mainly been performed by mechanical and chemical exfoliation with very low yields. in particular, the two-dimensional layer of molybdenum disulfide (MoS2) has recently attracted much interest due to its direct-gap property and potential application in optoelectronics and energy harvesting. However, the synthetic approach to obtain high-quality and large-area MoS2 atomic thin layers is still rare. In this account, a controlled thermal reduction-sulfurization method is used to synthesize large-MoOx thin films are first deposited on Si/SiO2 substrates, which are then sulfurized (under vacuum) at high temperatures. Samples with different thicknesses have been analyzed by Raman spectroscopy and TEM, and their photoluminescence properties have been evaluated. We demonstrated the presence of mono-, bi-, and few-layered MoS2 on as-grown samples. It is well known that the electronic structure of these materials is very sensitive to the number of layer, ranging from indirect band gap semiconductor in the bulk phase to direct band gap semiconductor in monolayers. This synthetic approach is simple, scalable, and applicable to other transition metal dichalcogenides. Meanwhile, the obtained MoS2 films are transferable to arbitrary substrates, providing great opportunities to make layered composites by stacking various atomically thin layers.

• Current Photovoltaic Research
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• v.1 no.2
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• pp.82-89
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• 2013

$Cu_2ZnSnS_4$ thin film have been fabricated by rapid thermal annealing of dc-sputtered metal precursor with Cu/ZnSn/Cu stack in sulfur ambient. A CZTS film with a good uniformity was formed at $560^{\circ}C$ in 6 min. $Cu_2SnS_3$ and $Cu_3SnS_4$ secondary phases were present at $540^{\circ}C$ and a trace amount of $Cu_2SnS_3$ secondary phase was present at $560^{\circ}C$. Single-phase large-grained CZTS film with rough surface was formed at $560^{\circ}C$. Solar cell with best efficiency of 4.7% ($V_{oc}=632mV$, $j_{sc}=15.8mA/cm^2$, FF = 47.13%) for an area of $0.44cm^2$ was obtained for the CZTS absorber grown at $560^{\circ}C$ for 6 min. The existence of second phase at lower-temperature annealing and rough surface at higher-temperature annealing caused the degradation of cell performance. Also poor back contact by void formation deteriorated cell performance. The fill factor was below 0.5; it should be increased by minimizing voids at the CZTS/Mo interface. Our results suggest that CZTS absorbers can be grown by rapid thermal annealing of metallic precursors in sulfur ambient for short process times ranging in minutes.

• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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• pp.99.1-99.1
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• 2012

The thin-film photovoltaic absorbers (CdTe and $Cu(In,Ga)Se_2$) can achieve solar conversion efficiencies of up to 20% and are now commercially available, but the presence of toxic (Cd,Se) and expensive elemental components (In, Te) is a real issue as the demand for photovoltaics rapidly increases. To overcome these limitations, there has been substantial interest in developing viable alternative materials, such as $Cu_2ZnSnS_4$ (CZTS) is an emerging solar absorber that is structurally similar to CIGS, but contains only earth abundant, non-toxic elements and has a near optimal direct band gap energy of 1.4 - 1.6 eV and a large absorption coefficient of ~104 $cm^{-1}$. The CZTS absorber layers are grown and investigated by various fabrication methods, such as thermal evaporation, e-beam evaporation with a post sulfurization, sputtering, non-vacuum sol-gel, pulsed laser, spray-pyrolysis method and electrodeposition technique. In the present work, we report an alternative aqueous chemical approach based on chemical bath deposition (CBD) method for large area deposition of CZTS thin films. Samples produced by our method were analyzed by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, absorbance and photoluminescence. The results show that this inexpensive and relatively benign process produces thin films of CZTS exhibiting uniform composition, kesterite crystal structure, and some factors like triethanolamine, ammonia, temperature which strongly affect on the morphology of CZTS film.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.08a
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• pp.361-361
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• 2011

Cu(InGa)(SeS2) (CIGS) thin film solar cells have recently reached an efficiency of 20%. Recent studies suggest a double graded band gap structure of the CIGS absorber layer to be a key issue in the production of high efficiency thin film solar cell using by sputtering process method. In this study, Cu(InGa)(SeS2) absorbers were manufactured by selenization and surfulization, we have deposited CIG precusor by sputtering and Se layer by evaporation before selenization. The objective of this study is to find out surfulization effects to improve Voc and to compare with non-surfulization Cu(InGa)Se2 absorbers. Even if we didn't analysis Ga depth profile of Cu(InGa)(SeS2) absorbers, we confirmed increasing of Eg and Voc through surlization process. In non-surfulization Cu(InGa)Se2 absorbers, Eg and Voc are 0.96eV and 0.48V. Whereas Eg and Voc of Cu(InGa)(SeS2) absorbers are 1.16eV and 0.57V. And the efficiency of 9.58% was achieved on 0.57cm2 sized SLG substrate. In this study, we will be discussed to improve Eg and Voc through surfulization and the other method without H2S. gas.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2016.11a
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• pp.173.1-173.1
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• 2016

전이금속 디칼코게나이드는 서로 다른 전이 금속원소와 칼코겐 원소의 결합으로 이루어진 층상 구조의 물질로서, 그래핀과 비슷한 2D 결정성 구조를 지니면서도, 그래핀과는 달리 밴드갭을 가지는 반도체적 성질 때문에 최근 많은 연구가 진행되고 있다. 특히 $WS_2$는 촉매, 전자, 광전자, 센서와 같은 반도체등 다양한 소자에 적용된다. $WS_2$ 합성 방법에는 기계적 박리법, 화학기상증착법, 용액법 등이 있다. 기계적 박리법은 방법이 간단하나 수율이 낮고 균일하게 얻어지지 않으며, 화학기상증착법은 고가의 고온공정이라는 한계점을 가지고 있다. 반면에 용액법은 제조공정이 쉬우며, 저가 대량생산이 가능하다는 이점이 있다. 더욱이 본래 용액법에서는 $WS_2$를 합성하기 위해 $WO_3$를 추가적으로 합성 후 진행하였지만, 쉽게 제조 가능한 $WO_3$ colloidal 용액을 이용하면 sulfurization을 진행하여 $WS_2$를 합성할 수 있다. colloidal 용액을 이용한 합성법은 입자크기 조절이 가능하기 때문에 균일한 나노입자를 uniform 하게 형성할 수 있는 장점이 있다. 본 연구에서는 $WO_3$ colloidal 용액을 spin coating 과 sulfurzation 공정을 거쳐 2D triangle $WS_2$의 합성 및 특성을 분석하였다. 2D $WS_2$의 나노결정구조, 입자 형상 및 광학 특성을 주사전자현미경, 라만 분광기, x-ray 회절분석기 등을 통해 확인하였다. 또한, 합성된 $WS_2$를 이용하여 트랜지스터를 제작하여 전기적 특성을 확인하였다.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.28 no.3
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• pp.112-117
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• 2018

The metal alkoxide, CuCo-glycerate nanospheres (NSs), were successfully synthesized as Cu-Co bimetallic sulfides hierarchical multi-shelled hollow nanospheres ($CuCo_2S_4$ HMHNSs) through solvothermal synthesis. In this reaction mechanism, the solvothermal temperature and the amount of glycerol as a cosurfactant play significant role to optimize the morphology of CuCo-glycerate NSs. Furthermore, $CuCo_2S_4$ HMHNSs were obtained under optimized sulfurization reaction time of 10 h via anion exchange reaction between glycerate and sulfur ions. Finally, the structural and chemical compositions of CuCo-glycerate NSs and $CuCo_2S_4$ HMHNSs were confirmed through field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM), X-ray diffraction (XRD) and electrochemical performances.

• Current Photovoltaic Research
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• v.3 no.4
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• pp.135-139
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• 2015

$Cu_2SnS_3$ (CTS) based thin film solar cells (TFSCs) are of great interest because of its earth abundant, low-toxic and eco-friendly material with high optical absorption coefficient of $10^4cm^{-1}$. In this study, the DC sputtered precursor thin films have been sulfurized using rapid thermal annealing (RTA) system in the graphite box under Ar gas atmosphere for 10 minute. The systematic variation of sulfur powder during annealing process has been carried out and their effects on the structural, morphological and optical properties of CTS thin films have been investigated. The preliminary power conversion efficiency of 1.47% with a short circuit current density of $33.9mA/cm^2$, an open circuit voltage of 159.7 mV, and a fill factor of 27% were obtained for CTS thin film annealed with 0.05g of S powder, although the processing parameter s have not yet been optimized.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.20 no.7
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• pp.594-599
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• 2007

[ $CulnS_2$ ] thin films were synthesized by sulfurization of Cu/In Stacked elemental layer deposited onto glass Substrates by vacuum furnace annealing at temperature $200^{\circ}C$. And structural and electrical properties were measured in order to certify optimum conditions for growth of the ternary compound semiconductor $CuInS_2$ thin films with non-stoichiometry composition. $CuInS_2$ thin film was well made at the annealed $200^{\circ}C$ of SLG/Cu/In/S stacked elemental layer which was prepared by thermal evaporator, and chemical composition of the thin film was analyzed nearly as the proportion of 1 : 1 : 2. Physical properties of the thin film were investigated at various fabrication conditions substrate temperature, annealing and temperature, annealing time by XRD, FE-SEM and Hall measurement system. The compositional deviations from the ideal chemical formula for $200^{\circ}C$ material can be conveniently described by non-molecularity$({\Delta}x=[Cu/In]-1)$ and non-stoichiometry $({\Delta}y=[{2S/(Cu+3In)}-1])$. The variation of ${\Delta}x$ would lead to the formation of equal number of donor and accepters and the films would behave like a compensated material. The ${\Delta}y$ parameter is related to the electronic defects and would determine the type of the majority charge carriers. Films with ${\Delta}y>0$ would behave as p-type material while ${\Delta}y<0$ would show n-type conductivity. At the sane time, carrier concentration, hall mobility and resistivity of the thin films was $9.10568{\times}10^{17}cm^{-3},\;312.502cm^2/V{\cdot}s\;and\;2.36{\times}10^{-2}\;{\Omega}{\cdot}cm$, respectively.