• 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.

• Current Photovoltaic Research
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• v.7 no.4
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• pp.103-110
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• 2019

Cu(In,Ga)₃Se₅ (β-CIGS) has a band gap of 1.35 eV, which is an optimum value for high solar-energy conversion efficiency. The effects of Cu and Ga content on the cell performance were investigated previously. However, the effect of Se content on the cell performance is not well understood yet. In this work, β-CIGS films were fabricated by three-stage co-evaporation of elemental sources with various Se fluxes at the third stage instead of at all stages. The average composition of five samples was Cu_1.05(In_0.59,Ga_0.41)3Se_y, where the stoichiometric y value is 5.03 and the stoichiometric Se/metal (Se/M) ratio is 1.24. We varied the Se/metal ratio in a range from 1.18 to 1.28. We found that the best efficiency was achieved when the Se/M ratio was 1.24, which is exactly the stoichiometric value where the CIGS grains on the CIGS surface were tightly connected and faceted. With the optimum Se/M ratio, we were able to enhance the cell efficiency of a β-CIGS solar cell from 9.6% to 12.0% by employing a Na₂S post deposition treatment. Our results indicate that Na₂S post deposition treatment is very effective to enhance the cell efficiency to a level on par with that in α-CIGS cell.

• Korean Journal of Materials Research
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• v.5 no.8
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• pp.988-996
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• 1995

CuInSe$_2$this films as a light absorber layer were fabricated by vacuum evaporation using In$_2$Se$_3$and Cu$_2$Se precursors and their properties were analyzed. Indium selenide films of 0.5${\mu}{\textrm}{m}$ thickness were first deposited by vacuum evaporation of In$_2$Se$_3$ on a Corning 7059 glass substrate. The films deposited at suscepor temperature of 40$0^{\circ}C$ showed a flat surface morphology with densely Packed grain structure. CuInSe$_2$films directly formed by evaporating Cu$_2$Se on the predeposited In$_2$Se$_2$films also showed a very flat surface when the susceptor temperature was $700^{\circ}C$. Cu$_2$Se, a second phase in the CuInSe$_2$film, was removed by evaporating additional In$_2$Se$_3$on the CuInSe$_2$film at $700^{\circ}C$. The grain size of 1.2${\mu}{\textrm}{m}$ thick CuInSe$_2$, film was about 2${\mu}{\textrm}{m}$ and the film had a (112) preferred orientation. As the amount of deposited In$_2$Se$_3$increased, the electrical resistivity of CuInSe$_2$films increased because of the decrease of hole concentration. But the optical band gap was almost constant at the value of 1.04eV, The CuInSe$_2$film grown on a Mo/glass substrate had a similar smooth microstructure compared to that on a glass substrate. A solar cell with ZnO/CdS/CuInSe$_2$/Mo structure may be realized based on the above CuInSe$_2$films.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.02a
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• pp.159-159
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• 2011

Among the semiconductor ternary compounds in the I-III-$VI_2$ series, $CulnS_2$ ($CulnSe_2$) are one of the promising materials for photovoltaic applications because of the suitability of their electrical and optical properties. The $CuInS_2$ thin film is one of I-III-$VI_2$ type semiconductors, which crystallizes in the chalcopyrite structure. Its direct band gap of 1.5 eV, high absorption coefficient and environmental viewpoint that $CuInS_2$ does not contain any toxic constituents make it suitable for terrestrial photovoltaic applications. A variety of techniques have been applied to deposit $CuInS_2$ thin films, such as single/double source evaporation, coevaporation, rf sputtering, chemical vapor deposition and chemical spray pyrolysis. This is the first report that $CuInS_2$ thin films have been prepared by Aerosol Jet Deposition (AJD) technique which is a novel and attractive method because thin films with high deposition rate can be grown at very low cost. In this study, $CuInS_2$ thin films have been prepared by Aerosol Jet Deposition (AJD) method which employs a nozzle expansion. The mixed fluid is expanded through the nozzle into the chamber evacuated in a lower pressure to deposit $CuInS_2$ films on Mo coated glass substrate. In this AJD system, the characteristics of $CuInS_2$ films are dependent on various deposition parameters, such as compositional ratio of precursor solution, flow rate of carrier gas, stagnation pressure, substrate temperature, nozzle shape, nozzle size and chamber pressure, etc. In this report, $CuInS_2$ thin films are deposited using the deposition parameters such as the compositional ratio of the precursor solution and the substrate temperature. The deposited $CuInS_2$ thin films will be analyzed in terms of deposition rate, crystal structure, and optical properties.

• New & Renewable Energy
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• v.1 no.2 s.2
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• pp.6-10
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• 2005

[ $CulnSe2$ ]계 화합물은 직접천이형 반도체로 광흡수계수가 매우 높아 박막형 태양전지 제조에 매우 유리하다. 또한 화학적으로 안정하며 Ga, Al 등을 첨가하면 에너지 금지대폭을 조절할 수 있어 Wide Bandgap 태양전지 및 탠덤구조 태양전지를 제조하기에도 용이하다. CIS 물질에서 In을 $20-30\%$ 정도 치환한 $Cu(In,\;Ga)Se_2(CIGS)$ 태양전지의 경우 19.5%의 세계 최고 효율을 보고하고 있으며 이는 다결정 실리콘 태양전지의 효율과 비슷한 수준이다. 본 연구에서는 동시 질공증발법을 이용하여 증착한 CIGS 박막 및 $CuGaSe_2(CGS)$ 박막을 이용하여 태양전지를 제조하였다. 공정의 재현성 및 결정립계가 큰 광흡수층 제조를 위하여 실시간 기판 온도 모니터링 시스템을 도입하였으며 버퍼층으로는 용액성장한 CdS 박막을 사용하였다. SLG/MO/CIGS(CGS)/CdS/ZnO/Al 구조의 태양전지를 제조하여 면적 $0.5cm^2$에서 각각 $17\%(CIGS)$와 $7\%(CGS)$의 효율을 얻었다.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.26 no.9
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• pp.701-706
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• 2013

We have focused on the conversion efficiency of CIGS thin film solar cell prepared by co-evaporation method as well as the optimization of process condition. The total thickness of back electrode was fixed at 1 ${\mu}m$ and the structural, electric and optical properties of CIGS thin film were investigated by varying the thickness of Mo:Na bottom layer from 0 to 500 nm. From the experimental results, the content of Na was appeared as 0.28 atomic percent when the thickness of Mo:Na layer was 300 nm with compactly densified plate-shape surface morphology. From the XRD measurements, (112) plane was the strongest preferential orientation together with secondary (220) and (204) planes affecting to the crystallization. The lowest roughness and resistivity were 2.67 nm and 3.9 ${\Omega}{\cdot}cm$, respectively. In addition, very high carrier density and hole mobility were recorded. From the optimization of Mo:Na layer, we have achieved the conversion efficiency of 9.59 percent.

• Proceedings of the Korean Vacuum Society Conference
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• 2014.02a
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• pp.99-99
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• 2014

Transparent oxide semiconductors (TOSs) are. currently attracting attention for application to transparent electrodes in optoelectronic devices and active channel layers in thin-film transistors. One of the key issues for the realization of next generation transparent electronic devices such as transparent complementary metal-oxide-semiconductor thin-film transistors (CMOS TFTs), transparent wall light, sensors, and transparent solar cell is to develop p-type TOSs. In this talks, I will introduce issues and status related to p-type TOSs such as LnCuOQ (Ln=lanthanide, Q=S, Se), $SrCu_2O_2$, $CuMO_2$ (M=Al, Ga, Cr, In), ZnO, $Cu_2O$ and SnO. The growth and properties of SnO and Cu-based oxides and their application to electronic devices will be discussed.

• Current Photovoltaic Research
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• v.3 no.1
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• pp.21-26
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• 2015

High efficiency $Cu(In,Ga)Se_2$ solar cells are generally prepared above $500^{\circ}C$. Lowering the process temperature can allow wider selection of substrate material and process window. In this paper, the three-stage co-evaporation process widely used to grow CIGS thin film at high temperature was modified to reduce the maximum substrate temperature. Below $400^{\circ}C$ the CIGS films show poor crystal growth and lower solar cell performance, in spite of external Na doping by NaF. As a new approach, Cu source instead of Cu with Se in the second stage was applied on the $(In,Ga)_2Se_3$ precursor at $400^{\circ}C$ and achieved a better crystal growth. The distribution of Ga in the films produce by new method were investigated and solar cells were fabricated using these films.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.97-97
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• 2013

Recently, Cu2ZnSn(S,Se)4 (CZTSS), 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 CZTSS-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 104 cm-1, and high theoretical conversion efficiency of 32.2% in thin film solar cells. Despite these promising characteristics, research into CZTSS 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%. I will briefly overview the recent technological development of CZTSS thin film solar cells and then introduce our research results mainly related to sputter based process. CZTSS thin film solar cells are prepared by sulfurization of stacked both metallic and sulfide precursors. Sulfurization process was performed in both furnace annealing system and rapid thermal processing system using S powder as well as 5% diluted H2S gas source at various annealing temperatures ranging from $520^{\circ}C$ to $580^{\circ}C$. Structural, optical, microstructural, and electrical properties of absorber layers were characterized using XRD, SEM, TEM, UV-Vis spectroscopy, Hall-measurement, TRPL, etc. The effects of processing parameters, such as composition ratio, sulfurization pressure, and sulfurization temperature on the properties of CZTSS absorber layers will be discussed in detail. CZTSS thin film solar cell fabricated using metallic precursors shows maximum cell efficiency of 6.9% with Jsc of 25.2 mA/cm2, Voc of 469 mV, and fill factor of 59.1% and CZTS thin film solar cell using sulfide precursors shows that of 4.5% with Jsc of 19.8 mA/cm2, Voc of 492 mV, and fill factor of 46.2%. In addition, other research activities in our lab related to the formation of CZTS absorber layers using solution based processes such as electro-deposition, chemical solution deposition, nano-particle formation will be introduced briefly.

• Proceedings of the Materials Research Society of Korea Conference
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• 2010.05a
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• pp.35.1-35.1
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• 2010

The Cu(In,Ga)Se2(CIGS) thin film solar cells have been achieved until almost 20% efficiency by NREL. These solar cells include chemically deposited CdS as buffer layer between CIGS absorber layer and ZnO window layer. Although CIGS solar cells with CdS buffer layer show excellent performance, many groups made hard efforts to overcome its disadvantages in terms of high absorption of short wavelength, Cd hazardous element. Among Cd-free candidate materials, the CIGS thin film solar cells with Zn compound buffer layer seem to be promising with 15.2%(module by showa shell K.K.), 18.6%(small area by NREL). However, few groups were successful to report high-efficiency CIGS solar cells with Zn compound buffer layer, compared to be known how to fabricate these solar cells. Each group's chemical bah deposition (CBD) condition is seriously different. It may mean that it is not fully understood to grow high quality Zn compound thin film on the CIGS using CBD. In this study, we focused to clarify growth mechanism of chemically deposited Zn compound thin film on the CIGS, especially. Additionally, we tried to characterize junction properties with unfavorable issues, that is, slow growth rate, imperfect film coverage and minimize these issues. Early works reported that film deposition rate increased with reagent concentration and film covered whole rough CIGS surface. But they did not mention well how film growth of zinc compound evolves homogeneously or heterogeneously and what kinds of defects exist within film that can cause low solar performance. We observed sufficient correlation between growth quality and concentration of NH3 as complex agent. When NH3 concentration increased, thickness of zinc compound increased with dominant heterogeneous growth for high quality film. But the large amounts of NH3 in the solution made many particles of zinc hydroxide due to hydroxide ions. The zinc hydroxides bonded weakly to the CIGS surface have been removed at rinsing after CBD.