• Journal of Electrical Engineering and Technology
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• v.9 no.3
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• pp.1009-1015
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• 2014

Chalcopyrite $CuInSe_2$ (CIS) thin films were prepared without Se- / S-containing gas by co-sputtering using $CuSe_2$ and $InSe_2$ selenide-targets and rapid thermal annealing. The grain size increased to a maximum of 54.68 nm with a predominant (112) plane. The tetragonal distortion parameter ${\eta}$ decreased and the inter-planar spacing $d_{(112)}$ increased in the RTA-treated CIS thin films annealed at a $400^{\circ}C$, which indicates better crystal quality. The increased carrier concentration of RTA-treated p-type CIS thin films led to a decrease in resistivity due to an increase in Cu composition at annealing temperatures ${\geq}350^{\circ}C$. The optical band gap energy ($E_g$) of CIS thin films decreased to 1.127 eV in RTA-treated CIS thin films annealed at $400^{\circ}C$ due to the improved crystallinity, elevated carrier concentration and decreased In composition.

• Current Photovoltaic Research
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• v.3 no.1
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• pp.27-31
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• 2015

It is known that sulfide at the $Cu(In,Ga)Se_2$ ($CIGSe_2$) surface plays a positive role in $CIGSe_2$ solar cells. We investigated the substitution of S with Se on the $CIGSe_2$ surface in S atmosphere. We observed that the sulfur content in the $CIGSe_2$ films changed according to sulfurization temperature and Cu/(In+Ga) ratio. The sulfur content in the $CIGSe_2$ films increased with increasing the annealing temperature and Cu/(In+Ga) ratio. Also Cu migration toward the surface increased at higher temperature. Since high Cu concentration at the $CIGSe_2$ surface is detrimental role, it is necessary to reduce the S annealing temperature as low as $200^{\circ}C$. The cell performance was improved at $200^{\circ}C$ sulfurization.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.78.2-78.2
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• 2010

Cu(In,Ga)Se2 (CIGS)박막태양전지는 간단한구조와 가격경쟁력 및 고효율화 가능성에 대한 기대감에 의해 많은 연구가 수행되어오고 있다. 특히 높은 흡수계수와 적절한 밴드갭, 큰 결정크기와 같은 물질의 특성들이 장점으로 작용하고 있기 때문이다. 또한 CIGS박막태양전지는 다른 태양전지에 비해 광열화가 적다는 장점도 가지고 있다. CIGS 박막은 CuInSe2내의 In 사이트에 Ga을 도핑함으로서 형성이 되는데 그때의 밴드갭은 약 1.4eV이며 이를 형성하기 위해 많은 방법들이 제안되고 있는데, CIGS박막 형성 시 가장 중요시 여겨야 될 인자는 구성원소로부터 최적화된 조성비를 찾는 것이다. 이러한 관점에서 볼때 evaporation법이나 sputtering법같은 진공방식의 공정법이 비진공방식에 비해 최적의 조성비를 찾는 것이 수월할 것으로 생각된다. selenization을 하기전에, 동시증착이나 다층박막형성을 통해 Cu-In-Se의 조합이 일반적으로 이루어진다. 어떤방법이든 Se의 부가적인 공급이 이루어지는데 시작 전구체의 조합에서 그 해법을 제시하는 것에 대한 논의가 많이 부족한 현실로서, CuInSe2의 단일전구체에 의한 박막형성과 특성평가에 대해 구체적인 논의가 필요하다. 본 실험에서는 Cu-In-Se 전구체를 CuInSe2 단일 타겟에서부터 RF 마그네트론 스퍼터링법을 이용하여 박막증착을 하여 Se의 Rapid Thermal Process(RTA)법을 통해 Se이 순차적으로 공급되었다. 이때 형성되는 박막의 태양전지 흡수층 적용을 위한 광학적, 전기적 및 구조적에 대한 논의된다. Soda lime glass(SLG)와 Corning 1737 유리를 기판으로 하여 아세톤-에탄올을 이용, 초음파세척을 실시하였다. 스퍼터 공정을 하기전에 흡착된 물분자를 제거하기 위하여 약 30분간 $120^{\circ}C$로 열을 가해주었으며, 공정을 위한 총 아르곤 가스의 양은 약 50sccm이며 이때의 공정압력은 20mtorr로 고정하였다. 우선 RF power와 기판온도에 따른 단일전구체 형성을 관찰하기 위하여 각각 30~80W, RT~$400^{\circ}C$로 변화를 주어 박막을 형성한 후 모든 sample에 대하여 $500^{\circ}C$분위기에 effusion cell을 이용하여 Se 분위기에서 결정화를 실시하였다. 샘플의 두께는 Surface profiler로 측정하였고 단면은 전자주사현미경으로 관찰되었다. 동시에 SEM이미지를 통하여 morphology와 grain size 및 EDX를 통하여 조성분석을 하였다. 밴드갭, 투과율 및 흡수계수는 UV-VIS-NIR분광분석법을 통하여 수행되었으며, 전기적 특성분석을 위해 4-point-probe와 Hall effect측정을 수행하였다. 공정변수에 따른 단일타겟으로 얻어 결정화된 CuInSe2박막의 자세한 결과와 논의에 대하여 발표한다.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2004.11a
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• pp.234-238
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• 2004

A stoichiometric mixture of evaporating materials for $CuInSe_2$ single crystal thin films was prepared from horizontal electric furnace. To obtain the single crystal thin films, $CuInSe_2$ mixed crystal was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the hot wall epitaxy (HWE) system. The source and substrate temperatures were $620^{\circ}C$ and $410^{\circ}C$, respectively. The crystalline structure of the single crystal thin films was investigated by the photoluminescence and double crystal X-ray diffraction (DCXD). The carrier density and mobility of $CuInSe_2$ single crystal thin films measured with Hall effect by van der Pauw method are $9.62{\times}10^{l6}\;cm^{-3}$ and $296\;cm^2/V{\cdot}s$ at 293 K, respectively. The temperature dependence of the energy band gap of the $CuInSe_2$ obtained from the absorption spectra was well described by the Varshni's relation, $E_g(T)\;=\;1.1851\;eV\;-\;(8.99{\times}10^{-4}\;eV/K)T^2/(T+153K)$. The crystal field and the spin-orbit splitting energies for the valence band of the $CuInSe_2$ have been estimated to be 0.0087 eV and 0.2329 eV at 10K, respectively, by means of the photocurrent spectra and the Hopfield quasicubic model. These results indicate that the splitting of the ${\Delta}_{so}$ definitely exists in the $\Gamma_6$ states of the valence band of the $CuInSe_2$. The three photocurrent peaks observed at 10K are ascribed to the $A_1-$, $B_1-$, and $C_1$-exciton peaks for n = 1.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2005.07a
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• pp.414-415
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• 2005

A solar cell is an element to transform the solar light energy into the electric energy in a moment. The single crystal element of high quality on which many studies were conducted in the past has a high efficiency of energy transformation, but its price competitiveness is so poor that it has failed to be popularized However, recently, in terms of an environment-friendly alternative energy, studies on applicability of the polycrystal solar cell have been actively under way. Among subject substances for such solar cell, $CuInSe_2$ has several good physical properties so that the greatest attention is paid to it as an optical absorption layer material for a low-cost solar cell of high efficiency. In order to manufacture the $CuInSe_2$ compound thin film, the unit element was deposited by using the sputtering method and the evaporation method and the heat treatment process was used in an electric furnace. Thereby, we intended to get a single-phase $CuInSe_2$ compound thin 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.

• 한국신재생에너지학회:학술대회논문집
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• 2006.06a
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• pp.210-213
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• 2006

나노입자를 이용하여 치밀한 $Cu(In,\;Ga)Se_2$ 태양전지용 광흡수층을 제조하기 위해 먼저, 콜로이달 방법으로 합성된 20nm이하의 CIGS 나노입자를 저가의 스프레이 법을 이용하여 CIGS 막을 제조하였다. 제조된 CIGS막을 two-zone RTP (rapid temperature Process) 방법으로 Se 분위기 안에서 열처리를 행하였다. 입자의 치밀화를 위해 기판의 온도, Se 증발온도와 수송가스의 유량을 조절하여 CIGS 입자성장을 행하였다. 그러나, Se의 증발온도가 높을수록 CIGS와 MO 박막 사이에서 $MoSe_2$ 층이 형성되었다. 형성된 $MoSe_2$층의 부피 팽창으로 인해 하부의 유리기판과 Mo층 사이에서 peeling off 현상이 발생했다. 이러한 Peeling off현상을 억제하면서 CIGS 나노입자 성장을 하기 위해, Se 공급을 빨리 할 수 있도록 Se의 증기압을 높였으며, 최적조건에서 급속 열처리 공정을 통해 CIGS 나노입자 성장과 치밀화를 위한 소결거동을 관찰하였다.

• Journal of Powder Materials
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• v.29 no.5
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• pp.370-375
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• 2022

Cu-doped ZnSe quantum dots were successfully synthesized in an aqueous solution using an internal doping method. The effects of ligand type, CuSe synthesis temperature, and heating time on Cu-doped ZnSe synthesis were systematically investigated. Of MPA, GSH, TGA, and NAC used as ligands, MPA was the optimal ligand as determined by PL spectrum analysis. In addition, the emission wavelength was found to depend on the synthesis temperature of the internal doping core of CuSe. As the temperature increased, the doping of Cu²⁺ was enhanced, and the emission wavelength band was redshifted; accordingly, the emission peaks moved from blue to green (up to 550 nm). Thus, the synthesis of Cu:ZnSe using internal doping in aqueous solutions is a potential method for ecomanufacturing of color-tuned ZnSe quantum dots for display applications.

• 한국신재생에너지학회:학술대회논문집
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• 2011.11a
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• pp.53.1-53.1
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• 2011

현재 태양전지시장에서 비중이 많은 실리콘 태양전지는 높은 효율에 비해 제조 단가가 비싸다는 단점을 가지고 있다. 이에 비해 칼코파라이트 구조의 $CuInSe_2$ (CIS)계 화합물은 직접 천이형 반도체로서 높은 광흡수 계수($1{\times}105cm-{\acute{e}1$)와 밴드갭 조절의 용이성 및 열적 안정성 등으로 인해 고효율 박막 태양전지용 광흡수층 재료로 많은 관심을 끌고 있다. CIS 계 물질에 속하는 Cu(InGa)$Se_2$ (CIGS) 태양전지의 경우 양산화에 sputtering방식사용하고 Showa Shell에서는 대면적 CIGS 모듈 효율 13.4%를 달성한 바 있다. 현재 CIGS는 열처리하는 방법으로 selenization 공정을 사용하는데 이 공정은 유독한 $H_2Se$ gas를 이용해야 한다는 점과 긴 시간 동안 열처리를 해야 하는 단점을 가지고 있다. 따라서 이러한 단점을 보완하기 위해 본 연구에서는 전자빔을 사용하여 후속 공정을 실시하였다. 전자빔을 사용할 경우 낮은 온도에서 precursor를 처리하며 짧은 시간에 공정이 끝난다는 장점이 있다. 본 연구에서는 sodalime glass위에 조성비(Cu 60.87% Se 38.66%)인 Cu_2Se$ target(4.002"${\times}0.123$") 을 DC sputter를 이용하여 DC power를 50W,100W를 주고 Working pressure를 20,15,10,5,3,1mtorr로 조절하여 증착하였다. 전자빔의 세기 조건을 3Kv, Rf power 200W, Ar 7sccm로 전자빔 조사 시간을 1,2,3,4,5min으로 늘려가며 최적화 실험 하였고 최적화된 조건으로 $Cu_2Se$ target에 조사 하였다. 박막의 특성평가는 전자빔 조사 전/후에 대해 XRD, SEM, XRF, Hall measurement, UV-VIS을 이용하여 분석평가를 하였다. 이 실험은 $Cu_2Se$상이 자라는 특성과 표면 상태에 따라 CIGS박막을 증착하였을 때 나타나는 효율 변화를 알아 보기위한 초기 공정 실험이다.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.20 no.7
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• pp.600-605
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• 2007

Process variables for manufacturing the $CuInSe_2$ thin film were established in order to clarify optimum conditions for growth of the thin film depending upon process conditions (substrate temperature, sputtering pressure, DC/RF Power), and then by changing a number of vapor deposition conditions and Annealing conditions variously, structural and electrical characteristics were measured. Thereby, optimum process variables were derived. For the manufacture of the $CuInSe_2$, Cu, In and Se were vapor-deposited in the named order. Among them, Cu and In were vapor-deposited by using the sputtering method in consideration of their adhesive force to the substrate, and the DC/RF power was controlled so that the composition of Cu and In might be 1 : 1, while the surface temperature having an effect on the quality of the thin film was changed from $100^{\circ}C\;to\;300^{\circ}C$ at intervals of $50^{\circ}C$. The diffract fringe of X-ray, which depended upon the substrate temperature and the Annealing temperature of the manufactured $CuInSe_2$ thin film, was investigated. scanning electron microgaphs of represents a case that a sample manufactured at the substrate temperature of $100^{\circ}C$ was thermally treated at $200{\times}350^{\circ}C$. As a result, at $500^{\circ}C$ of the Annealing temperature, their chemical composition was measured in the proportion of 1 : 1 : 2. It could be known that under this condition, the most excellent thin film was formed, compared with the other conditions.