• Current Photovoltaic Research
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• v.4 no.3
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• pp.87-92
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• 2016

The effects of selenization pressure on the structural, optical and electrical properties of the CIGS thin films prepared by RF magnetron sputtering using a single quaternary target were investigated. At selenization pressures lower than atmospheric pressure, CIGS thin films formed non-stoichiometric compounds due to deficiencies of Se vapor. In contrast, when selenization process was conducted at above atmospheric pressure, the residence time of Se vapor inside the tube increased so that the Se element could be incorporated within vacant sites of the CIGS structure, resulting in the formation of stoichiometric CIGS thin films. High quality CIGS thin films could be obtained when the selenization process was performed at pressures greater than atmospheric and $550^{\circ}C$.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 1991.10a
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• pp.3-6
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• 1991

CuInSe$_2$ films have been prepared by selenium vapor annealing of sputtered Cu/In layer. The properties of selenized CuInSe$_2$films have been studied as a function of selenization temperature for two sputtered thicknesses. A large indium loss occurs in the sputtered Cu/In layer during the selenization. The indium loss with the selenization temperature is confirmed by the increase in the amount of CuxSe phase at lower temperature and the decrease in the crystallinity of chalocpyrite CuInSe$_2$phase at higher temperature. The variations of the electrical properties in the selenized films with the selenization conditions are due primarily to the variation of hole concentration. The variation of the hole concentration can be explanined by the indium loss away the sputtered Cu/In layer.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.02a
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• pp.404-405
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• 2011

Cu(InGa)$Se_2$ (CIGS) 박막 태양전지의 저가 및 대면적화를 위한 양산화 공정인 two-step process (sputter/selenization) 공정에서는 sputtering으로 형성한 metal precursor stack을 $H_2$ Se gas를 이용하여 selenization하는 공정을 주로 이용한다. 하지만 이러한 selenization 공정은 유독한 $H_2$ Se gas를 이용해야 한다는 점과 긴 시간 동안 열처리를 해야 하는 단점을 가지고 있다. 이에 metal precursor stack 위에 Se 막을 우선 증착하고, Rapid Thermal Process (RTP)를 이용하여 selenization하는 방법이 현재 많은 관심을 끌고 있다. 본 논문에서는 sputtering 이후 RTP를 이용한 CIGS 흡수층 제작에 대한 선행연구의 일환으로 co-evaporator 장비를 이용하여 다양한 구조의 precursor를 제작하고 RTP 조건에 따른 selenization 효과를 연구하였다. Co-evaporator를 이용하여 CIGS, CIG/Se, CuGa/In/Se, In/CuGa/Se 4가지 구조의 precursor stack을 Mo coated soda lime glass 위에 제작하였다. 이때 amorphous 상태의 precursor stack을 만들기 위하여 기판에 열은 가하여 주지 않았으며, 각각의 stack 구조에서 가지고 있는 Cu, In, Ga, Se의 총량을 동일하게 유지하기 위하여 각 stack의 증착 시간을 동일하게 유지하였다. Selenization을 위한 RTP 조건은 550, $600^{\circ}C$ 각각에 대하여 1, 5, 10분으로 split을 진행하였다. Precursor stack의 증착 후 관찰한 XRD 결과는 비정질 상태를 잘 나타내었으며, SEM 결과 CIGS precursor stack을 제외한 나머지 구조의 stack에서는 In 박막의 surface roughness로 인하여 박막의 평탄화가 좋지 않음을 확인하였다. CIGS precursor stack의 경우, RTP 온도와 시간 split와 상관없이 결정화가 잘 이루어졌으나 grain의 성장이 부족하였다. 이에 비하여 CIG/Se, CuGa/In/Se, In/CuGa/Se 구조의 precursor stack의 경우, $550^{\circ}C$ 열처리에서는 InSe의 결정상이 관찰 되었으며 $600^{\circ}C$, 5분 이상 열처리에서 CIGS 결정상이 관찰되었다. 이러한 결과는 Se이 metal 원소들과 함께 있는 CIGS 구조에 비하여 metal precursor stack 위에 Se을 증착한 stack 구조들의 경우는 CIGS 결정을 형성하기 위해 Se이 metal 층들로 확산되어 반응을 하여야 하므로 상대적으로 많은 열에너지가 필요한 것으로 이해할 수 있으며, RTP를 이용한 selenization 공정으로 CIGS 박막 태양전지의 흡수층 형성이 가능함을 확인하였다.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.26 no.7
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• pp.503-509
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• 2013

In this study, $Cu(In_{1-x},Ga_x)Se_2$ (CIGS) thin films were prepared on the Mo coated soda-lime glass by the DC magnetron sputtering and a subsequent selenization process. For the selenization process, selenization rapid thermal process(RTP) with cracker cell, which was helpful to smaller an atomic of Se, was adopted. To make CIGS layer, they were then annealed with the cracked Se. Based on this selenization method, we made several CIGS thin film and investigated the effects of In deposition time, and selenization time. Through x-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS), and atomic force microscopy (AFM), it is found that the Mo/In/CuGa structure and the high sputtering power shows the dominant chalcopyrite structure and have a uniform distribution of the grain size. The CIGS films with the In deposition time of 5 min has the best structure due to the smooth surface. And CIGS films with the selenization time of 50 min show good crystalline growth without any voids.

• Current Photovoltaic Research
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• v.3 no.3
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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.

• Proceedings of the Materials Research Society of Korea Conference
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• 2002.05a
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• pp.73-73
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• 2002

• Current Photovoltaic Research
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• v.2 no.1
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• pp.8-13
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• 2014

ZnSe/$Zn_3P_2$ heterojunctions with a substrate configuration were fabricated using a series of cost-effective processes. Thin films of ZnTe and $Zn_3P_2$ were successively grown by close-spaced sublimation onto Mo-coated glass substrates. ZnSe layers thinner than 100nm were formed by annealing the $Zn_3P_2$ films in selenium vapor. Surface selenization generated a high density of micro-cracks which, along with voids, provided shunt paths and severely deteriorated the diode characteristics. Annealing the $Zn_3P_2$ film at $300^{\circ}C$ in a $ZnCl_2$ atmosphere before surface selenization produced a dense microstructure and prevented micro-crack generation. The mechanism of micro-crack generation by the selenization was described and the suppression effect of $ZnCl_2$ treatment on the micro-crack generation was explained. ZnSe/$Zn_3P_2$ heterojunctions with low leakage current ($J_0$ < $1{\mu}A/cm^2$) were obtained using an optimized surface selenization process with $ZnCl_2$ treatment. However, the series resistance was very high due to the presence of an electrical barrier between the ZnTe and $Zn_3P_2$ layers.

• Journal of the Korean Ceramic Society
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• v.35 no.8
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• pp.871-877
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• 1998

$CuInSe_2$ thin films have been formed by two-step method in which Cu-In alloy layer was first deposited and then it was selenized. Cu-In alloy layers were deposited by co-sputtering method at ambient tem-perature. XRD analysis showed that both of $Cu_{11}In_{9}$ and CuIn$_2$ phases were formed from these films. $Cu_{11}In_{9}$ peak intensity was increased increased with varying the composition from In-rich to Cu-rich. The metallic layers were selenized either in low pressure of 10 mTorr or in atmospheric pressure(AP) Less compounds of Cu-Se and In-Se were observed during the early stage of selenization and also $CuInSe_2$ thin films selenized in vacuum showed lower roughness larger grain size and better crystallinity than those in AP.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.02a
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• pp.410-410
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• 2011

Chalcopyrite계 화합물 $CuInGaSe_2$($CIGSe_2$)는 높은 광흡수율과 전기적 특성 및 안정성, 그리고 1.02~1.67 eV 범위의 최적의 에너지 밴드갭을 가져 박막태양전지용 광흡수층 재료로 많은 관심을 받고 있다. 일반적으로 $CIGSe_2$ 박막태양전지의 광흡수층을 형성하는 공정은 고효율 태양전지 제작이 가능한 진공공정을 이용한다. $CIGSe_2$ 광흡수층을 형성하는데 있어 진공 공정을 용액기반 공정으로 대처한다면 저비용으로 보다 간단하면서 효율적인 태양전지의 제조가 가능 할 것으로 기대된다. 본 연구에서는 $CIGSe_2$ 광흡수층을 2 단계에 걸쳐 제작하였다. 먼저 Cu, In, Ga 성분을 포함하는 용액을 이용하여 CIG 전구체막을 형성한 후, 다음 단계로 selenization 공정을 진행함으로써 $CIGSe_2$ 박막을 제작하였다. $CIGSe_2$의 결정 성장을 위하여 selenization 공정의 열처리 온도와 시간을 조절하여 CIG 전구체막과 Se 원소의 결합반응을 최적화할 수 있는 공정 조건을 확보하였으며 이를 통해 우수한 결정 및 전기적 특성을 갖는 $CIGSe_2$박막을 제조하였다. 제작된 $CIGSe_2$ 박막의 광전변환 효율을 측정하여 단위셀로서의 구현이 가능함을 확인하였으며 XRD, SEM, EDS, UV-visible을 통하여 $CIGSe_2$박막의 특성을 분석하였다.

• 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.