• 한국표면공학회지
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• 제46권1호
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• pp.16-21
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• 2013

CIGS (Cu-In-Ga-Se) films were deposited on the Mo coated soda lime glass (Mo/SLG) by RF magnetron sputtering using a single sintered target with different chemical compositions. Heat treatment of the CIGS films were carried out under three different conditions, 1step ($350^{\circ}C$ for 2 hour and $550^{\circ}C$ for 2 hour) and 2step ($350^{\circ}C$ for 1 hour and $550^{\circ}C$ for 1 hour). In the case of CIGS films post-annealed on 2step method, grain size remarkably increased compared to other methods, indicating that chemical composition [Cu/(Ga+In) = 1] of CIGS films was same as CIGS target. After heat treatment by 2step method, band gap energy of the CIGS film deposited at RF 80 W showed 1.4 eV which is broadly similar to identical band gap energy (1.2 eV) of CIGS film prepared by evaporation method. Therefore, 2step heat treatment method could be expected to low temperature process.

• 센서학회지
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• 제10권6호
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• pp.328-337
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• 2001

수평 전기로에서 $CdGa_2Se_4$ 다결정을 합성하여 HWE 방법으로 $CdGa_2Se_4$ 단결정 박막을 반절연성 GaAs(100) 위에 성장하였다. $CdGa_2Se_4$ 단결정 박막은 증발원과 기판의 온도를 각각 $630^{\circ}C$, $420^{\circ}C$로 성장하였다. 10K에서 측정한 광발광 exciton 스펙트럼과 이중결정 X-선 요동곡선(DCRC)의 반치폭(FWHM)을 분석하여 단결정 박막의 최적 성장 조건을 얻었다. Hall 효과는 van der Pauw 방법에 의해 측정되었으며, 온도에 의존하는 운반자 농도와 이동도는 293K에서 각각 $8.27{\times}10^{17}/cm^3$, $345\;cm^2/V{\cdot}s$였다. 광전류 봉우리의 10K에서 단파장대의 가전자대 갈라짐(splitting)에 의해서 측정된 ${\Delta}Cr$ (crystal field splitting)은 106.5 meV, ${\Delta}So$ (spin orbit splitting)는 418.9 meV였다. 10K의 광발광 측정으로부터 고품질의 결정에서 볼 수 있는 free exciton 과 매우 강한 세기의 중성 주개 bound exciton등의 피크가 관찰되었다. 이때 중성 주개 bound exciton의 반치폭과 결합 에너지는 각각 8 meV와 13.7 meV였다. 또한 Haynes rule에 의해 구한 불순물의 활성화 에너지는 137 meV 였다.

• 한국전기전자재료학회논문지
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• 제18권2호
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• pp.125-129
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• 2005

Two kinds of physical treatments were examined for the analysis both of intrinsic surface and interior nature of CuInS $e_2$[CIS] and CuGaS $e_2$[CGS] films grown in separated systems. For the first method, a selenium protection layer which was immediately deposited after the growth of the CIS was investigated. The Se cap layer protects CISe surface from oxidation and contamination during the transport under ambient atmosphere. The Se cap was removed by thermal annealing at temperature above 15$0^{\circ}C$. After the decapping treatment at 2$25^{\circ}C$ for 60 min, ultraviolet photoemission and inverse photoemission measurements of the CIS film showed that its valence band maximum(VBM) and conduction band minimum (CBM) are located at 0.58 eV below and 0.52 eV above the Fermi level $E_{F}$, respectively. For the second treatment, an Ar ion beam etching was exploited. The etching with ion kinetic energy $E_{k}$ above 500 eV resulted in broadening of photoemission spectra of core signals and occasional development of metallic feature around $E_{F}$. These degradations were successfully suppressed by decreasing $E_{k}$ below 400 eV. CGS films etched with the beam of $E_{k}$ = 400 eV showed a band gap of 1.7 eV where $E_{F}$ was almost centered.st centered.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2014년도 제46회 동계 정기학술대회 초록집
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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.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2007년도 춘계학술대회
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• pp.339-342
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• 2007

$Cu(In_{1-x}Ga_{x})Se_2$(CIGS)는 매우 큰 광흡수계수를 가지고 있으므로 박막형 태양전지의 광흡수층 재료로서 많은 연구가 진행되고 있다. 박막이 태양전지의 광흡수층으로 이용되기 위해서는 큰 결정크기와 평탄한 표면, 적당한 전기적 특성을 가져야 한다. 이러한 특성들은 CIGS 박막의 조성에 큰 영향을 받고 있는 것으로 보고되고 있다. 본 연구에서는 동시증발법을 이용하여 Cu/(In+Ga) 비를 0.9로 고정한 후 Ga 조성(Ga/(In+Ga)의 비 : 0.32, 0.49, 0.69, 0.8, 1)을 변화시켜 Wide band gap CIGS 박막태양전지를 만들었다. 기판은 soda line glass를 사용하였고 뒷면 전극으로는 Mo를 스퍼터링법으로 증착하였다. 또한 버퍼층으로는 기존에 쓰이고 있는 CdS를 CBD(Chemical Bath Deposition)법으로 층착시켰으며, 윈도우층으로는 i-ZnO/n-ZnO를 스파터링 법으로 층착하였다. 그리고 앞면전극으로는 Al을 E-beam 으로 증착하였다. 분석은 XRD, SEM, QE로 분석하였다. 위 실험에서 얻은 결과로는 Ga/(In+Ga)비가 증가할수록 Cu(In,Ga)Se2 박막은 회절 peak들이 큰 회절각으로 이동하였고, 이것은 Ga 원자와 In 원자의 원자반경의 차이에서 기인된 것으로 사료된다. 또한 Ga 조성이 증가할수록 단파장 쪽으로 이동하는 것을 볼 수 있으며, Voc가 증가하다가 에너지 밴드캡이 1.62 eV 이상에서는 Voc가 감소하는 것을 볼 수 있는데 이것은 Ga 조성이 증가할수록 에너지 밴드캡이 커지면서 defect level 이 존재하기 때문인 것으로 사료된다. Ga/(In+Ga)비가 1일 때의 변환효율은 8.5 %이고， Voc : 0.74 (V), Jsc : 17.2 ($mA/cm^{2}$), F.F : 66.6(%) 이다.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2012년도 춘계학술발표대회
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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.

• 한국재료학회지
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• 제23권3호
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• pp.183-189
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• 2013

$Cu_2ZnSn(S,Se)_4$ material is receiving an increased amount of attention for solar cell applications as an absorber layer because it consists of inexpensive and abundant materials (Zn and Sn) instead of the expensive and rare materials (In and Ga) in $Cu(In,Ga)Se_2$ solar cells. We were able to achieve a cell conversion efficiency to 4.7% by the selenization of a stacked metal precursor with the Cu/(Zn + Sn)/Mo/glass structure. However, the selenization of the metal precursor results in large voids at the absorber/Mo interface because metals diffuse out through the top CZTSe layer. To avoid the voids at the absorber/Mo interface, binary selenide compounds of ZnSe and $SnSe_2$ were employed as a precursor instead of Zn and Sn metals. It was found that the precursor with Cu/$SnSe_2$/ZnSe stack provided a uniform film with larger grains compared to that with $Cu_2Se/SnSe_2$/ZnSe stack. Also, voids were not observed at the $Cu_2ZnSnSe_4$/Mo interface. A severe loss of Sn was observed after a high-temperature annealing process, suggesting that selenization in this case should be performed in a closed system with a uniform temperature in a $SnSe_2$ environment. However, in the experiments, Cu top-layer stack had more of an effect on reducing Sn loss compared to $Cu_2Se$ top-layer stack.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2009년도 하계학술대회 논문집
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• pp.442-443
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• 2009

We prepared and characterized particle based CIGS thin film using a thermal evaporator. CIGS powder were obtained at $240^{\circ}C$ for 6 hours from the reaction of $CuCl_2$, $InCl_3$, $GaCl_3$, Se powder in solvent. The CIGS thin film deposited on a sodalime glass. The CIGS thin film were identified to have a typical chalcopyrite tetragonal structure by using UV/Vis-spectroscopy, X-ray diffraction(XRD), Auger Electron Spectroscopy(AES), Scanning Electron Microscopy(SEM).

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2011년도 춘계학술대회 초록집
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• pp.125.2-125.2
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• 2011

CuInGaSe2 (CIGS)을 포함한 Chalcopyrite계 물질은 직접천이형 반도체이면서, ${\sim}1{\times}10^5cm^{-1}$ 이상의 광흡수계수를 보이며, 조성제어를 통한 밴드갭 조절이 가능해 차세대 고효율 박막태양전지재료로 매우 주목받고 있다. 최근, CIGS 박막태양전지 제조를 위해 CIGS 흡수층의 여러 가지 박막제조 공정들이 개발되고 있으나, 동시증착법과 소위 2단계법이라 일컬어지는 금속 전구체 스퍼터링 증착 후 셀렌화 공정을 가장 대표적인 공정이라 말 할 수 있다. 동시증착법은 실험실 수준의 소면적 셀에서 20%에 가까운 높은 효율의 CIGS 박막태양전지 제조에 성공하였음에도 불구하고, 상용화를 위한 대면적 셀 제조를 위해 해결해야 할 문제들이 아직 남아있다. 또한, 2단계법의 경우는 스퍼터링 공정을 기반으로 대면적 셀 제조에는 용이하나, CIGS/Mo 계면에서의 Ga 응집현상의 발생 및 셀렌화 공정에 사용되는 독성가스($H_2Se$)의 문제 등이 남아 있어 새로운 시각에서의 접근 방법이 요구되고 있다. 본 연구에서는 CIGS 4성분계 단일 타겟을 사용, RF 스퍼터링 공정을 통해 $200{\times}200mm^2$ 기판 위에 CIGS 박막을 제조하여 그 특성을 분석하였다. XRD 분석결과, 동시증착법에서 일반적으로 관찰되는 CIGS/Mo 계면에서의 $MoSe_2$ 상의 존재는 관찰되지 않았으며, CIGS 단일상의 다결정 박막이 제조되었음을 알 수 있었다. 또한, CIGS 박막제조 후, RTA 공정을 통해 CIGS 박막의 결정성이 향상됨을 관찰 할 수 있었으며, SIMS 분석결과, Mo층의 공정 조건에 따라 CIGS/Mo 계면에서의 금속원소 (In, Ga, Mo)의 상호확산이 크게 억제됨을 알 수 있었다. 그 외의 특성평가 결과들을 통하여 CIGS 4성분계 단일 타겟을 사용한 CIGS 박막태양전지 제조의 유용성에 대해 논의하고자 한다.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2012년도 춘계학술발표대회
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• pp.92-92
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• 2012

Chalcopyrite-type Cu(In,Ga)Se2 (CIGS) is one of the most attractive compound semiconductor materials for thin film solar cells. Among various approaches to prepare the CIGS thin film, the powder process offers an extremely simple and materials-efficient method. Here, we present the mechano-chemical synthesis of CIGS compound powders and their use as an ink material for screen-printing. During the synthesis process, milling time and speed were varied in the range of 10~600 min and 100~300 rpm, respectively. Both phase evolution and powder characteristics were carefully monitored by X-ray diffraction (XRD) method, scanning electron microscope (SEM) observation, and particle size analysis by scanning mobility particle spectrometer (SMPS) and aerodynamic particle sizer (APS). We found the optimal milling condition as 200 rpm for 120 min but also found that a monolithic phase of CIGS powders without severe particle aggregation was difficult to be obtained by the mechano-chemical milling alone. Therefore, the optimized milling condition was combined with an adequate heat-treatment (300oC for 60 min) to provide the monolithic CIGS powder of a single phase with affordable particle characteristics for the preparation of CIGS thin film. The powder was used to prepare an ink for screen printing with which dense CIGS thin films were fabricated under the controlled selenization. The morphology and electrical properties of the thin films were analyzed by SEM images and hall measurement, respectively.