• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2007년도 춘계학술대회
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• pp.257-260
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• 2007

In this study, $CuInSe_{2}$ (CISe) and $CuInZnSe_{2}$ (CIZSe) thin films were prepared on Corning 1737 glass by radio frequency (RF) magnetron sputtering from binary chalcogenide mixed powder targets. The targets were initially prepared by mixing appropriate weights of CuSe, InSe powder and various ZnSe contents. From the film bulk analysis result, it is observed that Zn concentration in the films increases proportionally with the addition of ZnSe in the sputtering targets. Under optimized conditions, CISe and CIZSe thin films grow as a chalcopyrite structure with strong (112), (220/204) and (312/116) reflections. Films are found to exhibit a high absorption coefficient of $10^{4}$ $cm^{-1}$. An increasing of optical band gap from 1.0 eV (CISe) to 1.25 eV (CIZSe) is found to be proportional with an increasing of Zn concentration as expected. All films have a p-type semiconductor characteristic with a carrier concentration in the order of 1014 $cm^{-3}$, a mobility about $10^{1}$ $cm^{2{\cdot}-1}{\cdot}s^{-1}$ and a resistivity at the range of $10^{2}-10^{6}$ W${\cdot}$m.

• 한국재료학회지
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• 제21권8호
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• pp.461-467
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• 2011

Cu(In, Ga)$Se_2$ (CIGS) precursor films were electrodeposited on Mo/glass substrates in acidic solutions containing $Cu^{2+}$, $In^{3+}$, $Ga^{3+}$, and $Se^{4+}$ ions at -0.6 V (SCE) and pH. 1.8. In order to induce recrystallization, the electrodeposited $Cu_{1.00}In_{0.81}Ga_{0.09}Se_{2.08}$ (25.0 at.% Cu + 20.2 at.% In + 2.2 at.% Ga + 52.0 at.% Se) precursor films were annealed under a high Se gas atmosphere for 15, 30, 45, and 60 min, respectively, at $500^{\circ}C$. The Se amount in the film increased from 52 at.% to 62 at.%, whereas the In amount in the film decreased from 20.8 at.% to 9.1 at.% as the annealing time increased from 0 (asdeposited state) to 60 min. These results were attributed to the Se introduced from the furnace atmosphere and reacted with the In present in the precursor films, resulting in the formation of the volatile $In_2Se$. CIGS precursor grains with a cauliflower shape grew as larger grains with the $CuSe_2$ and/or $Cu_{2-x}Se$ faceted phases as the annealing times increased. These faceted phases resulted in rough surface morphologies of the CIGS films. Furthermore, the CIGS layers were not dense because the empty spaces between the grains were not removed via annealing. Uniform thicknesses of the $MoSe_2$ layers occurred at the 45 and 60 min annealing time. This implies that there was a stable reaction between the Mo back electrode and the Se diffused through the CIGS film. The results obtained in the present research were sufficiently different from comparable studies where the recrystallization annealing was performed under an atmosphere of Ar gas only or a low Se gas pressure.

• 한국재료학회지
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• 제29권9호
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• pp.553-558
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• 2019

$Cu_2ZnSn(S,Se)_4(CZTSSe)$ thin film solar cells areone of the most promising candidates for photovoltaic devices due to their earth-abundant composition, high absorption coefficient and appropriate band gap. The sputtering process is the main challenge to achieving high efficiency of CZTSSe solar cells for industrialization. In this study, we fabricated CZTSSe absorbers on Mo coated soda lime glass using different pressures during the annealing process. As an environmental strategy, the annealing process is performed with S and Se powder, without any toxic $H_2Se$ and/or $H_2S$ gases. Because CZTSSe thin films have a very narrow stable phase region, it is important to control the condition of the annealing process to achieve high efficiency of the solar cell. To identify the effect of process pressure during the sulfo-selenization, we experiment with varying initial pressure from 600 Torr to 800 Torr. We fabricate a CZTSSe thin film solar cell with 8.24 % efficiency, with 435 mV for open circuit voltage($V_{OC}$) and $36.98mA/cm^2$ for short circuit current density($J_{SC}$), under a highest process pressure of 800 Torr.

• Current Photovoltaic Research
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• 제7권1호
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• pp.1-8
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• 2019

The $Cu(In,Ga)Se_2$ (CIGS) thin film obtained by two-step process (metal deposition and Se annealing) has a rough surface morphology and many voids at the CIGS/Mo interface. To solve the problem a precursor that contains Se was employer by depositing a (In,Se)/(Cu,Ga) stacked layer. We devised a two-step annealing (vacuum pre-annealing and Se annealing) for the precursor because direct annealing of the precursor in Se environment resulted in the small grains with unwanted demarcation between stacked layers. After vacuum pre-annealing up to $500^{\circ}C$ the CIGS film consisted of CIGS phase and secondary phases including $In_4Se_3$, InSe, and $Cu_9(In,Ga)_4$. The secondary phases were completely converted to CIGS phase by a subsequent Se annealing. A void-free CIGS/Mo interface was obtained by the two-step annealing process. Especially, the CIGS film prepared by vacuum annealing $450^{\circ}C$ and subsequent Se annealing $550^{\circ}C$ showed a densely-packed grains with smooth surface, well-aligned bamboo grains on the top of the film, little voids in the film, and also little voids at the CIGS/Mo interface. The smooth surface enhanced the cell performance due to the increase of shunt resistance.

• 대한전기학회:학술대회논문집
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• 대한전기학회 2002년도 하계학술대회 논문집 C
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• pp.1584-1586
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• 2002

CuIn$Se_2$ (CIS) and related compounds such as Cu($In_xGa_{1-x})Se_2$(CIGS) have been studied by their potential for use in photovoltaic devices. CIS thin film materials which have high absorption coefficient and wide bandgap, have attracted much attention as an alternative to crystalline and amorphous silicon solar cells currently in use. Cu-rich CIGS film have very low resistivity, due to coexistence of the semimetallic $Cu_{2-x}Se$. In-rich CIGS films show high resistivity, since these films are compensated films without the $Cu_{2-x}Se$ phase. Optical properties of the CIGS films also change in accordance with the resistivity for the Cu/(In+Ga) ratio. The Cu-rich films have different spectra from In-rich films in near infrared wavelengths.

• Current Photovoltaic Research
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• 제1권1호
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• pp.38-43
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• 2013

$Cu(In,Ga)_3Se_5$ is a candidate material for the top cell of $Cu(In,Ga)Se_2$ tandem cells. This phase is often found at the surface of the $Cu(In,Ga)Se_2$ film during $Cu(In,Ga)Se_2$ cell fabrication, and plays a positive role in $Cu(In,Ga)Se_2$ cell performance. However, the exact properties of the $Cu(In,Ga)_3Se_5$ film have not been extensively studied yet. In this work, $Cu(In,Ga)_3Se_5$ films were fabricated on Mo-coated soda-lime glass substrates by a three-stage co-evaporation process. The Cu content in the film was controlled by varying the deposition time of each stage. X-ray diffraction and Raman spectroscopy analyses showed that, even though the stoichiometric Cu/(In+Ga) ratio is 0.25, $Cu(In,Ga)_3Se_5$ is easily formed in a wide range of Cu content as long as the Cu/(In+Ga) ratio is held below 0.5. The optical band gap of $Cu_{0.3}(In_{0.65}Ga_{0.35})_3Se_5$ composition was found to be 1.35eV. As the Cu/(In+Ga) ratio was decreased further below 0.5, the grain size became smaller and the band gap increased. Unlike the $Cu(In,Ga)Se_2$ solar cell, an external supply of Na with $Na_2S$ deposition further increased the cell efficiency of the $Cu(In,Ga)_3Se_5$ solar cell, indicating that more Na is necessary, in addition to the Na supply from the soda lime glass, to suppress deep level defects in the $Cu(In,Ga)_3Se_5$ film. The cell efficiency of $CdS/Cu(In,Ga)_3Se_5$ was improved from 8.8 to 11.2% by incorporating Na with $Na_2S$ deposition on the CIGS film. The fill factor was significantly improved by the Na incorporation, due to a decrease of deep-level defects.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2009년도 춘계학술대회 논문집
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• pp.130-133
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• 2009

$Cu_2ZnSnSe_4$(CZTSe) is one of the promising materials for the solar cell due to its abundant availability in the nature. In this study, we report the fabrication of CZTSe thin film by Pulsed Laser Deposition(PLD) method using quaternary compound target on sodalime glass substrate. The quaternary CZTSe compound target was synthesized by solid state reaction method using elemental powders of Cu, Zn, Sn and Se. Powders were milled in high purity ethanol using zirconia ball with mixed size of 1 and 3 mm at the same proportions for 72 hours milling time. The structural, chemical and mechanical properties of the synthesized CZTSe powders were investigated prior to the deposition process. The CZTSe compound powder, and $500^{\circ}C$ of sintering temperature shows the best properties for PLD target. Results show that the as-deposited CZTSe thin films with the precursors by PLD have a composition near-stoichiometric.

• Journal of Electrochemical Science and Technology
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• 제4권4호
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• pp.140-145
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• 2013

This study describes the electrodeposition of $Cu_2Se$ thin films with a two-step approach that is based on the initial modification of polycrystalline Au electrode with a selenium overlayer followed by a cathodic stripping of the layer as $Se^{2-}$ in a 1 M lactic acid electrolyte containing $Cu^{2+}$ ions. For this two-step approach to be effective, the $Cu^{2+}$ reduction potential should be shifted to more negative potentials passed potentials for the reduction of Se to $Se^{2-}$. This was accomplished by the complexation of $Cu^{2+}$ ions with lactic acid. The resultant $Cu_2Se$ films were characterized by linear sweep voltammetry combined with electrochemical quartz crystal microgravimetry, UV-vis absorption spectrometry and Raman spectroscopy. Photoelectrochemical experiments revealed that $Cu_2Se$ synthesized thus, behaved as a p-type semiconductor.

• 전기화학회지
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• 제13권2호
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• pp.89-95
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• 2010

Cu(In, Ga)$Se_2$ (CIGS) 박막은 다원화합물이기 때문에 제조공정이 매우 까다롭다. 진공장치를 사용하는 제조 방법으로 동시증착법, 스퍼터링법 +셀렌화가 있고, 비진공 제조 방법으로 전기화학적인 전착법이 있다. 각 방법에 있어서도 출발 물질의 종류에 따라 다양한 제조 방법이 동원 될 수 있다. 진공증착에 의한 방법은 고품질의 박막을 얻는데 사용 되고 있으나 고가의 진공장비가 사용되므로 대면적화에 따른 제조비용 측면에서 문제가 있다. 이에 비하여, 전착법은 간단하면서도 저가로 대면적화를 이룰 수 있다는 장점 때문에, 많은 관심이 기울여지고 있다. 본 연구에서는 Mo/Glass전극위에 Ga/(In + Ga) = 0.3의 성분비를 만족시키는 CIGS 박막을 전기화학적으로 제조하기 위하여, $Cu^{2+}$, $In^{3+}$, $Ga^{3+}$, $Se^{4+}$ 4성분을 모두 포함하는 전해질 수용액 내에서, 4성분의 이온들이 동시에 환원되는 전위를 조절하여 CIGS 박막을 전착 하였다. SEM을 이용하여 얻어진 CIGS 박막의 전착된 시료의 표면을 관찰하였고, EDS로 그 조성을 분석하였다. 또한, XRD를 이용하여 전착시료의 열처리 전후의 결정성변화를 조사하였다.

• 전기화학회지
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• 제14권2호
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• pp.61-70
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• 2011

Thin film solar cells with chalcopyrite $CuInSe_2/Cu(In,Ga)Se_2$ absorber materials, commonly known as "CIS/CIGS solar cells" have recently attracted significant research interest as a potential alternative energy-harvesting system for the next generation. Among the different deposition techniques available for the CIGS absorber layer, electrodeposition is an effective and low cost alternative to vacuum based deposition methods. This article reviews progress in the area of CIGS solar cells with an emphasis on electrodeposited absorber layer. Existing challenges in fabrication of stoichiometric absorber layer are highlighted.