• 한국전기전자재료학회논문지
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• 제16권10호
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• pp.871-880
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• 2003

Single crystal CuAlSe$_2$ layers were grown on thoroughly etched semi-insulating GaAs(100) substrate at 410 C with hot wall epitaxy (HWE) system by evaporating CuAlSe$_2$ source at 680 C. The crystalline structure of the single crystal thin films was investigated by the photoluminescence(PL) and double crystal X -ray diffraction (DCXD). The carrier density and mobility of single crystal CuAlSe$_2$ thin films measured with Hall effect by van der Pauw method are 9.24${\times}$10$\^$16/ cm$\^$-3/ and 295 cm$^2$/V $.$ s at 293 K, respectively. The temperature dependence of the energy band gap of the CuAlSe$_2$ obtained from the absorption spectra was well described by the Varshni's relation, Eg(T) = 2.8382 eV - (8.86 ${\times}$ 10$\^$-4/ eV/K)T$^2$/(T + 155K). After the as-grown single crystal CuAlSe$_2$ thin films were annealed in Cu-, Se-, and Al-atmospheres, the origin of point defects of single crystal CuAlSe$_2$ thin films has been investigated by PL at 10 K. The native defects of V$\_$cd/, V$\_$se/, Cd$\_$int/, and Se$\_$int/ obtained by PL measurements were classified as donors or acceptors. And we concluded that the heat-treatment in the Cu-atmosphere converted single crystal CuAlSe$_2$ thin films to an optical n-type. Also, we confirmed that Al in CuAlSe$_2$/GaAs did not form the native defects because Al in single crystal CuAlSe$_2$ thin films existed in the form of stable bonds.

• 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.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2005년도 추계학술대회 논문집 Vol.18
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• pp.76-77
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• 2005

Single crystal $CuAlSe_2$ layers were grown on thoroughly etched semi-insulating GaAs(100) substrate at 410$^{\circ}C$ with hot wall epitaxy (HWE) system by evaporating $CuAlSe_2$ source at $680^{\circ}C$. The crystalline structure of the single crystal thin films was investigated by the photoluminescence(PL) and double crystal X-ray diffraction (DCXO). The temperature dependence of the energy band gap of the $CuAlSe_2$ obtained from the absorpt ion spectra was wel1 described by the Varshni's relation, $E_g$(T) = 2.8382 eV - ($8.86\times10^{-4}$ eV/H)$T_2$/(T + 155K). After the as-grown single crystal $CuAlSe_2$ thin films were annealed in Cu-, Se-, and Al-atmospheres, the origin of point defects of single crystal $CuAlSe_2$ thin films has been investigated by PL at 10 K. The native defects of $V_{cd}$, $V_{se}$, $Cd_{int}$, and $Se_{int}$ obtained by PL measurements were classified as donors or acceptors. And we concluded that the heat-treatment in the Cu-atmosphere converted single crystal $CuAlSe_2$ thin films to an optical n-type. Also. we confirmed that hi in $CuAlSe_2$/GaAs did not form the native defects because Al in single crystal $CuAlSe_2$ thin films existed in the form of stable bonds.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2011년도 추계학술대회 초록집
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• pp.47.1-47.1
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• 2011

We report on a direct measurement of two-dimensional chemical and electrical distribution on the surface of photovoltaic Cu(In,Ga)$Se_2$ thin-films using a nano-scale spectroscopic and electrical characterization, respectively. The Raman measurement reveals non-uniformed surface phonon vibration which comes from different compositional distribution and defects in the nature of polycrystalline thin-films. On the other hand, potential analysis by scanning Kelvin probe force microscopy shows a higher surface potential or a small work function on grain boundaries of the thin-films than on the grain surfaces. This demonstrates the grain boundary is positively charged and local built-in potential exist on grain boundary, which improve electron-hole separation on grain boundary. Local electrical transport measurements with scanning probe microscopy on the thin-films indicates that as external bias is increases, local current is started to flow from grain boundary and saturated over 0.3 V external bias. This accounts for carrier behavior in the vicinity of grain boundary with regard to defect states. We suggest that electron-hole separation at the grain boundary as well as chemical and electrical distribution of polycrystalline Cu(In,Ga)$Se_2$ thin-films.

• 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.

• 대한전기학회:학술대회논문집
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• 대한전기학회 2000년도 하계학술대회 논문집 C
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• pp.1625-1627
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• 2000

Cu(InGa)$Se_2$(CIGS) thin film absorbers with various Cu/(In+Ga) atomic ratios were prepared by a three-stage process using a co-evaporation appartus. The effect of Na on the structural and electrical properties of CIGS films were studied and their effects on the CIGS/Mo thin film solar cells were investigated. Soda-lime glass and Corning glass were used as substrates to compare the effect of Na diffusion into CIGS film. The resistivity of CIGS films was not changed in the Cu-poor lesion due to diffusion of Na from soda-lime glass but was mainly determined by the surface resistivity controlled by excess Na.

• 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.

• 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.

• Current Photovoltaic Research
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• 제5권4호
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• pp.135-139
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• 2017

We fabricated two different transparent conducting oxide thin films of ZnO doped with Ga ($Ga_2O_3$ 0.9 wt%) as well as Al ($Al_2O_3$ 2.1 wt%) (GAZO) and ZnO doped only with Al ($Al_2O_3$ 3 wt%) (AZO). It was investigated how it affects the moisture resistance of the transparent electrode. In addition, $Cu(In,Ga)Se_2$ thin film solar cells with two transparent oxides as front electrodes were fabricated, and the correlation between humidity resistance of transparent electrodes and device performance of solar cells was examined. When both transparent electrodes were exposed to high temperature distilled water, they showed a rapid increase in sheet resistance and a decrease in the fill factor of the solar cell. However, AZO showed a drastic decrease in efficiency at the beginning of exposure, while GAZO showed that the deterioration of efficiency occurred over a long period of time and that the long term moisture resistance of GAZO was better.

• 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.