• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.26 no.3
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• pp.232-239
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• 2013

Thin light-active layers of the $CuInSe_2$ solar cell were prepared on Mo-coated sodalime glass substrates by one-step electrodeposition and post-annealing. The structure, morphology, and composition of $CuInSe_2$ film could be controlled by deposition parameters, such as the composition of metallic precursors, the concentration of complexing agents, and the temperature of post-annealing with elemental selenium. A dense and uniform Cu-poor $CuInSe_2$ film was successfully obtained in a range of parametric variation of electrodeposition with a constant voltage of -0.5 V vs. a Ag/AgCl reference electrode. The post-annealing of the film at high temperature above $500^{\circ}C$ induced crystallization of $CuInSe_2$ with well-developed grains. The KCN-treatment of the annealed $CuInSe_2$ films further induced Cu-poor $CuInSe_2$ films without secondary phases, such as $Cu_2Se$. The structure, morphology, and composition of $CuInSe_2$ films were compared with respect to the conditions of electrodeposition and post-annealing using SEM, XRD, Raman, AES and EDS analysis. And the conditions for preparing device-quality $CuInSe_2$ films by electrodeposition were proposed.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2003.07a
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• pp.386-391
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• 2003

Sing1e 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 (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 $295\;cm^2/V{\cdot}\;s$ 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, $E_g(T)\;=\;2.8382\;eV\;-\;(8.86\;{\times}\;10^{-4}\;eV/K)T^2/(T\;+\;155K)$. 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 accepters. 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.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.16 no.10
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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.

• Proceedings of the Materials Research Society of Korea Conference
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• 1997.10a
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• pp.120-120
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• 1997

• Proceedings of the Materials Research Society of Korea Conference
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• 1998.05a
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• pp.98-98
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• 1998

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2005.11a
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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.

• 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.

• Current Photovoltaic Research
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• v.1 no.1
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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.

• Korean Journal of Materials Research
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• v.21 no.8
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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.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.98.1-98.1
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• 2010

본 실험에서는 $CuInSe_2$ 3원물질을 화학량론적 조성비가 되도록 박막을 제조하기 위해 각 단위원소를 원자비에 맞춰 전자선가열 진공증착기를 사용하여 Cu, In, Se 순으로 증착하였다. $90^{\circ}C$이하의 온도에서 $CuIn_2$, In상이 주를 이루며, $100^{\circ}C$이상에서는 $Cu_{11}In_9$상이 나타나기 시작하고 In상이 증가하였다. $10^{-3}torr$이상의 진공석영관에서 열처리와 동시에 Selenization을 통해 제작된 $CuInSe_2$박막은 열처리온도 $250^{\circ}C$에서는 CuxSe, CuSe등의 2차상들이 나타나다가 $450^{\circ}C$이상의 고온에서 $CuInSe_2$ 단일상을 형성하였다. 이로부터 진공중에서 반응을 시켰을 때, 더 낮은 온도에서 반응이 일어나고 열역학적으로 보다 안정한 소수의 화합물들이 쉽게 형성됨을 확인할 수 있었다. 특히 $250^{\circ}C$에서는 Sphalerite 구조를 가지다가 $350^{\circ}C$이상의 온도에서 Selenization하였을 때 Chalcopyrite 구조를 가졌다. 박막이 두꺼워지면서 결정립의 크기가 커지고 응력이 작아지는 특성을 보였다. 에너지 밴드갭은($E_g$)은 Cu/In 성분비율이 클수록 작은값을 보였으며, 결절립크기가 증대되므로 결국 흡수계수가 낮아짐을 알 수 있다. 또한 두께가 증가할수록 전반적으로 흡수계수가 증가하였고 Cu/In의 성분비율이 0.97일 때 기초흡수파장은 1,169nm이고 에너지밴드갭은 1.06eV이었으며, 두께 $1.5{\mu}m$이상일 때 전반적으로 양호한 상태의 p-type $CuInSe_2$박막을 제작하였다.