• 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.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.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.85.2-85.2
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• 2010

$Cu_2ZnSnSe_4$ (CZTSe) is one of candidate to alternate $Cu(In,Ga)Se_2$ as solar absorber material for solar cell. The expensive elements of In and Ga are replaced by Zn and Sn, respectively to lower the material cost. In this study we fabricated CZTSe thin film by selenization of single precursor layer consisted metallic constituent. Precursor compositions ratio were selected to have Cu-poor and Zn-rich content and prepared by RF magnetron sputtering. Thermal processing was applied to introduce selenium into as-deposited films at temperatures ranging from 350 to 500 for time up to 120 minutes. Single precursor films showed amorphous structure and consist of individual elements of Cu, Zn, and Sn. It was confirmed by XRD analysis that synthesis of CZTSe compound is occurred from lower temperature process, although concurrently additional phases such as binary cooper selenides are also existed. The quality of CZTSe crystal was improved as temperature increased. We also investigated the optical and electrical properties of as-selenized CZTSe as well.

• Korean Journal of Materials Research
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• v.23 no.3
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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.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.08a
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• pp.426-426
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• 2012

The CIGS absorber has outstanding advantages in the absorption coefficient and conversation efficiency. The CIGS thin film solar cells have been researched for commercialization and increasing the conversion efficiency. CIG precursors were deposited on the Mo coated glass substrate by magnetron sputtering with multilayer structure, which is CuIn/CuGa/CuIn/CuGa. Then, the metallic precursors were selenized under high Se pressure by RTP method which included. Se vapor was supplied using Se cracker cell instead of toxic hydrogen selenide gas. Se beam flux was controlled by variable reservoir zone (R-zone) temperature during selenization process. Cracked Se source reacted with CIG precursors in a small quantity of Se because of small size molecules with high activation energy. The CIGS thin films were studied by FESEM, EDX, and XRD. The CIGS solar cell was also developed by layering of CdS and ZnO layers. And the conversion efficiency of the CIGS solar cell was characterization. It was reached at 6.99% without AR layer.

• Journal of the Korean institute of surface engineering
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• v.46 no.2
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• pp.61-67
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• 2013

Thin film solar cells have attracted much attention due to their high cell efficiency, comparatively low process cost, and applicability to flexible substrates. In particular, CIGS solar cells have been widely studied and produced because they demonstrated the highest cell efficiency. However, the deposition process of CIGS films generally includes the selenization process conducted at elevated temperature using toxic $H_2Se$ gas. To avoid this selenization process, CIGS thin films were, in this study, deposited by RF sputtering using single composite CIGS target. In addition, the effects of sputtering bias voltage and heat treatment on the microstructural and morphological changes in deposited CIGS films were investigated and discussed.

• Journal of the Korean Institute of Illuminating and Electrical Installation Engineers
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• v.27 no.3
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• pp.107-112
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• 2013

Cu(In,Ga)$Se_2$ (CIGS) thin films were annealed on molybdenium/sodalime glass substrates of $300{\times}300mm^2$ by rapid thermal processing (RTP) with 2-step rising-temperature times in $N_2$ ambient. Morphological property, structural characteristics and chemical composition of the precursor of CIGS thin films were influenced directly with a change of $1^{st}$-step rising-temperature time in RTP whereas there is no significant difference with the different $2^{nd}$-step rising-temperature time (final crystallization temperature). The shorter $1^{st}$-step rising-temperature time in RTP obtained the higher photovoltaic cell efficiency from 7.469% to 8.479% even though the ideal composition in CIGS thin films could not be accoplished in this study.

• Korean Journal of Materials Research
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• v.20 no.12
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• pp.661-668
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• 2010

Cu(In,Ga)$Se_2$(CIGS) photovoltaic thin films were electrodeposited on Mo/glass substrates with an aqueous solution containing 2 mM $CuCl_2$, 8 mM $InCl_3$, 20 mM $GaCl_3$ and 8mM $H_2SeO_3$ at the electrodeposition potential of -0.6 to -1.0 V(SCE) and pH of 1.8. The best chemical composition of $Cu_{1.05}In_{0.8}Ga_{0.13}Se_2$ was found to be achieved at -0.7 V(SCE). The precursor Cu-In-Ga-Se films were annealed for crystallization to chalcopyrite structure at temperatures of 100-$500^{\circ}C$ under Ar gas atmosphere. The chemical compositions, microstructures, surface morphologies, and crystallographic structures of the annealed films were analyzed by EPMA, FE-SEM, AFM, and XRD, respectively. The precursor Cu-In-Ga-Se grains were grown sparsely on the Mo-back contact and also had very rough surfaces. However, after annealing treatment beginning at $200^{\circ}C$, the empty spaces between grains were removed and the grains showed well developed columnar shapes with smooth surfaces. The precursor Cu-In-Ga-Se films were also annealed at the temperature of $500^{\circ}C$ for 60 min under Se gas atmosphere to suppress the Se volatilization. The Se amount on the CIGS film after selenization annealing increased above the Se amount of the electrodeposited state and the $MoSe_2$ phase occurred, resulting from the diffusion of Se through the CIGS film and interaction with Mo back electrode. However, the selenization-annealed films showed higher crystallinity values than did the films annealed under Ar atmosphere with a chemical composition closer to that of the electrodeposited state.

• Current Photovoltaic Research
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• v.3 no.3
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• pp.85-90
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• 2015

Two-step processes for preparing $Cu(In,Ga)Se_2$ absorber layers consist of precursor layer formation and subsequent annealing in a Se-containing atmosphere. Among the various deposition methods for precursor layer, the nonvacuum (wet) processes have been spotlighted as alternatives to vacuum-based methods due to their potential to realize low-cost, scalable PV devices. However, due to its porous nature, the precursor layer deposited on Mo substrate by nonvacuum methods often suffers from thick $MoSe_2$ formation during selenization under a high Se vapor pressure. On the contrary, selenization under a low Se pressure to avoid $MoSe_2$ formation typically leads to low crystal quality of absorber films. Although TiN has been reported as a diffusion barrier against Se, the additional sputtering to deposit TiN layer may induce the complexity of fabrication process and nullify the advantages of nonvacuum deposition of absorber film. In this work, Mo oxide layers via thermal oxidation of Mo substrate have been explored as an alternative diffusion barrier. The morphology and phase evolution was examined as a function of oxidation temperature. The resulting Mo/Mo oxides double layers were employed as a back contact electrode for $CuInSe_2$ solar cells and were found to effectively suppress the formation of $MoSe_2$ layer.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.96-98
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• 2009

This report summarizes our recent efforts to produce large-grained CIGS materials from porous nanoparticle thin films. In our approach, a $Cu_xSe$ nanoparticle colloid were first prepared by reacting a mixture of CuI in pyridine with $Na_2Se$ in methanol at reduced temperature. purified colloid was sprayed onto heated molybdenum-coated sodalime glass substrates to form thin film. After thermal processing of the thin film under a selenium ambient. $Cu_xSe$ colloid and thin film were characterized by scanning electron microscopy, x-ray diffraction. The optical(direct) band gap energy of $Cu_xSe$ thin films is 1.5 eV.