• 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.

• Proceedings of the Materials Research Society of Korea Conference
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• 2003.11a
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• pp.154-154
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• 2003

A stoichiometric mixture of evaporating materials for CuGaSe2 single crystal thin films was prepared from horizontal electric furnace. Using extrapolation method of X-ray diffraction patterns for the polycrystal CuGaSe2, it was found tetragonal structure whose lattice constant at and co were 5.615 ${\AA}$ and 11.025 ${\AA}$, respectively. To obtain the single crystal thin films, CuGaSe2 mixed crystal was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the hot wall epitaxy (MWE) system. The source and substrate temperatures were Slot and 450$^{\circ}C$, respectively. The crystalline structure of the single crystal thin films was investigated by the photoluminescence and double crystal X-ray diffraction (UXD). The carrier density and mobility of CuGaSe2 single crystal thin films measured with Hall effect by van der Pauw method are 5.0l${\times}$10$\^$17/ cm$\^$-3/ and 245 $\textrm{cm}^2$/V$.$s at 293K, respectively. The temperature dependence of the energy band gap of the CuGaSe2 obtained from the absorption spectra was well described by the Varshni's relation, Eg(T) = 1.7998 eV - (8.7489${\times}$10$\^$-4/ eV/K)T$^2$/(T + 335 K. After the as-grown CuGaSe2 single crystal thin films was annealed in Cu-, Se-, and Ca-atmospheres, the origin of point defects of CuGaSe2 single crystal thin films has been investigated by the photoluminescence(PL) at 10 K The native defects of V$\_$CU/, V$\_$Se/, Cu$\_$int/, and Se$\_$int/ obtained by PL measurements were classified as a donors or accepters type. And we concluded that the heat-treatment in the Cu-atmosphere converted CuGaSe2 single crystal thin films to an optical n-type. Also, we confirmed that Ga in CuGaSe2/GaAs did not form the native defects because Ga in CuGaSe2 single crystal thin films existed in the form of stable bonds.

• Korean Journal of Materials Research
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• v.20 no.8
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• pp.434-438
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• 2010

The selenization process has been a promising method for low-cost and large-scale production of high quality CIGS film. However, there is the problem that most Ga in the CIGS film segregates near the Mo back contact. So the solar cell behaves like a $CuInSe_2$ and lacks the increased open-circuit voltage. In this study we investigated the Ga distribution in CIGS films by using the $Ga_2Se_3$ layer. The $Ga_2Se_3$ layer was applied on the Cu-In-Ga metal layer to increase Ga content at the surface of CIGS films and to restrict Ga diffusion to the CIGS/Mo interface with Ga and Se bonding. The layer made by thermal evaporation was showed to an amorphous $Ga_2Se_3$ layer in the result of AES depth profile, XPS and XRD measurement. As the thickness of $Ga_2Se_3$ layer increased, a small-grained CIGS film was developed and phase seperation was showed using SEM and XRD respectively. Ga distributions in CIGS films were investigated by means of AES depth profile. As a result, the [Ga]/[In+Ga] ratio was 0.2 at the surface and 0.5 near the CIGS/Mo interface when the $Ga_2Se_3$ thickness was 220 nm, suggesting that the $Ga_2Se_3$ layer on the top of metal layer is one of the possible methods for Ga redistribution and open circuit voltage increase.

• ETRI Journal
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• v.34 no.5
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• pp.779-782
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• 2012

$CuIn_{1-x}Ga_xSe_2$ (CIGS) thin films are grown on Mo/soda lime glass using a reactive sputtering process in which a Se cracker is used to deliver reactive Se molecules. The Cu and $(In_{0.7}Ga_{0.3})_2Se_3$ targets are simultaneously sputtered under the delivery of reactive Se. The effects of Se flux on film composition are investigated. The Cu/(In+Ga) composition ratio increases as the Se flux increases at a plasma power of less than 30 W for the Cu target. The (112) crystal orientation becomes dominant, and crystal grain size is larger with Se flux. The power conversion efficiency of a solar cell fabricated using an 800-nm CIGS film is 8.5%.

• Journal of the Korean Solar Energy Society
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• v.23 no.2
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• pp.59-70
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• 2003

A stoichiometric mixture of evaporating materials for $CuGaSe_2$ single crystal thin films was prepared from horizontal electric furnace. Using extrapolation method of X-ray diffraction patterns for the polycrystal $CuGaSe_2$, it was found tetragonal structure whose lattice constant $a_0$ and $c_0$ were $5.615{\AA}$ and $11.025{\AA}$, respectively. To obtain the single crystal thin films, $CuGaSe_2$ mixed crystal was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the hot wall epitaxy (HWE) system. The source and substrate temperatures were $610^{\circ}C$ and $450^{\circ}C$, respectively. The crystalline structure of the single crystal thin films was investigated by the photoluminescence and double crystal X-ray diffraction (DCXD). The carrier density and mobility of $CuGaSe_2$ single crystal thin films measured with Hall effect by van der Pauw method are $5.01\times10^{17}cm^{-3}$ and $245cm^2/V{\cdot}s$ at 293K. respectively. The temperature dependence of the energy band gap of the $CuGaSe_2$ obtained from the absorption spectra was well described by the Varshni's relation, $E_g$(T)=1.7998 eV-($8.7489\times10^{-4}$ eV/K)$T^2$/(T+335K). After the as-grown $CuGaSe_2$ single crystal thin films was annealed in Cu-, Se-, and Ga-atmospheres, the origin of point defects of $CuGaSe_2$ single crystal thin films has been investigated by the photoluminescence(PL) at 10 K. The native defects of $V_{CU},\;V_{Se},\;Cu_{int}$ and $Se_{int}$ obtained by PL measurements were classified as a donors or acceptors type. And we concluded that the heat-treatment in the Cu-atmosphere converted $CuGaSe_2$ single crystal thin films to an optical n-type. Also, we confirmed that Ga in $CuGaSe_2$/GaAs did not form the native defects because Ga in $CuGaSe_2$ single crystal thin films existed in the form of stable bonds.

• Proceedings of the KIEE Conference
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• 2002.07c
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• pp.1587-1589
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• 2002

Photovoltaics is considered as one of the most promising new energy technology, because its energy source is omni present, pollution-free and inexhaustive. It is agreed that these solar cells must be thin film type because thin film process is cost-efficive in the fact that it uses much less raw materials and can be continuous. The defect chalcopyrite material $CuIn_3Se_5$ has been identified as playing an essential role in efficient photovoltaic action in $CuInSe_2$-based devicesm It has been reported to be of n-type conductivity, forming a p-n junction with its p-type counterpart CuInSe2. Because the most efficient cells consist of the $Cu(In,Ga)Se_2$ quarternary, knowledge of some physical properties of the Ga-containing defect chalcopyrite $Cu(In,Ga)_3Se_5$ may help us better understand the junction phenomena in such devices.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2003.07a
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• pp.352-356
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• 2003

A stoichiometric mixture of evaporating materials for $CuGaSe_2$ single crystal am films was prepared from horizontal electric furnace. Using extrapolation method of X-ray diffraction patterns for the polycrystal $CuGaSe_2$, it was found tetragonal structure whose lattice constant $a_0$ and $c_0$ were $5.615\;{\AA}\;and\;11.025\;{\AA}$, respectively. To obtain the single crystal thin films, $CuGaSe_2$ mixed crystal was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the hot wall epitaxy (HWE) system. The source and substrate temperatures were $610^{\circ}C$ and $450^{\circ}C$, respectively, The crystalline structure of the single crystal thin films was investigated by the photoluminescence and double crystal X-ray diffraction (DCXD). The carrier density and mobility of $CuGaSe_2$ single crystal 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 $CuGaSe_2$ obtained from the absorption spectra was well described by the Varshni's relation, $E_g(T)\;:\;1.7998\;eV\;-\;(8.7489\;{\times}\;10^{-4}\;eV/K)T^2(T\;+\;335\;K)$. After the as-grown $CuGaSe_2$ single crystal thin films was annealed in Cu-, Se-, and Ga-atmospheres, the origin of point defects of $CuGaSe_2$ single crystal thin films has been investigated by the photoluminescence(PL) at 10 K. The native defects of $V_{CU}$, $V_{Se}$, $CU_{int}$, and $Se_{int}$, obtained by PL measurements were classified as a donors or accepters type. And we concluded that the heat-treatment in the Cu-atmosphere converted $CuGaSe_2$ single crystal thin films to an optical n-type. Also, we confirmed that Ga in $CuGaSe_2/GaAs$ did not form the native defects because Ga in $CuGaSe_2$ single crystal thin films existed in the form of stable bonds.

• Current Photovoltaic Research
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• v.7 no.4
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• pp.103-110
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• 2019

Cu(In,Ga)₃Se₅ (β-CIGS) has a band gap of 1.35 eV, which is an optimum value for high solar-energy conversion efficiency. The effects of Cu and Ga content on the cell performance were investigated previously. However, the effect of Se content on the cell performance is not well understood yet. In this work, β-CIGS films were fabricated by three-stage co-evaporation of elemental sources with various Se fluxes at the third stage instead of at all stages. The average composition of five samples was Cu_1.05(In_0.59,Ga_0.41)3Se_y, where the stoichiometric y value is 5.03 and the stoichiometric Se/metal (Se/M) ratio is 1.24. We varied the Se/metal ratio in a range from 1.18 to 1.28. We found that the best efficiency was achieved when the Se/M ratio was 1.24, which is exactly the stoichiometric value where the CIGS grains on the CIGS surface were tightly connected and faceted. With the optimum Se/M ratio, we were able to enhance the cell efficiency of a β-CIGS solar cell from 9.6% to 12.0% by employing a Na₂S post deposition treatment. Our results indicate that Na₂S post deposition treatment is very effective to enhance the cell efficiency to a level on par with that in α-CIGS cell.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2003.07a
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• pp.331-334
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• 2003

Photovoltaics is considered as one of the most promising new energy technology, because its energy source is omni present, pollution-free and inexhaustive. It is agreed that these solar cells must be thin film type because thin film process is cost-efficive in the fact that it uses much less raw materials and can be continuous. The defect chalcopyrite material $CuIn_3Se_5$ has been identified as playing an essential role in efficient photovoltaic action in $CuInSe_2$-based devicesm It has been reported to be of n-type conductivity, forming a p-n junction with its p-type counterpart $CuInSe_2$. Because the most efficient cells consist of the $Cu(In,Ga)Se_2$ quarternary, knowledge of some physical properties of the Ga-containing defect chalcopyrite $Cu(In,Ga)_3Se_5$ may help us better understand the junction phenomena in such devices.

• Solar Energy
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• v.20 no.2
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• pp.43-54
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• 2000

We prepared and characterized $Cu(In_{1-x}Ga_x)Se_2$(CIGS) films using a elemental co-evaporation method for absorbing layer of high efficiency thin film solar cells. The CIGS films deposited on a soda-lime glass exhibited low resistivity because of higher carrier concentration. Na was accumulated at the CIGS surface and the 0 and Se were also accumulated at the surface, suggesting that oxidation is a driving force of Na accumulation. The structure of CIGS film was modified or a secondary phase was formed in the Cu-poor CIGS bulk films probably due to the incorporation of Na into Cu vacancy sites. As the Ga/(In+Ga) ratio increased, the diffraction peaks of $Cu(In_{1-x}Ga_x)Se_2$ films were shifted to larger angle and splitted, and the grain size of $Cu_{0.91}(In_{1-x}Ga_x)Se_2$ films became smaller. All $Cu_{0.91}(In_{1-x}Ga_x)Se_2$ films showed the p-type conductivity regardless of the Ga/(In+Ga) ratio. Ag/n-ZnO/i-ZnO/CdS/$Cu_{0.91}(In_{0.7}Ga_{0.3})Se_2$/Mo solar cells were fabricated. The currently best efficiency in this study was 14.48% for $0.18cm^2$ area ($V_{oc}=581.5mV,\;J_{sc}=34.88mA$, F.F=0.714).