• Current Photovoltaic Research
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• v.3 no.3
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• pp.75-79
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• 2015

Recently, $Cu_2ZnSn(S_xSe_{1-x})_4$ (CZTSSe) has been received a tremendous attraction as light absorber material in thin film solar cells (TFSCs), because of its earth abundance, inexpensive and non-toxic constituents and versatile material characteristics. Kesterite CZTSSe thin films were synthesized by sulfo-selenization of sputtered Cu/Sn/Zn stacked metallic precursors. The sulfo-selenization of Cu/Sn/Zn stacked metallic precursor thin films has been carried out in a graphite box using rapid thermal annealing (RTA) technique. Annealing process was done under sulfur and selenium vapor pressure using Ar gas at $520^{\circ}C$ for 10 min. The effect of tuning Se/(S+Se) precursor composition ratio on the properties of CZTSSe films has been investigated. The XRD, Raman, FE-SEM and XRF results indicate that the properties of sulfo-selenized CZTSSe thin films strongly depends on the Se/(S+Se) composition ratio. In particular, the CZTSSe TFSCs with Se/(S+Se) = 0.37 exhibits the best power conversion efficiency of 4.83% with $V_{oc}$ of 467 mV, $J_{sc}$ of $18.962mA/cm^2$ and FF of 54%. The systematic changes observed with increasing Se/(S+Se) ratio have been discussed in detail.

• 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).

• 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.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.08a
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• pp.295-295
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• 2010

Nanoparticles of the compound semiconductor, Cu(In, Ga)Se2 (CIGS), were synthesized in solution under ambient pressure below $100^{\circ}C$ and characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), optical absorption spectroscopy and energy-dispersive X-ray (EDX) analyses. These materials have chalcopyrite crystal structures and the particle sizes less than 100 nm. Synthetic conditions were studied for the crystallized CIGS nanoparticles formation to prevent from side products of Cu2Se, Cu2-xSe, and CuSe etc. The single phase CIGS nanoparticles were applied to coating of thin films photovoltaic cells. The electro deposition of CIGS thin films is also a good non-vacuum technology and under investigation. In aqueous solutions, the different chemical compositions of CIGS thin films were obtained, depending on pH, concentration of starting materials and deposition potentials. The surface morphology of the prepared CIGS thin films depends on the complexing ligands to the solutions during the electrochemical deposition.

• Current Photovoltaic Research
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• v.2 no.4
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• pp.177-181
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• 2014

$Cu_2ZnSn(S_xSe_{1-x})_4$ (CZTSSe) absorber thin films were prepared on Mo coated soda lime glass substrates by sulfo-selenization of sputtered stacked Zn-Sn-Cu precursor thin films. The Zn-Sn-Cu precursor thin films were sulfo-selenized inside a graphite box containing S and Se powder using rapid thermal processing furnace at $540^{\circ}C$ in Ar atmosphere with pre-treatment at $300^{\circ}C$. The effect of different S/Se ratio on the structural, compositional, morphological and electrical properties of the CZTSSe thin films were studied using XRD (X-ray diffraction), XRF (X-ray fluorescence analysis), FE-SEM (field-emission scanning electron microscopy), respectively. The XRD, FE-SEM, XRF results indicated that the properties of sulfo-selenized CZTSSe thin films were strongly related to the S/Se composition ratio. In particular, the CZTS thin film solar cells with S/(S+Se)=0.25 shows best conversion efficiency of 4.6% ($V_{oc}$ : 348 mV, $J_{sc}$ : $26.71mA/cm^2$, FF : 50%, and active area : $0.31cm^2$). Further detailed analysis and discussion for effect of S/Se composition ratio on the properties CZTSSe thin films will be discussed.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2004.04b
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• pp.51-55
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• 2004

$CdS_{0.69}Se_{0.31}$ single crystal grown by sublimation method. Hall effect measurement were carried out by the Van der Pauw method. The measurement values under the temperature were found to be carrier density $n=1.95{\times}10^{23}m^{-3}$, Hall coeffcient $RH=3.21{\times}10^{-5}m^3/c$, conductivity ${\sigma}=362.41{\Omega}^{-1}m^{-1}$, and Hall mobility ${\mu}=1.16{\times}10^{-2}m^2/v.s.$ Heterojunction solar cells of $n-CdS_{0.69}Se_{0.31}/p-Cu_{2-x}S_{0.69}Se_{0.31}$ were fabricated by the substitution reaction. The open-circuit voltage, short-circuit currint density, fill factor and power conversion efficiency of $n-CdS_{0.69}Se_{0.31}/p-Cu_{2-x}S_{0.69}Se_{0.31}$ heterojunction solar cell under $80mW/cm^2$ illumination were found to be 0.41V, $19.5mA/cm^2$, 0.75 and 9.99%, respectivity.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.12 no.4
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• pp.202-209
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• 2002

The stochiometric mix of evaporating materials for the $CuInSe_2$single crystal thin films was prepared from horizontal furnace. To obtain the single crystal thin films, $CuInSe_2$compound crystal was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the Hot Wall Epitaxy (HWE) system. The source and substrate temperature were $620^{\circ}C$ and $410^{\circ}C$, respectively. The crystalline structure of single crystal thin films was investigated by the photoluminescence and double crystal X-ray diffraction (DCXD). The carrier density and mobility of $CuInSe_2$single crystal thin films measured from Hall effect by van der Pauw method. From the photocurrent spectrum by illumination of perpendicular light on the c-axis of the $CuInSe_2$single crystal thin film, we have found that the values of spin orbit splitting $\Delta$So and the crystal field splitting $\Delta$Cr. From the photoluminescence measurement on $CuInSe_2$single crystal thin film, we observed free exciton ($E_x$) existing only high quality crystal and neutral bound exciton ($A^{\circ}$, X) having very strong peak intensity. Then, the full-width-at-half-maximum (FWHM) and binding energy of neutral donor bound exciton were 7 meV and 5.9 meV, respectivity. By haynes rule, an activation energy of impurity was 59 meV.

• Proceedings of the KIEE Conference
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• 1998.07d
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• pp.1264-1267
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• 1998

$Cu(In_xGa_{1-x})Se_2$ thin films were prepared and characterized with various Ga contents. As the Ga content increased, the grain size of CIGS film became smaller. The 2 $\theta$ values in XRD patterns were shifted to larger values and the overlapped peaks were splitted. The energy bandgap increased from 1.04 to 1.67 eV and the resistivity decreased. The solar cell fabricated with ZnO/CdS/$Cu(In_{0.7}Ga_{0.3})Se_2/Mo$ structure yielded an efficeincy of 14.48% with an acitive area of 0.18 $cm^2$. The efficiency decreased with further increase of Ga content.

• Solar Energy
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• v.13 no.1
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• pp.49-58
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• 1993

[ $CdS_{0.46}Se_{0.54}$ ] single crystal was grown by a sublimation method. The crystal structure and the temperature dependence of carrier density and mobility of $CdS_{0.46}Se_{0.54}$ single crystal were studied. Heterojunction solar cells of $n-CdS_{0.46}Se_{0.54}/p-Cu_{2-X}S_{0.46}Se_{0.54}$ were fabricated by the substitution reaction. The spectral response, the J-V characteristics and the conversion efficiency of the $n-CdS_{0.46}Se_{0.54}/p-Cu_{2-X}S_{0.46}Se_{0.54}$ heterojunction solar cells were studied. The open-circuit voltage, short-circuit density, fill factor and conversion efficiency of $n-CdS_{0.46}Se_{0.54}/p-Cu_{2-X}S_{0.46}Se_{0.54}$ heterojunction solar cells under $80mW/cm^2$ illumination were found to be 0.48V, $21mA/cm^2$, 0.75 and 9.5%, respectively.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2007.06a
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• pp.97-98
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• 2007

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 $4.87{\times}10^{17}\;cm^{-3}$ and $129\;cm^2/V{\cdot}s$ 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, $E_g(T)\;=\;1.7998\;eV\;-\;(8.7489\;{\times}\;10^{-4}\;eV/K)T^2/(T\;+\;335\;K)$.