• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.20 no.10
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• pp.829-838
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• 2007

The stochiometric mix of evaporating materials for the $CdGa_2Se_4$ single crystal thin films was prepared from horizontal furnace. To obtain the single crystal thin films, $CdGa_2Se_4$ mixed crystal was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the Hot Wall Epitaxy (HWE) system. The source and substrate temperature were $630^{\circ}C$ and $420^{\circ}C$, 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 $CdGa_2Se_4$ single crystal thin films measured from Hall effect by van der Pauw method are $8.27{\times}10^{17}\;cm^{-3},\;345\;cm^2/V{\cdot}s$ at 293 K. respectively. The temperature dependence of the energy band gap of the $CdGa_2Se_4$ obtained from the absorption spectra was well described by the Varshni's relation, $Eg(T)\;=\;2.6400\;eV\;-\;(7.721{\times}10^{-4}\;eV/K)T^2/(T+399\;K)$. After the as-grown single crystal $CdGa_2Se_4$ thin films were annealed in Cd-, Se-, and Ga -atmospheres, the origin of point defects of single crystal $CdGa_2Se_4$ 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. We concluded that the heat-treatment in the Cd-atmosphere converted single crystal $CdGa_2Se_4$ thin films to an optical p-type. Also, we confirmed that Ga in $CdGa_2Se_4/GaAs$ did not form the native defects because Ga in single crystal $CdGa_2Se_4$ thin films existed in the form of stable bonds.

• 한국신재생에너지학회:학술대회논문집
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• 2007.06a
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• pp.257-260
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• 2007

In this study, $CuInSe_{2}$ (CISe) and $CuInZnSe_{2}$ (CIZSe) thin films were prepared on Corning 1737 glass by radio frequency (RF) magnetron sputtering from binary chalcogenide mixed powder targets. The targets were initially prepared by mixing appropriate weights of CuSe, InSe powder and various ZnSe contents. From the film bulk analysis result, it is observed that Zn concentration in the films increases proportionally with the addition of ZnSe in the sputtering targets. Under optimized conditions, CISe and CIZSe thin films grow as a chalcopyrite structure with strong (112), (220/204) and (312/116) reflections. Films are found to exhibit a high absorption coefficient of $10^{4}$ $cm^{-1}$. An increasing of optical band gap from 1.0 eV (CISe) to 1.25 eV (CIZSe) is found to be proportional with an increasing of Zn concentration as expected. All films have a p-type semiconductor characteristic with a carrier concentration in the order of 1014 $cm^{-3}$, a mobility about $10^{1}$ $cm^{2{\cdot}-1}{\cdot}s^{-1}$ and a resistivity at the range of $10^{2}-10^{6}$ W${\cdot}$m.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2005.11a
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• pp.111-112
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• 2005

To obtain the single crystal thin films, $CuInSe_2$, mixed crystal was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the hot wail epitaxy (HWE) system. The source and substrate temperatures were 620$^{\circ}C$ and 410$^{\circ}C$, 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 mobilily of $CuInSe_2$ single crystal thin films measured with Hall effect by van der Pauw method are $9.62\times10^{16}$ $cm^{-3}$ and $296cm^2/V{\cdot}s$ at 293 K, respectively. The temperature dependence of the energy band gap of the CulnSe$_2$ obtained from the absorption spectra was well described by the Varshni's relation E$_g$(T) = 1.1851 eV - ($8.99\times10^{-4}$ ev/K)T$_2$/(T + 153K). After the as-grown $CuInSe_2$ single crystal thin films was annealed in Cu-, Se-, and In-atmospheres the origin of point defects of $CuInSe_2$ single crystal thin films has been investigated by the photoluminescence(PL) at 10 K. The nat ive 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 $CuInSe_2$ single crystal thin films to an optical n-type. Also, we confirmed that In in $CuInSe_2$/GaAs did not form the native defects because In in $CuInSe_2$ single crystal thin films existed in the form of stable bonds.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.675-675
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• 2013

CIGS thin films have received a great attention as a promising material for solar cells due to their high absorption coefficient, appropriate bandgap, long-term stability, and low cost production. CIGS thin films have been deposited by various methods such as co-evaporation, sputtering, spray pyrolysis and electro-deposition. In this study, Cu(In,Ga)Se2(CIGS) thin films were prepared using a single quaternary target by rf magnetron sputtering. The effect of sulfurization on the structural, compositional and electrical properties of the films was examined in order to develop the deposition process. An optimal sulfurization process will be selected for the preparation of CIGS thin films with good structural, optical and electrical properties by applying various sulfurization processes. In addition, the electrical properties of CIGS thin films were investigated by post-deposition annealing process. The carrier concentration of CIG(SSe) thin films after sulfurization was increased from $10^{14}cm^{-3}$ to $10^{16}cm^{-3}$ and the resistivity was increased from 10 ${\Omega}cm$ to $10^3$ ${\Omega}cm$. It is confirmed that CIG(SSe) thin films prepared at optimal deposition condition have similar atomic ratio to the target value after sulfurization.

• Korean Journal of Materials Research
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• v.23 no.11
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• pp.638-642
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• 2013

Chalcopyrite $CuInSe_2$(CIS) is considered to be an effective light-absorbing material for thin film photovoltaic solar cells. CIS thin films have been electrodeposited onto Mo coated and ITO glass substrates in potentiostatic mode at room temperature. The deposition mechanism of CIS thin films has been studied using the cyclic voltammetry (CV) technique. A cyclic voltammetric study was performed in unitary Cu, In, and Se systems, binary Cu-Se and In-Se systems, and a ternary Cu-In-Se system. The reduction peaks of the ITO substrate were examined in separate $Cu^{2+}$, $In^{3+}$, and $Se^{4+}$ solutions. Electrodeposition experiments were conducted with varying deposition potentials and electrolyte bath conditions. The morphological and compositional properties of the CIS thin films were examined by field emission scanning electron microscopy (FE-SEM) and energy dispersive spectroscopy (EDS). The surface morphology of as-deposited CIS films exhibits spherical and large-sized clusters. The deposition potential has a significant effect on the film morphology and/or grain size, such that the structure tended to grow according to the increase of the deposition potential. A CIS layer deposited at -0.6 V nearly approached the stoichiometric ratio of $CuIn_{0.8}Se_{1.8}$. The growth potential plays an important role in controlling the stoichiometry of CIS films.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2004.11a
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• pp.171-174
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• 2004

The stochiometric $AgGaSe_2$ polycrystalline mixture of evaporating materials for the $AgGaSe_2$ single crystal thin film was prepared from horizontal furnace. To obtain the single crystal thin films, $AgGaSe_2$ mixed crystal and semi-insulating GaAs(100) wafer were used as source material and substrate for the Hot Wall Epitaxy (HWE) system, respectively. The source and substrate temperature were fixed at $630^{\circ}C$ and $420^{\circ}C$, respectively. The thickness of grown single crystal thin films is $2.1{\mu}m$. The single crystal thin films were investigated by photoluminescence and double crystal X-ray diffraction(DCXD) measurement. The carrier density and mobility of $AgGaSe_2$ single crystal thin films measured from Hall effect by van der Pauw method are $4.89{\times}10^{17}\;cm^{-3},\;129cm^2/V{\cdot}s$ at 293K, respectively. From the photocurrent spectrum by illumination of perpendicular light on the c - axis of the $AgGaSe_2$ single crystal thin film, we have found that the values of spin orbit splitting ${\Delta}S_o$ and the crystal field splitting ${\Delta}C_r$ were 0.1762 eV and 0.2494 eV at 10 K, respectively. From the photoluminescence measurement of $AgGaSe_2$ single crystal thin film, we observed free excition $(E_X)$ observable only in high quality crystal and neutral bound exciton $(D^o,X)$ having very strong peak intensity And, the full width at half maximum and binding energy of neutral donor bound excition were 8 meV and 14.1 meV, respectively. By Haynes rule, an activation energy of impurity was 141 meV.

• 한국신재생에너지학회:학술대회논문집
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• 2007.11a
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• pp.270-273
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• 2007

In this report, Indium-free and Indium-reduced thin film materials for solar absorber were studied in order to search alternative materials for thin film solar cell. The films of $Cu_2ZnSnSe_4$ and $Cu_2ZnSnSe_2$ were deposited using mixed binary chalcogenides powders. From the film bulk analysis result, it is observed that Cu concentration is a function of substrate temperature as well as CuSe mole ratio in the target. Under optimized conditions, $Cu_2ZnSnSe_4$ and $Cu_2ZnSnSe_2$ thin films grow with strong (112), (220/204) and (312/116) reflections. Films are found to exhibit a high absorption coefficient of $10^4$ $cm^{-1}$. $Cu_2ZnSnSe_4$ film shows a 1.5 eV band gap. On the other side, an increasing of optical band gap from 1.0 eV to 1.25 eV ($CuInSnSe_2$) is found to be proportional with an increasing of Zn concentration. All films have a p-type semiconductor characteristic with a carrier concentration in the order of $10^{14}$ $cm^{-3}$, a mobility about $10^1$ $cm^{2{\cdot}-1.}S^{-1}$ and a resistivity at the range of $10^2-10^6$ ${\Omega}{\cdot}m$.

• 한국신재생에너지학회:학술대회논문집
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• 2011.11a
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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.

• Current Photovoltaic Research
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• v.2 no.3
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• pp.88-94
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• 2014

The structural, optical and electrical properties of sputter-deposited CIGS films were directly influenced by the sputtering process parameters such as substrate temperature, working pressure, RF power and distance between target and substrate. CIGS thin films deposited by using a quaternary target revealed to be Se deficient due to Se low vapor pressure. This Se deficiency affected the overall stoichiometry of the films, causing the films to be Cu-rich. Current tends to pass through the Cu-Se channels which act as the shunting path increasing the film conductivity. The crystal structure of CIGS thin films depends on the substrate orientation due to the influence of surface morphology, grain size and stress of Mo substrate. The excess of Cu was removed from the CIGS films by KCN treatment, achieving a suitable Cu concentration (referred as Cu-poor) for the fabrication of solar cell. Due to high Cu concentrations on the CIGS film surface induced by Cu-Se phases after CIGS film deposition, KCN treatment proved to be necessary for the fabrication of high efficiency solar cells. Also during KCN treatment, dislocation density and lattice parameter decreased as excess Cu was removed, resulting in increase of bandgap and the decrease of conductivity of CIGS films. It was revealed that Cu-Se secondary phase could be removed by KCN wet etching of CIGS films, allowing the fabrication of high efficiency absorber layer.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2001.11b
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• pp.167-170
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• 2001

The stochiometric mix of evaporating materials for the $CdGa_{2}Se_{4}$ single crystal thin films was prepared from horizontal furnace. To obtain the single crystal thin films, $CdGa_{2}Se_{4}$ mixed crystal was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the Hot Wall Epitaxy (HWE) system. The source and substrate temperature were $630^{\circ}C$ and $420^{\circ}C$, 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 $CdGa_{2}Se_{4}$ single crystal thin films measured from Hall effect by van der Pauw method are $8.27{\times}10^{17}cm^{-3},345cm^{2}/V{\cdot}s$ at 293 K, respectively. 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 were 106.5 meV and 418.9 meV at 10 K, respectively. From the photoluminescence measurement on $CdGa_{2}Se_{4}$ single crystal thin film, we observed free excition (Ex) existing only high Quality crystal and neutral bound exiciton $(D^{0},X)$ having very strong peak intensity. Then, the full-width-at-half-maximum(FWHM) and binding energy of neutral donor bound excition were 8 meV and 13.7 meV, respectivity. By Haynes rule, an activation energy of impurity was 137 meV.