• Current Photovoltaic Research
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• 제3권3호
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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.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2003년도 하계학술대회 논문집 Vol.4 No.1
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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.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2004년도 추계학술대회 논문집 Vol.17
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• pp.234-238
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• 2004

A stoichiometric mixture of evaporating materials for $CuInSe_2$ single crystal thin films was prepared from horizontal electric furnace. To obtain the single crystal thin films, $CuInSe_2$ 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 $620^{\circ}C$ 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 mobility of $CuInSe_2$ single crystal thin films measured with Hall effect by van der Pauw method are $9.62{\times}10^{l6}\;cm^{-3}$ and $296\;cm^2/V{\cdot}s$ at 293 K, respectively. The temperature dependence of the energy band gap of the $CuInSe_2$ obtained from the absorption spectra was well described by the Varshni's relation, $E_g(T)\;=\;1.1851\;eV\;-\;(8.99{\times}10^{-4}\;eV/K)T^2/(T+153K)$. The crystal field and the spin-orbit splitting energies for the valence band of the $CuInSe_2$ have been estimated to be 0.0087 eV and 0.2329 eV at 10K, respectively, by means of the photocurrent spectra and the Hopfield quasicubic model. These results indicate that the splitting of the ${\Delta}_{so}$ definitely exists in the $\Gamma_6$ states of the valence band of the $CuInSe_2$. The three photocurrent peaks observed at 10K are ascribed to the $A_1-$, $B_1-$, and $C_1$-exciton peaks for n = 1.

• 한국재료학회지
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• 제18권6호
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• pp.294-297
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• 2008

In this paper, a novel non-vacuum technique is described for the fabrication of a $CuInSe_2$ (CIS) absorber layer for thin film solar cells using a low-cost precursor solution. A solution containing Cu- and Inrelated chemicals was coated onto a Mo/glass substrate using the Doctor blade method and the precursor layer was then selenized in an evaporation chamber. The precursor layer was found to be composed of CuCl crystals and amorphous In compound, which were completely converted to chalcopyrite CIS phase by the selenization process. Morphological, crystallographic and compositional analyses were performed at each step of the fabrication process by SEM, XRD and EDS, respectively.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2005년도 추계학술대회 논문집 Vol.18
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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.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2010년도 춘계학술대회 초록집
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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.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2006년도 추계학술대회
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• pp.566-569
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• 2006

태양전지는 태양광에너지를 바로 전기에너지로 전환시키는 소자이다. 과거에 많이 연구되던 고품질의 단결정 소자는 높은 에너지 변환효율을 가지고 있으나 가격 경쟁력이 크게 뒤져 일반화되지 못하였다. 최근에는 다결정 태양전지의 응웅 가능성에 대한 연구가 활발히 진행되어 오고 있다. 이중 $CuInSe_2$는 여러 가지 좋은 물성을 가지고 있어서, 저가의 고효율 태양전지를 위한 광흡수층 재료로 가장 주목받고 있다. $CuInSe_2$ 화합물 박막을 제조하기 위해 단위원소를 spttering법 과 Evaporeation법을 사용하여 증착하고 전기로에서 열처리 공정을 사용하여 single-phase 화합물 $CuInSe_2$ 박막을 얻고자 하였다.

• 한국태양에너지학회:학술대회논문집
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• 한국태양에너지학회 2012년도 춘계학술발표대회 논문집
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• pp.400-403
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• 2012

$Cu_2ZnSnSe_4$(CZTSe) is emerged as a promising material for thin-film solar cells because of non-toxic, inexpensive and earth abundant more than $Cu(In,Ga)Se_2$ materials. For fabricating compound semiconductor thin-film solar cells, CdS is widely used for a buffer layer which fabricated by a chemical bath deposition method (CBD). Through the experiment, we controlled deposition temperature and mol ratio of solution conditions to find the proper grain 크기 and exact composition. The optimum CdS layers were characterized in terms of surface morphology by using a scanning electron microscope (SEM) and atomic force microscope (AFM). The optimized CdS layer process was applied on CZTSe thin-films. The thickness of buffer layer related with device performance of solar cells which controlled by deposition time. Local surface potential of CdS/CZTSe thin-films was investigated by Kelvin probe force microscopy (KPFM). From these results, we can deduce local electric properties with different thickness of buffer layer on CZTSe thin-films. Therefore, we investigated the effect of CdS buffer layer thickness on the CZTSe thin-films for decreasing device losses. From this study, we can suggest buffer layer thickness which contributes to efficiencies and device performance of CZTSe thin-film solar cells.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2002년도 하계학술대회 논문집
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• pp.383-386
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• 2002

Polycrystalline Cu(In,Ga)Se$_2$(CIGS) thin-films were grown by co-evaporation on a soda lime glass substrate. In this paper the effects of the Se evaporation temperature on the properties of CuIn0.75Ga0.25Se2 (CIGS) thin films. Structure, surface morphology and optical properties of CIGS thin films deposited at various Se evaporation temperatures have been investigated using a number of analysis techniques. X-ray diffraction (XRD) analysis shows that CIGS films exhibit a strong <112> preferred orientation. As expected, at higher Se evaporation temperatures the films displayed a lower degree of crystallinity. The <112> peak was also enhanced and other CIGS peaks appeared simultaneously. These results were supported by experimental work using scanning electron microscopy When the Se evaporation temperature was increased, the average grain size also decreased together with a reduction Cu content. The Se evaporation temperature also had a significant inf1uence on the transmission spectra. Increasing the Se evaporation temperature, the cell efficiency was improved dramatically to 11.75% with Voc = 556 mV, Jsc = 32.17 mA/cm2 and FF = 0.66. The Se evaporation temperature is an important parameter in thin film deposition regardless of the deposition technique being used to deposit thin films

• Current Photovoltaic Research
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• 제3권3호
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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.