• Current Photovoltaic Research
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• v.4 no.1
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• pp.16-20
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• 2016

$Cu_2ZnSnS_4$ (CZTS) thin films were fabricated by successive electrodeposition of layers of precursor elements followed by sulfurization of an electrodeposited Cu-Zn-Sn precursor. In order to improve quality of the CZTS films, we tried to optimize the deposition condition of absorber layers. In particular, I have conducted optimization experiments by changing the Cu-layer deposition time. The CZTS absorber layers were synthesized by different Cu-layer conditions ranging from 10 to 16 minutes. The sulfurization of Cu/Sn/Zn stacked metallic precursor thin films has been conducted in a graphite box using rapid thermal annealing (RTA). The structural, morphological, compositional, and optical properties of CZTS thin films were investigated using X-ray diffraction (XRD), Field emission scanning electron microscopy (FE-SEM), Raman spectroscopy, and X-ray Flourescenece Spectrometry (XRF). Especially, the CZTS TFSCs exhibits the best power conversion efficiency of 4.62% with $V_{oc}$ of 570 mV, $J_{sc}$ of $18.15mA/cm^2$ and FF of 45%. As the time of deposition of the Cu-layer to increasing, the properties were confirmed to be systematically changed. And we have been discussed in detail below.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2002.07b
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• pp.869-873
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• 2002

$Cu_2ZnSnS_4$ (CZTS) thin film is one of the candidate materials for the solar cell. It has an excellent optical absorption coefficient as well as appropriate 1.4~1.5eV band gap. The purpose of this study is replacing a half of high-cost Indium(In) atoms with low-cost Zinc(Zn) atoms and the other half with low-cost Tin(Sn) atoms in the lattice of CIS. In annealing process of thin films deposited with mixture target, the thin films were appeared the peeling. The resistivity was decreased. Thin films were deposited on ITO glass substrates using a compound target which were made by $CU_2S$, ZnS, $SnS_2$ powder were sintered in the atmosphere of Al at room temperature by rf magnetron sputtering We investigated potentialities of a low-cost material for the solar cell by measuring of thin film composition, the structure and optical properties. We could get an appropriate $Cu_2ZnSnS_4$ composition A (112) preferred orientation was appeared without annealing temperature as shown in the diffraction peaks of the CIS cells and was available for photovoltaic thin film materials. The band gap increased from 1.4 to 1.7eV as the composition ratio of Zn/Sn.. The optical absorption coefficient of the thin film was above $10^4cm^{-1}$.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2007.11a
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• pp.262-263
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• 2007

Effect of co-doping on optical and electrical properties of $SnO_2$ based thin films were studied. $SnO_2$ ceramic targets with up to 50mol% $CuSb_2O_6$ were prepared by sintering mixed-oxide compact in the temperature range of $1100^{\circ}C{\sim}1300^{\circ}C$ in air. Thin films were then deposited onto glass substrates by pulsed laser deposition where substrate temperature was maintained in the range of $500{\sim}650^{\circ}C$ with oxygen pressure of 3m~7.5mTorr and energy density of $1Jcm^{-2}$. It was found that with the increase amount of dopant, the electrical properties of thin films tended to improve with the smallest resistivity value obtained at about 8mol% doping, further increase, however, usually impaired the optical transmission in the visible range.

• Korean Journal of Materials Research
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• v.28 no.10
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• pp.564-569
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• 2018

$Cu_2ZnSn(S,Se)_4$ (CZTSSe) films were prepared on Mo coated soda lime glass substrates by sulfo-selenization of sputtered stacked Zn-Sn-Cu(CZT) precursor films. The precursor was dried in a capped state with aqueous NaOH solution. The CZT precursor films were sulfo-selenized in the S + Se vapor atmosphere. Sodium was doped during the sulfo-selenization treatment. The effect of sodium doping on the structural and electrical properties of the CZTSSe thin films were studied using FE-SEM(field-emission scanning electron microscopy), XRD(X-ray diffraction), XRF(X-ray fluorescence spectroscopy), dark current, SIMS(secondary ion mass spectrometry), conversion efficiency. The XRD, XRF, FE-SEM, Dark current, SIMS and cell efficiency results indicated that the properties of sulfo-selenized CZTSSe thin films were strongly related to the sodium doping. Further detailed analysis and discussion for effect of sodium doping on the properties CZTSSe thin films will be discussed.

• 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.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.688-688
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• 2013

Al-doped ZnO (AZO) thin films have attracted a lot of attention as a cheap transparent conducting oxide (TCO) material that can replace the expensive Sn-doped In2O3. In particular, AZO thin films are widely used as a window layer of chalcogenide-based thin film solar cells such as Cu(In,Ga)Se2 and Cu2ZnSnS4 (CZTS). Mostly important requirements for the window layer material of the thin film solar cells are the high transparency and the low sheet resistance, because they influence the light absorption by the activelayer and the electron collection from the active layer, respectively. In this study, we prepared the AZO thin films by RF magnetron sputtering using a ZnO/Al2O3 (98：2wt%) ceramic target, and the effect of the sputtering condition such as the working pressure, RF power, and the working distance on the optical, electrical, and crystallographic properties of the AZO thin films was investigated. The AZO thin films with optimized properties were used as a window layer of CZTS thin film solar cells. The CZTS active layers were prepared by the electrochemical deposition and the subsequent sulfurization process, which is also one of the cost-effective synthetic approaches. In addition, the solar cell properties of the CZTS thin film solar cells, such as the photocurrent density-voltage (J-V) characteristics and the external quantum efficiency (EQE) were investigated.

• 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.

• 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.

• Current Applied Physics
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• v.18 no.12
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• pp.1571-1576
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• 2018

Recent study shows that the main reason for limiting CZTS device performance lies in the low open circuit voltage, and crucial factor that could affect the $V_{oc}$ is secondary phases like ZnS existing in absorber layer and its interfaces. In this work, the $Cu_2ZnSnS_4$ thin film solar cells were prepared by sputtering CuSn and CuZn alloy targets. Through tuning the Zn/Sn ratios of the CZTS thin films, the crystal structure, morphology, chemical composition and phase purity of CZTS thin films were characterized by X-Ray Diffraction (XRD), scanning electron microscopy (SEM) equipped with an energy dispersive spectrometer (EDS) and Raman spectroscopy. The statistics data show that the CZTS solar cell with a ratio of Zn/Sn = 1.2 have the best power convention efficiency of 5.07%. After HCl etching process, the CZTS thin film solar cell with the highest efficiency 5.41% was obtained, which demonstrated that CZTS film solar cells with high efficiency could be developed by sputtering CuSn and CuZn alloy targets.

• 한국태양에너지학회:학술대회논문집
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• 2012.03a
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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.