• 한국재료학회지
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• 제23권11호
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• pp.613-619
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• 2013

$Cu_2ZnSn(S_x,Se_{1-x})_4$ (CZTSSe) thin films were prepared by sulfurization of evaporated precursor thin films. Precursor was prepared using evaporation method at room temperature. The sulfurization was carried out in a graphite box with S powder at different temperatures. The temperatures were varied in a four step process from $520^{\circ}C$ to $580^{\circ}C$. The effects of the sulfurization temperature on the micro-structural, morphological, and compositional properties of the CZTSSe thin films were investigated using X-ray diffraction (XRD), Raman spectra, field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). The XRD and Raman results showed that the sulfurized thin films had a single kesterite crystal CZTSSe. From the FE-SEM and TEM results, the $Mo(S_x,Se_{1-x})_2$ (MoSSe) interfacial layers of the sulfurized CZTS thin films were observed and their thickness was seen to increase with increasing sulfurization temperature. The microstructures of the CZTSSe thin films were strongly related to the sulfurization temperatures. The voids in the CZTSSe thin films increased with the increasing sulfurization temperature.

• Transactions on Electrical and Electronic Materials
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• 제10권4호
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• pp.135-139
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• 2009

$H_2S$ micro-gas sensors have been developed employing $SnO_2$:CuO composite thin films. The films were prepared by e-beam evaporation of Sn and Cu metals on silicon substrates, followed by oxidation at high temperatures. Results of various studies, such as scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) reveal that $SnO_2$ and CuO are mutually non-reactive. The CuO grains, which in turn reside in the inter-granular regions of $SnO_2$, inhibit grain growth of $SnO_2$ as well as forming a network of p-n junctions. The film showed more than a 90% relative resistance change when exposed to $H_2S$ gas at 1 ppm in air at an operating temperature of $350^{\circ}C$ and had a short response time of 8 sec.

• 한국표면공학회지
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• 제35권1호
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• pp.39-46
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• 2002

$Cu_2$$ZnSnS_4$(CZTS) thin film is one of the candidate materials for the solar cell. It has an excellent optical absorption coefficient as well as appropriate 1.4~1.5eV band gap. The purpose of this study is replacing a half of high-cost Indium(In) atoms with low-cost Zinc(Zn) atoms and the other half with low-cost Tin(Sn) atoms in the lattice of CIS. Thin films were deposited on ITO glass substrates using a compact target which were made by $Cu_2$S, ZnS, SnS$_2$ powder at room temperature by rf magnetron sputtering and were annealed in the atmosphere of Ar and $S_2$(g). We investigated potentialities of a low-cost material for the solar cell by measuring of thin film composition, the structure and optical properties. We could get an appropriate $Cu_2$$ZnSnS_4$ composition. Structure was coarsened with increasing temperature and (112), (200), (220), (312) planes appeared to conform to all the reflection Kesterite structure. A (112) preferred orientation was advanced with increasing the 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 1.51 to 1.8eV as the annealing temperature increased. The optical absorption coefficient of the thin film was about $10^4$$cm^{-1}$.

• Current Photovoltaic Research
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• 제3권2호
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• pp.54-60
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• 2015

ZnSnO thin films were deposited by atomic layer deposition (ALD) process using diethyl zinc ($Zn(C_2H_5)_2$) and tetrakis (dimethylamino) tin ($Sn(C_2H_6N)_4$) as metal precursors and water vapor as a reactant. ALD process has several advantages over other deposition methods such as precise thickness control, good conformality, and good uniformity for large area. The composition of ZnSnO thin films was controlled by varying the ratio of ZnO and $SnO_2$ ALD cycles. The ALD ZnSnO film was an amorphous state. The band gap of ZnSnO thin films increased as the Sn content increased. The CIGS solar cell using ZnSnO buffer layer showed about 18% energy conversion efficiency. With such a high efficiency with the ALD ZnSnO buffer and no light soaking effect, AlD ZnSnO buffer mighty be a good candidate to replace Zn(S,O) buffer in CIGSsolar cells.

• Journal of Electrochemical Science and Technology
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• 제8권3호
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• pp.206-214
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• 2017

SnS films have been prepared by electrodeposition technique onto Cu and ITO substrates using acidic solutions containing tin chloride and sodium thiosulfate with sodium citrate as an additive. The effects of sodium citrate on the electrochemical behavior of electrolyte bath containing tin chloride and sodium thiosulfate were investigated by cyclic voltammetry and chronoamperometry techniques. Deposited films were characterized by XRD, FTIR, SEM, optical, photoelectrochemical, and electrical measurements. XRD data showed that deposited SnS with sodium citrate on both substrates were polycrystalline with orthorhombic structures and preferential orientations along (111) directions. However, SnS films with sodium citrate on Cu substrate exhibited a good crystalline structure if compared with that deposited on ITO substrates. FTIR results confirmed the presence of SnS films at peaks 1384 and $560cm^{-1}$. SEM images revealed that SnS with sodium citrate on Cu substrate are well covered with a smooth and uniform surface morphology than deposited on ITO substrate. The direct band gap of the films is about 1.3 eV. p-type semiconductor conduction of SnS was confirmed by photoelectrochemical and Hall Effect measurements. Electrical properties of SnS films showed a low electrical resistivity of $30{\Omega}cm$, carrier concentration of $2.6{\times}10^{15}cm^{-3}$ and mobility of $80cm^2V^{-1}s^{-1}$.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2009년도 춘계학술대회 논문집
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• pp.85-87
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• 2009

Despite the success of $Cu(In,Ga)Se_2$ (CIGS) based PV technology now emerging in several industrial initiatives, concerns about the cost of In and Ga are often expressed. It is believed that the cost of those elements will eventually limit the cost reduction of this technology. one candidate to replace CIGS is $Cu_2ZnSnSe_4$ (CZTSe), fabricated by co-evaporation technique. Effects of substrate temperature of $Cu_2ZnSnSe_4$ absorber layer on the performance of thin films solar cells were investigated. As substrate temperature increased, the grain size of $Cu_2ZnSnSe_4$ films increased presumably. At a optimal condition of substrate temperature is $320^{\circ}C$, the solar cell shows a conversion efficiency of 1.79% with $V_{OC}$ of 0.213V, JSC of $16.91mA/cm^2$ and FF of 49.7%.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2014년도 제46회 동계 정기학술대회 초록집
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• pp.398.1-398.1
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• 2014

The $Cu_2ZnSnSe_4$ (CZTSe) thin films solar cell is one of the next generation candidates for photovoltaic materials as the absorber of thin film solar cells because it has optimal bandgap (Eg=1.0eV) and high absorption coefficient of $10^4cm^{-1}$ in the visible length region. More importantly, CZTSe consists of abundant and non-toxic elements, so researches on CZTSe thin film solar cells have been increasing significantly in recent years. CZTSe thin film has very similar structure and properties with the CIGS thin film by substituting In with Zn and Ga with Sn. In this study, As-deposited CZTSe thin films have been deposited onto soda lime glass (SLG) substrates at different deposition condition using Pulsed Laser Deposition (PLD) technique without post-annealing process. The effects of deposition conditions (deposition time, deposition temperature) onto the structural, compositional and optical properties of CZTSe thin films have been investigated, without experiencing selenization process. The XRD pattern shows that quaternary CZTSe films with a stannite single phase. The existence of (112), (204), (312), (008), (316) peaks indicates all films grew and crystallized as a stannite-type structure, which is in a good agreement with the diffraction pattern of CZTSe single crystal. All the films were observed to be polycrystalline in nature with a high (112) predominant orientation at $2{\theta}{\sim}26.8^{\circ}$. The carrier concentration, mobility, resistivity and optical band gap of CZTSe thin films depending on the deposition conditions. Average energy band gap of the CZTSe thin films is about 1.3 eV.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
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• pp.318.1-318.1
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• 2013

Nowadays Cu2ZnSnS4 (CZTS) solar cell is attracting a lot of attention as a strong alternative to CIGS solar cell due to nontoxic and inexpensive constituent elements of CZTS. From various processes for the fabrication of CZTS solar cell, solution-based deposition of CZTS thin films is well-known non-vacuum process and many researchers are focusing on this method because of large-area deposition, high-throughput, and efficient material usage. Typically the solution-based process consists of two steps, coating of precursor solution and annealing of the precursor thin films. Unlike vacuum-based deposition, precursor solution contains unnecessary elements except Cu, Zn, Sn, and S in order to form high quality precursor thin films, and thus the precise control of precursor thin film preparation is essential for achieving high efficient CZTS solar cells. In this work, we have investigated the effect of preparation condition of CZTS precursor thin films on the performance of CZTS solar cells. The composition of CZTS precursor solution was controlled for obtaining optimized chemical composition of CZTS absorber layers for high-efficiency solar cells. Pre-annealing process of the CZTS precursor thin films was also investigated to confirm the effect of thermal treatment on chemical composition and carbon residues of CZTS absorber layers. The change of the morphology of CZTS precursor thin film by the preparation condition was also observed.

• Bulletin of the Korean Chemical Society
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• 제35권7호
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• pp.1985-1988
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• 2014

$Cu_2ZnSnSe_4$ (CZTSe) thin films were synthesized on transparent conducting oxide glass substrates via a simple, non-toxic, and low-cost process using a precursor solution paste. A three-step heating process (oxidation, sulfurization, and selenization) was employed to synthesize a CZTSe thin film as an absorber layer for use in thin-film solar cells. In particular, we focused on the effects of sulfurization conditions on CZTSe film formation. We found that sulfurization at $400^{\circ}C$ involves the formation of secondary phases such as $CuSe_2$ and $Cu_2SnSe_3$, but they gradually disappeared when the temperature was increased. The formed CZTSe thin films showed homogenous and good crystallinity with grain sizes of approximately 600 nm. A solar cell device was tentatively fabricated and showed a power conversion efficiency of 2.2% on an active area of 0.44 $cm^2$ with an open circuit voltage of 365 mV, a short current density of 20.6 $mA/cm^2$, and a fill factor of 28.7%.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2012년도 춘계학술발표대회
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• pp.98.2-98.2
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• 2012

Thin film solar cells are growing up in the market due to their high efficiency and low cost. Especially CdTe and $CuInGaSe_2$ based solar cells are leading the other cells, but due to the limited percentage of the elements present in our earth's crust like Tellurium, Indium and Gallium, the price of the solar cells will increase rapidly. Copper Zinc Tin Sulfide (CZTS) and Copper Zinc Tin Selenide (CZTSe) semiconductor (having a kesterite crystal structure) are getting attention for its solar cell application as the absorber layer. CZTS and CZTSe have almost the same crystal structure with more environmentally friendly elements. Various authors have reported growth and characterization of CZTSe films and solar cells with efficiencies about 3.2% to 8.9%. In this study, a novel method to prepare CZTSe has been proposed based on selenization of stacked Copper Selenide ($Cu_2Se$), Tin Selenide ($SnSe_2$) and Zinc Selenide (Zinc Selenide) in six possible stacking combinations. Depositions were carried out through RF magnetron sputtering. Selenization of all the samples was performed in Close Space Sublimation (CSS) in vacuum at different temperatures for three minutes. Characterization of each sample has been performed in Field Emission SEM, XRD, Raman spectroscopy, EDS and Auger. In this study, the properties and results of $Cu_2ZnSnSe_4$ thin films grown by selenization will be presented.