• Current Photovoltaic Research
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• v.9 no.3
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• pp.84-95
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• 2021

The power conversion efficiency of Cu₂ZnSnSe₄ (CZTSe) solar cells depends on the absorber layer thickness; however, changes in the characteristics of the cells with varying absorber layer thickness are unclear. In this study, we investigated the changes in the characteristics of CZTSe solar cells for varying absorber layer thickness. Five absorber thicknesses were employed: CZTSe1 2.78 ㎛, CZTSe2 1.01 ㎛, CZTSe3 0.55 ㎛, CZTSe4 0.29 ㎛, and CZTSe5 0.15-0.23 ㎛. The efficiency of the CZTSe solar cells decreased as the absorber thickness decreased, resulting in power conversion efficiencies of 10.45% (CZTSe1), 8.67% (CZTSe2), 7.14% (CZTSe3), 3.44% (CZTSe4), and 1.54% (CZTSe5). As the thickness of the CZTSe absorber layer decreased, the electron-hole recombination at the grain boundaries and the absorber-back-contact interface increased. This caused an increase in the current loss, owing to light loss in the long-wavelength region. In addition, as the thickness of the CZTSe absorber layer decreased, more ZnSe was produced, and the resulting defects and defect clusters led to an open-circuit voltage loss.

• Proceedings of the Korean Vacuum Society Conference
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• 2014.02a
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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.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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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%.

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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• pp.254-254
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• 2016

Tin dioxide (SnO2) thin film is one of the most important n-type semiconducting materials having a high transparency and chemical stability. Due to their favorable properties, it has been widely used as a base materials in the transparent conducting substrates, gas sensors, and other various electronic applications. Up to now, SnO2 thin film has been extensively studied by a various deposition techniques such as RF magnetron sputtering, sol-gel process, a solution process, pulsed laser deposition (PLD), chemical vapor deposition (CVD), and atomic layer deposition (ALD) [1-6]. Among them, ALD or plasma-enhanced ALD (PEALD) has recently been focused in diverse applications due to its inherent capability for nanotechnologies. SnO2 thin films can be prepared by ALD or PEALD using halide precursors or using various metal-organic (MO) precursors. In the literature, there are many reports on the ALD and PEALD processes for depositing SnO2 thin films using MO precursors [7-8]. However, only ALD-SnO2 processes has been reported for halide precursors and PEALD-SnO2 process has not been reported yet. Herein, therefore, we report the first PEALD process of SnO2 thin films using SnCl4 and oxygen plasma. In this work, the growth kinetics of PEALD-SnO2 as well as their physical and chemical properties were systemically investigated. Moreover, some promising applications of this process will be shown at the end of presentation.

• Journal of Powder Materials
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• v.28 no.3
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• pp.239-245
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• 2021

The SnSe single crystal shows an outstanding figure of merit (ZT) of 2.6 at 973 K; thus, it is considered to be a promising thermoelectric material. However, the mass production of SnSe single crystals is difficult, and their mechanical properties are poor. Alternatively, we can use polycrystalline SnSe powder, which has better mechanical properties. In this study, surface modification by atomic layer deposition (ALD) is chosen to increase the ZT value of SnSe polycrystalline powder. SnSe powder is ground by a ball mill. An ALD coating process using a rotary-type reactor is adopted. ZnO thin films are grown by 100 ALD cycles using diethylzinc and H₂O as precursors at 100℃. ALD is performed at rotation speeds of 30, 40, 50, and 60 rpm to examine the effects of rotation speed on the thin film characteristics. The physical and chemical properties of ALD-coated SnSe powders are characterized by scanning and tunneling electron microscopy combined with energy-dispersive spectroscopy. The results reveal that a smooth oxygen-rich ZnO layer is grown on SnSe at a rotation speed of 30 rpm. This result can be applied for the uniform coating of a ZnO layer on various powder materials.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.22 no.3
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• pp.127-133
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• 2012

To achieve low-cost and high-efficiency of thin-film solar cells applications, the sol-gel method that can be coated on a large area substrate, obtain homogeneous thin films of high purity was used. We studied structural and optical characteristics versus annealing temperature of $Cu_2ZnSnS_4$ which has kesterite structure by substitution low-cost sulfur (S) instead of high-cost selenium (Se). By analyzing XRD patterns, main peak was observed at $2{\theta}=28.5^{\circ}$ when Zn/Sn ratio is 0.8/1.2. And when we observed kesterite structure which has orientation of (112) direction, the more annealing temperature increase the bigger strength of (112) direction is. $Cu_2ZnSnS_4$ thin film showed characteristics of kesterite structure at $550^{\circ}C$. And when we calculated lattice constant, a = 5.5047 and $c=11.014{\AA}$ as same JCPDS (Joint Committee on Powder Standards) data measured. We measured optical transmittance to analyze optical characteristics. Optical transmittance was lower than 65 % at visible ray (${\lambda}=380{\sim}770nm$).

• Current Photovoltaic Research
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• v.3 no.2
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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.

• Korean Journal of Materials Research
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• v.23 no.3
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• pp.183-189
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• 2013

$Cu_2ZnSn(S,Se)_4$ material is receiving an increased amount of attention for solar cell applications as an absorber layer because it consists of inexpensive and abundant materials (Zn and Sn) instead of the expensive and rare materials (In and Ga) in $Cu(In,Ga)Se_2$ solar cells. We were able to achieve a cell conversion efficiency to 4.7% by the selenization of a stacked metal precursor with the Cu/(Zn + Sn)/Mo/glass structure. However, the selenization of the metal precursor results in large voids at the absorber/Mo interface because metals diffuse out through the top CZTSe layer. To avoid the voids at the absorber/Mo interface, binary selenide compounds of ZnSe and $SnSe_2$ were employed as a precursor instead of Zn and Sn metals. It was found that the precursor with Cu/$SnSe_2$/ZnSe stack provided a uniform film with larger grains compared to that with $Cu_2Se/SnSe_2$/ZnSe stack. Also, voids were not observed at the $Cu_2ZnSnSe_4$/Mo interface. A severe loss of Sn was observed after a high-temperature annealing process, suggesting that selenization in this case should be performed in a closed system with a uniform temperature in a $SnSe_2$ environment. However, in the experiments, Cu top-layer stack had more of an effect on reducing Sn loss compared to $Cu_2Se$ top-layer stack.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.97-97
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• 2013

Recently, Cu2ZnSn(S,Se)4 (CZTSS), which is one of the In- and Ga- free absorber materials, has been attracted considerable attention as a new candidate for use as an absorber material in thin film solar cells. The CZTSS-based absorber material has outstanding characteristics such as band gap energy of 1.0 eV to 1.5 eV, high absorption coefficient on the order of 104 cm-1, and high theoretical conversion efficiency of 32.2% in thin film solar cells. Despite these promising characteristics, research into CZTSS based thin film solar cells is still incomprehensive and related reports are quite few compared to those for CIGS thin film solar cells, which show high efficiency of over 20%. I will briefly overview the recent technological development of CZTSS thin film solar cells and then introduce our research results mainly related to sputter based process. CZTSS thin film solar cells are prepared by sulfurization of stacked both metallic and sulfide precursors. Sulfurization process was performed in both furnace annealing system and rapid thermal processing system using S powder as well as 5% diluted H2S gas source at various annealing temperatures ranging from $520^{\circ}C$ to $580^{\circ}C$. Structural, optical, microstructural, and electrical properties of absorber layers were characterized using XRD, SEM, TEM, UV-Vis spectroscopy, Hall-measurement, TRPL, etc. The effects of processing parameters, such as composition ratio, sulfurization pressure, and sulfurization temperature on the properties of CZTSS absorber layers will be discussed in detail. CZTSS thin film solar cell fabricated using metallic precursors shows maximum cell efficiency of 6.9% with Jsc of 25.2 mA/cm2, Voc of 469 mV, and fill factor of 59.1% and CZTS thin film solar cell using sulfide precursors shows that of 4.5% with Jsc of 19.8 mA/cm2, Voc of 492 mV, and fill factor of 46.2%. In addition, other research activities in our lab related to the formation of CZTS absorber layers using solution based processes such as electro-deposition, chemical solution deposition, nano-particle formation will be introduced briefly.

• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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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.