• Applied Chemistry for Engineering
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• v.26 no.5
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• pp.526-532
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• 2015

Solar cells with other alternative energies are being importantly recognized related with post-2020 climate change regime formation. In a point of view of materials, solar cells are classified to organic and inorganic solar cells which can provide a plant-scale electricity. In particular, recent studies about compound semiconductor solar cells, such as III-V tandem solar cells, chalcopyrite-series CIGSSe solar cells, and kesterite-series CZTSSe solar cells were rapidly accelerated. In this report, we introduce a research trend and technical issues for the compound semiconductor solar cells.

• Korean Journal of Materials Research
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• v.31 no.11
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• pp.619-625
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• 2021

Cu₂ZnSn(S,Se)₄ (CZTSSe) based thin-film solar cells have attracted growing attention because of their earth-abundant and non-toxic elements. However, because of their large open-circuit voltage (V_oc)-deficit, CZTSSe solar cells exhibit poor device performance compared to well-established Cu(In,Ga)(S,Se)₂ (CIGS) and CdTe based solar cells. One of the main causes of this large V_oc-deficit is poor absorber properties for example, high band tailing properties, defects, secondary phases, carrier recombination, etc. In particular, the fabrication of absorbers using physical methods results in poor surface morphology, such as pin-holes and voids. To overcome this problem and form large and homogeneous CZTSSe grains, CZTSSe based absorber layers are prepared by a sputtering technique with different RTA conditions. The temperature is varied from 510 ℃ to 540 ℃ during the rapid thermal annealing (RTA) process. Further, CZTSSe thin films are examined with X-ray diffraction, X-ray fluorescence, Raman spectroscopy, IPCE, Energy dispersive spectroscopy and Scanning electron microscopy techniques. The present work shows that Cu-based secondary phase formation can be suppressed in the CZTSSe absorber layer at an optimum RTA condition.

• Current Photovoltaic Research
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• v.5 no.1
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• pp.20-24
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• 2017

Recently, three-dimensional (3D) light harvesting structures are highly attracted because of their high light harvesting capacity and charge collection efficiencies. In this study, we have fabricated $Cu_2ZnSn(S_xSe_{1-x})_4$ based 3D thin film solar cells on PR patterned Molybdenum (Mo) substrates using photolithography technique. Specifically, Mo patterns were deposited on PR patterned Mo substrates by sputtering and the thin Cu-Zn-Sn stacked layer was deposited over this Mo patterns by sputtering technique. The stacked Zn-Sn-Cu precursor thin films were sulfo-selenized to form CZTSSe pattern. Finally, CZTSSe absorbers were coated with thin CdS layer using chemical bath deposition and ZnO window layer was deposited over CZTSSe/CdS using DC sputtering technique. Fabricated 3-D solar cells were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF) analysis, Field-emission scanning electron microscopy (FE-SEM) to study their structural, compositional and morphological properties, respectively. The 3% efficiency is achieved for this kind of solar cell. Further efforts will be carried out to improve the performance of solar cell through various optimizations.

• Korean Journal of Materials Research
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• v.29 no.9
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• pp.553-558
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• 2019

$Cu_2ZnSn(S,Se)_4(CZTSSe)$ thin film solar cells areone of the most promising candidates for photovoltaic devices due to their earth-abundant composition, high absorption coefficient and appropriate band gap. The sputtering process is the main challenge to achieving high efficiency of CZTSSe solar cells for industrialization. In this study, we fabricated CZTSSe absorbers on Mo coated soda lime glass using different pressures during the annealing process. As an environmental strategy, the annealing process is performed with S and Se powder, without any toxic $H_2Se$ and/or $H_2S$ gases. Because CZTSSe thin films have a very narrow stable phase region, it is important to control the condition of the annealing process to achieve high efficiency of the solar cell. To identify the effect of process pressure during the sulfo-selenization, we experiment with varying initial pressure from 600 Torr to 800 Torr. We fabricate a CZTSSe thin film solar cell with 8.24 % efficiency, with 435 mV for open circuit voltage($V_{OC}$) and $36.98mA/cm^2$ for short circuit current density($J_{SC}$), under a highest process pressure of 800 Torr.

• 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.

• Korean Journal of Materials Research
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• v.32 no.11
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• pp.481-488
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• 2022

The Cu₂ZnSn(S_xSe_1-x)₄ (CZTSSe) absorbers are promising thin film solar cells (TFSCs) materials, to replace existing Cu(In,Ga)Se₂ (CIGS) and CdTe photovoltaic technology. However, the best reported efficiency for a CZTSSe device, of 13.6 %, is still too low for commercial use. Recently, partially replacing the Zn²⁺ element with a Cd²⁺element has attracting attention as one of the promising strategies for improving the photovoltaic characteristics of the CZTSSe TFSCs. Cd²⁺ elements are known to improve the grain size of the CZTSSe absorber thin films and improve optoelectronic properties by suppressing potential defects, causing short-circuit current (J_sc) loss. In this study, the structural, compositional, and morphological characteristics of CZTSSe and CZCTSSe thin films were investigated using X-ray diffraction (XRD), X-ray fluorescence spectrometer (XRF), and Field-emission scanning electron microscopy (FE-SEM), respectively. The FE-SEM images revealed that the grain size improved with increasing Cd²⁺ alloying in the CZTSSe thin films. Moreover, there was a slight decrease in small grain distribution as well as voids near the CZTSSe/Mo interface after Cd²⁺ alloying. The solar cells prepared using the most promising CZTSSe absorber thin films with Cd²⁺ alloying (8 min. 30 sec.) exhibited a power conversion efficiency (PCE) of 9.33 %, J_sc of 34.0 mA/cm², and fill factor (FF) of 62.7 %, respectively.

• Current Photovoltaic Research
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• v.11 no.3
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• pp.67-74
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• 2023

The earth-abundant element-based Cu₂ZnSn(S,Se)₄ (CZTSSe) thin film solar cells (TFSCs) have attracted greater attention in the photovoltaic (PV) community due to their rapid development in device power conversion efficiency (PCE) >13%. In the present work, we demonstrated the fine-tuning of the bandgap in the CZTSSe TFSCs by altering the sulfur (S) to the selenium (Se) chalcogenide ratio. To achieve this, the CZTSSe absorber layers are fabricated with different S/(S+Se) ratios from 0.02 to 0.08 of their weight percentage. Further compositional, morphological, and optoelectronic properties are studied using various characterization techniques. It is observed that the change in the S/(S+Se) ratios has minimal impact on the overall Cu/(Zn+Sn) composition ratio. In contrast, the S and Se content within the CZTSSe absorber layer gets altered with a change in the S/(S+Se) ratio. It also influences the overall absorber quality and gets worse at higher S/(S+Se). Furthermore, the device performance evaluated for similar CZTSSe TFSCs showed a linear increase and decrease in the open circuit voltage (V_oc) and short circuit current density (J_sc) of the device with an increasing S/(S+Se) ratio. The external quantum efficiency (EQE) measured also exhibited a linear blue shift in absorption edge, increasing the bandgap from 1.056 eV to 1.228 eV, respectively.

• Korean Journal of Materials Research
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• v.30 no.6
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• pp.285-291
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• 2020

Recent advances in technology using ultra-thin noble metal film in oxide/metal/oxide structures have attracted attention because this material is a promising alternative to meet the needs of transparent conduction electrodes (TCE). AZO/Ag/AZO multilayer films are prepared by magnetron sputtering for Cu₂ZnSn(S,Se)₄ (CZTSSe) of kesterite solar cells. It is shown that the electrical and optical properties of the AZO/Ag/AZO multilayer films can be improved by the very low resistivity and surface plasmon effects due to the deposition of different thicknesses of Ag layer between oxide layers fixed at AZO 30 nm. The AZO/Ag/AZO multilayer films of Ag 15 nm show high mobility of 26.4 ㎠/Vs and low resistivity and sheet resistance of 3.58^⁎10^-5 Ωcm and 5.0 Ω/sq. Also, the AZO/Ag (15 nm)/AZO multilayer film shows relatively high transmittance of more than 65 % in the visible region. Through this, we fabricated CZTSSe thin film solar cells with 7.51 % efficiency by improving the short-circuit current density and fill factor to 27.7 mV/㎠ and 62 %, respectively.

• 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.2 no.4
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• pp.177-181
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• 2014

$Cu_2ZnSn(S_xSe_{1-x})_4$ (CZTSSe) absorber thin films were prepared on Mo coated soda lime glass substrates by sulfo-selenization of sputtered stacked Zn-Sn-Cu precursor thin films. The Zn-Sn-Cu precursor thin films were sulfo-selenized inside a graphite box containing S and Se powder using rapid thermal processing furnace at $540^{\circ}C$ in Ar atmosphere with pre-treatment at $300^{\circ}C$. The effect of different S/Se ratio on the structural, compositional, morphological and electrical properties of the CZTSSe thin films were studied using XRD (X-ray diffraction), XRF (X-ray fluorescence analysis), FE-SEM (field-emission scanning electron microscopy), respectively. The XRD, FE-SEM, XRF results indicated that the properties of sulfo-selenized CZTSSe thin films were strongly related to the S/Se composition ratio. In particular, the CZTS thin film solar cells with S/(S+Se)=0.25 shows best conversion efficiency of 4.6% ($V_{oc}$ : 348 mV, $J_{sc}$ : $26.71mA/cm^2$, FF : 50%, and active area : $0.31cm^2$). Further detailed analysis and discussion for effect of S/Se composition ratio on the properties CZTSSe thin films will be discussed.