• 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.

• 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.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.

• 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.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.10 no.2
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• pp.39-48
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• 2022

A Se-containing Cu/SnSe₂/ZnSe precursor was employed to introduce S to the precursor to form Cu₂ZnSn(S,Se)₄ (CZTSSe) film. The morphology of CZTSSe films strongly varied with two different pre-annealing environments: S and N₂. The CZTSSe film with S pre-annealing showed a dense morphology with a smooth surface, while that with N₂ pre-annealing showed a porous film with a plate-shaped grains on the surface. CuS and Cu₂Sn(S,Se)₃ phases formed during the S pre-annealing stage, while SnSe and Cu₂SnSe₃ phases formed during the N₂ pre-annealing stage. The SnSe phase formed during N₂ pre-annealing generated SnS₂ phase that had plate shape and severely aggravated the morphology of CZTSSe film. The power conversion efficiency of the CZTSSe solar cell with S pre-annealing was low (1.9%) due to existence of Zn(S.Se) layer between CZTSSe and Mo substrate. The results indicated that S pre-annealing of the precursor was a promising method to achieve a good morphology for large area application.

• 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.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.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.23 no.11
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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.