• Journal of Electrochemical Science and Technology
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• v.9 no.4
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• pp.308-319
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• 2018

Single step electrodeposition of $Cu_2ZnSnS_4$ (CZTS) for solar cell applications was studied using an aqueous thiocyanate based electrolyte. The sodium thiocyanate complexing agent was found to decrease the difference in the deposition potential of the elements. X-ray diffraction analysis of the samples indicates the formation of kesterite phase CZTS. UV-vis studies reveal the band gap of the deposits to be in the range of 1.2 - 1.5 eV. The thickness of the deposit was found to decrease with increase in pH of the electrolyte. Nearly stoichiometric composition was obtained for CZTS films coated at pH 2 and 2.5. I-V characterization of the film with indium tin oxide (ITO) substrate in the presence and the absence of light source indicate that the resistance decrease significantly in the presence of light indicating suitability of the deposits for solar cell applications. Results of electrochemical impedance spectroscopic studies reveal that the cathodic process for sulfur reduction is the slowest among all the elements.

• Prospectives of Industrial Chemistry
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• v.20 no.2
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• pp.13-24
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• 2017

태양전지는 온실 가스 감축에 효과가 큰 기후 변화 대응 기술이다. 현재 상업화에 성공한 실리콘 태양전지의 뒤를 이어 박막 태양전지, 페로브스카이트 태양전지 등 차세대 태양전지가 가격과 효율 등을 극복하기 위하여 매우 많이 연구되고 있다. CZT(S,Se) 박막 태양전지는 차세대 태양전지의 유력 후보군인 CIGS, CdTe, 페로브스카이트 태양전지 등에 비해 범용 무독성 원소를 광흡수층으로 사용한다는 장점을 가지고 있지만 아직까지는 이들보다 효율이 낮아 상용화하기에는 많은 문제를 가지고 있다. CZT(S,Se) 박막태양전지의 기본적인 물성, 공정 등을 알아보고 고효율을 달성하는 방법에 대하여 알아보고자 한다.

• 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.

• Proceedings of the Materials Research Society of Korea Conference
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• 2011.10a
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• pp.35.1-35.1
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• 2011

New photovoltaic (PV) materials and manufacturing approaches are needed for meeting the demand for lower-cost solar cells. The prototypal thin-film photovoltaic absorbers (CdTe and $Cu(In,Ga)Se_2$) can achieve solar conversion efficiencies of up to 20% and are now commercially available, but the presence of toxic (Cd,Se) and expensive elemental components (In, Te) is a real issue as the demand for photovoltaics rapidly increases. To overcome these limitations, there has been substantial interest in developing viable alternative materials, such as $Cu_2ZnSnS_4$ (CZTS) is an emerging solar absorber that is structurally similar to CIGS, but contains only earth abundant, non-toxic elements and has a near optimal direct band gap energy of 1.4~1.6 ev and a large absorption coefficient of ${\sim}10^4\;cm^{-1}$. The CZTS absorber layers are grown and investigated by various fabrication methods, such as thermal evaporation, e-beam evaporation with a post sulfurization, sputtering, non-vacuum sol-gel, pulsed laser, spray-pyrolysis method and electrodeposition technique. In the present work, we report an alternative method for large area deposition of CZTS thin films that is potentially high throughput and inexpensive when used to produce monolithically integrated solar panel modules. Specifically, we have developed an aqueous chemical approach based on chemical bath deposition (CBD) with a subsequent sulfurization heat treatment. Samples produced by our method were analyzed by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, absorbance and photoluminescence. The results show that this inexpensive and relatively benign process produces thin films of CZTS exhibiting uniform composition, kesterite crystal structure, and good optical properties. A preliminary solar cell device was fabricated to demonstrate rectifying and photovoltaic behavior.

• 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.

• Korean Journal of Materials Research
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• v.23 no.6
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• pp.304-308
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• 2013

The effect of a sputter deposition sequence of Cu, Zn, and Sn metal layers on the properties of $Cu_2ZnSnS_4$ (CZTS) was systematically studied for solar cell applications. The set of Cu/Sn/Zn/Cu multi metal films was deposited on a Mo/$SiO_2$/Si wafer using dc sputtering. CZTS films were prepared through a sulfurization process of the Cu/Sn/Zn/Cu metal layers at $500^{\circ}C$ in a $H_2S$ gas environment. $H_2S$ (0.1%) gas of 200 standard cubic centimeters per minute was supplied in the cold-wall sulfurization reactor. The metal film prepared by one-cycle deposition of Cu(360 nm)/Sn(400 nm)/Zn(400 nm)/Cu(440 nm) had a relatively rough surface due to a well-developed columnar structure growth. A dense and smooth metal surface was achieved for two- or three-cycle deposition of Cu/Sn/Zn/Cu, in which each metal layer thickness was decreased to 200 nm. Moreover, the three-cycle deposition sample showed the best CZTS kesterite structures after 5 hr sulfurization treatment. The two- and three-cycle Cu/Sn/Zn/Cu samples showed high-efficient photoluminescence (PL) spectra after a 3 hr sulfurization treatment, wheres the one-cycle sample yielded poor PL efficiency. The PL spectra of the three-cycle sample showed a broad peak in the range of 700-1000 nm, peaked at 870 nm (1.425 eV). This result is in good agreement with the reported bandgap energy of CZTS.

• Current Photovoltaic Research
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• v.1 no.2
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• pp.109-114
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• 2013

$Cu_2ZnSnS_4$ (CZTS) nanoparticles were synthesized by a solvothermal method using copper (II) acetate, zinc acetate, tin chloride, and sulfur in diethylenetriamine solvent. Binary sulfide particles such as CuS, ZnS, SnS, and $SnS_2$ were obtained at $180^{\circ}C$; single-phase CZTS nanoparticles were obtained at $280^{\circ}C$. CZTS nanoparticles with spherical shape and grain size of 40 to 60 nm were obtained at $280^{\circ}C$. In the middle of 180 and $280^{\circ}C$, CZTS and ZnS phases were found. The time variation of reaction at $280^{\circ}C$ revealed that an amorphous state formed first instead of binary phases and then the amorphous phase was converted to crystalline CZTS state; it is different reaction path way from conventional solid-state reaction path of which binary phases react to form CZTS. CZTS films deposited and annealed from single-phase nanoparticles showed porous microstructure and poor adhesion. This indicates that a combination of CZTS and other flux phase is necessary to have a dense film for device fabrication.

• 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.

• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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• pp.99.1-99.1
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• 2012

The thin-film photovoltaic absorbers (CdTe and $Cu(In,Ga)Se_2$) can achieve solar conversion efficiencies of up to 20% and are now commercially available, but the presence of toxic (Cd,Se) and expensive elemental components (In, Te) is a real issue as the demand for photovoltaics rapidly increases. To overcome these limitations, there has been substantial interest in developing viable alternative materials, such as $Cu_2ZnSnS_4$ (CZTS) is an emerging solar absorber that is structurally similar to CIGS, but contains only earth abundant, non-toxic elements and has a near optimal direct band gap energy of 1.4 - 1.6 eV and a large absorption coefficient of ~104 $cm^{-1}$. The CZTS absorber layers are grown and investigated by various fabrication methods, such as thermal evaporation, e-beam evaporation with a post sulfurization, sputtering, non-vacuum sol-gel, pulsed laser, spray-pyrolysis method and electrodeposition technique. In the present work, we report an alternative aqueous chemical approach based on chemical bath deposition (CBD) method for large area deposition of CZTS thin films. Samples produced by our method were analyzed by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, absorbance and photoluminescence. The results show that this inexpensive and relatively benign process produces thin films of CZTS exhibiting uniform composition, kesterite crystal structure, and some factors like triethanolamine, ammonia, temperature which strongly affect on the morphology of CZTS film.

• Journal of the Korean institute of surface engineering
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• v.35 no.1
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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}$.