• 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.

• 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.

• Korean Journal of Materials Research
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• v.22 no.5
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• pp.259-273
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• 2012

Chalcogenide-based semiconductors, such as $CuInSe_2$, $CuGaSe_2$, Cu(In,Ga)$Se_2$ (CIGS), and CdTe have attracted considerable interest as efficient materials in thin film solar cells (TFSCs). Currently, CIGS and CdTe TFSCs have demonstrated the highest power conversion efficiency (PCE) of over 11% in module production. However, commercialized CIGS and CdTe TFSCs have some limitations due to the scarcity of In, Ga, and Te and the environmental issues associated with Cd and Se. Recently, kesterite CZTS, 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 CZTS-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 $10^4cm^{-1}$, and high theoretical conversion efficiency of 32.2% in thin film solar cells. Despite these promising characteristics, research into CZTS-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%. The recent development of kesterite-based CZTS thin film solar cells is summarized in this work. The new challenges for enhanced performance in CZTS thin films are examined and prospective issues are addressed as well.

• Journal of the Microelectronics and Packaging Society
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• v.15 no.4
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• pp.1-7
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• 2008

We studied a growth behavior of Intermetallic compounds(IMCs) during solder bumping with two reflow methods. Ti(50 nm), Cu($1{\mu}m$), Au(50 nm) and Ti(50 nm) thin films were deposited on $SiO_2$/Si wafer using the DC magnetron sputtering system as the under bump metallization(UBM). And the $5{\mu}m$ thick Cu bumps and $20{\mu}m$ thick Sn bumps were fabricated on UBM by electroplating. Sn bumps were reflowed in RTA(Rapid Thermal Annealing) system and convection reflow oven. When RTA system was used, reflow was possible without using flux and IMC thickness formed in the solder interface was thinner than that of a convectional method.

• Journal of the Korean Vacuum Society
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• v.4 no.S2
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• pp.95-99
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• 1995

keV ion beam irradiatin for surface modification and thin film growth have been discussed. keV ion beam irradiation in reactive gas environment has been developed for improving wettability of polymer, and for enhancing adhesion to metal film, and adventages of the method have been reviewed. An epitaxial Cu film on Si(100) substrate has been grown by ionized cluster beam and changes of crystallinity and surface roughness have been discussed. Stoichiometric $SnO_2$ films on Si(100) and glass have been grown by a hybrid ion beam Deposition(2 metal ion sources+1 gas ion source), and nonstoichiometric $SnO_2$ films are controlled by various deposition conditions in the HIB. Surface modification for polymer by kev ion irradiation have been developed. Wetting angle of water to PC has been changed from 68 degree to 49 degree with $Ar^+$ irradiation and to 8 degree with $Ar^+$ irradiation and the oxygen environment. Change of surface phenomena in a keV ion beam and characteristics of the grown films are suggested.

• Bulletin of the Korean Chemical Society
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• v.31 no.11
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• pp.3093-3098
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• 2010

The core-shell $SnO_2$@AO (A=Ni, Cu, Zn and Mg) films were prepared and the effects of coatings on photovoltaic properties were investigated. Studies on X-ray photoelectron spectroscopy, energy dispersive X-ray analysis and transmission electron microscopy showed the formation of divalent oxides on the surface of $SnO_2$ nanoparticles. It was commonly observed that all the dye-sensitized core-shell films exhibited higher photovoltage than the bare $SnO_2$ film. Transient photovoltage measurements confirmed that the improved photovoltages were related to the decreased time constants for electron recombination.

• Korean Journal of Materials Research
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• v.29 no.1
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• pp.1-6
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• 2019

Recent industrialization has led to a high demand for the use of fossil fuels. Therefore, the need for producing hydrogen and its utilization is essential for a sustainable society. For an eco-friendly future technology, photoelectrochemical water splitting using solar energy has proven promising amongst many other candidates. With this technique, semiconductors can be used as photocatalysts to generate electrons by light absorption, resulting in the reduction of hydrogen ions. The photocatalysts must be chemically stable, economically inexpensive and be able to utilize a wide range of light. From this perspective, cuprous oxide($Cu_2O$) is a promising p-type semiconductor because of its appropriate band gap. However, a major hindrance to the use of $Cu_2O$ is its instability at the potential in which hydrogen ion is reduced. In this study, gold is used as a bottom electrode during electrodeposition to obtain a preferential growth along the (111) plane of $Cu_2O$ while imperfections of the $Cu_2O$ thin films are removed. This study investigates the photoelectrochemical properties of $Cu_2O$. However, severe photo-induced corrosion impedes the use of $Cu_2O$ as a photoelectrode. Two candidates, $TiO_2$ and $SnO_2$, are selected for the passivation layer on $Cu_2O$ by by considering the Pourbaix-diagram. $TiO_2$ and $SnO_2$ passivation layers are deposited by atomic layer deposition(ALD) and a sputtering process, respectively. The investigation of the photoelectrochemical properties confirmed that $SnO_2$ is a good passivation layer for $Cu_2O$.

• 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.

• 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.

• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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• pp.65-65
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• 2012

Copper zinc tin sulfide ($Cu_2ZnSnS_4$, CZTS) is a very promising material as a low cost absorber alternative to other chalcopyrite-type semiconductors based on Ga or In because of the abundant and economical elements. In addition, CZTS has a band-gap energy of 1.4~1.5eV and large absorption coefficient over ${\sim}10^4cm^{-1}$, which is similar to those of $Cu(In,Ga)Se_2$(CIGS) regarded as one of the most successful absorber materials for high efficient solar cell. Most previous works on the fabrication of CZTS thin films were based on the vacuum deposition such as thermal evaporation and RF magnetron sputtering. Although the vacuum deposition has been widely adopted, it is quite expensive and complicated. In this regard, the solution processes such as sol-gel method, nanocrystal dispersion and hybrid slurry method have been developed for easy and cost-effective fabrication of CZTS film. Among these methods, the hybrid slurry method is favorable to make high crystalline and dense absorber layer. However, this method has the demerit using the toxic and explosive hydrazine solvent, which has severe limitation for common use. With these considerations, it is highly desirable to develop a robust, easily scalable and relatively safe solution-based process for the fabrication of a high quality CZTS absorber layer. Here, we demonstrate the fabrication of a high quality CZTS absorber layer with a thickness of 1.5~2.0 ${\mu}m$ and micrometer-scaled grains using two different non-vacuum approaches. The first solution-processing approach includes air-stable non-toxic solvent-based inks in which the commercially available precursor nanoparticles are dispersed in ethanol. Our readily achievable air-stable precursor ink, without the involvement of complex particle synthesis, high toxic solvents, or organic additives, facilitates a convenient method to fabricate a high quality CZTS absorber layer with uniform surface composition and across the film depth when annealed at $530^{\circ}C$. The conversion efficiency and fill factor for the non-toxic ink based solar cells are 5.14% and 52.8%, respectively. The other method is based on the nanocrystal dispersions that are a key ingredient in the deposition of thermally annealed absorber layers. We report a facile synthetic method to produce phase-pure CZTS nanocrystals capped with less toxic and more easily removable ligands. The resulting CZTS nanoparticle dispersion enables us to fabricate uniform, crack-free absorber layer onto Mo-coated soda-lime glass at $500^{\circ}C$, which exhibits a robust and reproducible photovoltaic response. Our simple and less-toxic approach for the fabrication of CZTS layer, reported here, will be the first step in realizing the low-cost solution-processed CZTS solar cell with high efficiency.