• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
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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.

• Bulletin of the Korean Chemical Society
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• 제35권7호
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• pp.1985-1988
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• 2014

$Cu_2ZnSnSe_4$ (CZTSe) thin films were synthesized on transparent conducting oxide glass substrates via a simple, non-toxic, and low-cost process using a precursor solution paste. A three-step heating process (oxidation, sulfurization, and selenization) was employed to synthesize a CZTSe thin film as an absorber layer for use in thin-film solar cells. In particular, we focused on the effects of sulfurization conditions on CZTSe film formation. We found that sulfurization at $400^{\circ}C$ involves the formation of secondary phases such as $CuSe_2$ and $Cu_2SnSe_3$, but they gradually disappeared when the temperature was increased. The formed CZTSe thin films showed homogenous and good crystallinity with grain sizes of approximately 600 nm. A solar cell device was tentatively fabricated and showed a power conversion efficiency of 2.2% on an active area of 0.44 $cm^2$ with an open circuit voltage of 365 mV, a short current density of 20.6 $mA/cm^2$, and a fill factor of 28.7%.

• 한국주조공학회지
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• 제40권6호
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• pp.135-145
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• 2020

Aluminum cast iron has excellent oxidation resistance, sulfurization resistance, and corrosion resistance. However, the ductility at room temperature is insufficient, and at temperatures above 600?, the strength drops sharply and practicality is limited. In the case of heat-resistant cast iron, high-temperature materials containing Cr and Ni account for 30 to 50% or more. However, these high-temperature materials are expensive. Aluminum heat-resistant cast iron is considered as a substitute for expensive heat-resistant materials. Oxidation due to the aging temperature and holding time conditions increases more in 0 wt.% Al-cast iron than in 2 and 4 wt.% Al-cast iron according to oxidized weight and gravimetric oxide layer thickness measurements. As a result of observing the cross-section of the oxide layer, it was found to contain 0 wt.% of Al-cast iron silicon oxide-containing SiO₂ or Fe₂SiO₄ oxide film. In cast iron containing aluminum, the thickness of the internal oxide layer due to aluminum increases as the aging temperature and retention time increase, and the amount of the iron oxide layer generated on the surface decreases.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2010년도 춘계학술대회 논문집
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• pp.17-17
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• 2010

Polycrystalline $CuInS_2$ thin films were performed from S/In/Cu Stacked elemental layer(SEL) method with post annealing. In thin method, the thin films were annealed in Vacuum of $10^{-3}$ torr or in S ambient. $CuInS_2$ thin films were manufctured by using the evaporation and the annealing with vacuum quartz furnace of sulfurization process was used in the vacuum chamber to the substrate temperature on the glass substrate the annealing temperature and characteristics thereof were investigated. The physical properties of the thin film were investigated under various fabrication conditions including the substrate temperature annealing time by XRD, FE-SEM, and Hall measurement system.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2010년도 춘계학술대회 초록집
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• pp.98.2-98.2
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• 2010

$CuInS_2$ thin films were synthesized by sulfurization of Cu/In Stacked elemental layer deposited onto glass Substrates by vacuum furnace annealing at temperature 200[$^{\circ}C$]. And structural and electrical properties were measured in order to certify optimum conditions for growth of the ternary compound semiconductor $CuInS_2$ thin films with non-stoichiometry composition. $CuInS_2$ thin film was well made at the heat treatment 200[$^{\circ}C$] of SLG/Cu/In/S stacked elemental layer which was prepared by thermal evaporator, and chemical composition of the thin film was analyzed nearly as the proportion of 1 : 1 : 2. Physical properties of the thin film were investigated at various fabrication conditions substrate temperature, annealing and temperature, annealing time by XRD, FE-SEM and hall measurement system. At the same time, carrier concentration, hall mobility and resistivity of the thin films was $9.10568{\times}10^{17}$ [$cm^{-3}$], 312.502 [$cm^2/V{\cdot}s$] and $2.36{\times}10^{-2}$ [${\Omega}{\cdot}cm$], respectively.

• 한국전기전자재료학회논문지
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• 제20권7호
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• pp.594-599
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• 2007

[ $CulnS_2$ ] thin films were synthesized by sulfurization of Cu/In Stacked elemental layer deposited onto glass Substrates by vacuum furnace annealing at temperature $200^{\circ}C$. And structural and electrical properties were measured in order to certify optimum conditions for growth of the ternary compound semiconductor $CuInS_2$ thin films with non-stoichiometry composition. $CuInS_2$ thin film was well made at the annealed $200^{\circ}C$ of SLG/Cu/In/S stacked elemental layer which was prepared by thermal evaporator, and chemical composition of the thin film was analyzed nearly as the proportion of 1 : 1 : 2. Physical properties of the thin film were investigated at various fabrication conditions substrate temperature, annealing and temperature, annealing time by XRD, FE-SEM and Hall measurement system. The compositional deviations from the ideal chemical formula for $200^{\circ}C$ material can be conveniently described by non-molecularity$({\Delta}x=[Cu/In]-1)$ and non-stoichiometry $({\Delta}y=[{2S/(Cu+3In)}-1])$. The variation of ${\Delta}x$ would lead to the formation of equal number of donor and accepters and the films would behave like a compensated material. The ${\Delta}y$ parameter is related to the electronic defects and would determine the type of the majority charge carriers. Films with ${\Delta}y>0$ would behave as p-type material while ${\Delta}y<0$ would show n-type conductivity. At the sane time, carrier concentration, hall mobility and resistivity of the thin films was $9.10568{\times}10^{17}cm^{-3},\;312.502cm^2/V{\cdot}s\;and\;2.36{\times}10^{-2}\;{\Omega}{\cdot}cm$, respectively.

• Current Photovoltaic Research
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• 제1권2호
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• pp.82-89
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• 2013

$Cu_2ZnSnS_4$ thin film have been fabricated by rapid thermal annealing of dc-sputtered metal precursor with Cu/ZnSn/Cu stack in sulfur ambient. A CZTS film with a good uniformity was formed at $560^{\circ}C$ in 6 min. $Cu_2SnS_3$ and $Cu_3SnS_4$ secondary phases were present at $540^{\circ}C$ and a trace amount of $Cu_2SnS_3$ secondary phase was present at $560^{\circ}C$. Single-phase large-grained CZTS film with rough surface was formed at $560^{\circ}C$. Solar cell with best efficiency of 4.7% ($V_{oc}=632mV$, $j_{sc}=15.8mA/cm^2$, FF = 47.13%) for an area of $0.44cm^2$ was obtained for the CZTS absorber grown at $560^{\circ}C$ for 6 min. The existence of second phase at lower-temperature annealing and rough surface at higher-temperature annealing caused the degradation of cell performance. Also poor back contact by void formation deteriorated cell performance. The fill factor was below 0.5; it should be increased by minimizing voids at the CZTS/Mo interface. Our results suggest that CZTS absorbers can be grown by rapid thermal annealing of metallic precursors in sulfur ambient for short process times ranging in minutes.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2012년도 춘계학술발표대회
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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.

• 한국결정성장학회지
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• 제28권3호
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• pp.112-117
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• 2018

금속 알콕사이드인 CuCo-glycerate 나노구의 용매열합성 과정을 통해 단분산된 Cu-Co 이중 금속 황화물 계층적 중공 구조의 나노구($CuCo_2S_4$ HMHNSs)를 합성하는데 성공하였다. 이 반응 메커니즘에서 용매열합성 온도와 보조 계면활성제인 glycerol의 양은 CuCo-glycerate 나노구의 형태를 최적화하는데 중요한 역할을 한다. 또한 $CuCo_2S_4$ HMHNSs는 glycerate와 황 이온 간의 음이온 교환 반응을 통해 10시간의 최적화된 황화 반응 조건하에서 성공적으로 합성되었다. 최종적으로 합성된 물질의 구조적, 화학적 특성은 SEM, TEM, XRD와 전기화학적 특성 평가에 의해 확인되었다.

• 한국응용과학기술학회지
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• 제37권4호
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• pp.723-732
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• 2020

RHDS 촉매는 코크와 황 화합물 그리고 금속인 바나듐이 표면에 침적되어 비활성화가 된다. 이러한 오염물을 제거하기 위해서 먼저 폐 RHDS 촉매에 묻어있는 중질유분의 세정, 코크와 황 화합물을 고온 배소 처리한 후, 과량으로 침적되어 있는 바나듐의 침출량을 조절하기 위하여 0.5, 1 wt% 옥살산 수용액을 이용하여 초음파 교반기에서 50 ℃, 10 sec 동안 교반하여 NOx 저감을 위한 SCR 촉매로의 적용 가능성을 확인하고자 하였다. 재생처리 한 RHDS 촉매의 성분은 XRF 를 사용하여 분석하였고, 상압 고정층 연속 흐름 반응기 상에서 NOx 저감 성능을 측정하였다. 옥살산 수용액 0.5 wt%, 10 sec 동안 초음파 침출한 촉매가 가장 안정적인 NOx 저감 성능을 보였으며, 375 ℃ 이상의 고온에서는 상용 촉매와 동등 수준의 NOx 저감 성능을 확인할 수 있었으나 저온영역 200 ℃에서 250 ℃까지는 상용 촉매보다 낮은 NOx 저감 성능을 보였다. 따라서 폐 RHDS 촉매를 재생처리 한 후 분말로 메탈 코로게이트 지지체에 워시코팅한 촉매는 상용 SCR 촉매로서 이용 가능함을 확인하였다.