• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.318.1-318.1
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• 2013

Nowadays Cu2ZnSnS4 (CZTS) solar cell is attracting a lot of attention as a strong alternative to CIGS solar cell due to nontoxic and inexpensive constituent elements of CZTS. From various processes for the fabrication of CZTS solar cell, solution-based deposition of CZTS thin films is well-known non-vacuum process and many researchers are focusing on this method because of large-area deposition, high-throughput, and efficient material usage. Typically the solution-based process consists of two steps, coating of precursor solution and annealing of the precursor thin films. Unlike vacuum-based deposition, precursor solution contains unnecessary elements except Cu, Zn, Sn, and S in order to form high quality precursor thin films, and thus the precise control of precursor thin film preparation is essential for achieving high efficient CZTS solar cells. In this work, we have investigated the effect of preparation condition of CZTS precursor thin films on the performance of CZTS solar cells. The composition of CZTS precursor solution was controlled for obtaining optimized chemical composition of CZTS absorber layers for high-efficiency solar cells. Pre-annealing process of the CZTS precursor thin films was also investigated to confirm the effect of thermal treatment on chemical composition and carbon residues of CZTS absorber layers. The change of the morphology of CZTS precursor thin film by the preparation condition was also observed.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.308.2-308.2
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• 2013

Cu2ZnSnSe (CZTS)는 CuInSe2 (CIS) 중 희소 원소인 In을 Zn 및 Sn 으로 치환하여 만든 화합물 반도체이다. CZTS 의 특징은 그 구성원소가 지각 중에 풍부하게 존재하고, 모든 원소의 독성이 극히 낮다는 것이다. 이에 비해 CIS 중에 In과 Se 의 지각 함유량은 0.05 ppm 이하이다. 따라서 CZTS 는 값이 싼 범용 원소만으로 구성된 새로운 태양전지 재료가 된다. 본 연구에서는 다양한 Se 비율로 동시 증발법으로 증착된 CZTS 박막의 후속 열처리 효과에 관하여 발표하고자 한다. 증착된 CZTS 박막은 적정량의 Se 비율과 후속 열처리를 통해서 이차상이 없는 CZTS 결정성을 나타내는 XRD 결과를 보여주었으면, 3.6% 의 효율을 보여주었다.

• Korean Journal of Materials Research
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• v.23 no.1
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• pp.7-12
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• 2013

The $Cu_2ZnSnS_4$ (CZTS) thin film solar cell is a candidate next generation thin film solar cell. For the application of an absorption layer in solar cells, CZTS thin films were deposited by pulsed laser deposition (PLD) at substrate temperature of $300^{\circ}C$ without post annealing process. Deposition time was carefully adjusted as the main experimental variable. Regardless of deposition time, single phase CZTS thin films are obtained with no existence of secondary phases. Irregularly-shaped grains are densely formed on the surface of CZTS thin films. With increasing deposition time, the grain size increases and the thickness of the CZTS thin films increases from 0.16 to $1{\mu}m$. The variation of the surface morphology and thickness of the CZTS thin films depends on the deposition time. The stoichiometry of all CZTS thin films shows a Cu-rich and S-poor state. Sn content gradually increases as deposition time increases. Secondary ion mass spectrometry was carried out to evaluate the elemental depth distribution in CZTS thin films. The optimal deposition time to grow CZTS thin films is 150 min. In this study, we show the effect of deposition time on the structural properties of CZTS thin film deposited on soda lime glass (SLG) substrate using PLD. We present a comprehensive evaluation of CZTS thin films.

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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• pp.402.2-402.2
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• 2016

In photoelectrochemical (PEC) water splitting, Cu2ZnSnS4 (CZTS) compound has attracted intense attention as a photocathode due to not only large optical absorption coefficient, but also earth-abundance of constituent elements and suitable band alignment. With rapid development of nanotechnology, one-dimensional nanostructures of CZTS have been investigated as a potential form to achieve high efficiency because the nanostructures are expected to be capable of capturing more light and enhancing charge separation and transport. Here, we report a well-controlled fabrication route for vertically-aligned CZTS nanorod arrays on anodic aluminium oxide (AAO) template via simple sol-gel process followed by deposition of ZnS or CdS buffer layers on the CZTS nanorod to enhance charge separation. The structure, morphology, composition, optical absorption, and PEC properties of the resulting CZTS nanorod samples were characterized using X-ray diffraction, Raman spectroscopy, transmission electron microscopy, energy dispersive X-ray spectrometry, scanning electron microscopy, and UV-vis spectroscopy.

• Korean Journal of Materials Research
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• v.25 no.12
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• pp.708-712
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• 2015

This study reports the effects of $H_2S$ gas concentration on the properties of $Cu_2ZnSnS_4(CZTS)$ thin films. Specifically, sulfurization process with low $H_2S$ concentrations of 0.05% and 0.1%, along with 5% $H_2S$ gas, was studied. CZTS films were directly synthesized on Mo/Si substrates by chemical bath deposition method using copper sulfate, zinc sulfate heptahydrate, tin chloride dihydrate, and sodium thiosulfate pentahydrate. Smooth CZTS films were grown on substrates at optimized chemical bath deposition condition. The CZTS films sulfurized at low $H_2S$ concentrations of 0.05 % and 0.1% showed very rough and porous film morphology, whereas the film sulfurized at 5% $H_2S$ yielded a very smooth and dense film morphology. The CZTS films were fully crystallized in kesterite crystal form when they were sulfurized at $500^{\circ}C$ for 1 h. The kesterite CZTS film showed a reasonably good room-temperature photoluminescence spectrum that peaked in a range of 1.4 eV to 1.5 eV, consistent with the optimal bandgap for CZTS solar cell applications.

• 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.

• 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.

• Current Photovoltaic Research
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• v.4 no.1
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• pp.16-20
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• 2016

$Cu_2ZnSnS_4$ (CZTS) thin films were fabricated by successive electrodeposition of layers of precursor elements followed by sulfurization of an electrodeposited Cu-Zn-Sn precursor. In order to improve quality of the CZTS films, we tried to optimize the deposition condition of absorber layers. In particular, I have conducted optimization experiments by changing the Cu-layer deposition time. The CZTS absorber layers were synthesized by different Cu-layer conditions ranging from 10 to 16 minutes. The sulfurization of Cu/Sn/Zn stacked metallic precursor thin films has been conducted in a graphite box using rapid thermal annealing (RTA). The structural, morphological, compositional, and optical properties of CZTS thin films were investigated using X-ray diffraction (XRD), Field emission scanning electron microscopy (FE-SEM), Raman spectroscopy, and X-ray Flourescenece Spectrometry (XRF). Especially, the CZTS TFSCs exhibits the best power conversion efficiency of 4.62% with $V_{oc}$ of 570 mV, $J_{sc}$ of $18.15mA/cm^2$ and FF of 45%. As the time of deposition of the Cu-layer to increasing, the properties were confirmed to be systematically changed. And we have been discussed in detail below.

• Journal of the Korea Convergence Society
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• v.13 no.3
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• pp.197-202
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• 2022

The CZTS solar cell is a thin film solar cell using an absorption layer composed of Cu, Zn, Sn, Se, and S, and is cheaper than a CIGS solar cell using In and Ga and more eco-friendly than a perovskite and CdTe solar cell using Pb and Cd. In this study, we conducted a bending test for flexible CZTS solar cells. Experiments were conducted in the direction of inner benidng with compressive stress and outer bending with tensile stress, and during the number of bending 1,000 times with a radius of curvature of 50 mmR, the efficiency of the solar cell decreased by up to 12.7%, and the biggest cause of efficiency reduction in both directions was a large decrease in parallel resistance.

• Proceedings of the Korean Vacuum Society Conference
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• 2014.02a
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• pp.444.1-444.1
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• 2014

높은 광흡수 계수를 갖는 Cu(In,Ga)Se2(CIGS) 화합물 박막 소재는 고효율 태양전지 양산을 위해 가장 전도유망한 재료이나 상대적으로 매장량이 적은 In 및 Ga을 사용한다는 소재적 한계가 있다. Cu2ZnSnSe4(CZTSe) 혹은 Cu2ZnSnS4(CZTS)와 같은 Cu-Zn-Sn-Se계 화합물 반도체는 CIGS 내 희소원소인 In과 Ga이 범용원소인 Zn 및 Sn으로 대체된 소재로써 미래형 저가 태양전지 개발을 위해 활발히 연구되고 있는데, 그 화합물 조합에 따라 0.8eV부터 1.5eV까지의 에너지 밴드갭을 갖는 것으로 알려져 있다. 본 연구에서는 열분해법으로 CZTS 나노 입자를 합성하였다. 용매로 Oleylamine을 사용하였는데, $220^{\circ}C{\sim}340^{\circ}C$의 온도 범위에서 3시간 30분 동안 CZTS 나노입자를 합성하였고, $240^{\circ}C$에서 3시간~5시간까지 합성하였다. 헥산을 이용하여 원심분리기와 초음파세척기로 용매인 Oleylamine을 제거하였고, 진공오븐에서 건조된 CZTS 분말의 FE-SEM(Field Emission Scanning Electron Microscope), XRD(X-Ray Diffraction), EDS(Energy Dispersive Spectroscopy) 분석 등을 통해 합성온도에 따른 구조적, 화학적 조성 변화를 조사하였다.