• 한국태양광발전학회지
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• 제3권3호
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• pp.18-31
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• 2017

박막 태양전지 기술은 현재 가장 큰 시장점유율을 보이고 있는 결정질 Si 태양전지의 차세대 후보로서 큰 관심을 받고 있다. 결정질 Si 태양전지보다 높은 효율로서, 저가로 생산할 수 있는 수준을 목표로 하여 $Cu(In,Ga)Se_2$ (CIGS) 를 비롯한 다양한 종류의 박막 태양전지들이 개발되고 있는데, 이 글에서는 최근에 범용성 초저가 박막 태양전지로 각광을 받고 있는 kesterite 박막 태양전지에 대해서 살펴보기로 한다. 가장 많이 연구되는 kesterite구조의 $Cu_2ZnSn(S,Se)_4$ (CZT(S,Se)) 박막 태양전지는 차세대 태양전지의 유력 후보군인 화합물태양전지 중에서 CdTe와 CIGS 그리고 새롭게 떠오르고 있는 페로브스카이트 등에 비해 범용 무독성 원소를 광흡수층으로 사용한다는 장점을 가지고 있지만 아직까지는 이들보다 효율이 낮아 상용화하기에는 좀 더 시간이 필요할 것으로 판단된다. CZT(S,Se)계 박막 태양전지의 기본적인 물성, 공정, 분석법 등을 알아보고 고효율을 달성하는 방법에 대하여 제시하고자 한다. 공정에 대한 상세한 최근 동향과 설명은 최근 한국공업화학회 소식지에 실린 강진규 박사의 리뷰논문을 참고하였다.

• 한국결정성장학회지
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• 제22권3호
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• pp.127-133
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• 2012

박막 태양전지의 저가 고효율화를 실현하기 위해 넓은 면적의 기판 위에 코팅이 가능하며 진공의 유지가 필요가 없고 장치가 간단하며 고순도의 균질한 박막을 얻을 수 있고 박막의 조성을 쉽게 조절할 수 있는 Sol-Gel법을 이용하였다. Se보다 저가이며 독성이 없고 풍부한 원료인 S로 치환하여 사용하며 Zn/Sn비 값을 조절하고 kesterite 구조를 갖는 $Cu_2ZnSnS_4$의열처리 온도에 따른 박막의 구조적, 광학적 특성에 미치는 변수들의 영향을 알아보았다. XRD pattern을 관찰한 결과 Zn/Sn비가 0.8/1.2일 때 $2{\theta}=28.5^{\circ}$에서 주피크가 가장 강하게 나타났으며 (112) 방향의 배향성을 가진 kesterite 상임을 확인 할 수 있었다. 열처리 온도가 증가할수록 (112) 면의 강도가 커지며 $550^{\circ}C$에서 열처리를 한 $Cu_2ZnSnS_4$ 박막은 kesterite 구조의 화학량론적 $Cu_2ZnSnS_4$ 특징을 나타내고 본 실험의 샘플의 격자상수를 측정한 값이 a = 5.5047 and $c=11.014{\AA}$이며 JCPDS(Joint Committee on Powder Standards)에 보고된 데이터 a = 5.427 and $c=10.848{\AA}$과 거의 일치 하였다. 광학적 특성을 알아보기 위해 측정한 광투과율은 가시광선 영역(380~770 nm)에서 전체적으로 65 % 이하로 나타났다.

• 한국재료학회지
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• 제22권5호
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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.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2007년도 추계학술대회 논문집
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• pp.305-305
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• 2007

• 한국재료학회지
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• 제25권12호
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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.

• 공업화학
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• 제26권5호
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• pp.526-532
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• 2015

신 기후변화대응(Post 2020)을 위한 대체에너지의 역할과 더불어 태양전지의 중요성이 높아져 가고 있다. 태양전지의 종류는 크게 재료관점에서 보면 유기물과 무기물 계열로 구분할 수 있지만 대규모 발전역할에서는 현재까지 실리콘과 같이 양산성과 안정성 기반의 무기물 태양전지가 주된 역할을 하고 있다. 특히 최근 몇 년간 화합물반도체 태양전지에 대한 연구는 급속도로 가속화되면서 3-5족 적층형 태양전지, chalcopyrite 계열 $CuInGa(S,Se)_2$ (CIGSSe) 태양전지와 kesterite 계열 $Cu_2ZnSn(S,Se)_4$ (CZTSSe) 태양전지 연구가 대표적으로 주류를 이루어 왔다. 따라서 화합물반도체 태양전지에서 주류를 이루고 있는 3-5족 적층형, CIGSSe 및 CZTSSe 태양전지들의 연구개발동향 및 기술적인 주요내용들에 대해 소개하고자 한다.

• 한국재료학회지
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• 제23권11호
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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.

• Current Photovoltaic Research
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• 제4권3호
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• pp.114-118
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• 2016

$Cu_{1.8}Zn_{1.2}(Sn_{1-x}Ge_x)S_4$ (CZTGeS) nanocrystals were mechanochemically synthesized from elemental precursor powders without using any organic solvents and any additives. The composition of CZTGeS nanocrystals were systematically varied with different Ge mole fraction (x) from 0.1 to 0.9. The XRD, Raman spectroscopy, high-resolution TEM, and diffuse reflectance studies show that the as-synthesized CZTGeS nanocrystals exhibited consistent changes in various structural and optical properties as a function of x, such as lattice parameters, wave numbers for $A_1$ Raman vibration mode, interplanar distances (d-spacing), and optical bandgap energies. The bandgap energy of the synthesized CZTGeS nanocrystals gradually increases from 1.40 to 1.61 eV with increasing x from 0.1 to 0.9, demonstrating that Ge-doping is useful means to tune the bandgap of mechanochemically synthesized nanocrystals-based kesterite thin-film solar cells. The preliminary solar cell performance is presented with an efficiency of 3.66%.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2012년도 춘계학술발표대회
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• pp.98.2-98.2
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• 2012

Thin film solar cells are growing up in the market due to their high efficiency and low cost. Especially CdTe and $CuInGaSe_2$ based solar cells are leading the other cells, but due to the limited percentage of the elements present in our earth's crust like Tellurium, Indium and Gallium, the price of the solar cells will increase rapidly. Copper Zinc Tin Sulfide (CZTS) and Copper Zinc Tin Selenide (CZTSe) semiconductor (having a kesterite crystal structure) are getting attention for its solar cell application as the absorber layer. CZTS and CZTSe have almost the same crystal structure with more environmentally friendly elements. Various authors have reported growth and characterization of CZTSe films and solar cells with efficiencies about 3.2% to 8.9%. In this study, a novel method to prepare CZTSe has been proposed based on selenization of stacked Copper Selenide ($Cu_2Se$), Tin Selenide ($SnSe_2$) and Zinc Selenide (Zinc Selenide) in six possible stacking combinations. Depositions were carried out through RF magnetron sputtering. Selenization of all the samples was performed in Close Space Sublimation (CSS) in vacuum at different temperatures for three minutes. Characterization of each sample has been performed in Field Emission SEM, XRD, Raman spectroscopy, EDS and Auger. In this study, the properties and results of $Cu_2ZnSnSe_4$ thin films grown by selenization will be presented.

• Current Photovoltaic Research
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• 제3권3호
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• pp.97-100
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• 2015

The kesterite $Cu_2ZnSnSe_4$ (CZTSe) thin film solar cells were synthesized by selenization of sputtered Cu/Sn/Zn metallic precursors on Mo coated soda lime glass substrate in Ar atmosphere. Cu/Sn/Zn metallic precursors were deposited by DC magnetron sputtering process with 30 W power at room temperature. As-deposited metallic precursors were placed in a graphite box with Se pellets and selenized using rapid thermal processing furnace at various temperature ($480^{\circ}C{\sim}560^{\circ}C$) without using a toxic $H_2Se$ gas. Effects of Selenization temperature on the morphological, crystallinity, electrical properties and cell efficiency were investigated by field emission scanning electron microscope (FE-SEM) and X-ray diffraction (XRD), J-V measurement system and solar simulator. Further details about effects of selenization temperature on CZTSe thin films will be discussed.