• Current Photovoltaic Research
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• v.4 no.3
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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%.

• 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.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.321.1-321.1
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• 2013

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, $260{\sim}340^{\circ}C$의 온도 범위에서 5시간 30분 동안 CZTS 나노입자를 합성하였고, $300^{\circ}C$에서 5시간 30분~9시간까지 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.

• Applied Chemistry for Engineering
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• v.5 no.2
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• pp.327-336
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• 1994

The synergistic effects in mechanical mixture catalysts of Mo-V-O and metal oxide were investigated for the selective oxidation of acrolein. The metal oxides used are $SnO_2$, ${\alpha}-Sb_2O_4$, $WO_3$, ${\alpha}-Al_2O_3$, CuO, $MnO_2$, $Cu_2O$, MgO, CoO, and ZnO. Mechanical mixtures of Mo-V-O plus $SnO_2$ or ${\alpha}-Sb_2O_4$ had resulted in higher conversion of acrolein and higher yield of acrylic acid than Mo-V-O. The origin of the synergy is attributed to the cooperation of Mo-V-O and $SnO_2$ or ${\alpha}-Sb_2O_4$, in which $SnO_2$ or ${\alpha}-Sb_2O_4$ forms dissociated oxygens at their oxygen vacancies and transports them to Mo-V-O. $Cu_2O$, MgO, CuO, and $MnO_2$, increased conversion of acrolein but decreased yield of acrylic acid. CoO and ZnO inhibited the catalytic performance of Mo-V-O. The different role of these metal oxides is explained in terms of their oxidation-reduction properties.

• Applied Chemistry for Engineering
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• v.26 no.5
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• pp.526-532
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• 2015

Solar cells with other alternative energies are being importantly recognized related with post-2020 climate change regime formation. In a point of view of materials, solar cells are classified to organic and inorganic solar cells which can provide a plant-scale electricity. In particular, recent studies about compound semiconductor solar cells, such as III-V tandem solar cells, chalcopyrite-series CIGSSe solar cells, and kesterite-series CZTSSe solar cells were rapidly accelerated. In this report, we introduce a research trend and technical issues for the compound semiconductor solar cells.

• Korean Journal of Materials Research
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• v.31 no.11
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• pp.619-625
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• 2021

Cu₂ZnSn(S,Se)₄ (CZTSSe) based thin-film solar cells have attracted growing attention because of their earth-abundant and non-toxic elements. However, because of their large open-circuit voltage (V_oc)-deficit, CZTSSe solar cells exhibit poor device performance compared to well-established Cu(In,Ga)(S,Se)₂ (CIGS) and CdTe based solar cells. One of the main causes of this large V_oc-deficit is poor absorber properties for example, high band tailing properties, defects, secondary phases, carrier recombination, etc. In particular, the fabrication of absorbers using physical methods results in poor surface morphology, such as pin-holes and voids. To overcome this problem and form large and homogeneous CZTSSe grains, CZTSSe based absorber layers are prepared by a sputtering technique with different RTA conditions. The temperature is varied from 510 ℃ to 540 ℃ during the rapid thermal annealing (RTA) process. Further, CZTSSe thin films are examined with X-ray diffraction, X-ray fluorescence, Raman spectroscopy, IPCE, Energy dispersive spectroscopy and Scanning electron microscopy techniques. The present work shows that Cu-based secondary phase formation can be suppressed in the CZTSSe absorber layer at an optimum RTA condition.

• Korean Chemical Engineering Research
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• v.55 no.1
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• pp.93-98
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• 2017

This experiment investigated characteristic changes in a $Cu_2ZnSnS_4$(CZTS) solar cell by applying a $Zn(O_x,S_{1-x})$ butter layer with various compositions on the upper side of the absorber layer. Among the four single layers such as $Zn(O_{0.76},S_{0.24})$, $Zn(O_{0.56},S_{0.44})$, $Zn(O_{0.33},S_{0.67})$, and $Zn(O_{0.17},S_{0.83})$, the $Zn(O_{0.76},S_{0.24})$ buffer layer was applied to the device due to its bandgap structure for suppressing electron-hole recombination. In the application of the $Zn(O_{0.76},S_{0.24})$ buffer layer to the device, the buffer layer in the device showed the composition of $Zn(O_{0.7},S_{0.3})$ because S diffused into the buffer layer from the absorber layer. The $Zn(O_{0.7},S_{0.3})$ buffer layer, having a lower energy level ($E_V$) than a CdS buffer layer, improved the $J_{SC}$ and $V_{OC}$ characteristics of the CZTS solar cell because the $Zn(O_{0.7},S_{0.3})$ buffer layer effectively suppressed electron-hole recombination. A substitution of the CdS buffer layer by the $Zn(O_{0.7},S_{0.3})$ buffer layer improved the efficiency of the CZTS solar cell from 2.75% to 4.86%.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2000.11a
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• pp.9-9
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• 2000

• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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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.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.08a
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• pp.25-25
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• 2010

Cu(In, Ga)$Se_2$ (CIGS), $CuInS_2$ (CIS) 등의 Se, S계 화합물 박막 소재를 활용한 태양전지는 높은 광흡수 계수, 상대적으로 높은 효율, 화학적 안정성, 도시적인 미관 등으로 인하여 최근 부각되고 있다. 하지만 CIGS, CIS 등의 Se, S계 박막 소재는 상대적으로 매장량이 적은(희유 원소) In, Ga을 사용하고 있는 약점이 있으며 특히 In의 경우는 LCD Display에 사용되는 ITO 필름으로 인해 가격이 상승하고 있다. 따라서 결정질 실리콘 태양전지의 경험에서와 같이 생산량의 급증에서 기인하는 소재 부족 문제를 미연에 방지하고 안정적인 성장을 이루기 위해서는 희유 원소인 In과 Ga을 저가 범용원소로 대체 하는 기술을 추가적으로 개발해야 한다. $Cu_2ZnSnS_4$ (CZTS) 박막 태양전지는 Se, S계 태양전지에서 III 족 원소인 In, Ga을 II-IV 원소인 Zn와 Sn으로 대체하는 기술로 기존의 CIGS계 태양전지가 보유하고 있는 장점을 유지하면서 저가 태양전지를 구현할 수 있는 대체 물질로 최근 많은 관심을 받고 있다. CZTS 박막 태양전지 관련 세계 기술동향 조사에 따르면, 최근 2008년에 일본 Nagaoka 대학의 Katagiri 그룹에서 스퍼터를 이용하여 제조한 CZTS 박막 태양전지의 최고 효율이 6.77%가 됨을 보고하였고, 2010년 초에는 IBM에서 스핀코팅법을 이용하여 제조한 CZT(S, Se) 박막 태양전지의 효율을 9.66%까지 올릴 수 있음을 Advanced Materials에 보고하였다. 본 발표에서는 우선 CZTS 박막태양전지 제조 및 특성 분석 관련 개요 및 세계 기술 개발 동향 분석 결과를 설명할 것이다. 또한 본 실험실, 에너지 기술 연구원 및 KIST, 영남대 등 국내에서 진행되고 있는 CZTS 관련 기술 개발 현황에 대하여 설명할 것이다.