• 한국진공학회:학술대회논문집
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• 한국진공학회 2012년도 제43회 하계 정기 학술대회 초록집
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• pp.440-440
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• 2012

Nanomaterials have emerged as new building blocks to construct light energy harvesting assemblies. Size dependent properties provide the basis for developing new and effective systems with semiconductor nanoparticles, quantized charging effects in metal nanoparticle or their combinations in 2 and 3 dimensions for expanding the possibility of developing new strategies for photovoltaic system. As top-down approach, we developed a simple and effective method for the large scale formation of self-assembled Cu(In,Ga)$Se_2$ (CIGS) nanostructures by ion beam irradiation. The compositional changes and morphological evolution were observed as a function of the irradiation time. As the ion irradiation time increased, the nano-dots were transformed into a nano-ridge structure due to the difference in the sputtering yields and diffusion rates of each element and the competition between sputtering and diffusion processes during irradiation. As bottom-up approach, we developed the growth of CIGS nanowires using thermal-chemical vapor deposition (CVD) method. Vapor-phase synthesis is probably the most extensively explored approach to the formation of 1D nanostructures such as whiskers, nanorods, and nanowires. However, unlike binary or ternary chalcogenides, the synthesis of quaternary CIGS nanostructures is challenging because of the difficulty in controlling the stoichiometry and phase structure. We introduced a method for synthesis of the single crystalline CIGS nanowires in the form of chalcopyrite using thermal-CVD without catalyst. It was confirmed that the CIGS nanowires are epitaxially grown on a sapphire substrate, having a length ranged from 3 to 100 micrometers and a diameter from 30 to 500 nm.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2010년도 춘계학술대회 초록집
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• pp.98.1-98.1
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• 2010

본 실험에서는 $CuInSe_2$ 3원물질을 화학량론적 조성비가 되도록 박막을 제조하기 위해 각 단위원소를 원자비에 맞춰 전자선가열 진공증착기를 사용하여 Cu, In, Se 순으로 증착하였다. $90^{\circ}C$이하의 온도에서 $CuIn_2$, In상이 주를 이루며, $100^{\circ}C$이상에서는 $Cu_{11}In_9$상이 나타나기 시작하고 In상이 증가하였다. $10^{-3}torr$이상의 진공석영관에서 열처리와 동시에 Selenization을 통해 제작된 $CuInSe_2$박막은 열처리온도 $250^{\circ}C$에서는 CuxSe, CuSe등의 2차상들이 나타나다가 $450^{\circ}C$이상의 고온에서 $CuInSe_2$ 단일상을 형성하였다. 이로부터 진공중에서 반응을 시켰을 때, 더 낮은 온도에서 반응이 일어나고 열역학적으로 보다 안정한 소수의 화합물들이 쉽게 형성됨을 확인할 수 있었다. 특히 $250^{\circ}C$에서는 Sphalerite 구조를 가지다가 $350^{\circ}C$이상의 온도에서 Selenization하였을 때 Chalcopyrite 구조를 가졌다. 박막이 두꺼워지면서 결정립의 크기가 커지고 응력이 작아지는 특성을 보였다. 에너지 밴드갭은($E_g$)은 Cu/In 성분비율이 클수록 작은값을 보였으며, 결절립크기가 증대되므로 결국 흡수계수가 낮아짐을 알 수 있다. 또한 두께가 증가할수록 전반적으로 흡수계수가 증가하였고 Cu/In의 성분비율이 0.97일 때 기초흡수파장은 1,169nm이고 에너지밴드갭은 1.06eV이었으며, 두께 $1.5{\mu}m$이상일 때 전반적으로 양호한 상태의 p-type $CuInSe_2$박막을 제작하였다.

• Current Photovoltaic Research
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• 제4권1호
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• pp.21-24
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• 2016

Chalcopyrite based (CIGS) thin films have considered to be a promising candidates for industrial applications. The growth of quality CIGS thin films without secondary phases is very important for further efficiency improvements. But, the identification of complex secondary phases present in the entire film is crucial issue due to the lack of powerful characterization tools. Even though X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and normal Raman spectroscopy provide the information about the secondary phases, they provide insufficient information because of their resolution problem and complexity in analyzation. Among the above tools, a normal Raman spectroscopy is better for analysis of secondary phases. However, Raman signal provide the information in 300 nm depth of film even the thickness of film is > $1{\mu}m$. For this reason, the information from Raman spectroscopy can't represent the properties of whole film. In this regard, the authors introduce a new way for identification of secondary phases in CIGS film using depth Raman analysis. The CIGS thin films were prepared using DC-sputtering followed by selenization process in 10 min time under $1{\times}10^{-3}torr$ pressure. As-prepared films were polished using a dimple grinder which expanded the $2{\mu}m$ thick films into about 1mm that is more than enough to resolve the depth distribution. Raman analysis indicated that the CIGS film showed different secondary phases such as, $CuIn_3Se_5$, $CuInSe_2$, InSe and CuSe, presented in different depths of the film whereas XPS gave complex information about the phases. Therefore, the present work emphasized that the Raman depth profile tool is more efficient for identification of secondary phases in CIGS thin film.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2015년도 제49회 하계 정기학술대회 초록집
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• pp.257.1-257.1
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• 2015

Cu(In,Ga)Se2 (CIGS) 박막 태양 전지에서 buffer layer는 CIGS 흡수층과 TCO 사이의 밴드갭 차이에 대한 문제점과 lattice mismatch를 해결하기 위해 필수적이다. 흔히 buffer layer 물질로는 CdS가 가장 많이 사용되고 있으나 Cd의 독성에 관한 문제가 야기되고 있다. 따라서 ZnS(O, OH) buffer layer가 친환경 물질로 기존의 CdS 버퍼 층의 대체 물질로 각광 받고 있으며, 단파장 범위에서 높은 투과율로 인해 wide band gap의 Chalcopyrite 태양 전지에 응용되는 buffer layer로 많은 연구가 이루어지고 있다. 또한 buffer layer를 최적화 하여 carrier lifetime과 양자 효율이 증가시킬 수 있는 특성을 가지고 있다. 이 연구에서는 Cu(In,Ga)Se2 (CIGS) 박막에 화학습식공정 (CBD) 방법을 이용하여 최적화된 ZnS(O, OH)의 증착 조건을 찾고, 고품질의 buffer layer를 제조하기 위한 실험에 초점을 맞췄다. 또한, buffer layer의 막질을 개선하고 균일한 막을 제조하기 위해 processing parameters인 시약의 농도, 제조 시간 및 온도 등의 다양한 변화를 통해 실험을 진행하였다. 그 후 최적화된 ZnS(O, OH) buffer layer의 특성 분석을 위해 X-ray diffraction(XRD), photoluminescence (PL), scanning electron microscope (SEM) and GD-OES을 이용하였고, 이를 통해 제조된 CIGS 박막 태양전지는 light induced current-voltage (LIV) and external quantum efficiency (EQE)를 통해 특성 분석을 실시 하였다. 결과적으로, 제조된 ZnS(O, OH) buffer layer의 $ZnSO4{\cdot}7H2O$의 농도는 0.16 M, Thiourea는 0.5 M, NH4OH는 7.5 M, 그리고 반응 온도는 77.5 oC의 조건 하에 CIGS 기판 위에 균일하고 균열이 없는 ZnS(O, OH) 박막을 제조하였으며 이때 제조된 태양전지의 소자 특성은 Voc = 0.478 V, Jsc = 35.79 mA/cm2, FF = 47.77%, ${\eta}=8,18 %$이다.

• 센서학회지
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• 제16권1호
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• pp.1-6
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• 2007

A silver indium sulfide ($AgInS_{2}$) epilayer was grown by the hot wall epitaxy method, which has not been reported in the literature. The grown $AgInS_{2}$ epilayer has found to be a chalcopyrite structure and evaluated to be high quality crystal. From the photocurrent measurement in the temperature range from 30 K to 300 K, the two peaks of A and B were only observed, whereas the three peaks of A, B, and C were seen in the PC spectrum of 10 K. These peaks are ascribed to the band-to-band transition. The valence band splitting of $AgInS_{2}$ was investigated by means of the photocurrent measurement. The crystal field splitting, ${\Delta}cr$, and the spin orbit splitting, ${\Delta}so$, have been obtained to be 0.150 eV and 0.009 eV at 10 K, respectively. And, the energy band gap at room temperature has been determined to be 1.868 eV. Also, the temperature dependence of the energy band gap, $E_{g}$(T), was determined.

• 자원환경지질
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• 제19권2호
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• pp.133-146
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• 1986

Primary uraninite and secondary uranium minerals such as torbernite, metatorbernite, tyuyamunite, metatyuyamunite, autunite and metaautunite have been identified from various types of uranium ores. Uranium minerals occur as accessory minerals in both the primary and secondary ores. Low·grade uranium ores consist of various kinds of primary and secondary minerals. Major constituent minerals of primary uranium ores are graphite. quartz. Ba-feldspar and sericite/muscovite, and accessories are calcite, chlorite, fluorapatite, barite, diopside, sphene, rutile, biotite, laumontite, heulandite, pyrite, sphalerite and chalcopyrite, and secondary minerals consist of kaolinite, gypsum and goethite. Uraninite grains occur as microscopic very fine-grained anhedral to euhedral disseminated particles in the graphitic matrix, showing well·stratified or zonal distribution of uranium on auto-radiographs of low-grade uranium ores. Some uraninite grains are closely associated with very fine-grained pyrite aggregates, showing an elliptical form parallel to the schistosity. Some uraninite grains include extremely fine-grained pyrite particle. Sphalerite and pyrite are often associated with uraninite in graphite-fluorapatite nodule. The size of uraninite is $2{\mu}m$ to $20{\mu}m$ in diameter. Low-grade uranium ores are classified into 5 types on the basis of geometrical pattern of mineralization. They are massive, banded, nodular, quartz or sulfide veinlet-rich and cavity filling types. Well-developed alternation of uranium-rich and uranium-poor layers, concentric distribution of uranium in graphite-fluorapatite nodule and geopetal fabrics due to the load cast of the nodule suggest that the uranium was originally deposited syngenetically. Uraninite crystals might have been formed from organo-uranium complex during diagenesis and recrystallized by metamorphism. Secondary uranium minerals such as torbernite, tyuyamunite and autunite have been formed by supergene leaching of primary ores and subsequent crystallization in cavities.

• 자원환경지질
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• 제3권3호
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• pp.169-176
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• 1970

Kubong Gold Mine is located in Kuryongri, Sayang-myun, Chungyang-gun, Choongchung-Namdo.(latitude $36^{\circ}24^{\prime}N$. longitude $126^{\circ}45^{\prime}30^{{\prime}{\prime}}E$) The mine was begun to work soon after the inhabitants of this village had accidently discovered the outcrops in April 1908. It is one of the largest gold mines in Korea which produces 4,500 tons of crude ore a month. The geology in the area consists of granitic gneiss, banded gneiss, augen-gneiss, mica schist, limesilicate of Pre-Cambrian series and sedimentary rocks(sandstones & conglomerates) of Daedong series. Basic dikes intrude the former formations. The country rock of the ore deposit is a group of the metamorphic rocks mentioned above. Gold-silver bearing quartz vein contains small amounts of pyrite, chalcopyrite, arsenopyrite, galena and sphalerite in which gold and silver occur as native state. The vein strikes $N30^{\circ}{\sim}60^{\circ}E$ and dips $20^{\circ}{\sim}50^{\circ}S$ and the average width of the vein is estimated 1 to 1.5m. Average grade of ore is Au:6~8gr/t and Ag:5~6gr/t. The ore shoot continues from the outcrop to the depth of -1760ML with dip of $20{\sim}25^{\circ}$ and strike extension reaches to 400m at the depth of -1440 ML and to more or less 200m at below. Highgrade of ore vein was found at the lowest level of the ore shoot at the time of recent field survey at the end of August 1970. Its average grade was estimated as Au:20gr/t and its width 1~2.5M in average. A series of futher prospecting for other new ore shoot or parallel veins are urgent and crosscut prospecting along the horizontal level is strongly recommended.

• 한국광물학회지
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• 제26권1호
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• pp.1-8
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• 2013

티오요소를 사용하여 삼조광업 정광으로부터 은을 친환경적으로 용출시키고자 하였다. 삼조광산의 광석은 황철석, 황동석, 방연석, 유비철석, 섬아연석 등과 같은 광석광물들로 구성되어 있다. 티오요소 용출실험에는 $750^{\circ}C$에서 소성시킨 소성정광을 사용하였다. 다양한 실험조건으로 용출실험을 수행한 결과, 본 실험 조건 중 가장 높은 은 용출율이 나타나는 조건은 티오요소 농도 0.8 g일 때, 황산 제2철 0.425 g일 때, 그리고 용출온도 $60^{\circ}C$일 때였다. 광액농도 10%일 때 은 용출율 91.5%를 얻었다. 그러나 고체 잔유물에 대해서 XRD 분석을 수행한 결과, 은 용출율이 가장 높은 고체 잔유물들에서 황철석, 방연석, 적철석 등이 나타났다. 이러한 결과로 미루어 볼 때 고체 잔유물에 포함된 은은 회수하지 못하고 소실될 것으로 예상된다.

• 자원환경지질
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• 제10권1호
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• pp.1-18
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• 1977

Chongyang tungsten ore deposits, one of the most important tungsten mines in South Korea, me open space filling hydrothermal vein deposits embedded in Precambrian biotite gneiss and, Cretaceous (?) granite porphyry. Some wolframite-bearing quartz veins are closely associated with -quartz porphyries which strike about $N15^{\circ}-25^{\circ}W$ and dip $800^{\circ}SE$ to vertical. Mineralization took place in near vertical vein systems of 5 to 2000 meter long in the biotite gneiss and granite porphyry stock during early Cretaceous and Tertiary (?) period. The hydrothermal mineral paragensis has indicated that there were two major stages: vein and vug stages. The principal vein mineral is wolframite in a gangue of quartz with small amount of fluorite, pyrite, beryl and carbonate minerals. Present in minor amounts are molybdenite, bithmuthinite, native bismuth, arsenopyrite, galena, chalcopyrite, pyrrhotite, sphalerite and scheelite. Fluid inclusion study from the minerls at Chongyang mine reveals that vein stage fluids attained a temperature range of $200^{\circ}C-355^{\circ}C$ and vug stage $160^{\circ}C-350^{\circ}C$. The filling temperatures show the higher range of $200^{\circ}-355^{\circ}C$ in quartz and $280^{\circ}C-348^{\circ}C$ in beryls, whereas the lower emperature range of $283^{\circ}C-295^{\circ}C$ in rhodochrosite and $160^{\circ}-253^{\circ}C$ in fluorites. These temperatures are in reasonably good agreement with mineral paragnesis in this ore deposits. Volfamite minerals were analysed for major components. $WO_3$, MnO and FeO by wet chemical method. Chemical analysis indicates that they contain 70.56-71.54% $WO_3$, 8.52-10.01% MnO and 10.00-11.58% FeO. MnO/FeO ratios of wolframites shows the range of 0.78-0.94 which maybe indicates a comparatively high temperature type of hydrothermal deposits.

• 자원환경지질
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• 제5권3호
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• pp.133-144
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• 1972

The mine of our present concern is situated at Shim-ri, Gusan-myon, Changwon-gun, Kyongsang-namdo, with lattitude $128^{\circ}35^{\prime}{\sim}36^{\prime}N$ and longitude $35^{\circ}03^{\prime}{\sim}04^{\prime}E$. This mine has not been noticed until the intermittent geological survey for the ore deposits were initiated from September, 1967 till 1970. The main mineralized zones, No.1 and No.2 zones, were studied by the diamond drilling of 9 holes down to the total depth of 1,140m, and found to have ore reserves of Cu 1.99% ore, estimated to reach around $358,000{\frac{M}{T}}$ (proved $117,000{\frac{M}{T}}$, indicated $241,000{\frac{M}{T}}$), which triggered the new exploitation of this mine. Geological composition of the district near the mine is mainly from the andesite belonging to the Silla Series of Kyongsang System and the distribution is broadly spread. Ore deposits are the hydrothermal one, filling the shear zone formed alongside the andesite main joint. There are two stripes of copper bearing mineralized zone which are about 40~70 meters apart and parallel to each other, in addition to which two others are expected. The strike of the main mineralized zone lies at $N15^{\circ}{\sim}20^{\circ}W$, the dip at $60^{\circ}{\sim}70^{\circ}NE$. The principal components of the ore mineral are chalcopyrite, bornite and as secondary, cuprite, tenorite, azurite and malachite. Pyrite, magnetite, specular hematite, very little of galena, sphalerite, quartz, epidote, zoisite, chlorite and calcite are found as gangue mineral. Confirmed by the drilling, the main mineralized zone, No.1 zone, has the length of 320m, average width of 1.62m, Ag 26g/t, Cu 1.84% and the average width of the ore zone except the narrow barren andesite horse interposed in the mineralized zone is 1.32m with Ag 32g/t and Cu 2.26%. The mineralized zone No.2 is 340m long, 1.00m wide with Ag 30g/t and Cu 2.15%. Neglecting the barren andesite horse the width is 0.73m with Ag 42g/t and Cu 2.94%.