• Title/Summary/Keyword: vapor-deposition

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Optimizing Graphene Growth on the Electrolytic Copper Foils by Controlling Surface Condition and Annealing Procedure (전해구리막의 표면 조건과 어닐링 과정을 통한 그래핀 성장 최적화)

  • Woo Jin Lee;Ha Eun Go;Tae Rim Koo;Jae Sung Lee;Joon Woo Lee;Soun Gi Hong;Sang-Ho Kim
    • Journal of the Korean institute of surface engineering
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    • v.56 no.3
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    • pp.192-200
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    • 2023
  • Graphene, a two-dimensional material, has shown great potential in a variety of applications including microelectronics, optoelectronics, and graphene-based batteries due to its excellent electronic conductivity. However, the production of large-area, high-quality graphene remains a challenge. In this study, we investigated graphene growth on electrolytic copper foil using thermochemical vapor deposition (TCVD) to achieve a similar level of quality to the cold-rolled copper substrate at a lower cost. The combined effects of pre-annealing time, graphenized temperature, and partial pressure of hydrogen on graphene coverage and domain size were analyzed and correlated with the roughness and crystallographic texture of the copper substrate. Our results show that controlling the crystallographic texture of copper substrates through annealing is an effective way to improve graphene growth properties, which will potentially lead to more efficient and cost-effective graphene production. At a hydrogen partial pressure that is disadvantageous in graphene growth, electrolytic copper had an average size of 8.039 ㎛2, whereas rolled copper had a size of 19.092 ㎛2, which was a large difference of 42.1% compared to rolled copper. However, at the proper hydrogen partial pressure, electrolytic copper had an average size of 30.279 ㎛2 and rolled copper had a size of 32.378 ㎛2, showing a much smaller difference of 93.5% than before. This observation suggests this potentially leads the way for more efficient and cost-effective graphene production.

Copper Mineralization in the Haman-Gunbuk Area, Gyeongsangnamdo-Province: Fluid Inclusion and Stable Isotope Study (경상남도 함안-군북지역의 동광화작용: 유체포유물 및 안정동위원소 연구)

  • 허철호;윤성택;최상훈;최선규;소칠섭
    • Economic and Environmental Geology
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    • v.36 no.2
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    • pp.75-87
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    • 2003
  • The Haman-Gunbuk mineralized area is located within the Cretaceous Gyeongsang Basin along the southeastern part of the Korean peninsula. Major ore minerals, magnetite, scheelite, molybdenite and chalcopyrite, together with base-metal sulfides and minor sulfosalts, occur in fissure-filling tourmaline, quartz and carbonates veins contained within Cretaceous sedimentary and volcanic rocks anu/or granodiorite (118{\pm}$3.0 Ma). The ore and gangue mineral paragenesis can be divided into three distinct stages: Stage 1, tourmaline+quartz+Fe-Cu ore mineralization; Stage II, quartz+sulfides+sulfosalts+carbonates; Stage 111, barren calcite. Earliest fluids are recorded in stage I and early por-tions of stage II veins as hypersaline (35~70 equiv. wt.% NaCl+KCl) and vapor-rich inclusions which homogenize from ~30$0^{\circ}C$ to $\geq$50$0^{\circ}C$. The high-salinity fluids are complex chloride brines with significant concentrations of sodium, potassium, iron, copper, and sulfur, though sulfide minerals are not associated with the early mineral assemblage produced by this fluid. Later solutions circulated through newly formed fractures and reopened veins, and are recorded as lower-salinity(less than ~20 equiv. wt.% NaCl) fluid inclusions which homogenize primarily from ~200 to 40$0^{\circ}C$. The oxygen and hydrogen isotopic compositions of fluid in the Haman-Gunbuk hydrothermal system represents a progressive shift from magmatic-hydrothermal dominance during early mineralization stage toward meteoric-hydrothermal dominance during late mineralization stage. The earliest hydrothermal fiuids to circu-late within the granodiorite stock localiring the ore body at Haman-Gunbuk could have exsolved from the crystal-lizing magma and unmixed into hypersaline liquid and $H_2O$-NaCl vapor. As these magmatic fluids moved throughfractures, tourmaline and early Fe, W, Mo, Cu ore mineralization occurred without concomitant deposition of othersulfides and sulfosalts. Later solutions of dominantly meteoric origin progressively formed hypogene copper and base-metal sulfides, and sulfosalt mineralization.

Optical Properties of SiNx Thin Films Grown by PECVD at 200℃ (200℃의 저온에서 PECVD 기법으로 성장한 SiNx 박막의 열처리에 따른 광학적 특성 변화 규명)

  • Lee, Kyung-Su;Kim, Eun-Kyeom;Son, Dae-Ho;Kim, Jeong-Ho;Yim, Tae-Kyung;An, Seung-Man;Park, Kyoung-Wan
    • Journal of the Korean Vacuum Society
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    • v.20 no.1
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    • pp.42-49
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    • 2011
  • We deposited $SiN_x$ thin films by using PECVD technique at $200^{\circ}C$ with various flow ratios of the $SiH_4/N_2$ gases. The photoluminescence measurements revealed that the maximum emission wavelength shifted to long wavelength as the ratio increased, however, positions of the several peak wavelengths, such as 1.9, 2.2, 2.4, and 3.1 eV, were independent on the ratio. Changes of the photoluminescence spectra were measured in the $N_{2}-$, $H_{2}-$, and $O_2$-annealed films. The luminescence intensities increased after the annealing process. In particular, the maximum emission wavelength shifted to short wavelength after $H_{2}-$ or $O_2$-annealing. But there were still several peaks on the spectra of all annealed films, several peak positions remained to be unchanged after the annealing. As for the light emission mechanism, we have considered the defect states of the Si- and N- dangling bonds in the $SiN_x$ energy gap, so that the energy transitions from/to the conduction/valence bands and the defect states in the gap were attributed to the light emission in the $SiN_x$ films. The experimental results point to the possibility of a Si-based light emission materials for flexible Si-based electro-optic devices.

Low Temperature Growth of MCN(M=Ti, Hf) Coating Layers by Plasma Enhanced MOCVD and Study on Their Characteristics (플라즈마 보조 유기금속 화학기상 증착법에 의한 MCN(M=Ti, Hf) 코팅막의 저온성장과 그들의 특성연구)

  • Boo, Jin-Hyo;Heo, Cheol-Ho;Cho, Yong-Ki;Yoon, Joo-Sun;Han, Jeon-G.
    • Journal of the Korean Vacuum Society
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    • v.15 no.6
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    • pp.563-575
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    • 2006
  • Ti(C,N) films are synthesized by pulsed DC plasma enhanced chemical vapor deposition (PEMOCVD) using metal-organic compounds of tetrakis diethylamide titanium at $200-300^{\circ}C$. To compare plasma parameter, in this study, $H_2$ and $He/H_2$ gases are used as carrier gas. The effect of $N_2\;and\;NH_3$ gases as reactive gas is also evaluated in reduction of C content of the films. Radical formation and ionization behaviors in plasma are analyzed in-situ by optical emission spectroscopy (OES) at various pulsed bias voltages and gas species. He and $H_2$ mixture is very effective in enhancing ionization of radicals, especially for the $N_2$. Ammonia $(NH_3)$ gas also highly reduces the formation of CN radical, thereby decreasing C content of Ti(C, N) films in a great deal. The microhardness of film is obtained to be $1,250\;Hk_{0.01}\;to\;1,760\;Hk_{0.01}$ depending on gas species and bias voltage. Higher hardness can be obtained under the conditions of $H_2\;and\;N_2$ gases as well as bias voltage of 600 V. Hf(C, N) films were also obtained by pulsed DC PEMOCYB from tetrakis diethyl-amide hafnium and $N_2/He-H_2$ mixture. The depositions were carried out at temperature of below $300^{\circ}C$, total chamber pressure of 1 Torr and varying the deposition parameters. Influences of the nitrogen contents in the plasma decreased the growth rate and attributed to amorphous components, to the high carbon content of the film. In XRD analysis the domain lattice plain was (111) direction and the maximum microhardness was observed to be $2,460\;Hk_{0.025}$ for a Hf(C,N) film grown under -600 V and 0.1 flow rate of nitrogen. The optical emission spectra measured during PEMOCVD processes of Hf(C, N) film growth were also discussed. $N_2,\;N_2^+$, H, He, CH, CN radicals and metal species(Hf) were detected and CH, CN radicals that make an important role of total PEMOCVD process increased carbon content.

Efficient Red-Color Emission of InGaN/GaN Double Hetero-Structure Formed on Nano-Pyramid Structure

  • Go, Yeong-Ho;Kim, Je-Hyeong;Gong, Su-Hyeon;Kim, Ju-Seong;Kim, Taek;Jo, Yong-Hun
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.08a
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    • pp.174-175
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    • 2012
  • (In, Ga) N-based III-nitride semiconductor materials have been viewed as the most promising materials for the applications of blue and green light emitting devices such as light-emitting diodes (LEDs) and laser diodes. Although the InGaN alloy can have wide range of visible wavelength by changing the In composition, it is very hard to grow high quality epilayers of In-rich InGaN because of the thermal instability as well as the large lattice and thermal mismatches. In order to avoid phase separation of InGaN, various kinds of structures of InGaN have been studied. If high-quality In-rich InGaN/GaN multiple quantum well (MQW) structures are available, it is expected to achieve highly efficient phosphor-free white LEDs. In this study, we proposed a novel InGaN double hetero-structure grown on GaN nano-pyramids to generate broad-band red-color emission with high quantum efficiency. In this work, we systematically studied the optical properties of the InGaN pyramid structures. The nano-sized hexagonal pyramid structures were grown on the n-type GaN template by metalorganic chemical vapor deposition. SiNx mask was formed on the n-type GaN template with uniformly patterned circle pattern by laser holography. GaN pyramid structures were selectively grown on the opening area of mask by lateral over-growth followed by growth of InGaN/GaN double hetero-structure. The bird's eye-view scanning electron microscope (SEM) image shows that uniform hexagonal pyramid structures are well arranged. We showed that the pyramid structures have high crystal quality and the thickness of InGaN is varied along the height of pyramids via transmission electron microscope. Because the InGaN/GaN double hetero-structure was grown on the nano-pyramid GaN and on the planar GaN, simultaneously, we investigated the comparative study of the optical properties. Photoluminescence (PL) spectra of nano-pyramid sample and planar sample measured at 10 K. Although the growth condition were exactly the same for two samples, the nano-pyramid sample have much lower energy emission centered at 615 nm, compared to 438 nm for planar sample. Moreover, nano-pyramid sample shows broad-band spectrum, which is originate from structural properties of nano-pyramid structure. To study thermal activation energy and potential fluctuation, we measured PL with changing temperature from 10 K to 300 K. We also measured PL with changing the excitation power from 48 ${\mu}W$ to 48 mW. We can discriminate the origin of the broad-band spectra from the defect-related yellow luminescence of GaN by carrying out PL excitation experiments. The nano-pyramid structure provided highly efficient broad-band red-color emission for the future applications of phosphor-free white LEDs.

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Transition Metal Dichalcogenide Nanocatalyst for Solar-Driven Photoelectrochemical Water Splitting (전이금속 디칼코제나이드 나노촉매를 이용한 태양광 흡수 광화학적 물분해 연구)

  • Yoo, Jisun;Cha, Eunhee;Park, Jeunghee;Lim, Soo A
    • Journal of the Korean Electrochemical Society
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    • v.23 no.2
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    • pp.25-38
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    • 2020
  • Photoelectrochemical water splitting has been considered as the most promising technology for generating hydrogen energy. Transition metal dichalcogenide (TMD) compounds have currently attracted tremendous attention due to their outstanding ability towards the catalytic water-splitting hydrogen evolution reaction (HER). Herein, we report the synthesis method of various transition metal dichalcogenide including MoS2, MoSe2, WS2, and WSe2 nanosheets as excellent catalysts for solar-driven photoelectrochemical (PEC) hydrogen evolution. Photocathodes were fabricated by growing the nanosheets directly onto Si nanowire (NW) arrays, with a thickness of 20 nm. The metal ion layers were formed by soaking the metal chloride ethanol solution and subsequent sulfurization or selenization produced the transition metal chalcogenide. They all exhibit excellent PEC performance in 0.5 M H2SO4; the photocurrent reaches to 20 mA cm-2 (at 0 V vs. RHE) and the onset potential is 0.2 V under AM1.5 condition. The quantum efficiency of hydrogen generation is avg. 90%. The stability of MoS2 and MoSe2 is 90% for 3h, which is higher than that (80%) of WS2 and WSe2. Detailed structure analysis using X-ray photoelectron spectroscopy for before/after HER reveals that the Si-WS2 and Si-WSe2 experience more oxidation of Si NWs than Si-MoS2 and Si-MoSe2. This can be explained by the less protection of Si NW surface by their flake shape morphology. The high catalytic activity of TMDs should be the main cause of this enhanced PEC performance, promising efficient water-splitting Si-based PEC cells.

Effect of substrate bias voltage on a-C:H film (기판 bias 전압이 a-C:H 박막의 특성에 미치는 영향)

  • 유영조;김효근;장홍규;오재석;김근식
    • Journal of the Korean Vacuum Society
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    • v.6 no.4
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    • pp.348-353
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    • 1997
  • Hydrogenated amorphous carbon(a-C:H) films were deposited on p-type Si(100) by DC saddle-field plasma enhanced CVD to investigate the effect of substrate bias on optical properties and structural changes. They were deposited using pure methane gas at a wide range of substrate bias at room temperature and 90 mtorr. The substrate bias voltage ($V_s$) was employed from $V_s=0 V$ to $V_s=400 V$. The information of optical properties was investigated by photoluminescence and transmitance. Chemical bondings of a-C:H have been explored from FT-IR and Raman spectroscopy. The thickness and relative hydrogen content of the films were measured by Rutherford backscattering spectroscopy (RBS) and elastic recoil detection (ERD) technigue. The growth rate of a-C:H film was decreased with the increase of $V_s$, but the hydrogen content of the film was increased with the increase of $V_s$. The a-C:H films deposited at the lowest $V_s$ contain the smallest amount of hydrogen with most of C-H bonds in the of $CH_2$ configuration, whereas the films produced at higher $V_s$ reveal dominant the $CH_3$ bonding structure. The emission of white photoluminescence from the films were observed even with naked eyes at room temperature and the PL intensity of the film has the maximum value at $V_s$=200 V. With $V_s$ lower than 200 V, the PL intensity of the film increased with V, but for V, higher than 200 V, the PL intensity decreased with the increase of $V_s$. The peak energy of the PL spectra slightly shifted to the higher energy with the increase of $V_s$. The optical bandgap of the film, determined by optical transmittance, was increased from 1.5 eV at $V_s$=0V to 2.3 eV at $V_s$=400 V. But there were no obvious relations between the PL peak and the optical gap which were measured by Tauc process.

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Interface structure and anisotropic strain relaxation of nonpolar a-GaN on r-sapphire

  • Gong, Bo-Hyeon;Jo, Hyeong-Gyun;Song, Geun-Man;Yun, Dae-Ho
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2010.06a
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    • pp.31-31
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    • 2010
  • The growth of the high-quality GaN epilayers is of significant technological importance because of their commercializedoptoelectronic applications as high-brightness light-emitting diodes (LEDs) and laser diodes (LDs) in the visible and ultraviolet spectral range. The GaN-based heterostructural epilayers have the polar c-axis of the hexagonal structure perpendicular to the interfaces of the active layers. The Ga and N atoms in the c-GaN are alternatively stacked along the polar [0001] crystallographic direction, which leads to spontaneous polarization. In addition, in the InGaN/GaN MQWs, the stress applied along the same axis contributes topiezoelectric polarization, and thus the total polarization is determined as the sum of spontaneous and piezoelectric polarizations. The total polarization in the c-GaN heterolayers, which can generate internal fields and spatial separation of the electron and hole wave functions and consequently a decrease of efficiency and peak shift. One of the possible solutions to eliminate these undesirable effects is to grow GaN-based epilayers in nonpolar orientations. The polarization effects in the GaN are eliminated by growing the films along the nonpolar [$11\bar{2}0$] ($\alpha$-GaN) or [$1\bar{1}00$] (m-GaN) orientation. Although the use of the nonpolar epilayers in wurtzite structure clearly removes the polarization matters, however, it induces another problem related to the formation of a high density of planar defects. The large lattice mismatch between sapphiresubstrates and GaN layers leads to a high density of defects (dislocations and stacking faults). The dominant defects observed in the GaN epilayers with wurtzite structure are one-dimensional (1D) dislocations and two-dimensional (2D) stacking faults. In particular, the 1D threading dislocations in the c-GaN are generated from the film/substrate interface due to their large lattice and thermal coefficient mismatch. However, because the c-GaN epilayers were grown along the normal direction to the basal slip planes, the generation of basal stacking faults (BSFs) is localized on the c-plane and the generated BSFs did not propagate into the surface during the growth. Thus, the primary defects in the c-GaN epilayers are 1D threading dislocations. Occasionally, the particular planar defects such as prismatic stacking faults (PSFs) and inversion domain boundaries are observed. However, since the basal slip planes in the $\alpha$-GaN are parallel to the growth direction unlike c-GaN, the BSFs with lower formation energy can be easily formed along the growth direction, where the BSFs propagate straightly into the surface. Consequently, the lattice mismatch between film and substrate in $\alpha$-GaN epilayers is mainly relaxed through the formation of BSFs. These 2D planar defects are placed along only one direction in the cross-sectional view. Thus, the nonpolar $\alpha$-GaN films have different atomic arrangements along the two orthogonal directions ($[0001]_{GaN}$ and $[\bar{1}100]_{GaN}$ axes) on the $\alpha$-plane, which are expected to induce anisotropic biaxial strain. In this study, the anisotropic strain relaxation behaviors in the nonpolar $\alpha$-GaN epilayers grown on ($1\bar{1}02$) r-plane sapphire substrates by metalorganic chemical vapor deposition (MOCVO) were investigated, and the formation mechanism of the abnormal zigzag shape PSFs was discussed using high-resolution transmission electron microscope (HRTEM).

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Carbon nanotube field emission display

  • Chil, Won-Bong;Kim, Jong-Min
    • Electrical & Electronic Materials
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    • v.12 no.7
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    • pp.7-11
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    • 1999
  • Fully sealed field emission display in size of 4.5 inch has been fabricated using single-wall carbon nanotubes-organic vehicle com-posite. The fabricated display were fully scalable at low temperature below 415$^{\circ}C$ and CNTs were vertically aligned using paste squeeze and surface rubbing techniques. The turn-on fields of 1V/${\mu}{\textrm}{m}$ and field emis-sion current of 1.5mA at 3V/${\mu}{\textrm}{m}$ (J=90${\mu}{\textrm}{m}$/$\textrm{cm}^2$)were observed. Brightness of 1800cd/$m^2$ at 3.7V/${\mu}{\textrm}{m}$ was observed on the entire area of 4.5-inch panel from the green phosphor-ITO glass. The fluctuation of the current was found to be about 7% over a 4.5-inch cath-ode area. This reliable result enables us to produce large area full-color flat panel dis-play in the near future. Carbon nanotubes (CNTs) have attracted much attention because of their unique elec-trical properties and their potential applica-tions [1, 2]. Large aspect ratio of CNTs together with high chemical stability. ther-mal conductivity, and high mechanical strength are advantageous for applications to the field emitter [3]. Several results have been reported on the field emissions from multi-walled nanotubes (MWNTs) and single-walled nanotubes (SWNTs) grown from arc discharge [4, 5]. De Heer et al. have reported the field emission from nan-otubes aligned by the suspension-filtering method. This approach is too difficult to be fully adopted in integration process. Recently, there have been efforts to make applications to field emission devices using nanotubes. Saito et al. demonstrated a car-bon nanotube-based lamp, which was oper-ated at high voltage (10KV) [8]. Aproto-type diode structure was tested by the size of 100mm $\times$ 10mm in vacuum chamber [9]. the difficulties arise from the arrangement of vertically aligned nanotubes after the growth. Recently vertically aligned carbon nanotubes have been synthesized using plasma-enhanced chemical vapor deposition(CVD) [6, 7]. Yet, control of a large area synthesis is still not easily accessible with such approaches. Here we report integra-tion processes of fully sealed 4.5-inch CNT-field emission displays (FEDs). Low turn-on voltage with high brightness, and stabili-ty clearly demonstrate the potential applica-bility of carbon nanotubes to full color dis-plays in near future. For flat panel display in a large area, car-bon nanotubes-based field emitters were fabricated by using nanotubes-organic vehi-cles. The purified SWNTs, which were syn-thesized by dc arc discharge, were dispersed in iso propyl alcohol, and then mixed with on organic binder. The paste of well-dis-persed carbon nanotubes was squeezed onto the metal-patterned sodalime glass throuhg the metal mesh of 20${\mu}{\textrm}{m}$ in size and subse-quently heat-treated in order to remove the organic binder. The insulating spacers in thickness of 200${\mu}{\textrm}{m}$ are inserted between the lower and upper glasses. The Y\ulcornerO\ulcornerS:Eu, ZnS:Cu, Al, and ZnS:Ag, Cl, phosphors are electrically deposited on the upper glass for red, green, and blue colors, respectively. The typical sizes of each phosphor are 2~3 micron. The assembled structure was sealed in an atmosphere of highly purified Ar gas by means of a glass frit. The display plate was evacuated down to the pressure level of 1$\times$10\ulcorner Torr. Three non-evaporable getters of Ti-Zr-V-Fe were activated during the final heat-exhausting procedure. Finally, the active area of 4.5-inch panel with fully sealed carbon nanotubes was pro-duced. Emission currents were character-ized by the DC-mode and pulse-modulating mode at the voltage up to 800 volts. The brightness of field emission was measured by the Luminance calorimeter (BM-7, Topcon).

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Geologic, Fluid Inclusion, and Sulfur Isotopic Studies of Hydrothermal Deposit in the Tanggueng District, West Java, Indonesia (인도네시아 서부자바 땅긍(Tanggueng)지역 열수광상의 지질, 유체포유물 및 황동위원소 연구)

  • Jae-Ho Lee;In-Joon Kim
    • Economic and Environmental Geology
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    • v.36 no.5
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    • pp.321-328
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    • 2003
  • The epithermal gold and base metal deposit of the Tanggeung district of West Java consists of four major veins(Celak, Cigodobras, Cilangkap and Pasirbedil) with NS to N10$^{\circ}$∼20$^{\circ}$E and N75$^{\circ}$W strikes. The veins occur within fractures cutting the crystal and lithic tuff of Jampang Formation(Oligo-Miocene) in and around the Mt. Subang of the western Java, Indonesia. The ore mineralization is characterized by the occurrence of pyrite, sphalerite, galena, chalcopyrite, and small amounts of bornite and Fe-oxides. Hydrothermal alteration, associated with the mineralization, was dominantly silicified and enveloped by the phyllitic(sericitic), argillic and propylitic alteration containing the disseminated pyrite. Gangue minerals consist of interstratified smectite-illite, chlorite, sericite, and minor kaolinite. The presence of vapor-rich fluid inclusions in quartz veins suggests that boiling occurred locally throughout ore deposition. Fluid inclusion studies suggest that the ore fluid evolved from initial high temperatures(〓34$0^{\circ}C$) to later lower temperatures(〓19$0^{\circ}C$). Salinities range from 0.0 to 8.3 wt percent NaCl equiv. The relatively high increase in salinity(up to 8.3 wt percent NaCl equiv) might be explained by a local boiling and by a participation of magmatic fluids, supported by the sulfur isotope results. Evidence of fluid boiling suggests that the pressure decreased from 200 bars to 120 bars. This corresponds to the depths of approximately 750 to 1,200 m in a hydrothermal system that changed from lithostatic to hydrostatic conditions. Using homogenization temperatures and paragenetic constraints, the calculated $\delta$$^{34}$ S values of $H_2S$ in ore fluid are -0.2 to 1.8 permil close to the 0 permil isotopic value of magmatic sulfur.