• Title/Summary/Keyword: In situ TEM

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PBMS의 교정 및 이를 이용한 진공 내 나노입자의 실시간 분석 연구

  • Kim, Dong-Bin;Mun, Ji-Hun;Kim, Hyeong-U;Kim, Deuk-Hyeon;Lee, Jun-Hui;Gang, Sang-U;Kim, Tae-Seong
    • Proceedings of the Korean Vacuum Society Conference
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    • 2015.08a
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    • pp.91-91
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    • 2015
  • 반도체 공정의 발전에 의해 최근 생산되는 메모리 등은 십 수 나노미터까지 좁아진 선 폭을 갖게 되었다. 이러한 이유로, 기존에는 큰 문제를 발생시키지 않던 나노미터 영역의 입자들이 박막 증착 공정과 같은 반도체 제조공정 수율을 저감시키게 되었다. 따라서 오염입자의 유입을 막거나 제어하기 위해 transmission electron microscopy (TEM)나 scanning electron microscopy (SEM)과 같은 전자현미경을 활용한 비 실시간 입자 측정 방법 및 광원을 이용하는 in-situ particle monitor (ISPM) 및 전기적 이동도를 이용한 scanning mobility particle sizer (SMPS) 등 다양한 원리를 이용한 실시간 입자 측정방법이 현재 사용중에 있다. 이 중 진공 내 입자의 수농도를 측정하기 위해 개발된 particle beam mass spectrometer (PBMS) 기술은 박막 증착 공정 등 chemical vapor deposition (CVD) 방법을 이용하는 진공공정에서 활용 가능하여 개발이 진행되어 왔다. 본 연구에서는 PBMS의 한계점인 입자 밀도, 형상 등의 특성분석이 용이하도록 PBMS와 scanning electron microscopy (SEM), 그리고 energy dispersive spectroscopy (EDS) 기술을 결합하여 입자의 직경별 개수농도, 각 입자의 형상 및 성분을 함께 측정 가능하도록 하였다. 협소한 반도체 제조공정 내부 공간에 적용 가능하도록 기존 PBMS 대비 크기 또한 소형화 하였다. 각 구성요소인 공기역학 집속렌즈, electron gun, 편향판, 그리고 패러데이 컵의 설치 및 물리적인 교정을 진행한 후 입자발생장치를 통해 발생시킨 sodium chloride 입자를 상압 입자 측정 및 분류장치인 SMPS 장치를 이용하여 크기별로 분류시켜 압력차를 통해 PBMS로 유입시켜 측정을 진행하였다. 나노입자의 입경분포, 형상 및 성분을 측정결과를 토대로 장치의 측정정확도를 교정하였다. 교정된 장치를 이용하여 실제 박막 증착공정 챔버의 배기라인에서 발생하는 입자의 수농도, 형상 및 성분의 복합특성 측정이 가능하였으며, 최종적으로 실제 공정에 적용가능하도록 장치 교정을 완료하였다.

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Preparation of AgCl/Ag3PO4/Diatomite Composite by Microemulsion Method for Rapid Photo-Degradation of Rhodamine B with Stability under Visible Light

  • Zhu, Hai-Tao;Ren, Qi-Fang;Jin, Zhen;Ding, Yi;Liu, Xin-Yu;Ni, Xi-Hui;Han, Meng-Li;Ma, Shi-Yu;Ye, Qing;Oh, Won-Chun
    • Korean Journal of Materials Research
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    • v.30 no.8
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    • pp.383-392
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    • 2020
  • In this paper, AgCl/Ag3PO4/diatomite photocatalyst is successfully synthesized by microemulsion method and anion in situ substitution method. X-ray diffraction (XRD), photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), and ultraviolet-visible spectroscopy (UV-Vis) are used to study the structural and physicochemical characteristics of the AgCl/Ag3PO4/diatomite composite. Using rhodamine B (RhB) as a simulated pollutant, the photocatalytic activity and stability of the AgCl/Ag3PO4/diatomite composite under visible light are evaluated. In the AgCl/Ag3PO4/diatomite visible light system, RhB is nearly 100 % degraded within 15 minutes. And, after five cycles of operation, the photocatalytic activity of AgCl/Ag3PO4/diatomite remains at 95 % of the original level, much higher than that of pure Ag3PO4 (40 %). In addition, the mechanism of enhanced catalytic performance is discussed. The high photocatalytic performance of AgCl/Ag3PO4/diatomite composites can be attributed to the synergistic effect of Ag3PO4, diatomite and AgCl nanoparticles. Free radical trapping experiments are used to show that holes and oxygen are the main active species. This material can quickly react with dye molecules adsorbed on the surface of diatomite to degrade RhB dye to CO2 and H2O. Even more remarkably, AgCl/Ag3PO4/diatomite can maintain above 95 % photo-degradation activity after five cycles.

Synthesis of Ceria Nanoparticles Using Supercritical Methanol with Various Surface Modifiers (초임계 메탄올을 이용한 표면개질된 세리아 나노입자의 합성)

  • Ahn, Ki Ho;Shin, Nae-Chul;Kim, Minsoo;Youn, Yong-Suk;Hong, Giyoung;Lee, Youn-Woo
    • Korean Chemical Engineering Research
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    • v.50 no.4
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    • pp.678-683
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    • 2012
  • Ceria is one of the most important catalytic materials which can be used in three-way catalysts, waste water treatment, petroleum refining, etc. So far, many methods have been studied to produce ceria nanoparticles. In this study, ceria nanoparticles were prepared via solvothermal synthesis using supercritical methanol in short reaction time using a batch reactor. The size of synthesized ceria nanoparticles in supercritical methanol is 6 nm without capping agent, which is smaller than that made in supercritical water at the same conditions of $400^{\circ}C$ and 30 MPa. Size difference results from density and critical point difference between water and methanol and slow reaction rate at the surface of ceria particles in supercritical methanol which reduces crystal growth rate. Several organic compounds were added to modify the surface of ceria nanoparticles, and in-situ surface modification was confirmed by FT-IR and TGA analysis. Surface modified ceria nanoparticles have excellent dispersibility in organic solvent. Size and shape of surface modified ceria particles can be controlled by adjusting molar ratio of modifier to precursor and selection of modifier.

CHARACTERISTICS OF HETEROEPITAXIALLY GROWN $Y_2$O$_3$ FILMS BY r-ICB FOR VLSI

  • Choi, S.C.;Cho, M.H.;Whangbo, S.W.;Kim, M.S.;Whang, C.N.;Kang, S.B.;Lee, S.I.;Lee, M.Y.
    • Journal of the Korean institute of surface engineering
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    • v.29 no.6
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    • pp.809-815
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    • 1996
  • $Y_2O_3$-based metal-insulator-semiconductor (MIS) structure on p-Si(100) has been studied. Films were prepared by UHV reactive ionized cluster beam deposition (r-ICBD) system. The base pressure of the system was about $1 \times 10^{-9}$ -9/ Torr and the process pressure $2 \times 10^{-5}$ Torr in oxygen ambience. Glancing X-ray diffraction(GXRD) and in-situ reflection high energy electron diffracton(RHEED) analyses were performed to investigate the crystallinity of the films. The results show phase change from amorphous state to crystalline one with increasingqr acceleration voltage and substrate temperature. It is also found that the phase transformation from $Y_2O_3$(111)//Si(100) to $Y_2O_3$(110)//Si(100) in growing directions takes place between $500^{\circ}C$ and $700^{\circ}C$. Especially as acceleration voltage is increased, preferentially oriented crystallinity was increased. Finally under the condition of above substrate temperature $700^{\circ}C$ and acceleration voltage 5kV, the $Y_2O_3$films are found to be grown epitaxially in direction of $Y_2O_3$(1l0)//Si(100) by observation of transmission electron microscope(TEM). Capacitance-voltage and current-voltage measurements were conducted to characterize Al/$Y_2O_3$/Si MIS structure with varying acceleration voltage and substrate temperature. Deposited $Y_2O_3$ films of thickness of nearly 300$\AA$ show that the breakdown field increases to 7~8MV /cm at the same conditon of epitaxial growing. These results also coincide with XPS spectra which indicate better stoichiometric characteristic in the condition of better crystalline one. After oxidation the breakdown field increases to 13MV /cm because the MIS structure contains interface silicon oxide of about 30$\AA$. In this case the dielectric constant of only $Y_2O_3$ layer is found to be $\in$15.6. These results have demonstrated the potential of using yttrium oxide for future VLSI/ULSI gate insulator applications.

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Pedogenesis of Forest Soils(Kandiustalfs) Derived from Granite Gneiss in Southern Part of Korea (우리나라 남부지역(南部地域) 화강편마암질(花崗片麻巖質) 삼림토양(森林土壤)의 토양생성(土壤生成))

  • Cho, Hi Doo
    • Journal of Korean Society of Forest Science
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    • v.86 no.2
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    • pp.186-199
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    • 1997
  • The soils derived from granite gneiss occupy almost one third of the land area in Korea. The soils under forest vegetation, formed on granite gneiss, in Sun chon-shi, Chollanam-do in southern part of Korea, were studied to evaluate the weathering and the transformation of primary minerals into secondary minerals, clay minerals. The studied soils contained large amounts of ferromagnesian minerals, weathered biotites and were well weathered, strongly acid and low in organic matters and in ration exchange capacity. The clay contents in the Bt horizon were almost two times higher than those in the C horizon. The O horizon had a thin layer which consisted of a little decomposed plant components with a granic fabric and high porosity, and showed the micromorphological characteristics of moder humus. The related distribution pattern of the E horizon were enaulic and large amounts of silts and small amounts of sand grains were another characteristics of the E horizon. The most striking micromorphological features were multilaminated clay coating and infillings in the voids in the Bt and C horizons, and generally limpid ferriargillans ejected from the biotites and imparted red color to the soils in the Bt horizon. High clay contents in the Bt horizon was not only due to clay translocation, but also due to intensive in situ mineral weathering in this horizon. The most significant pedogenic process, revealed by the petrographic microscope and SEM, was the formation of iron oxides from biotites, the formation of tubular halloysites and the weathering models of biotites; wedge weathering and layer weathering. The thick coating on the weathering biotites showed the characteristics of the weathering process and the synthetic hematites were revealed in clays by TEM. Total chemical analysis of clays revealed extensive loss of Ca, and Na and the concentration of Fe and Al. Mineralogical studies of clays by XRD showed that micas were almost completely weathered to kaolinite, vermiculite-kaolinite intergrade, hematite, gibbsite, while halloysites from other primary minerals. Some dioctahedral mica appeared to be resistant in the soils. Parent rock of the soils contained a considerable amounts of biotites and this forest soils showed especially a dominant characteristics of biotite weathering.

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Evaluation on Removal Efficiency of Methylene Blue Using Nano-ZnO/Laponite/PVA Photocatalyzed Adsorption Ball (Nano-ZnO/Laponite/PVA 광촉매 흡착볼의 메틸렌블루 제거효율 평가)

  • Oh, Ju Hyun;Ahn, Hosang;Jang, Dae Gyu;Ahn, Chang Hyuk;Lee, Saeromi;Joo, Jin Chul
    • Journal of Korean Society of Environmental Engineers
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    • v.35 no.9
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    • pp.636-642
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    • 2013
  • In order to overcome drawbacks (i.e., filtration and recovery) of conventional powder type photocatalysts, nano-ZnO/Laponite/PVA (ZLP) photocatalyzed adsorption balls were developed by using in situ mixing of nanoscale ZnO as a photocatalyst, and Laponite as both adsorbent and supporting media in deionized water, followed by the poly vinyl alcohol polymerization with boric acid. The optimum mixing ratio of nano-ZnO:Laponite:PVA:deionized water was found to be 3:1:1:16 (by weight), and the mesh and film produced by PVA polymerization with boric acid might inhibit both swelling of Laponite and detachment of nanoscale ZnO from ZLP balls. Drying ZLP balls with microwave (600 watt) was found to produce ZLP balls with stable structure in water, and various sizes (55~500 ${\mu}m$) of pore were found to be distributed based on SEM and TEM results. In the initial period of reaction (i. e., 40 min), adsorption through ionic interaction between methylene blue and Laponite was the main removal mechanism. After the saturation of methylene blue to available adsorption sites for Laponite, the photocatalytic degradation of methylene blue occurred. The effective removal of methylene blue was attributed to adsorption and photocatalytic degradation. Based on the results from this study, synthesized ZLP photocatalyzed adsorption balls were expected to remove recalcitrant organic compounds effectively through both adsorption and photocatalytic degradation, and the risks of environmental receptors caused by detachment of nanoscale photocatalysts can be reduced.

A bilayer diffusion barrier of atomic layer deposited (ALD)-Ru/ALD-TaCN for direct plating of Cu

  • Kim, Soo-Hyun;Yim, Sung-Soo;Lee, Do-Joong;Kim, Ki-Su;Kim, Hyun-Mi;Kim, Ki-Bum;Sohn, Hyun-Chul
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2008.06a
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    • pp.239-240
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    • 2008
  • As semiconductor devices are scaled down for better performance and more functionality, the Cu-based interconnects suffer from the increase of the resistivity of the Cu wires. The resistivity increase, which is attributed to the electron scattering from grain boundaries and interfaces, needs to be addressed in order to further scale down semiconductor devices [1]. The increase in the resistivity of the interconnect can be alleviated by increasing the grain size of electroplating (EP)-Cu or by modifying the Cu surface [1]. Another possible solution is to maximize the portion of the EP-Cu volume in the vias or damascene structures with the conformal diffusion barrier and seed layer by optimizing their deposition processes during Cu interconnect fabrication, which are currently ionized physical vapor deposition (IPVD)-based Ta/TaN bilayer and IPVD-Cu, respectively. The use of in-situ etching, during IPVD of the barrier or the seed layer, has been effective in enlarging the trench volume where the Cu is filled, resulting in improved reliability and performance of the Cu-based interconnect. However, the application of IPVD technology is expected to be limited eventually because of poor sidewall step coverage and the narrow top part of the damascene structures. Recently, Ru has been suggested as a diffusion barrier that is compatible with the direct plating of Cu [2-3]. A single-layer diffusion barrier for the direct plating of Cu is desirable to optimize the resistance of the Cu interconnects because it eliminates the Cu-seed layer. However, previous studies have shown that the Ru by itself is not a suitable diffusion barrier for Cu metallization [4-6]. Thus, the diffusion barrier performance of the Ru film should be improved in order for it to be successfully incorporated as a seed layer/barrier layer for the direct plating of Cu. The improvement of its barrier performance, by modifying the Ru microstructure from columnar to amorphous (by incorporating the N into Ru during PVD), has been previously reported [7]. Another approach for improving the barrier performance of the Ru film is to use Ru as a just seed layer and combine it with superior materials to function as a diffusion barrier against the Cu. A RulTaN bilayer prepared by PVD has recently been suggested as a seed layer/diffusion barrier for Cu. This bilayer was stable between the Cu and Si after annealing at $700^{\circ}C$ for I min [8]. Although these reports dealt with the possible applications of Ru for Cu metallization, cases where the Ru film was prepared by atomic layer deposition (ALD) have not been identified. These are important because of ALD's excellent conformality. In this study, a bilayer diffusion barrier of Ru/TaCN prepared by ALD was investigated. As the addition of the third element into the transition metal nitride disrupts the crystal lattice and leads to the formation of a stable ternary amorphous material, as indicated by Nicolet [9], ALD-TaCN is expected to improve the diffusion barrier performance of the ALD-Ru against Cu. Ru was deposited by a sequential supply of bis(ethylcyclopentadienyl)ruthenium [Ru$(EtCp)_2$] and $NH_3$plasma and TaCN by a sequential supply of $(NEt_2)_3Ta=Nbu^t$ (tert-butylimido-trisdiethylamido-tantalum, TBTDET) and $H_2$ plasma. Sheet resistance measurements, X-ray diffractometry (XRD), and Auger electron spectroscopy (AES) analysis showed that the bilayer diffusion barriers of ALD-Ru (12 nm)/ALD-TaCN (2 nm) and ALD-Ru (4nm)/ALD-TaCN (2 nm) prevented the Cu diffusion up to annealing temperatures of 600 and $550^{\circ}C$ for 30 min, respectively. This is found to be due to the excellent diffusion barrier performance of the ALD-TaCN film against the Cu, due to it having an amorphous structure. A 5-nm-thick ALD-TaCN film was even stable up to annealing at $650^{\circ}C$ between Cu and Si. Transmission electron microscopy (TEM) investigation combined with energy dispersive spectroscopy (EDS) analysis revealed that the ALD-Ru/ALD-TaCN diffusion barrier failed by the Cu diffusion through the bilayer into the Si substrate. This is due to the ALD-TaCN interlayer preventing the interfacial reaction between the Ru and Si.

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