• Title/Summary/Keyword: X-Ray Photoelectron Spectroscopy

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Low Temperature CO Oxidation over Cu-Mn Mixed Oxides (Cu-Mn 혼합산화물 상에서 일산화탄소의 저온산화반응)

  • Cho, Kyong-Ho;Park, Jung-Hyun;Shin, Chae-Ho
    • Clean Technology
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    • v.16 no.2
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    • pp.132-139
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    • 2010
  • The Cu-Mn mixed oxide catalysts with different molar ratios of Cu/(Cu+Mn) prepared by co-precipitation method have been investigated in CO oxidation at $30^{\circ}C$. The catalysts used in this study were characterized by X-ray Diffraction (XRD), $N_2$ sorption, X-ray photoelectron spectroscopy (XPS), and $H_2$-temperature programmed reduction $(H_2-TPR)$ to correlate with catalytic activities in CO oxidation. The $N_2$ adsorption-desorption isotherms of Cu-Mn mixed oxide catalysts showed a type 4 having pore range of 7-20 nm and BET surface area was increased from 17 to $205\;m^2{\cdot}g^{-1}$ with increasing of Mn content. The XPS analysis showed the surface oxidation state of Cu and Mn represented $Cu^{2+}$and the mixture of $Mn^{3+}$ and $Mn^{4+}$, respectively. Among the catalysts studied here, Cu/(Cu+Mn) = 0.5 catalyst showed the highest activity at $30^{\circ}C$ in CO oxidation and the catalytic activity showed a typical volcano-shape curve with respect to Cu/(Cu+Mn) molar ratios. The water vapor showed a prohibiting effect on the efficiency of the catalyst which is due to the competitive adsorption of carbon monoxide on the active sites of catalyst surface and finally the formation of hydroxyl group with active metals.

Development of novel oxyfluoride glasses and glass ceramics for photoluminescence material by a containerless processing (무용기 용융법을 활용한 형광소재용 결정화 유리 개발)

  • Hyerin Jo;Minsung Hwang;Youngjin Lee;Jaeyeop Chung
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.33 no.5
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    • pp.181-186
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    • 2023
  • In this study, novel Eu2O3-BaF2-La2O3-B2O3 oxyfluoride glasses and glass ceramics were developed by a containerless processing. Differential thermal analysis (DTA) analysis was performed to analyze the thermophysical properties of oxyfluoride glasses doped with Eu2O3, and photoluminescence (PL) characteristics were analyzed to evaluate the luminous efficiency depending on the degree of crystallinity. The glass transition temperature decreased with increasing BaF2 concentration since BaF2 acts as a network modifier in this glass system. In addition, thermal stability which can be estimated by the difference between the glass transition temperature and the onset temperature of the crystallization decreased with increasing BaF2 contents. The peak related to the BaF2 crystal was confirmed after the crystallization by X-ray Diffraction (XRD) analysis. Photoluminescence intensity increased after the crystallization which indicates that the Eu3+ ions are sited in BaF2 crystal. La 3d5/2 x-ray photoelectron spectroscopy (XPS) and F1s XPS spectra were analyzed to precisely understand the behavior of the fluorine ion in the glass structure. Fluorine tends to bond with the network modifying cations such as La3+ and Ba2+ ions and after the crystallization the La-F bonds decreased because F- ions used to form BaF2 crystals.

Effect of Doubly Plasma Oxidation Time on TMR Devices (이중절연층 산화공정에서 플라즈마 산화시간에 따른 터널자기저항 효과)

  • Lee, Ki-Yung;Song, Oh-Sung
    • Journal of the Korean Magnetics Society
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    • v.12 no.4
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    • pp.127-131
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    • 2002
  • We fabricated MTJ devices that have doubly oxidized tunnel barrier using plasma oxidation method to from oxidized AlO$\sub$x/ tunnel barrier. Doubly oxidation I, which sputtered 10 ${\AA}$-bottom Al layer and oxidized it with oxidation time of 10 s. Subsequent sputtering of 13 ${\AA}$-Al was performed and the metallic layer was oxidized for 50, 80 and 120 s., respectively. Doubly oxidation II, which sputtered 10 ${\AA}$-bottom Al layer and oxidized it varying oxidation time for 30∼120 s. Subsequent sputtering of 13 ${\AA}$-Al was performed and the metallic layer was oxidized for 210 sec. Double oxidation process specimen showed MR ratio of above 27% in all experiment range. Singly oxidation process. 13 ${\AA}$-Al layer and oxidized up to 210 s, showed less MR ratio and more narrow process window than those of doubly oxidation. Cross-sectional TEM images would that doubly oxidized barrowers were thinner and denser than singly oxidized ones. XPS characterization confirmed that doubly oxidation of Fe with bottom insulating layer. As a result, doubly oxidation could have superior MR ratio in process extent during long oxidation time because of preventing oxidation of bottom magnetic layer than singly oxidation.

대면적 플라즈마 공정에서 자장이 내장형 선형 유도결합형 플라즈마 특성에 미치는 영향에 관한 연구

  • 경세진;이영준;김경남;염근영
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 2003.05a
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    • pp.55-55
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    • 2003
  • 최근 높은 해상도의 평판 디스플레이 장치 특히 차세대 TFT-LCD를 개발하기 위해서는 건식식각공정의 개발이 필수 불가결하며 이는 플라즈마 공정장치의 대면적화가 가능해야 한다. 따라서 산업계는 이러한 제조 조건에 알맞는 대면적 플라즈마 반응기 개발을 추구하고 있다. 이를 위해서는 건식식각공정의 개발이 필수 불가결하며 이를 위해선 플라즈마 공정장 치의 대면적화가 가능해야 한다. 이러한 대면적 공정을 위해서는 낮은 공정압력, 고밀도, 높은 플라즈마 균일도가 요구된다. 또한 이러한 대면적 고밀도 플라즈마에의 적용을 위하여 새로운 유도결합형 플라즈마 소오스의 개발이 진행되고 있으며, 안정적인 300mm웨이퍼 공정을 위하여 여러 형태의 안테나가 연구되어지고 있다. 그러나 차세대 TFT-LCD에 적용 가 능하게끔 기존의 ICP 소오스를 직접적으로 대면적화 하는데 있어서는 안테나의 인덕턴스의 값이 키지며, 유전물질의 두께 증가 및 그에 따른 재료비의 상슴에 의해 그 한계점을 나타 내었다. 본 연구에서는 차세대 TFT-LCD 및 POP 대면적 공정에 적용 가능한 고밀도 플라즈마를 발생시키기 위해서 내장형 유도결합형 선형 안테나를 사용하였다. 내장형 유도결합형 선형 안테나가 가지고 있는 고유의 정전기적 결합효과를 최소화시키기 위해 직사각형모양의 플라즈마 챔버(830mm*1,020mm)에서 영구자석을 사용하였다. 영구자석을 사용하여 외부자 장을 인가하였을 때가, 그럴지 않은 때보다 RF 안테나에 걸리는 코일의 전압을 낮춰주었으며, 영구자석의 배열에 따라 코일의 인덕턴스의 값이 크게 변함을 알 수 있었다. 그리고, 최적화된 자장의 배열은 플라즈마의 이온밀도를 증가시켰으며, 플라즈마 균일도 또한 10% 이 내로 유지됨을 알 수 있었다. 따른 식각 메커니즘에 대하여 알아보고자 하였다. $CF_4/Cl_2$ gas chemistry 에 첨 가 가스로 $N_2$와 Ar을 첨 가할 경 우 텅 스텐 박막과 하부 layer 간의 etch selectivity 증가는 관찰되지 않았으며, 반면에 첨가 가스로 $O_2$를 사용할 경우, $O_2$의 첨가량이 증가함에 따라 etch s selectivity 는 계속적으로 증가렴을 관찰할 수 있었다. 이는 $O_2$ 첨가에 따라 형성되는 WOF4 에 의한 텅스텐의 etch rates 의 감소에 비하여, $Si0_2$ 등의 형성에 의한 poly-Si etch rates 이 더욱 크게 감소하였기 때문으로 사료된다. W 과 poly-Si 의 식각 특성을 이해하기 위하여 X -ray photoelectron spectroscopy (XPS)를 사용하였으며, 식각 전후의 etch depth 를 측정하기 위하여 stylus p pmfilometeT 를 이용하였다.X> 피막이 열처리 전후에 보아는 기계적 특성의 변화 양상은 열역학적으로 안정한 Wurzite-AlN의 석출에 따른 것으로 AlN 석출상의 크기에 의존하며, 또한 이러한 영향은 $(Ti_{1-x}AI_{x})N$ 피막에 존재하는 AI의 함량이 높고, 초기에 증착된 막의 업자 크기가 작을 수록 클 것으로 여겨진다. 그리고 환경의 의미의 차이에 따라 경관의 미학적 평가가 달라진 것으로 나타났다.corner$적 의도에 의한 경관구성의 일면을 확인할수 있지만 엄밀히 생각하여 보면 이러한 예의 경우도 최락의 총체적인 외형은 마찬가지로

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Interfacial disruption effect on multilayer-films/GaN : Comparative study of Pd/Ni and Ni/Pd films

  • 김종호;강희재;김차연;전용석;서재명
    • Proceedings of the Korean Vacuum Society Conference
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    • 2000.02a
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    • pp.113-113
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    • 2000
  • 직접천이형 wide band gap(3.4eV) 반도체중의 하나인 GaN를 청색 및 자외선 laser diode, 고출력 전자장비 등으로 응용하기 위해서는 낮은 접합저항을 갖는 Ohmic contact이 선행되어야 한다. 그러나 만족할만한 p-type GaN의 Ohmic contact은 아직 실현되고 있지 못하며, 이는 GaN와 접합 금속과의 구체적인 반응의 연구를 필요로 한다. 본 연구에서 앞서 Pt, Pt, Ni등의 late transition metal을 p-GaN에 접합시킨 결과 이들은 접합 당시 비교적 평탄하나 후열 처리과정에서 비교적 낮은 온도에서 기판과 열팽창계수의 차이로 인하여 평탄성을 잃어버리면서 barrier height가 증가한다는 사실을 확인하였다. 따라서 본 연구에서는 이러한 열적 불안정성을 극복하기 위하여 Ni과 Pd를 차례로 증착하고 가열하면서 interfacial reaction, film morphology, Fermi level의 움직임을 monchromatic XPS(x-ray photoelectron spectroscopy) 와 SAM(scanning Auger microscopy) 그리고 ex-situ AFM을 이용하여 밝히고자 하였다. 특히 후열처리에 의한 계면 반응에 수반되는 구성 금속원소 간의 합금현상과 금속 층의 평탄성이 밀접한 관계가 있다는 것을 확인하였다. 이러한 합금과정에서 나타나는 금속원소들의 중심 준위의 이동을 체계적으로 규명하기 위해서 Pd1-xNix와 Pd1-xGax 합금들의 표준시료를 arc melting method로 만들어 농도에 따른 금속원소들의 중심 준위의 이동을 측정하여, Pd/Ni/p-GaN 및 Ni/Pd/p-GaN 계에서 열처리 온도에 따른 interfacial reaction을 확인하였다. 그 결과 두 계가 상온에서 nitride 및 alloy를 형성하지 않고 고르게 증착되고, 열처리 온도를 40$0^{\circ}C$에서 $650^{\circ}C$까지 증가시킴에 따라 계면반응의 부산물인 metallic Ga은 증가하고 있으마 nitride는 여전히 형성되지 않는 것을 확인하였다. 증착당시 Ni이 계면에 있는 Pd/Ni/p-GaN의 경우에는 52$0^{\circ}C$까지의 열처리에 의하여 Ni과 Pd가 골고루 섞이고 그 평탄성도 유지되고 barier height의 변화도 없었다. 더 높은 $650^{\circ}C$ 가열에 의해서는 surface free energy가 작은 Ga의 활발한 편석 현상으로 인해 표면은 Ga이 풍부한 Pd-Ga의 합금층으로 덮이고, 동시에 작은 pinhole들이 발생하며 barrier height도 0.3eV 가량 증가하게 된다. 반면에 증착당시 Pd이 계면에 있는 Ni/Pd/p-GaN의 경우에는 40$0^{\circ}C$의 가열까지는 두 금속이 그들 계면에서부터 섞이나, 52$0^{\circ}C$의 가열에 의해 이미 barrier height가 0.2eV 가량 증가하기 시작하였다. 더 높은 $650^{\circ}C$가열에 의해서는 커다란 pinhole, 0.5eV 가량의 barrier height 증가, Pd clustering이 동시에 관찰되었다. 따라서 Ni과 Pd의 일함수는 물론 thermal expansion coefficient가 거의 같으며 surface free energy도 거의 일치한다는 점을 감안하면, 이렇게 뚜렷한 열적 안정성의 차이는 GaN와 contact metal과의 반응시작 온도(disruption onset temperature)의 차이에 기인함을 알 수 있었다. 즉 계면에서의 반응에 의해 편석되는 Ga에 의해 박막의 strain이 이완되면, pinhole 등의 박막결함이 줄어 들고, 이는 계면의 N의 out-diffusion을 방지하여 p-type GaN의 barrier height 증가를 막게 된다.

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Structural and Electrical Properties of Fluorine-doped Zinc Tin Oxide Thin Films Prepared by Radio-Frequency Magnetron Sputtering

  • Pandey, Rina;Cho, Se Hee;Hwang, Do Kyung;Choi, Won Kook
    • Proceedings of the Korean Vacuum Society Conference
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    • 2014.02a
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    • pp.335-335
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    • 2014
  • Over the past several years, transparent conducting oxides have been extensively studied in order to replace indium tin oxide (ITO). Here we report on fluorine doped zinc tin oxide (FZTO) films deposited on glass substrates by radio-frequency (RF) magnetron sputtering using a 30 wt% ZnO with 70 wt% SnO2 ceramic targets. The F-doping was carried out by introducing a mixed gas of pure Ar, CF4, and O2 forming gas into the sputtering chamber while sputtering ZTO target. Annealing temperature affects the structural, electrical and optical properties of FZTO thin films. All the as-deposited FZTO films grown at room temperature are found to be amorphous because of the immiscibility of SnO2 and ZnO. Even after the as-deposited FZTO films were annealed from $300{\sim}500^{\circ}C$, there were no significant changes. However, when the sample is annealed temperature up to $600^{\circ}C$, two distinct diffraction peaks appear in XRD spectra at $2{\Theta}=34.0^{\circ}$ and $52.02^{\circ}$, respectively, which correspond to the (101) and (211) planes of rutile phase SnO2. FZTO thin film annealed at $600^{\circ}C$ resulted in decrease of resistivity $5.47{\times}10^{-3}{\Omega}cm$, carrier concentration ~1019 cm-3, mobility~20 cm2 V-1s-1 and increase of optical band gap from 3.41 to 3.60 eV with increasing the annealing temperatures and well explained by Burstein-Moss effect. Change of work function with the annealing temperature was obtained by ultraviolet photoemission spectroscopy. The increase of annealing temperature leads to increase of work function from ${\phi}=3.80eV$ (as-deposited FZTO) to ${\phi}=4.10eV$ ($600^{\circ}C$ annealed FZTO) which are quite smaller than 4.62 eV for Al-ZnO and 4.74 eV for SnO2. Through X-ray photoelectron spectroscopy, incorporation of F atoms was found at around the binding energy of 684.28 eV in the as-deposited and annealed FZTO up to 400oC, but can't be observed in the annealed FZTO at 500oC. This result indicates that F atoms in FZTO films are loosely bound or probably located in the interstitial sites instead of substitutional sites and thus easily diffused into the vacuum from the films by thermal annealing. The optical transmittance of FZTO films was higher than 80% in all specimens and 2-3% higher than ZTO films. FZTO is a possible potential transparent conducting oxide (TCO) alternative for application in optoelectronics.

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Energy Band Structure, Electronic and Optical properties of Transparent Conducting Nickel Oxide Thin Films on $SiO_2$/Si substrate

  • Denny, Yus Rama;Lee, Sang-Su;Lee, Kang-Il;Lee, Sun-Young;Kang, Hee-Jae;Heo, Sung;Chung, Jae-Gwan;Lee, Jae-Cheol
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.02a
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    • pp.347-347
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    • 2012
  • Nickel Oxide (NiO) is a transition metal oxide of the rock salt structure that has a wide band gap of 3.5 eV. It has a variety of specialized applications due to its excellent chemical stability, optical, electrical and magnetic properties. In this study, we concentrated on the application of NiO thin film for transparent conducting oxide. The energy band structure, electronic and optical properties of Nickel Oxide (NiO) thin films grown on Si by using electron beam evaporation were investigated by X-Ray Photoelectron Spectroscopy (XPS), Reflection Electron Energy Loss Spectroscopy (REELS), and UV-Spectrometer. The band gap of NiO thin films determined by REELS spectra was 3.53 eV for the primary energies of 1.5 keV. The valence-band offset (VBO) of NiO thin films investigated by XPS was 3.88 eV and the conduction-band offset (CBO) was 1.59 eV. The UV-spectra analysis showed that the optical transmittance of the NiO thin film was 84% in the visible light region within an error of ${\pm}1%$ and the optical band gap for indirect band gap was 3.53 eV which is well agreement with estimated by REELS. The dielectric function was determined using the REELS spectra in conjunction with the Quantitative Analysis of Electron Energy Loss Spectra (QUEELS)-${\varepsilon}({\kappa},{\omega})$-REELS software. The Energy Loss Function (ELF) appeared at 4.8, 8.2, 22.5, 38.6, and 67.0 eV. The results are in good agreement with the previous study [1]. The transmission coefficient of NiO thin films calculated by QUEELS-REELS was 85% in the visible region, we confirmed that the optical transmittance values obtained with UV-Spectrometer is the same as that of estimated from QUEELS-${\varepsilon}({\kappa},{\omega})$-REELS within uncertainty. The inelastic mean free path (IMFP) estimated from QUEELS-${\varepsilon}({\kappa},{\omega})$-REELS is consistent with the IMFP values determined by the Tanuma-Powell Penn (TPP2M) formula [2]. Our results showed that the IMFP of NiO thin films was increased with increasing primary energies. The quantitative analysis of REELS provides us with a straightforward way to determine the electronic and optical properties of transparent thin film materials.

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Effects of Anodic Voltages of Photcatalytic TiO2 and Doping in H2SO4 Solutions on the Photocatalytic Activity (광촉매 TiO2의 황산용액에서의 양극산화전압과 도핑이 광촉매 활성에 미치는 영향)

  • Lee, Seung-Hyun;Oh, Han-Jun;Chi, Choong-Soo
    • Korean Journal of Materials Research
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    • v.22 no.8
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    • pp.439-444
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    • 2012
  • To compare the photocatalytic performances of titania for purification of waste water according to applied voltages and doping, $TiO_2$ films were prepared in a 1.0 M $H_2SO_4$ solution containing $NH_4F$ at different anodic voltages. Chemical bonding states of F-N-codoped $TiO_2$ were analyzed using surface X-ray photoelectron spectroscopy (XPS). The photocatalytic activity of the co-doped $TiO_2$ films was analyzed by the degradation of aniline blue solution. Nanotubes were formed with thicknesses of 200-300 nm for the films anodized at 30 V, but porous morphology was generated with pores of 1-2 ${\mu}m$ for the $TiO_2$ anodized at 180 V. The phenomenon of spark discharge was initiated at about 98 V due to the breakdown of the oxide films in both solutions. XPS analysis revealed the spectra of F1s at 684.3 eV and N1s at 399.8 eV for the $TiO_2$ anodized in the $H_2SO_4-NH_4F$ solution at 180 V, suggesting the incorporation of F and N species during anodization. Dye removal rates for the pure $TiO_2$ anodized at 30 V and 180 V were found to be 14.0% and 38.9%, respectively, in the photocatalytic degradation test of the aniline blue solution for 200 min irradiation; the rates for the F-N-codoped $TiO_2$ anodized at 30 V and 180 V were found to be 21.2% and 65.6%, respectively. From the results of diffuse reflectance absorption spectroscopy (DRS), it was found that the absorption edge of the F-N-codoped $TiO_2$ films shifted toward the visible light region up to 412 nm, indicating that the photocatalytic activity of $TiO_2$ is improved by appropriate doping of F and N by the addition of $NH_4F$.

Influence of Acid and Base Surface Treatment of Multi-Walled Carbon Nanotubes on Mechanical Interfacial Properties of Carbon Fibers-Reinforced Composites (산-염기 표면처리된 MWNTs의 첨가가 탄소섬유 강화 복합재료의 기계적 계면특성에 미치는 영향)

  • Jung, Gun;Nah, Chang-Woon;Seo, Min-Kang;Byun, Joon-Hyung;Lee, Kyu-Hwan;Park, Soo-Jin
    • Polymer(Korea)
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    • v.36 no.5
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    • pp.612-616
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    • 2012
  • In this work, the effect of chemical treatments of multi-walled carbon nanotubes (MWNTs) on the mechanical interfacial properties of carbon fiber fabric-reinforced composites was investigated. The surface properties of the MWNTs were determined by acid and base values, Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) analyses. The mechanical interfacial properties of the composites were assessed by interlaminar shear stress (ILSS) and critical stress intensity factor ($K_{IC}$). The chemical treatments based on acid and base reactions led to a significant change of surface characteristics of the MWNTs, especially A-MWNTs/carbon fibers/epoxy composites had higher mechanical properties than those of B-MWNTs and non-treated MWNTs/carbon fibers/epoxy composites. These results were probably due to the improvement of interfacial bonding strength, resulting from the acid-base interaction and hydrogen bonding between the epoxy resins and the MWNT fillers.

Preparation of Al2O3 Thin Films by Atomic Layer Deposition Using Dimethylaluminum Isopropoxide and Water and Their Reaction Mechanisms

  • An, Ki-Seok;Cho, Won-Tae;Sung, Ki-Whan;Lee, Sun-Sook;Kim, Yun-Soo
    • Bulletin of the Korean Chemical Society
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    • v.24 no.11
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    • pp.1659-1663
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    • 2003
  • $Al_2O_3$ thin films were grown on H-terminated Si(001) substrates using dimethylaluminum isopropoxide [DMAl: $(CH_3)_2AlOCH(CH_3)_2$], as a new Al precursor, and water by atomic layer deposition (ALD). The selflimiting ALD process by alternate surface reactions of DMAI and $H_2O$ was confirmed from measured thicknesses of the aluminum oxide films as functions of the DMAI pulse time and the number of DMAI-$H_2O$ cycles. Under optimal reaction conditions, a growth rate of ~1.06 ${\AA}$ per ALD cycle was achieved at the substrate temperature of $150\;^{\circ}C$. From a mass spectrometric study of the DMAI-$D_2O$ ALD process, it was determined that the overall binary reaction for the deposition of $Al_2O_3\;[2\;(CH_3)_2AlOCH(CH_3)_2\;+\;3\;H_2O\;{\rightarrow}\;Al_2O_3\;+\;4\;CH_4\;+\;2\;HOCH(CH_3)_2]$can be separated into the following two half-reactions: where the asterisks designate the surface species. Growth of stoichiometric $Al_2O_3$ thin films with carbon incorporation less than 1.5 atomic % was confirmed by depth profiling Auger electron spectroscopy. Atomic force microscopy images show atomically flat and uniform surfaces. X-ray photoelectron spectroscopy and cross-sectional high resolution transmission electron microscopy of an $Al_2O_3$ film indicate that there is no distinguishable interfacial Si oxide layer except that a very thin layer of aluminum silicate may have been formed between the $Al_2O_3$ film and the Si substrate. C-V measurements of an $Al_2O_3$ film showed capacitance values comparable to previously reported values.