• Title/Summary/Keyword: sputtering

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Properties of the interfacial oxide and high-k dielectrics in $HfO_2/Si$ system ($HfO_2/Si$시스템의 계면산화막 및 고유전박막의 특성연구)

  • 남서은;남석우;유정호;고대홍
    • Proceedings of the Korea Crystallographic Association Conference
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    • 2002.11a
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    • pp.45-47
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    • 2002
  • 반도체 소자의 고집적화 및 고속화가 요구됨에 따라 MOSFET 구조의 게이트 절연막으로 사용되고 있는 SiO₂ 박막의 두께를 감소시키려는 노력이 이루어지고 있다. 0.1㎛ 이하의 소자를 위해서는 15Å 이하의 두께를 갖는 SiO₂가 요구된다. 하지만 두께감소는 절연체의 두께와 지수적인 관계가 있는 누설전류를 증가시킨다[1-3]. 따라서 같은 게이트 개패시턴스를 유지하면서 누설전류를 감소시키기 위해서는 높은 유전상수를 갖는 두꺼운 박막이 요구되는 것이다. 그러므로 약 25정도의 높은 유전상수를 갖고 5.2~7.8 eV 정도의 비교적 높은 bandgap을 갖으며, 실리콘과 열역학적으로 안정한 물질로 알려진 HfO2[4-5]가 최근 큰 관심을 끌고 있다. 본 연구에서는 HfO₂ 박막을 실제 소자에 적용하기 위하여 전극 및 열처리에 따른 HfO₂ 박막의 미세구조 및 전기적 특성에 관한 연구를 수행하였다. 이를 위해, HfO₂ 박막을 reactive DC magnetron sputtering 방법으로 증착하고, XRD, TEM, XPS를 사용하여 ZrO₂ 박막의 미세구조를 관찰하였으며, MOS 캐패시터 구조의 C-V 및 I-V 특성을 측정하여 HfO₂ 박막의 전기적 특성을 관찰하였다. HfO₂ 타겟을 스퍼터링하면 Ar 스퍼터링에 의해 에너지를 가진 산소가 기판에 스퍼터링되어 Si 기판과 반응하기 때문에 HfO₂ 박막 형성과 더불어 Si 기판이 산화된다[6]. 그래서 HfO₂같은 금속 산화물 타겟 대신에 순수 금속인 Hf 타겟을 사용하고 반응성 기체로 O₂를 유입시켜 타겟이나 시편위에서 high-k 산화물을 만들면 SiO/sub X/ 계면층을 제어할 수 있다. 이때 저유전율을 갖는 계면층은 증착과 열처리 과정에서 형성되고 특히 500℃ 이상에서 high-k/Si를 열처리하면 계면 SiO₂층은 증가하는 데, 이것은 산소가 HfO₂의 high-k 박막층을 뚫고 확산하여 Si 기판을 급속히 산화시키기 때문이다. 본 방법은 증착에 앞서 Si 표면을 희석된 HF를 이용해 자연 산화막과 오염원을 제거한 후 Hf 금속층과 HfO₂ 박막을 직류 스퍼터링으로 증착하였다. 우선 Hf 긍속층이 Ar 가스 만의 분위기에서 증착되고 난 후 공기중에 노출되지 않고 연속으로 Ar/O₂ 가스 혼합 분위기에서 반응 스퍼터링 방법으로 HfO₂를 형성하였다. 일반적으로 Si 기판의 표면 위에 자연적으로 생기는 비정질 자연 산화막의 두께는 10~15Å이다. 그러나 Hf을 증착한 후 단면 TEM으로 HfO₂/Si 계면을 관찰하면 자연 산화막이 Hf 환원으로 제거되기 때문에 비정질 SiO₂ 층은 관찰되지 않았다. 본 실험에서는 HfO2의 두께를 고정하고 Hf층의 두께를 변수로 한 게이트 stack의 물리적 특성을 살펴보았다. 선증착되는 Hf 금속층을 0, 10, 25Å의 두께 (TEM 기준으로 한 실제 물리적 두께) 로 증착시키고 미세구조를 관찰하였다. Fig. 1(a)에서 볼 수 있듯이 Hf 금속층의 두께가 0Å일때 13Å의 HfO₂를 반응성 스퍼터링 방법으로 증착하면 HfO₂와 Si 기판 사이에는 25Å의 계면층이 생기며, 이것은 Ar/O₂의 혼합 분위기에서의 스퍼터링으로 인한 Si-rich 산화막 또는 SiO₂ 박막일 것이다. Hf 금속층의 두께를 증가시키면 계면층의 성장은 억제되는데 25Å의 Hf 금속을 증착시키면 HfO₂ 계면층은 10Å미만으로 관찰된다. 그러므로 Hf 금속층이 충분히 얇으면 플라즈마내 산소 라디칼, 이온, 그리고 분자가 HfO₂ 층을 뚫고 Si 기판으로 확산되어 SiO₂의 계면층을 성장시키고 Hf 금속층이 두꺼우면 SiO/sub X/ 계면층을 환원시키면서 Si 기판으로의 산소의 확산은 막기 때문에 계면층의 성장은 억제된다. 따라서 HfO₂/Hf(Variable)/Si 계에서 HfO₂ 박막이 Si 기판위에 직접 증착되면, 순수 HfO₂ 박막의 두께보다 높은 CET값을 보이고 Hf 금속층의 두께를 증가시키면 CET는 급격하게 감소한다. 그러므로 HfO₂/Hf 박막의 유효 유전율은 단순 반응성 스퍼터링에 의해 형성된 HfO₂ 박막의 유전율보다 크다. Fig. 2에서 볼 수 있듯이 Hf 금속층이 너무 얇으면 계면층의 두께가 두꺼워 지고 Hf 금속층이 두꺼우면 HfO₂층의 물리적 두께가 두꺼워지므로 CET나 EOT 곡선은 U자 형태를 그린다. Fig. 3에서 Hf 10초 (THf=25Å) 에서 정전 용량이 최대가 되고 CET가 20Å 이상일 때는 high-k 두께를 제어해야 하지만 20Å 미만의 두께를 유지하려면 계면층의 두께를 제어해야 한다.

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Electrochemical Characteristics of Cu3Si as Negative Electrode for Lithium Secondary Batteries at Elevated Temperatures (리튬 이차전지 음극용 Cu3Si의 고온에서의 전기화학적 특성)

  • Kwon, Ji-Y.;Ryu, Ji-Heon;Kim, Jun-Ho;Chae, Oh-B.;Oh, Seung-M.
    • Journal of the Korean Electrochemical Society
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    • v.13 no.2
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    • pp.116-122
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    • 2010
  • A $Cu_3Si$ film electrode is obtained by Si deposition on a Cu foil using DC magnetron sputtering, which is followed by annealing at $800^{\circ}C$ for 10 h. The Si component in $Cu_3Si$ is inactive for lithiation at ambient temperature. The linear sweep thermammetry (LSTA) and galvano-static charge/discharge cycling, however, consistently illustrate that $Cu_3Si$ becomes active for the conversion-type lithiation reaction at elevated temperatures (> $85^{\circ}C$). The $Cu_3Si$ electrode that is short-circuited with Li metal for one week is converted to a mixture of $Li_{21}Si_5$ and metallic Cu, implying that the Li-Si alloy phase generated at 0.0 V (vs. Li/$Li^+$) at the quasi-equilibrium condition is the most Li-rich $Li_{21}Si_5$. However, the lithiation is not extended to this phase in the constant-current charging (transient or dynamic condition). Upon de-lithiation, the metallic Cu and Si react to be restored back to $Cu_3Si$. The $Cu_3Si$ electrode shows a better cycle performance than an amorphous Si electrode at $120^{\circ}C$, which can be ascribed to the favorable roles provided by the Cu component in $Cu_3Si$. The inactive element (Cu) plays as a buffer against the volume change of Si component, which can minimize the electrode failure by suppressing the detachment of Si from the Cu substrate.

Development of B4C Thin Films for Neutron Detection (스퍼터링 코팅기법을 이용한 중성자 검출용 B4C 박막 개발)

  • Lim, Chang Hwy;Kim, Jongyul;Lee, Suhyun;Cho, Sang-Jin;Choi, Young-Hyun;Park, Jong-Won;Moon, Myung Kook
    • Journal of Radiation Protection and Research
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    • v.40 no.2
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    • pp.79-86
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    • 2015
  • $^3He$ gas has been used for neutron monitors as the neutron converter owing to its advantages such as high sensitivity, good ${\gamma}$-discrimination capability, and long-term stability. However, $^3He$ is becoming more difficult to obtain in last few years due to a global shortage of $^3He$ gas. Accordingly, the cost of a neutron monitor using $^3He$ gas as a neutron converter is becoming more expensive. Demand on a neutron monitor using an alternative neutron conversion material is widely increased. $^{10}B$ has many advantages among various $^3He$ alternative materials, as a neutron converter. In order to develop a neutron converter using $^{10}B$ (actually $B_4C$), we calculated the optimal thickness of a neutron converter with a Monte Carlo simulation using MCNP6. In addition, a neutron converter was fabricated by the Ar sputtering method and the neutron signal detection efficiencies were measured with respect to various thicknesses of fabricated a neutron converter. Also, we developed a 2-dimensional multi-wire proportional chamber (MWPC) for neutron beam profile monitoring using the fabricated a neutron converter, and performed experiments for neutron response of the neutron monitor at the 30 MW research reactor HANARO at the Korea Atomic Energy Research Institute. The 2-dimensional MWPC with boron ($B_4C$) neutron converter was proved to be useful for neutron beam monitoring, and can be applied to other types of neutron imaging.

Effects of an $Al_2$O$_3$Surfasce Protective Layer on the Sensing Properties of $SnO_2$Thin Film Gas Sensors (Al$_2$O$_3$ 표면 보호층이 박막형 $SnO_2$ 가스센서의 감지 특성에 미치는 영향)

  • Seong, Gyeong-Pil;Choe, Dong-Su;Kim, Jin-Hyeok;Mun, Jong-Ha;Myeong, Tae-Ho
    • Korean Journal of Materials Research
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    • v.10 no.11
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    • pp.778-783
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    • 2000
  • Effects of the $Al_2$O$_3$surface protective layer, deposited on the SnO$_2$sensing layer by aerosol flame deposition (AFD) method, on the sensing properties of SnO$_2$thin film ags sensors were investigated.Effects of Pt doping to the $Al_2$O$_3$surface protective layer on the selectivity of CH$_4$ gas were also investigated. 0.3$\mu\textrm{m}$ thick SnO$_2$thin sensing layers on Pt electrodes were prepared by R.F. magnetron sputtering with R.F. power of 50 W, at working pressure of 4mTorr, and at 20$0^{\circ}C$ for 30 min. $Al_2$O$_3$surface protective layers on SnO$_2$layers were prepared by AFD using a diluted aluminum nitrade (Al(NO$_3$).9$H_2O$) solution. The sensitivity of CO gas in the SnO$_2$gas sensor with an $Al_2$O$_3$surface protective layer was significantly decreased. But that of CH$_4$gas remained almost same with pure SnO$_2$gas sensor. This result shows that the selectivity of CH$_4$gas is increased because of the $Al_2$O$_3$surface protective layer. In the case of SnO$_2$gas sensors with Pt-doped $Al_2$O$_3$surface protective layers, low sensing property to CO gas and high sensing property to CH$_4$were observed. This results in the increasing of selectivity of CH$_4$gas selectivity are discussed.

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Spectral Response of $TiO_{2}$/Se : Te Heterojunction for Color Sensor (컬러센서를 위한 $TiO_{2}$/Se : Te 이종접합의 스펙트럼 응답)

  • Woo, Jung-Ok;Park, Wug-Dong;Kim, Ki-Wan;Lee, Wu-Il
    • Journal of Sensor Science and Technology
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    • v.2 no.1
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    • pp.101-108
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    • 1993
  • $TiO_{2}$/Se : Te heterojunction for color sensor has been fabricated by RF reactive sputtering and thermal evaporation methods onto glass substrate. The optimum deposition condition of $TiO_{2}$ films was such that RF power was 120 W, substrate temperature was $100^{\circ}C$, oxygen concentration was 50%, working pressure was 50 mTorr for the $TiO_{2}$ film thickness of $1000{\AA}$. In this case, the optical transmittance of $TiO_{2}$ film at 550 nm-wavelength was 85%, resistivity was $2{\times}10^9{\Omega}{\cdot}cm$, refractive index was 2.3, and optical bandgap was 3.58 eV. The composition ratio of 0 to Ti by AES analysis was 1.7. When $TiO_{2}$ films were annealed at $400^{\circ}C$ for 30 min. in $O_{2}$ ambient, the optical transmittance of $TiO_{2}$ films at the wavelength range of $300{\sim}580$ nm was improved from 0 to 25%. When Se : Te films were annealed at $190^{\circ}C$ for 1 min., photosensitivity under illumination of 1000 lux was 0.75. The optical bandgap of Se : Te films was 1.7 eV. The structures of Se : Te films were the hexagonal with (100) and (110) orientation. The spectral response of a-Se was improved by the addition of Te, especially in the long wavelength region. The $TiO_{2}$/Se : Te heterojunction showed wide spectral response, and more improved one than that of a-Si film in the blue light region.

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Study on High Sensitivity Metal Oxide Nanoparticle Sensors for HNS Monitoring of Emissions from Marine Industrial Facilities (해양산업시설 배출 HNS 모니터링을 위한 고감도 금속산화물 나노입자 센서에 대한 연구)

  • Changhan Lee;Sangsu An;Yuna Heo;Youngji Cho;Jiho Chang;Sangtae Lee;Sangwoo Oh;Moonjin Lee
    • Journal of the Korean Society of Marine Environment & Safety
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    • v.28 no.spc
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    • pp.30-36
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    • 2022
  • A sensor is needed to continuously and automatically measure the change in HNS concentration in industrial facilities that directly discharge to the sea after water treatment. The basic function of the sensor is to be able to detect ppb levels even at room temperature. Therefore, a method for increasing the sensitivity of the existing sensor is proposed. First, a method for increasing the conductivity of a film using a conductive carbon-based additive in a nanoparticle thin film and a method for increasing ion adsorption on the surface using a catalyst metal were studied.. To improve conductivity, carbon black was selected as an additive in the film using ITO nanoparticles, and the performance change of the sensor according to the content of the additive was observed. As a result, the change in resistance and response time due to the increase in conductivity at a CB content of 5 wt% could be observed, and notably, the lower limit of detection was lowered to about 250 ppb in an experiment with organic solvents. In addition, to increase the degree of ion adsorption in the liquid, an experiment was conducted using a sample in which a surface catalyst layer was formed by sputtering Au. Notably, the response of the sensor increased by more than 20% and the average lower limit of detection was lowered to 61 ppm. This result confirmed that the chemical resistance sensor using metal oxide nanoparticles could detect HNS of several tens of ppb even at room temperature.