掺CH4的SiCOH低介电常数薄膜结构与介电性能研究

以十甲基环五硅氧烷和甲烷作为反应气体,采用电子回旋共振等离子体化学气相沉积(ECR-CVD)方法制备了k=2.45,485℃下的热稳定性优良的SiCOH低介电常数薄膜.通过薄膜结构的FTIR谱分析,比较了十甲基环五硅氧烷(D5)液态源和不同甲烷流量下制备的薄膜的键结构差异,发现在沉积过程中甲烷含量的增大,一方面有利于D5源环结构的保留,另一方面有利于薄膜中形成高密度的CHn基团.高密度碳氢大分子基团的存在降低了薄膜密度,结合薄膜中形成的本构孔隙、低极化率Si-C键以及-OH键减少的共同作用,导致薄膜介电常数的降低.     

SiCOH低介电常数薄膜的性质和键结构分析

以十甲基环五硅氧烷为反应源、采用电子回旋共振等离子体化学气相沉积（ECR_CVD）方法制备了具有低介电常数，且电绝缘性能和热稳定性优良的SiCOH薄膜. 通过对富氏变换红外光谱(FTIR)的分析，比较了反应源和薄膜键结构的差异，证实薄膜中一方面保持了源中由Si—O—Si键构成的环结构，另一方面形成了由大键角Si—O—Si键构成的鼠笼式结构，在沉积过程中失去的主要是侧链的—CH3基团. 薄膜经过400℃热处理后，其介电常数由385降低到285，对其FTIR谱的分析指出，薄膜中鼠笼式结构比例的增加可能是薄膜介电常数降低的原因. 关键词： 低介电常数 SiCOH薄膜 化学键结构     

Si—OH基团对SiCOH低k薄膜性能的影响与控制

研究了十甲基环五硅氧烷(D5)的电子回旋共振等离子体沉积的SiCOH薄膜中Si—OH基团对介电性能和漏电流的影响.结果表明Si—OH含量的增大会导致介电常数k的增大、漏电流的降低和介电色散的增强.由于Si—OH结构的强极化补偿了薄膜密度减小带来的介电常数降低，导致总的介电常数k增大.高Si—OH含量下漏电流的降低是由于封端的Si—OH基团降低了薄膜中Si—O网络的连通概率p而导致网络电导下降的缘故.介电色散的增强与Si—OH封端结构的快极化过程有关.改变放电参数以提高电子能量，从而提高源的电离程度，使更多的Si—OH基团断裂并通过缩合反应形成Si—O—Si网络，可以进一步降低薄膜的介电常数. 关键词： SiCOH薄膜 Si—OH结构 介电性能 ECR放电等离子体     

O2掺杂对SiCOH低k薄膜结构与电学性能的影响

以十甲基环五硅氧烷(D5)和氧气(O₂)作为反应气体，采用电子回旋共振等离子体化学气相沉积(ECR-CVD)方法制备了k＝2.62的SiCOH薄膜.研究了O₂掺杂对薄膜结构与电学性能的影响.结果表明，采用O₂掺杂可以在保持较低介电常数的前提下极大地降低薄膜的漏电流，提高薄膜的绝缘性能，这与薄膜中Si-O立体鼠笼、Si-OH结构含量的提高有关. 关键词： SiCOH薄膜 2掺杂')" href="#">O₂掺杂 介电性能 键结构     

O2掺杂对SiCOH低k薄膜结构与电学性能的影响

以+甲基环五硅氧烷(D5)和氧气(O2)作为反应气体,采用电子回旋共振等离子体化学气相沉积(ECR-CvD)方法制备了κ=2.62的SiCOH薄膜.研究了O2掺杂对薄膜结构与电学性能的影响.结果表明,采用O2掺杂可以在保持较低介电常数的前提下极大地降低薄膜的漏电流,提高薄膜的绝缘性能,这与薄膜中Si-O立体鼠笼、Si-OH结构含量的提高有关.     

CHx掺杂SiCOH低介电常数薄膜的物性热稳定性分析

研究了真空热处理对掺CH.的SiCOH低介电常数薄膜的电流.电压(I-V)特性、电容.电压(C-V)特性、疏水性能以及微结构的影响.结果表明:在热处理过程中,热稳定性较差的碳氢基团发生了热解吸,使薄膜的漏电流减小、绝缘性能改善,并使薄膜的导电行为更趋于空间电荷限流过程.碳氢基团的热解吸使SiCOH/Si界面的界面态发生改变,导致SiCOH薄膜MIS结构的平带电压VFB发生漂移.封端的碳氢基团热解吸使薄膜表面的开口孔结构减少,薄膜表面变得更平整.但是碳氢基团为疏水基团,其热解吸导致薄膜的疏水性能降低.     

CHx掺杂SiCOH 低介电常数薄膜的物性热稳定性分析

研究了真空热处理对掺CH₄的SiCOH低介电常数薄膜的电流-电压(I-V)特性、电容-电压(C-V)特性、疏水性能以及微结构的影响. 结果表明：在热处理过程中,热稳定性较差的碳氢基团发生了热解吸,使薄膜的漏电流减小、绝缘性能改善,并使薄膜的导电行为更趋于空间电荷限流过程. 碳氢基团的热解吸使SiCOH/Si界面的界面态发生改变,导致SiCOH薄膜MIS结构的平带电压V_FB发生漂移. 封端的碳氢 关键词： SiCOH薄膜 热处理 结构与性能     

纳电子器件中的超低介电常数材料与多孔SiCOH薄膜研究

65nm以下线宽的纳电子器件，要求采用介电常数k小于2的超低介电常数材料作为层间和线间绝缘介质，等离子体增强的化学气相沉积技术制备的硅基纳米多孔薄膜，提供了实现k〈2的可能性，多孔SiCOH薄膜成为最具希望的候选材料，但是，纳米孔的引入带来了材料其他性能恶化、集成工艺困难、薄膜微结构分析等许多新问题．文章介绍了多孔SiCOH（超）低k薄膜研究的主要进展及面临的挑战．     

微波电子回旋共振等离子体增强化学气相沉积法沉积氟化非晶碳薄膜的研究

使用三氟甲烷和苯的混合气体,利用微波电子回旋共振等离子体增强化学气相沉积法制备了F/C比在0.11—0.62之间的α-C∶F薄膜.研究了微波功率对薄膜沉积和结构的影响,发现微波功率的升高提高了薄膜的沉积速率,降低了薄膜的F/C比,也降低了薄膜中CF和CF₃基团的密度,而使CF₂基团的密度保持不变.在高微波功率下可以获得主要由CF₂基团和C=C结构组成的α-C∶F薄膜.薄膜的介电频率关系(1×10³—1×10⁶Hz)和损耗频率关系(1×10²—1×10⁵Hz)均呈指数规律减小,是缺陷中心间简单隧穿引起的跳跃导电所致.α-C∶F薄膜的介电极化主要来源于电子极化 关键词： 氟化非晶碳薄膜 ECR等离子体沉积 键结构 介电性质     

热退火对等离子体增强化学气相沉积SiCOH薄膜结构与性能的影响

热退火是多孔低介电常数薄膜制备过程中的重要一环, 对薄膜结构及性能具有重要影响. 本文以四乙氧基硅烷和双戊烯为前驱体, 采用等离子体增强化学气相沉积方法制备了SiCOH薄膜, 对其进行了氮气氛围下的热退火处理, 分析了热退火对薄膜结构与性能的影响, 探究了退火过程中薄膜结构变化的可能的反应机理. 傅里叶变换红外光谱和固体核磁共振谱结果表明, 沉积薄膜是一种有机无机杂化薄膜. 退火过程中, 薄膜中的-CH₂, -CH₃等有机组分被分解除去, 形成了以稳定的Si-O-Si等无机组分为骨架的多孔结构, 并通过氮气吸附/脱附等温线测试得到了验证. 在此期间, 薄膜骨架微结构亦发生一系列调整, C=C, Si-C含量增加, Si、O、C等元素间发生进一步键合. C=C 含量的提高, 使得薄膜的消光系数和漏电流密度增大. 实验证明, 退火后薄膜具有低折射率、低介电常数特性, 是一类具有优异的介电性能和力学性能的材料, 作为芯片后端互连层间介质具有极大的应用潜力.     

Effect of humidity and UV-assistance on the preparation of erbium doped alumina by aerosol MOCVD process

The effect of deposition temperature, relative humidity of carrier gas and UV-assistance on the growth of Erbium-doped aluminium oxide films has been studied. The films were prepared from aluminium acetylacetonate (Al(C₅H₇O₂)₃) and erbium (III) Tris(2,2,6,6-tetramethyl-3,5-heptanedionate) (Er(TMHD)₃) by UV and aerosol-assisted metal-organic chemical vapour deposition, using air with controlled humidity as carrier gas. Amorphous transparent films were deposited between 350 and 460 °C. It was observed that UV assistance allows a large decrease down to 5 kJ/mol of the activation energy of the deposition reaction for deposition temperatures lower than 420 °C. More over, depositing under high air humidity induced higher deposition rate, lower level of organic contamination and higher film density. Under these conditions Er-doped aluminium oxide films with a refractive index value of 1.71 were obtained at 460 °C.     

The 1.58 μm transparency window of methane (6165-6750 cm): Empirical line list and temperature dependence between 80 and 296 K

The empirical line parameters of over 12,000 methane transitions have been obtained at 80 K in the 1.58 μm transparency window (6165-6750 cm⁻¹) which is of importance for planetary applications. This line list (WKC-80K) was constructed from high sensitivity spectra of normal abundance methane recorded by CW-Cavity Ring Down Spectroscopy at low temperature. The minimum intensity reported is on the order of 5×10⁻³⁰ cm/molecule. High resolution Fourier transform spectra have also been recorded using enriched CH₃D samples at 90-120 K in order to facilitate identification of monodeuterated methane features in the methane line list at 80 K. The CH₃D relative contribution in the considered region is observed to be much larger at 80 K than at room temperature. In particular, CH₃D is found dominant in a narrow spectral window near 6300 cm⁻¹ corresponding to the highest transparency region.Using a similar line list constructed at room temperature (Campargue A, Wang L, Liu AW, Hu SM and Kassi S. Empirical line parameters of methane in the 1.63-1.48 μm transparency window by high sensitivity Cavity Ring Down Spectroscopy. Chem Phys 2010;373:203-10.), the low energy values of the transitions observed both at 80 K and at room temperature were derived from the variation of their line intensities. Empirical lower states and J-values have been obtained for 5671 CH₄ and 1572 CH₃D transitions representing the most part of the absorbance in the region. The good quality of these derived energy values is demonstrated by the marked propensity of the corresponding CH₄ lower state J values to be close to integers. The WKC line lists at 80 K and room temperature provided as Supplementary Material allow one accounting for the temperature dependence of methane absorption between these two temperatures. The importance of the 80 K line list for the study of Titan and other methane containing planetary atmospheres is underlined and further improvements are proposed. The resulting information will advance the theoretical modeling of the methane spectrum in the 1.58 μm transparency window.     

The CH3D absorption spectrum in the 1.58 μm transparency window of methane: Empirical line lists at 81 K and 294 K and temperature dependence

In spite of its low isotopic abundance in methane (about 5×10⁻⁴), CH₃D contributes greatly to the very weak absorption in the 1.58 μm methane transparency window. This methane window deserves to be characterized in details because it is important for planetary applications in particular for Titan and the giant planets. In this work, we recorded the CH₃D spectrum by high sensitivity differential absorption spectroscopy (α_min≈5×10⁻⁸ cm⁻¹) both at room temperature and at 81 K. A list of more than 9000 lines was constructed from the 81 K spectrum for the 6099–6530 cm⁻¹ region. In order to get the temperature dependence of the line intensities, the low energy values have to be determined. The rovibrational assignments available in the literature provide low energy values for about 380 strong transitions of the region. This is insufficient to characterize the temperature dependence of the CH₃D absorption between 6200 and 6400 cm⁻¹. In this interval, a list of 5500 lines was constructed from the room temperature spectrum. The empirical energy values of the transitions were derived from the ratio of the intensities at 81 K and 294 K. The exact and empirical lower state energies included in the final line lists provided as Supplementary Material, allow for accounting for the temperature dependence of the CH₃D spectrum in the entire 6099–6530 cm⁻¹ region.Our measurements have been compared to the spectroscopic parameters and assignments available in the literature in particular those adopted in the HITRAN database. Improvements and corrections are proposed for the wavenumber calibration and for some lower state energies.     

The properties of boron carbide/silicon heterojunction diodes fabricated by Plasma-Enhanced Chemical Vapor Deposition

p-n heterojunction diodes have been fabricated from boron carbide (B_1–x C _x ) and n-type Si(111). Boron carbide thin films were deposited on Si(111) using Plasma-Enhanced Chemical Vapor Deposition (PECVD) from nido-pentaborane (B₅H₉) and methane (CH₄). Composition of boron carbide thin films was controlled by changing the relative partial pressure ratio between nido-pentaborane and methane. The properties of the diodes were strongly affected by the composition and thickness of boron carbide layer and operation temperatures. Boron carbide/silicon heterojunction diodes show rectifying properties at temperatures below 300° C. The temperature dependence of reverse current is strongly dependent upon the energy of the band gap of the boron carbide films.     

A high level computational study of the CH4/CF4 dimer: how does it compare with the CH4/CH4 and CF4/CF4 dimers?

The interaction within the methane–methane (CH₄/CH₄), perfluoromethane–perfluoromethane (CF₄/CF₄) methane–perfluoromethane dimers (CH₄/CF₄) was calculated using the Hartree–Fock (HF) method, multiple orders of Møller–Plesset perturbation theory [MP2, MP3, MP4(DQ), MP4(SDQ), MP4(SDTQ)], and coupled cluster theory [CCSD, CCSD(T)], as well as the PW91, B97D, and M06-2X density functional theory (DFT) functionals. The basis sets of Dunning and coworkers (aug-cc-pVxZ, x?=?D, T, Q), Krishnan and coworkers [6-311++G(d,p), 6-311++G(2d,2p)], and Tsuzuki and coworkers [aug(df, pd)-6-311G(d,p)] were used. Basis set superposition error (BSSE) was corrected via the counterpoise method in all cases. Interaction energies obtained with the MP2 method do not fit with the experimental finding that the methane–perfluoromethane system phase separates at 94.5?K. It was not until the CCSD(T) method was considered that the interaction energy of the methane–perfluoromethane dimer (?0.69?kcal?mol^?1) was found to be intermediate between the methane (?0.51?kcal?mol^?1) and perfluoromethane (?0.78?kcal?mol^?1) dimers. This suggests that a perfluoromethane molecule interacts preferentially with another perfluoromethane (by about 0.09?kcal?mol^?1) than with a methane molecule. At temperatures much lower than the CH₄/CF₄ critical solution temperature of 94.5?K, this energy difference becomes significant and leads perfluoromethane molecules to associate with themselves, forming a phase separation. The DFT functionals yielded erratic results for the three dimers. Further development of DFT is needed in order to model dispersion interactions in hydrocarbon/perfluorocarbon systems.     

Role of carbon in the formation of hard Ge1−xCx thin films by reactive magnetron sputtering

We have deposited germanium carbide (Ge_1−xC_x) films on Si(1 0 0) substrate via radio-frequency (RF) reactive magnetron sputtering in a CH₄/Ar mixture discharge, and explored the effects of carbon content (x) on the chemical bonding and hardness for the obtained films. We find that x significantly influences the chemical bonding, which leads to a pronounced change in the hardness of the film. To reveal the relationship between the chemical bonding and hardness, first-principles calculations have been carried out. It is shown that as x increases from 0 to 0.33, the fraction of sp³ C-Ge bonds in the film increases at the expense of Ge-Ge bonds, which promotes formation of a strong covalently bonded network, and thus enhances the hardness of the film. However, as x further increases from 0.33 to 0.59, the fraction of sp³ C-Ge bonds in the film gradually reduces, while that of sp³ C-H and graphite-like sp² C-C bonds increases, which damages the compact network structure, resulting in a sharp decrease in the hardness. This investigation suggests that the medium x (0.17<x<0.40) is most favorable to the preparation of hard Ge_1−xC_x films due to the formation of dominant sp³ C-Ge bonds.     

类富勒烯纳米晶CNx薄膜及其场致电子发射特性

利用微波等离子体增强化学气相沉积技术制备出了CN_x薄膜,并利用x射线光电子能谱、x射线衍射、扫描电子显微镜和Raman光谱等测试手段对所制备的CN_x薄膜的微结构和成分进行了分析.研究了其场致电子发射特性.发现薄膜的结构和场发射特性与反应系中的甲烷、氮气及氢气的流量比有关,当甲烷、氢气及氮气流量比为8/50/50 sccm时,制备的薄膜具有弯曲层状的纳米石墨晶体结构（类富勒烯结构）和很好的场发射特性.场发射阈值电场降低至1.1V/μm.当电场为5.9V/μm时,平 关键词： 类富勒烯 x薄膜')" href="#">CN_x薄膜 场致电子发射 微波等离子体增强化学气相沉积     

Raman spectroscopic characterization of CH4 density over a wide range of temperature and pressure

The positions of the CH₄ Raman ν₁ symmetric stretching bands were measured in a wide range of temperature (from −180 °C to 350 °C) and density (up to 0.45 g/cm³) using high‐pressure optical cell and fused silica capillary capsule. The results show that the Raman band shift is a function of both methane density and temperature; the band shifts to lower wavenumbers as the density increases and the temperature decreases. An equation representing the observed relationship among the CH₄ ν₁ band position, temperature, and density can be used to calculate the density in natural or synthetic CH₄‐bearing inclusions. Copyright © 2014 John Wiley & Sons, Ltd.     

The effect of Si surface nitridation on the interfacial structure and electrical properties of (La2O3)0.5(SiO2)0.5 high-k gate dielectric films

Thermal stability, interfacial structures and electrical properties of amorphous (La₂O₃)_0.5(SiO₂)_0.5 (LSO) films deposited by using pulsed laser deposition (PLD) on Si (1 0 0) and NH₃ nitrided Si (1 0 0) substrates were comparatively investigated. The LSO films keep the amorphous state up to a high annealing temperature of 900 °C. HRTEM observations and XPS analyses showed that the surface nitridation of silicon wafer using NH₃ can result in the formation of the passivation layer, which effectively suppresses the excessive growth of the interfacial layer between LSO film and silicon wafer after high-temperature annealing process. The Pt/LSO/nitrided Si capacitors annealed at high temperature exhibit smaller CET and EOT, a less flatband voltage shift, a negligible hysteresis loop, a smaller equivalent dielectric charge density, and a much lower gate leakage current density as compared with that of the Pt/LSO/Si capacitors without Si surface nitridation.