Diffusion reaction of oxygen in HfO2/SiO2/Si stacks

We study the oxidation mechanism of silicon in the presence of a thin HfO2 layer. We performed a set of annealing in 18O2 atmosphere on HfO2/SiO2/Si stacks observing the 18O distribution in the SiO2 layer with time-of-flight secondary ion mass spectrometry (ToF-SIMS). The 18O distribution in HfO2/SiO2/Si stacks upon 18O2 annealing suggests that what is responsible for SiO2 growth is the molecular O2, whereas no contribution is found of the atomic oxygen to the oxidation. By studying the dependence of the oxidation velocity from oxygen partial pressure and annealing temperature, we demonstrate that the rate-determining step of the oxidation is the oxygen exchange at the HfO2/SiO2 interface. When moisture is chemisorbed in HfO2 films, the oxidation of the underlying silicon substrate becomes extremely fast and its kinetics can be described as a wet silicon oxidation process. The silicon oxidation during O2 annealing of the atomic layer deposited HfO2/Si is fast in its early stage due to chemisorbed moisture and becomes slow after the first 10 s.     

Structural and electronic properties of HfO2 films on Si through H2O2 wet oxidation with improved thermal stability

The thermal stability and material properties of HfO₂ thin films on Si substrates with and without H₂O₂ wet chemical oxidation were investigated. The HfO₂ samples were deposited through plasma-enhanced atomic layer deposition and subjected to thermal annealing. They were then examined using X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, reflection electron energy loss spectroscopy, and conductive atomic force microscopy. For the Si substrate without H₂O₂ wet chemical oxidation, a native oxide (~1.8 nm) was formed on the substrate before HfO₂ deposition. After the annealing process at 600°C, the band gap (E_g) of the HfO₂ films increased from 6.0 to 6.2 eV due to the diffusion of Si into HfO₂. Furthermore, the conduction and valence band offsets (ΔE_c and ΔE_v, respectively) between HfO₂ and Si changed from 1.02 to 1.42 and 3.86 to 3.66 eV, respectively. After the H₂O₂ wet oxidation of the Si substrate, a 1.5-nm chemical oxide was formed instead of a native oxide. The band offset and E_g values of HfO₂ were similar before and after 600°C annealing (ΔE_v = 3.86 eV, ΔE_c = 1.02 eV, and E_g = 6.0 eV), implying the high thermal stability of the HfO₂ films. Accordingly, wet oxidation not only prevents diffusion from chemical oxide but also markedly improves the oxide leakage current, which is useful for developing highly efficient and thermally stable HfO₂ gate oxides in Si-based integrated circuit devices.     

Round-robin test of medium-energy ion scattering for quantitative depth profiling of ultrathin HfO2/SiO2/Si films

Medium-energy ion scattering (MEIS) has been used for quantitative depth profiling with single atomic layer resolution to determine the composition, thickness, and interface structure of ultrathin films and nanoparticles. To assure the consistency of the MEIS analysis, an international round-robin test (RRT) with nominally 1-, 3-, 5-, and 7-nm thick HfO₂ films was conducted among 12 institutions. The measurements were performed at each participating laboratory under their own conditions, and the collected data were analyzed. For the data analysis, the Moliere potential, the stopping and range of ions in matter (SRIM) 95 and new fitted electronic stopping power and the Chu straggling were used. For analyzing the MEIS data from the magnetic sector and electrostatic analyzers, the neutralization corrections of Marion and Young for 100-keV H⁺ and He⁺ ions and of Armstrong for 400- to 500-keV He⁺ ions were used. The standard deviations were 5.3% for the composition, 15.3% for the thickness, and 13.3% for the Hf content, and they were improved to 7.3%, 4.5%, and 7.0% by using refitted electronic stopping powers based on the experimental data. Hence, this study suggests that correct electronic stopping powers are critical for quantitative MEIS analysis.     

About the synthesis and thermal stability of SiO2-aerogel

Aerogels are extremely porous high-tech materials based on inorganic oxides, especially silica. The paper describes synthesis and properties of SiO₂-aerogel, and changes occurring during heating of SiO₂-aerogel in the temperature range from 20 to 1000°C. Four thermoanalytical methods were used: Thermodilatometry, Differential thermal analysis, Thermogravimetry and Derivative thermogravimetry.     

Characterization of various crystalline structures at the SiO2/Si interface by positrons

The nature of the interface of the Si (0 0 1) surface with grown, native oxide is examined by a slow-positron beam equipped with coincidence Doppler broadening (DB). Measurements are combined with theoretical calculations of high-momentum DB profiles of Si, divacancy in Si, Brazilian quartz and the interface itself. From this comparison, the conclusion is drawn that an ordered structure exists at the interface. This structure resembles low quartz or a SiO₂ structure with a lower density than low quartz.     

Surface oxidation states in Si/SiO2 nanostructures prepared from Si/SiO2 mixtures

Silica nanospheres have been produced by a novel technique where surface Si oxidation states can be adjusted using the ratio of metalloid ions/metalloid atoms in the starting mixture. When the proportions of Si4+/Si0 are equal in the synthesis, the resulting solid is considerably more reactive than Cab-O-Sil toward the phenol hydroxylation reaction and the surface shows an average Si oxidation state of +3. On the other hand, those silica nanospheres, produced from a mixture of Si4+/Si0 = 0.25, showed a lower reactivity comparable to that of Cab-O-Sil which XPS demonstrates has a surprisingly low average Si oxidation state close to +1. We speculate that the silicon surface oxidation state and the number of surface silanol groups play important roles in determining the activity of the solid toward the phenol hydroxylation reaction. In expanding our earlier report4 on the copper-silica system, we establish that the surface chemistry of the silica nanospheres is apparently different from that of fumed, amorphous silica. These results suggest that we are developing a technique that can be generalized to create supported, mixed metal oxides having tunable average surface oxidation states.     

Photoluminescence from (Si/SiO2)n superlattices and their use as emitters in [SiO2/Si]n SiO2 [Si/SiO2]m microcavities

Si/SiO2 superlattices are recently under investigation to add optical functionality to silicon based microelectronics. In such superlattices quantum-confinement should drive Si to become a good light emitter. Emission properties can be further improved and controlled by placing the emitter in optical microcavities. In this paper emission properties of (Si/SiO2), superlattices grown by Low Pressure Chemical Vapour Deposition will be compared with the ones obtained by other growth techniques and the origin of the emission will be discussed. Emission properties can be further improved and controlled by placing the emitter in optical microcavities. Optical properties of microcavities produced with standard complementary metal-oxide-semiconductor techniques containing Si/SiO2 superlattices as light emitter will be reviewed and a comparison between properties estimated from calculations and experiments will be given.     

Effects of post-deposition annealing on chemical composition of SiNx film in SiO2/SiNx/SiO2/Si stacked structure

To systematically evaluate the quality of SiN_x films in multi-stacked structures, we investigated the effects of post-deposition annealing (PDA) on the film properties of SiN_x within the SiO₂/SiN_x/SiO₂/Si stacked structure by performing X-ray photoelectron spectroscopy (XPS), X-ray reflectivity (XRR), Fourier transform infrared (FT-IR) spectroscopy, and scanning transmission electron microscope–electron energy loss spectroscopy (STEM-EELS) analyses. The XPS results showed that PDA induces the oxidation of the SiN_x layer. In particular, new finding is that Si-rich SiN_x in the SiN_x layer is preferentially oxidized by PDA even in multi-stacked structure. The XRR results showed that the SiN_x layer becomes thinner, whereas the interface layer between the SiN_x layer and Si becomes thicker. It is concluded by STEM-EELS and XPS that this interface layer is SiON layer. The density of N–H and Si–H bonding within the stacked structure strongly depends on the PDA temperature. Our study helps elucidate the properties of SiN_x films in stacked structures from various perspectives.     

Composition and thermal stability of SiO2-based hybrid materials TEOS-MTEOS system

Hybrid materials with different amounts of organics permanently bound on the inorganic network obtained in the TEOS-MTEOS (tetraethoxysilan-methyltriethoxysilan) system are used for obtaining coatings with different optical and mechanical properties. To study the thermal stability of the mentioned materials, compositions with different molar ratios of the precursors were prepared. The influence of the solvent and water amounts on the gelation process was also investigated. The gels obtained were characterised by IR spectrometry and their decomposition temperatures were determined by DTA/TG. Thermal stability of the gels is rather influenced by their composition than the conditions of the gelation process. This revised version was published online in July 2006 with corrections to the Cover Date.     

尼龙6/SiO_2纳米复合材料的制备及其力学性能和热稳定性

以表面含有氨基的可反应性纳米SiO2(RNS-A)和表面含有烷基碳链的可分散性纳米SiO2(DNS-3)作为填料,利用原位聚合法制备了尼龙6/SiO2纳米复合材料(相应的复合材料分别简记为RPA和DP3);采用透射电子显微镜观察了复合材料中纳米SiO2的表面形貌,并利用热失重分析仪测定了复合材料的热稳定性,进而考察了纳米SiO2表面功能基团对尼龙6力学性能和热稳定性的影响.结果显示,纳米SiO2能够很好地分散在尼龙6基体中,并使尼龙6的热分解温度提高10℃左右.与此同时,RPA的最大拉伸强度和冲击强度较纯尼龙6的分别提高34.5%和12.5%,DP3的最大拉伸强度和冲击强度分别提高18.2%和45.7%.这表明两种纳米SiO2均可以有效地提高尼龙6的力学性能和热稳定性;可以推测,纳米SiO2的增强效应与其在尼龙6基体材料中的分散和界面作用有关.     

TiO2/SiO2复合材料的制备与表征

以钛酸四丁酯和正硅酸乙酯为原料,采用溶胶凝胶法和水解法相结合,在室温下制备了两种形态的TiO2/SiO2复合材料.采用透射电镜、傅里叶红外光谱、X射线衍射和紫外-可见光谱等测试方法对所得复合材料进行了表征,并对其光催化降解甲基橙溶液的性能进行了研究.结果表明:对TiO2进行表面处理制备的TiO2/SiO2复合材料比以SiO2为载体制备的TiO2/SiO2复合材料在光催化和抗紫外线性能上更优异.     

TiO2/SiO2气凝胶微球的制备及其表征

以TiOSO4和硅溶胶为原料, 加入甲酰胺作为干燥控制化学添加剂, 采用W/O乳状液中的溶胶-凝胶法制备TiO2/SiO2凝胶微球, 通过正硅酸乙酯母液浸泡、溶剂交换、陈化和常压干燥技术制备TiO2/SiO2气凝胶微球, 采用光学显微镜、SEM、TEM和BET比表面及孔分布测定等手段对所得样品进行表征. 典型的气凝胶微球样品是由粒径15 nm左右, 粒度分布相当均匀的球状纳米粒子构成的轻质纳米多孔材料, 表观密度为177 kg•m-3, 比表面积372 m2•g-1, 平均孔径22.78 nm, 孔隙率高达92.0％, 微球的宏观粒径为50 m. 依据制备条件的变化, TiO2/SiO2气凝胶微球的宏观粒径可控在10～200 m之间, 表观密度为150～300 kg•m-3, 比表面积为300～400 m2•g-1, 平均孔径在18.71～22.78 nm之间变化.     

Iron adsorption on SiO2/Si(111)

The adsorption of ferric and ferrous iron onto the native oxide of the SiO₂/Si(111) surface has been evaluated using X‐ray photoelectron spectroscopy (XPS). Through a series of immersion experiments, performed at room temperature and pH 1, it has been shown that the ferric species is strongly adsorbed onto the hydrophilic surface, while ferrous iron remains in solution. Dehydroxylation of the silica surface by etching with hydrofluoric acid reduces the concentration of receptive Si‐OH groups, thereby limiting iron adsorption. The experiments were reproduced in a combined ultrahigh vacuum‐electrochemical system (UHV‐EC), which allowed a carbon‐free surface to be prepared before contacting the iron solutions, and confirmed the strong affinity of ferric iron towards the SiO₂/Si(111) surface. Copyright © 2007 John Wiley & Sons, Ltd.     

Gd2CuO4薄膜与Si, SiO2/Si基底界面相互作用研究

采用XRD和俄歇电子能谱（AES）等技术研究了钙钛矿型Gd2CuO4薄膜与基底Si和SiO2/Si的界面相互作用,发现衬底对Gd2CuO4薄膜的晶化特性有很大影响,以单晶Si为基镀时,Gd2CuO4薄膜经600℃热处理1h即可形成钙钛矿型晶体结构,而以SiO2/Si为基底时,经700℃热处理1h能形成较完善的钙钛矿型晶体结构,Gd2CuO4薄膜的晶粒度随热处理温度的升高而增大,热处理时间对晶粒度则影响较小,AES深度剖析表明,形成的薄膜组成均匀,在界面上有一定程度的扩散,以Si为基底时,Gd2CuO4与基底Si相互扩散,以SiO2/Si为基底时则主要是薄膜中Gd,Cu向SiO2层中的扩散,AES线性分析表明,在薄膜与基底的界面上,各元素的俄歇电子动能发现位移,表明基底作用使界面上元素的化学环境发生了变化。     

Li2B12Si2: the first ternary compound in the system Li/B/Si: synthesis, crystal structure, hardness, spectroscopic investigations, and electronic structure

We present the synthesis, crystal structure, hardness, IR/Raman and UV/Vis spectra, and FP-LAPW calculations of the electronic structure of Li(2)B(12)Si(2), the first ternary compound in the system Li/B/Si. Yellow, transparent single crystals were synthesized from the elements in tin as solvent at 1500 degrees C in h-BN crucibles in arc-welded Ta ampoules. Li(2)B(12)Si(2) crystallizes orthorhombic in the space group Cmce (no. 64) with a=6.1060(6), b=10.9794(14), c=8.4050(8) A, and Z=4. The crystal structure is characterized by a covalent network of B(12) icosahedra connected by Si atoms and Li atoms located in interstitial spaces. The structure is closely related to that of MgB(12)Si(2) and fulfils the electron-counting rules of Wade and Longuet-Higgins. Measurements of Vickers (H(V)=20.3 GPa) and Knoop microhardness (H(K)=20.4 GPa) revealed that Li(2)B(12)Si(2) is a hard material. The band gap was determined experimentally and calculated by theoretical means. UV/Vis spectra revealed a band gap of 2.27 eV, with which the calculated value of 2.1 eV agrees well. The IR and Raman spectra show the expected oscillations of icosahedral networks. Theoretical investigations of bonding in this structure were carried out with the FP-LAPW method. The results confirm the applicability of simple electron-counting rules and enable some structural specialties to be explained in more detail.     

纳米复合材料CoFe2O4/SiO2的制备和表征

采用溶胶-凝胶法制备了(CoFe2O4)x/(SiO2)1-x纳米复合材料. 利用TG/DTA, XRD和Mssbauer效应研究了热处理过程中干凝胶的变化及样品的结构、晶粒尺寸和磁性. 结果表明, 随着SiO2含量的增加, 样品中CoFe2O4的晶粒尺寸和内磁场逐渐变小, 并从磁有序状态转变为超顺磁状态.     

负载型Ni-B非晶态合金催化剂的表征

作为一种新型的催化加氢材料 ,非晶态合金具有高的活性及选择性 ,近年来引起了人们的注意［１］．尤其将非晶态合金负载化 ,可以提高其表面积和热稳定性 ,抑制非晶态合金的晶化 ,增加了非晶态合金催化剂的工业应用前景．文献已报导了对负载型非晶态合金催化剂的制备、化学及结构修饰、催化性能、催化剂的失活及抗硫性能的研究［２,３］．应该说 ,相比于淬冷法和化学还原法制备的超细微粒非晶态合金 ,负载化有效地提高了非晶态合金的热稳定性．但是 ,当负载型非晶态合金催化剂应用于催化反应时 ,仍存在着结构逐渐变化的过程［４］．本文以Ｎ…