Atomic layer deposition of TiO2 and Al‐doped TiO2 films on Ir substrates for ultralow leakage currents

TiO₂ and Al‐doped TiO₂ (ATO) films were grown on Ir substrates by atomic layer deposition using O₃ as the oxygen source. With increasing O₃ feeding time, the crystalline structure of the TiO₂ films was transformed from anatase to rutile. Above an O₃ feeding time of 35 s, the films crystallized as only rutile due to the formation of IrO₂ layer at the interface. The TiO₂ and ATO films showed higher dielectric constants of 78 and 51, respectively. The films on Ir showed superior leakage properties compared to the films on Ru due to the high work‐function of Ir. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of crystalline structure of TiO2 substrates on initial growth of atomic layer deposited Ru thin films

Ru thin films were grown on polymorphic TiO₂ thin film substrates at 230 and 250 °C by atomic layer deposition using 2,4-(dimethylpentadienyl)(ethylcyclopentadienyl)Ru and an O₂ gas. While the Ru films grown on amorphous and rutile TiO₂ substrates showed a relatively long incubation cycle number of approximately 350 and 100 at 230 and 250 °C, respectively, the Ru films grown on anatase TiO₂ substrates exhibited a significantly shorter incubation delay which was attributed to the catalytic activity of anatase TiO₂. This difference in the incubation cycle affected the surface morphology of the Ru films on different TiO₂ substrates.     

Structural properties of Al2O3 dielectrics grown on TiN metal substrates by atomic layer deposition

We investigated on the structural properties of Al₂O₃ dielectrics grown on TiN metal substrates using an atomic layer deposition technique with tri-methyl-aluminum and either O₃ or H₂O as the precursor and oxidant, respectively. The structural and morphological features of these films were examined by atomic force microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy measurements. We find that Al₂O₃ dielectric films with the O₃ oxidant exhibit a rough morphology, a thick TiO₂ film, and a small amount of contaminants such as carbon and hydrogen. The reason for the rapid diffusion of oxygen atoms into the TiN lattice leads to the formation of TiO₂ layer on the TiN substrate. This is due to the higher oxidation potential of the O₃ compared to the H₂O.     

Oxidation and reduction of thin Ru films by gas plasma

The oxidation and reduction of Ru thin films grown on a Si(1 0 0) surface were studied by X-ray photoemission spectroscopy (XPS). Ru thin films were oxidized with O₂ plasma generated by an rf discharge, and their XPS spectra were measured. The spectra were decomposed into several components for Ru suboxides attributable to different stages of oxidation. After sufficient exposure to oxygen, a stoichiometric rutile RuO₂ layer was found to have formed near the surface. Thermal annealing at 500 K resulted in a thicker RuO₂ layer. Experiments demonstrated that the Ru oxide layer can be removed by H(D) atoms via the desorption of water molecules.     

Electron spin resonance investigation of the substitution of Fe3^＋ for Ti4^＋ ions in rutile TiO2 single crystal

A Fe doped rutile TiO 2 single crystal is grown in an O 2 atmosphere by the floating zone technique.Electron spin resonance (ESR) spectra clearly demonstrate that Fe 3+ ions are substituted for the Ti 4+ ions in the rutile TiO 2 matrix.Magnetization measurements reveal that the Fe:TiO 2 crystal shows paramagnetic behaviour in a temperature range from 5 K to 350 K.The Fe 3+ ions possess weak magnetic anisotropy with an easy axis along the c axis.The annealed Fe:TiO 2 crystal shows spin-glass-like behaviours due to the aggregation of the ferromagnetic clusters.     

Effect of amorphous TiO2 buffer layer on the phase formation of CaBi4Ti4O15 ferroelectric thin films

Amorphous buffer layers of TiO₂ were introduced between CaBi₄Ti₄O₁₅ thin films and Pt bottom electrodes through chemical solution deposition techniques. Several tens of nanometers thick alkoxy-derived TiO₂ layers were found to be critical for acceleration of the phase transition in the thin films. Unlike thin film crystallized directly onto a highly (111) oriented Pt bottom electrode, the thin film on an amorphous TiO₂ layer was almost single phase perovskite and showed random orientation. The crystallinity of the CaBi₄Ti₄O₁₅ thin film was much higher than that crystallized directly onto the Pt bottom electrode. The dielectric and ferroelectric properties of the CaBi₄Ti₄O₁₅/TiO₂ stacked thin films on Pt coated Si substrates are evaluated, leading to the potential of the amorphous buffer layer for the integrated devices being clarified. PACS 77.84.-s; 68.37.-d; 81.15.-z     

甲醇分子在金红石TiO2(110)和锐钛矿TiO2(001)表面吸附和反应的活性位点

通过高分辨的扫描隧道显微术研究并比较了金红石型TiO₂(110)-(1×1)和锐钛矿型TiO₂(001)-(1×4)两种表面的活性位点． 在金红石型TiO₂(110)-(1×1)表面, 观察到氧空位缺陷是O₂和CO₂分子的活性吸附位点,而五配位的Ti原子是水分子和甲醇分子的光催化反应活性位点．在锐钛矿型TiO₂(001)-(1×4)表面,观察到完全氧化的表面,Ti原子更可能是六配位的,H₂O和O₂分子均不易在这些Ti原子上吸附．经还原后表面出现富Ti的缺陷位点, 这些缺陷位点对H₂O和O₂分子表现出明显的活性． 锐钛矿型TiO₂(001)-(1×4)表面的吸附和反应活性并不具有很高的活性,某种程度上其表现出的活性似乎低于金红石型TiO₂(110)-(1×1)表面．     

Phase growth control in low temperature PLD Co: TiO2 films by pressure

This paper reports on the structural and optical properties of Co-doped TiO₂ thin films grown onto (0001)Al₂O₃ substrates by non-reactive pulsed laser deposition (PLD) using argon as buffer gas. It is shown that by keeping constant the substrate temperature at as low as 310 °C and varying only the background gas pressure between 7 Pa and 70 Pa, it is possible to grow either epitaxial rutile or pure anatase thin films, as well as films with a mixture of both polymorphs. The optical band gaps of the films are red shifted in comparison with the values usually reported for undoped TiO₂, which is consistent with n-type doping of the TiO₂ matrix. Such band gap red shift brings the absorption edge of the Co-doped TiO₂ films into the visible region, which might favour their photocatalytic activity. Furthermore, the band gap red shift depends on the films’ phase composition, increasing with the increase of the Urbach energy for increasing rutile content.     

Synthesis of spinel lithium titanate anodes incorporated with rutile titania nanocrystallites by spray drying followed by calcination

Lithium insertion into spinel Li₄Ti₅O₁₂ incorporated with rutile TiO₂ was investigated in order to clarify the redox mechanism responsible for the first plateau at 1.5 V vs. Li/Li⁺. Spherical Li₄Ti₅O₁₂ powders with an average diameter of 2-3 μm can be achieved by spray drying followed by sintering process. The Li/Ti molar ratio in the precursor is selected as the factor for preparing spinel Li₄Ti₅O₁₂ powders with different concentrations of rutile TiO₂. The specific capacity from the first plateau at 1.5 V contributes to the major portion in the overall capacity. The rutile TiO₂ in spinel Li₄Ti₅O₁₂ anodes tends to improve the specific capacity at the first plateau. This can be attributed to two possible reasons: (i) rutile TiO₂ provides an additional number of sites (i.e., oxygen octahedral vacancy in rutile TiO₂) for the Li insertion, and (ii) less amount of residual Li oxides results in high electronic conductivity. The Li₄Ti₅O₁₂ anodes display high rate capability with low irreversible capacity, indicating good reversibility of insertion/de-insertion of Li ions. The results presented in this work show unambiguously that the presence of rutile TiO₂ in spinel Li₄Ti₅O₁₂ has a positive effect on the performance promotion of Li₄Ti₅O₁₂ anodes.     

Preparation of synthetic rutile from high titanium slag using microwave heating

In this work, we demonstrate a novel synthesis of synthetic rutile from high titanium slag. This rutile TiO₂ was obtained by a simple one-step microwave roasting route. The influence of microwave roasting temperature and duration on the phase transformation of high titanium slag has been assessed. X-ray diffraction (XRD) results indicate that the intensity of anosovite (Fe₃Ti₃O₁₀) phase, which were the major phase of high titanium slag of carbon thermal reduction of ilmenite ores, decreased rapidly while the peaks for rutile TiO₂ phase increased with increase in the microwave roasting temperature. The scanning electron microscope (SEM) images revealed formation and the particle-size distribution of rutile TiO₂ phase. Based on XRD and SEM analysis, confirmed the dependence of phase structure, composition and crystallite size on the process conditions of microwave roasting.     

不同晶相结构和形貌TiO2负载Ru催化剂的CO选择甲烷化

用水热法得到的钛酸纳米纤维前体,通过不同后处理方法合成了多种纳米结构的TiO₂．采用N₂等温吸附和BET比表面、X射线衍射、透射电镜和能量分散X射线分析表征了TiO₂及负载Ru催化剂的微结构,包括比表面、晶相结构和形貌以及Ru纳米颗粒尺寸分布等．对负载Ru催化剂在富氢条件下CO选择甲烷化反应活性测试表明：金红石相TiO₂和TiO₂-B为载体负载的Ru催化剂比锐钛矿相TiO₂负载的Ru催化剂表现出更高的反应性能．其活性区别说明了不同晶相结构和形貌TiO₂载体与Ru纳米颗粒的相互作用存在差异．     

Oxidation of TiNi surface with hyperthermal oxygen molecular beams

We report results of our detailed studies on the initial oxidation process of TiNi with a 2 eV hyperthermal oxygen molecular beam (HOMB) and thermal O₂ in the backfilling. The oxidation processes are monitored by X-ray photoemission spectroscopy (XPS) measurements in conjunction with synchrotron radiation (SR). In the early stage of oxidation, the precursor mediated dissociative adsorption is the dominant reaction mechanism. In the oxide formation process at higher O coverage, HOMB has the advantage in the dissociation process of O₂ molecule and can grow TiO₂ layers with the underlying TiO_x-rich and/or Ni-rich layers. We succeeded in fabricating thick Ni-free TiO₂ layer, possibly blue colored rutile TiO₂, combining HOMB and surface annealing.     

过渡金属(Fe,Co,Ni,Zn)掺杂金红石TiO2的电子结构和光学性质

采用基于密度泛函理论的第一性原理方法对未掺杂以及不同浓度过渡金属Fe,Co,Ni,Zn掺杂金红石TiO₂的超晶胞体系进行了几何优化,并讨论了其晶格常数,电子能带结构和光学性质.研究结果表明:掺杂前后的晶格参数与实验值偏差在3.6%以下;适量的过渡金属掺杂不但影响体系能带结构,拓宽光吸收范围,而且扮演着俘获电子的重要角色,有利于光生电子-空穴对的有效分离以及增强光吸收能力;Fe,Co,Ni,Zn最佳理论掺杂体系分别为Ti_0.75Fe_0.25O₂,Ti_0.75Co_0.25O₂,Ti_0.75Ni_0.25O₂,Ti_0.83Zn_0.17O₂;Fe,Co,Ni3d态分裂为t_2g和e_g态,分别贡献于价带高能级和导带低能级部分,促进了电子-空穴对的生成,从而可提高TiO₂的光催化性能;Zn3d态电子成对填满轨道,不易被激发,故光催化活性无明显提高.     

Integration of individual TiO2 nanotube on the chip: Nanodevice for hydrogen sensing

Titania (TiO₂) exists in several phases possessing different physical properties. In view of this fact, we report on three types of hydrogen sensors based on individual TiO₂ nanotubes (NTs) with three different structures consisting of amorphous, anatase or anatase/rutile mixed phases. Different phases of the NTs were produced by controlling the temperature of post‐anodization thermal treatment. Integration of individual TiO₂ nanotubes on the chip was performed by employing metal deposition function in the focused ion beam (FIB/SEM) instrument. Gas response was studied for devices made from an as‐grown individual nanotube with an amorphous structure, as well as from thermally annealed individual nanotubes exhibiting anatase crystalline phase or anatase/rutile heterogeneous structure. Based on electrical measurements using two Pt complex contacts deposited on a single TiO₂ nanotube, we show that an individual NT with an anatase/rutile crystal structure annealed at 650 °C has a higher gas response to hydrogen at room temperature than samples annealed at 450 °C and as‐grown. The obtained results demonstrate that the structural properties of the TiO₂ NTs make them a viable new gas sensing nanomaterial at room temperature. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

光沉积Ru和RuO2的锐钛矿TiO2纳米片的光解水产氧

采用水热法以HF作为结构调控剂合成了主要暴露（001）面的锐钛矿TiO₂纳米片,通过光沉积方法分别合成了负载Ru和RuO₂物种的光催化剂。利用X射线衍射、透射电镜和氢气程序升温还原等分析表征了催化剂的结构性质。通过光解水产氧反应来研究催化剂的催化性能,详细考察了Ru含量、负载方式以及氧化和还原处理等因素的影响,光解水产氧速率的差异证明了Ru物种在不同晶面的电荷-空穴分离效应。与负载单一助催化剂的Ru/TiO₂和RuO₂/TiO₂样品相比,活性最优的0.5%Ru-1.0%RuO₂/TiO₂样品由于负载了双助催化剂,其催化活性得到更大的提高,证实了在锐钛矿TiO₂上的晶面电荷-空穴分离效应.     

Structural characterization of titanium oxide layers prepared by plasma based ion implantation with oxygen on Ti6Al4V alloy

Ti6Al4V alloy was implanted with oxygen by using plasma based ion implantation (PBII) at pulsed voltage ranging from −10 to −50 kV with a frequency of 100 Hz. In order to maintain a lower implantation temperature, an oil cooling working table was employed. The structure of the modified layers was characterized by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The results show that the thickness of the titanium oxide layer increases significantly with the increase of implanted voltage. The structure of the modified layer changes along depth. It is found that the surface layer consists of TiO₂, and the subsurface layer is a mixing structure of TiO_2, Ti₂O₃ and TiO. There is crystalline rutile phase existing in the modified layer of sample implanted at high implanted voltage. In addition, in the outmost modified surface, aluminum present as oxidized state, and vanadium could not be detected.     

Fabrication of coaxial nanowire heterostructures: SiO x nanowires with conformal TiO2 coatings

Silica nanowires, grown via the active oxidation of a silicon substrate, have been coated with TiO₂ using two coating methods: solution-based deposition of Ti-alkoxides and atomic layer deposition. Analysis of as-deposited and annealed films shows that it is possible to produce stable conformal coatings of either the anatase or rutile phases of TiO₂ on nanowires with diameters greater than 100 nm when annealed between 500–600°C and 800–900°C, respectively, with annealing at higher temperatures (1050°C) producing coatings with a highly facetted rutile morphology. The efficacy of the process is shown to depend on nanowire diameter, with nanowires having diameters less than about 100 nm fusing together during solution-based coating and decomposing during TiO₂ atomic layer deposition. The use of a suitable buffer layer is shown to be an effective means of minimizing nanowire decomposition. Finally, annealing coated nanowires under active oxidation conditions (1100°C) is shown to be an effective technique for depositing additional conformal SiO _x coatings, thereby providing a means of fabricating multi-layered coaxial nanostructures.     

Plasma-electrolytic formation, composition and catalytic activity of manganese oxide containing structures on titanium

In the present work, we report the data about formation of TiO₂-rutile or TiO₂ and Mn₂O₃, Mn₃O₄ containing oxide structures on titanium in aqueous electrolytes by means of plasma-electrolytic deposition. The layers formed are characterized by X-ray diffraction, electron probe microanalysis and scanning electron microscopy methods. The PEO coatings on titanium formed in sodium tetraborate solution contain the TiO₂ stabile rutile modification that is important when utilizing such a structure as a catalyst carrier. Manganese acetate adding into the electrolyte leads to formation of layers that contain Mn₂O₃, Mn₃O₄ and TiO₂-rutile in outer region. The manganese content in the surface layer depends on the formation conditions as well as on manganese acetate concentration in the electrolyte. Catalytic activity of the layers in CO → CO₂ reaction is studied in the static and flow conditions. The manganese-containing layers obtained possess the catalytic activity in CO → CO₂ oxidation reaction at the temperature range of 250-350 °C. The catalytic activity depends on the concentration and surface distribution of manganese as well as on the layers morphology.     

Effect of heat treatment on morphology, crystalline structure and photocatalysis properties of TiO2 nanotubes on Ti substrate and freestanding membrane

Highly ordered titanium oxide (TiO₂) nanotubes were prepared by electrolytic anodization of titanium electrodes. Morphological evolution and phase transformations of TiO₂ nanotubes on a Ti substrate and that of freestanding TiO₂ membranes during the calcinations process were studied by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction microscopy. The detailed results and mechanisms on the morphology and crystalline structure were presented. Our results show that a compact layer exists between the tubular layer and Ti substrate at 600 °C, and the length of the nanotubes shortens dramatically at 750 °C. The freestanding membranes have many particles on their tubes during calcinations from 450 to 900 °C. The TiO₂ nanotubes on the Ti substrate transform to rutile crystals at 600 °C, while the freestanding TiO₂ membranes retain an anatase crystal with increasing temperature to 800 °C. The photocatalytic activity of TiO₂ nanotubes on a Ti substrate annealed at different temperatures was investigated by the degradation of methyl orange in aqueous solution under UV light irradiation. Due to the anatase crystals in the tubular layer and rutile crystals in the compact layer, TiO₂ nanotubes annealed at 450 °C with pure anatase crystals have a better photocatalytic activity than those annealed at 600 °C or 750 °C.     

Dielectric response of Ba0.75Sr0.25TiO3 epitaxial films to electric field and temperature

The structure and dielectric parameters of the intermediate ferroelectric layer in the (001)SrRuO₃ ∥ (100)Ba_0.75Sr_0.25TiO₃ ∥ (001)SrRO₃ heterostructure grown by laser ablation on (001)La_0.294Sr_0.706Al_0.647Ta_0.353O₃ were studied. Tensile mechanical stresses accounted for the polar axis in the ferroelectric, being oriented predominantly parallel to the substrate plane. The remanent polarization in the Ba_0.75Sr_0.25TiO₃ layer increased approximately linearly with decreasing temperature in the interval 320–200 K. The real part of the dielectric permittivity of the intermediate ferroelectric layer reached a maximum ?′/?₀=4400 at T _M≈285 K (f=100 kHz). The narrow peak in the temperature dependence of the dielectric loss tangent for the Ba_0.75Sr_0.25TiO₃ ferroelectric layer, observed for T<T _M, shifted toward lower temperatures with decreasing frequency and increasing bias voltage applied to the electrodes.