Conformity and structure of titanium oxide films grown by atomic layer deposition on silicon substrates

Conformity and phase structure of atomic layer deposited TiO₂ thin films grown on silicon substrates were studied. The films were grown using TiCl₄ and Ti(OC₂H₅)₄ as titanium precursors in the temperature range from 125 to 500 °C. In all cases perfect conformal growth was achieved on patterned substrates with elliptical holes of 7.5 μm depth and aspect ratio of about 1:40. Conformal growth was achieved with process parameters similar to those optimized for the growth on planar wafers. The dominant crystalline phase in the as-grown films was anatase, with some contribution from rutile at relatively higher temperatures. Annealing in the oxygen ambient resulted in (re)crystallization whereas the effect of annealing depended markedly on the precursors used in the deposition process. Compared to films grown from TiCl₄, the films grown from Ti(OC₂H₅)₄ were transformed into rutile in somewhat greater extent, whereas in terms of step coverage the films grown from Ti(OC₂H₅)₄ remained somewhat inferior compared to the films grown from TiCl₄.     

TiO2/WO3微纳米纤维复合材料的制备及光催化性能

通过溶胶-凝胶和静电纺丝技术相结合的方法, 成功制备不同复合浓度聚乙烯吡咯烷酮(PVP)/钛酸四正丁酯(Ti(OC₄H₉)₄)/钨酸铵(N₅H₃₇W₆O₂₄·H₂O)前驱体。通过控温煅烧获得不同煅烧温度、不同复合浓度的TiO₂/WO₃微纳米纤维复合材料。采用X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、场发射扫描电子显微镜(FE-SEM)和紫外-可见漫反射光谱(UV-Vis )技术对样品进行表征。以亚甲基蓝(MB)的光降解为模型反应, 研究TiO₂/WO₃微纳米纤维复合材料在紫外光照射下的光催化活性。结果表明, 煅烧温度500℃时, n(Ti):n(W) = 12:1形成WO₃掺杂的TiO₂微纳米纤维及n(Ti):n(W) = 4:1形成的TiO₂/WO₃复合微纳米纤维的光催化活性均高于纯TiO₂。     

Preparation and activity evaluation of p-n junction photocatalyst NiO/TiO2

p–n Junction photocatalyst NiO/TiO₂ was prepared by sol–gel method using Ni(NO₃)₂·6H₂O and tetrabutyl titanate [Ti(OC₄H₉)₄] as the raw materials. The p–n junction photocatalyst NiO/TiO₂ was characterized by UV–vis diffuse reflection spectrum, X-ray powder diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity of the photocatalyst was evaluated by photocatalytic reduction of Cr₂O₇²⁻ and photocatalytic oxidation of rhodamine B. The results show that, for photocatalytic reduction of Cr₂O₇²⁻, the optimum percentage of doped-NiO is 0.5% (mole ratio of Ni/Ti). The photocatalytic activity of the p–n junction NiO/TiO₂ is much higher than that of TiO₂ on the photocatalytic reduction of Cr₂O₇²⁻. However, the photocatalytic activity of the p–n junction photocatalyst NiO/TiO₂ is much lower than that of TiO₂ on the photocatalytic oxidation of rhodamine B. Namely, the p–n junction photocatalyst NiO/TiO₂ has higher photocatalytic reduction activity, but lower photocatalytic oxidation activity. Effects of heat treatment on the photocatalytic activity of p–n junction photocatalyst NiO/TiO₂ were investigated. The mechanisms of influence on the photocatalytic activity were also discussed by the p–n junction principle.     

Controllable formation of Er–Yb codoped Al2O3 films by the non-aqueous sol–gel method

1 mol%Er³⁺–10 mol%Yb³⁺ codoped Al₂O₃ thin films have been prepared on thermally oxidized SiO₂/Si(110) substrates by a dip-coating process in the non-aqueous sol–gel method from the hydrolysis of aluminum isopropoxide [Al(OC₃H₇)₃] under isopropanol environment. Addition of N,N-dimethylformamide (DMF) as a drying control chemical additive (DCCA) into the sol suppresses formation of the cracks in the Er³⁺–Yb³⁺ codoped Al₂O₃ thin films when the rare-earth ion is doped with a high doping concentration. Homogeneous, smooth and crack-free Er³⁺–Yb³⁺ codoped Al₂O₃ thin films form at the conditions by a molar ratio of 1:1 for DMF:Al(OC₃H₇)₃. A strong photoluminescence spectrum with a broadband extending from 1.400 to 1.700 µm centered at 1.533 µm is obtained for the Er³⁺–Yb³⁺ codoped Al₂O₃ thin films, which is unrelated to the addition of DMF. Controllable formation of the Er³⁺–Yb³⁺ codoped Al₂O₃ thin films may be explained by the fact that the DMF assisted the deprotonation process of Al–OH at the surfaces of gel particles, resulting in enhancement of the degree of polymerization of sols and improvement of the mechanical properties of gel thin films.     

Effect of SnO2 on the photocatalytical properties of TiO2 films

TiO₂/SnO₂ thin films with different tin atomic percentages were successfully prepared on glass substrates by the spray pyrolysis method from an alcoholic solution of TiO[C₅H₇O₂]₂ with different concentrations of SnCl₄. The TiO₂/SnO₂ thin films prepared at 450 °C presented the anatase phase in polycrystalline configuration from %Sn = 0 in the starting solution up to %Sn = 20, at higher tin content the films present an amorphous configuration. The resulting thin films have a homogeneous surface structure with some porosity. The photocatalytical properties of the films were evaluated with the degradation of methylene blue. The products of the degradation reaction were identified by ¹H nuclear magnetic resonance and the film properties were studied by atomic force microscopy, scanning electron microscopy, UV–Vis spectroscopy, and X-ray diffraction.     

Sensitivity enhancement for H2 gas detection using a SnO2–Ag2O–PdOx nanocrystalline system

Thick film H₂ sensors were fabricated using SnO₂ loaded with Ag₂O and PdO_x. The composition that gave highest sensitivity for H₂ was in the wt.% ratio of SnO₂:Ag₂O:PdO_x as 93:5:2. The nano-crystalline powders of SnO₂–Ag₂O–PdO_x composites synthesized by sol–gel method were screen printed on alumina substrates. Fabricated sensors were tested against gases like H₂, CH₄, C₃H₈, C₂H₅OH and SO₂. The composite material was found sensitive against H₂ at the working temperature 125 °C, with minor interference of other gases. H₂ gas as low as 100 ppm can be detected by the present fabricated sensors. It was found that the sensors based on SnO₂–Ag₂O–PdO_x nanocrystalline system exhibited high performance, high selectivity and very short response time to H₂ at ppm level. These characteristics make the sensor to be a promising candidate for detecting low concentrations of H₂.     

大尺寸硅酸铋晶体的原料合成、晶体生长及闪烁性能研究

以Si(OC₂H₅)₄和Bi(NO₃)₃·5H₂O作为前驱体、柠檬酸作为溶剂, 按化学计量比配料, 采用溶胶-凝胶法合成并经高温烧结制备了纯相Bi₄Si₃O₁₂多晶粉末, 每批次可合成250 g。以此为原料、<001 >取向BSO为籽晶, 在坩埚下降炉内生长了BSO晶体, 讨论了晶体的析晶行为, 获得了30 mm × 30 mm × 210 mm的高质量BSO晶体。闪烁性能测试表明, 该晶体能量分辨率为18.9%, 光输出为同等条件下CSI(T1)晶体的7.2%。     

N与La共掺杂纳米TiO_2/电气石复合材料的制备及其光催化性能

采用超声辅助溶胶-凝胶法,以钛酸丁酯为原料,尿素为N源,硝酸镧为La源,制备了N与La共掺杂纳米TiO_2/电气石复合材料。采用XRD、UV-Vis、SEM-EDS和XPS对复合材料的结构和性能进行了表征。以2,4,6-三硝基甲苯作为目标污染物,考察了N与La共掺杂纳米TiO_2/电气石复合材料的光催化活性及再生利用性能。结果表明:N与La共掺杂并负载电气石后,两者协同作用使TiO_2晶粒更加细化,光吸收范围向可见光区拓展,N与La共掺杂纳米TiO_2/电气石复合材料具有良好的光催化活性和再生利用性能,且在模拟可见光照射条件下对2,4,6-三硝基甲苯具有良好的去除效果。     

Catalytic CVD growth of Si–C and Si–C–O alloy films by using alkylsilane and related compounds

Cat-CVD method has been applied to the growth of Si–C and Si–C–O alloy thin films. Growth mechanism has been studied with emphasis on the effects of filament materials. Growth rates and alloy compositions were measured for W, Ta, Mo and Pt filaments at the filament temperatures ranging from 1300 to 2000 °C. Si_1−xC_x films with x ranging from 0.38 to 0.7 could be grown by using single molecule source Si(CH₃)₂H₂ (dimethylsilane). Si–C–O ternary alloy films was successfully prepared by using Si(OC₂H₅)₄ (tetraethoxysilane) and Si(CH₃)₂(OCH₃)₂ (dimethyldimethoxysilane) molecules.     

电解液组分对TiCP/Ti6Al4V复合材料微弧氧化膜耐蚀性及耐磨性影响

采用微弧氧化技术在 TiC_P/Ti6Al4V 复合材料表面制备陶瓷膜。在NaAlO₂和NaH₂PO₂两种溶液体系中通过添加不同添加剂 NaOH、C₁₀H₁₂CaNa₂N₂O₈·4H₂O和Na₂SiO₃, 研究电解液组分对陶瓷膜组织、耐蚀性和耐磨性的影响。结果表明: 在NaH₂PO₂电解液体系中生成的膜层由金红石型和锐钛矿型TiO₂相组成, 而在NaAlO₂体系中除了生成TiO₂外, 还生成了Al₂TiO₅和γ-Al₂O₃。添加NaOH可以加快微弧氧化反应速率, 添加NaAlO₂和Na₂SiO₃有利于提高膜层的硬度, NaH₂PO₂溶液体系中形成的膜层厚度是NaAlO₂溶液体系的2~3倍。 在NaAlO₂和NaH₂PO₂电解液体系中生成的膜层, 其耐腐蚀性能排序均为: Na₂SiO₃>C₁₀H₁₂CaNa₂N₂O₈·4H₂O>NaOH。在NaAlO₂电解液体系中生成的膜层的耐磨性能排序为: Na₂SiO₃>NaOH>C₁₀H₁₂CaNa₂N₂O₈·4H₂O, 而在NaH₂PO₂电解液体系中生成的膜层的耐磨性能排序为: Na₂SiO₃>C₁₀H₁₂CaNa₂N₂O₈·4H₂O>NaOH。TiC_P/Ti6Al4V复合材料经过微弧氧化处理后, 耐磨性和耐蚀性均优于基体, 在NaH₂PO₂+Na₂SiO₃电解液中生成的微弧氧化膜的耐蚀性最好, 耐磨性也较好, 其腐蚀电流密度较钛基复合材料基体降低约2个数量级, 因此综合性能最好。     

Comparison of the electrochemical behavior of CeO2–SnO2 and CeO2–TiO2 electrodes produced by the Pechini method

CeO₂–SnO₂ and CeO₂–TiO₂ thin films were prepared by the Pechini method and their characteristics were compared, using a fractional factorial design to quantify the effect of five preparation variables. It was observed that CeO₂–SnO₂ electrodes show a greater electrochemical response than the CeO₂–TiO₂ films. The best intercalation charge densities were 18.11 and 9.91 mC/cm² for CeO₂–SnO₂ and CeO₂–TiO₂, respectively. Both films were optically inactive with transparencies, in most cases, higher than 90%.     

Preparation and optical properties of sol–gel derived Er-doped Al2O3–Ta2O5 films

Thin films of the system xAl₂O₃–(100 − x)Ta₂O₅–1Er₂O₃ were prepared by a sol–gel method and a dip-coating technique. The influences of the composition and the crystallization of the films on Er³⁺ optical properties were investigated. Results of X-ray diffraction indicated that the crystallization temperature of Ta₂O₅ increased from 800 to 1000 °C with increased values of x. In crystallized films, the intensities of the visible fluorescence and upconversion fluorescence tend to decrease with an increase in x values, due to the high phonon energy of Al₂O₃; the strongest fluorescence is observed in a crystallized film for x = 4 heat treated at 1000 °C. In amorphous films obtained by heat treatment at relatively low temperatures the Er³⁺ fluorescence could not be observed because strong fluorescence from organic residues remaining in the films thoroughly covered the Er³⁺ fluorescence. On the other hand, the Er³⁺ upconversion fluorescence in the amorphous films was observed to be stronger than that in the crystallized films. The strongest upconversion fluorescence is observed in an amorphous film for x = 75 heat treated at 800 °C.     

锐钛矿型TiO2纳米棒薄膜的溶胶-凝胶法制备研究

以钛酸丁酯Ti（OC₄H₉）₄、冰醋酸、去离子水和聚乙二醇（PEG）1000为原料,采用溶胶-凝胶法和旋转涂膜工艺,在玻璃衬底上制备出锐钛矿型TiO₂纳米棒。利用X射线衍射仪（XRD）、SEM和紫外可见光谱（UV/Vis）对TiO₂纳米棒薄膜进行了表征。结果表明,实验制备的TiO₂纳米棒为锐钛矿晶型,在TiO₂反应体系中,胶体粒子在加热过程中偶联在一起,1h后形成了TiO₂纳米棒,其直径为30～50nm,长度为100～200nm。同时,在42mL钛的胶体溶液中添加0.30g PEG（1000）后,纳米TiO₂薄膜的可见光透射峰值降低,TiO₂薄膜表面孔径为20～50nm。     

Characterization of Cat-CVD grown Si–C and Si–C–O dielectric films for ULSI applications

Si–C films with the Si compositions ranging from 40 to 70% have been grown by Cat-CVD using dimethylsilane [DMSi, Si(CH₃)₂H₂] compounds. Tetraethoxysilane [TEOS, Si(OC₂H₅)₄] and dimethyldimethoxysilane [DMDMOS, Si(CH₃)₂(OCH₃)₂] gas source gave us Si–C–O (C-doped SiO_x) films with wide ternary alloy compositions. The dielectric constant of a Si–C film has been evaluated by C–V measurements (at 1 MHz) using Al/Si–C/n-Si(001)/Cu MIS structure. The relative dielectric constant value of a Si–C film was estimated to be 3.0. The resistivity of the Si–C layer with 1 mm diameter and 0.24 μm thickness was estimated to be more than 24.5 Gohm·cm. These results gave us promising characteristics of Si–C and Si–C–O films grown by alkylsilane- and alcoxysilane-based Cat-CVD.     

可磁分离ZnFe2O4-TiO2/还原氧化石墨烯复合材料的制备及光催化性能

以TiO2(P25)、 Fe(NO3)3·9H2O、 Zn(NO3)2·6H2O和氧化石墨烯(GO)为原料,通过一步溶剂热法合成可磁分离的ZnFe2O4-TiO2/还原氧化石墨烯(rGO)复合材料。采用UV-Vis、 Raman、 XRD、 SEM和EDS对ZnFe2O4-TiO2/rGO复合材料进行表征,并研究不同rGO比例的ZnFe2O4-TiO2/rGO对模拟染料废水亚甲基蓝(MB)的光催化降解性能。GO在溶剂热反应过程中,被还原成rGO。由于ZnFe2O4和rGO的加入,不仅使ZnFe2O4-TiO2/rGO实现对可见光的吸收,而且使其具有磁性,便于分离和回收利用。当GO质量分数为5wt%时, ZnFe2O4-TiO2/rGO显现出对MB最佳的光催化活性, 60 min光照后的降解率达到99.1%。通过光催化活性物种捕获实验得出ZnFe2O4-TiO2/rGO复合材料降解MB的过程中,活性物种主要为·OH和·O2-, TiO2导带(CB)中的光生电子(e+)转移到ZnFe2O4的价带(VB),遵循Z型转移机制。光催化剂稳定性实验表明, ZnFe2O4-TiO2/rGO复合材料具有优越的稳定性,可作为太阳光照射下降解有机染料的光催化剂。     

Microstructures, densification and mechanical properties of TiC–Al2O3–Al composite by field-activated combustion synthesis

Dense TiC–Al₂O₃–Al composite was prepared with Al, C and TiO₂ powders by means of electric field-activated combustion synthesis and infiltration of the molten metal (here Al) into the synthesized TiC–Al₂O₃ ceramic. An external electric field can effectively improve the adiabatic combustion temperature of the reactive system and overcome the thermodynamic limitation of reaction with x < 10 mol. Thereby, it can induce a self-sustaining combustion synthesis process. During the formation of Al₂O₃–TiC–Al composite, Al is molten first, and reacted with TiO₂ to form Al₂O₃, followed by the formation of TiC through the reaction between the displaced Ti and C. Highly dense TiC–Al₂O₃–Al with relative density of up to 92.5% was directly fabricated with the application of a 14 mol excess Al content and a 25 V cm⁻¹ field strength, in which TiC and Al₂O₃ particles possess fine-structured sizes of 0.2–1.0 μm, with uniform distribution in metal Al. The hardness, bending strength and fracture toughness of the synthesized TiC–Al₂O₃–Al composite are 56.5 GPa, 531 MPa and 10.96 MPa m^1/2, respectively.     

RuO2–TiO2 mixed oxides prepared from the hydrolysis of the metal alkoxides

The hydrolysis of ruthenium alkoxide/titanium tetraethoxide mixtures to gels and powders containing 30–40 mol% Ru was investigated. Basic or neutral conditions led to powders consisting of 2–10 nm diameter crystalline RuO₂ nanoparticles embedded in a matrix of crystalline (anatase) and amorphous TiO₂. Acid hydrolysis conditions gave gels containing smaller, amorphous RuO₂ nanoparticles (1–3 nm). In all samples the RuO₂ nanoparticles tended to clump into aggregates up to 0.5 μm across. Acid or neutral hydrolysis of ruthenium ethoxide gave samples which displayed lower surface Ru:Ti ratios as measured by XPS compared to the bulk (XRF), and also contained more low-valent Ru (as measured by XRF), probably due to incomplete hydrolysis of the precursors. These samples also contained more Ru metal after calcination (XRD). Calcination (450 °C) was accompanied by Ru-promoted combustion of organic material and led to crystalline (anatase) TiO₂ and Ti_xRu_1−xO₂ solid solution (rutile phase).     

Fe2O3 films for Ξ optics: Raman and XAS characterization

Two different sol-gel syntheses, both starting from inorganic salts as precursors, Fe(NO₃)₃ · 9H₂O or FeCl₃ - 6H₂O, have been employed to prepare, by dip-coating, films of -Fe₂O₃, which are currently investigated for their high non-linear optical susceptibility Ξ⁽³⁾. Thermal treatments at 500°C lead to the -Fe₂O₃ hematite structure for both preparations as indicated by XRD and Raman. Information on the differences in the local order between the two preparations are obtained by X-ray absorption spectroscopy (XAS) measurements.     

Synthesis, structure refinement and characterization of tetrahydrated acid gadolinium diphosphate HGdP2O7·4H2O

Synthesis and single crystal structure are reported for a new gadolinium acid diphosphate tetrahydrate HGdP₂O₇·4H₂O. This salt crystallizes in the monoclinic system, space group P2₁/n, with the following unit-cell parameters: a = 6.6137(2) Å, b = 11.4954(4) Å, c = 11.377(4) Å, β = 87.53(2)° and Z = 4. Its crystal structure was refined to R = 0.0333 using 1783 reflections. The corresponding atomic arrangement can be described as an alternation of corrugated layers of monohydrogendiphosphate groups and GdO₈ polyhedra parallel to the () plane. The cohesion between the different diphosphoric groups is provided by strong hydrogen bonding involving the W4 water molecule.

IR and Raman spectra of HGdP₂O₇·4H₂O confirm the existence of the characteristic bands of diphosphate group in 980–700 cm⁻¹ area. The IR spectrum reveals also the characteristic bands of water molecules vibration (3600–3230 cm⁻¹) and acidic hydrogen ones (2340 cm⁻¹). TG and DTA investigations show that the dehydration of this salt occurs between 79 and 900 °C. It decomposes after dehydration into an amorphous phase. Gadolinium diphosphate Gd₄(P₂O₇)₃ was obtained by heating HGdP₂O₇·4H₂O in a static air furnace at 850 °C for 48 h.     

Preparation and visible-light-driven photoelectrocatalytic properties of boron-doped TiO2 nanotubes

In the present study, chemical vapour deposition (CVD) was applied to dope boron into TiO₂ nanotubes anodized Ti in C₂H₂O₄·2H₂O + NH₄F electrolyte with the goal of improving the photocatalytic (PC) activity under visible light. The undoped TiO₂ nanotubes had a highly self-organized structure. However, after doping through CVD, TiO₂ nanotubes suffered from an observable disintegration of morphological integrity. X-ray diffraction (XRD) results confirmed that annealing temperature had an influence on the phase structure and boron impurities could retard anatase–rutile phase transition. Diffuse reflectance absorption spectra (DRS) analysis indicated that B-doped samples displayed stronger absorption in both UV and visible range. B-doped TiO₂ nanotubes electrode annealed at 700 °C through CVD showed higher photoelectrocatalytic (PEC) efficiency in methyl orange (MO) degradation than that annealed at 400 °C and 550 °C. MO degradation was substantially enhanced with the increasing applied bias potential. Moreover, there was a synergetic effect between the electrochemical and photocatalytic processes, and the synergetic factor R reached 1.45. B-doped TiO₂ nanotubes electrode showed good stability after 10 times by repeating photoelectrocatalysis of MO.