重氧空位对金红石型和锐钛矿型TiO2导电性能影响的模拟计算

基于密度泛函理论框架下的第一性原理平面波超软赝势方法,构建了未掺杂与相同重氧空位金红石型和锐钛矿型TiO_1.9375超胞模型,分别对模型进行了几何结构优化、能带结构分布和态密度分布的计算. 结果表明,氧空位后金红石型和锐钛矿型TiO₂体系体积均变大,同时,锐钛矿型TiO_1.9375超胞的稳定性、迁移率以及电导率均高于金红石型TiO_1.9375超胞. 计算结果和实验结果相一致. 关键词： 重氧空位 2')" href="#">金红石型和锐钛矿型TiO₂ 导电性能 第一性原理     

稀土钇、镧掺杂TiO2薄膜的拉曼谱分析

采用溶胶-凝胶法在石英玻璃衬底上用旋涂法制备了未掺杂、掺杂钇和掺杂镧的TiO₂薄膜样品,对样品在700—1100 ℃范围内进行退火处理,并对样品的拉曼光谱进行了分析.分析表明:随着退火温度的升高,未掺杂TiO₂薄膜发生了从锐钛矿相经混相最终向金红石相的转换,掺杂钇和掺杂镧对TiO₂薄膜的晶相转换起阻碍作用,掺杂镧的阻碍作用更强;稀土掺杂能使TiO₂薄膜晶粒细化,并使晶粒内部应力增大从而阻碍晶格振动,掺杂镧比掺杂钇的效果 关键词： 2薄膜')" href="#">TiO₂薄膜 稀土掺杂 拉曼光谱 溶胶-凝胶     

锐钛矿相和金红石相TiO2:Nb的光电性能研究

采用基于密度泛函理论的第一性原理计算了锐钛矿相和金红石相TiO₂:Nb的晶体结构、电子结构和光学性质. 结果表明, 在相等的摩尔掺杂浓度下(6.25%), 锐钛矿相TiO₂:Nb的导带底电子有效质量小于金红石相TiO₂:Nb, 且前者室温载流子浓度是后者的两倍左右, 即具有更大的施主杂质电离率, 从而解释了锐钛矿相TiO₂:Nb比金红石相TiO₂:Nb具有更优异电学性能的实验现象. 光学计算也表明锐钛矿相在可见光区有更大的透过率, 从而在理论上解释了锐钛矿相TiO₂:Nb比金红石相TiO₂:Nb更适于做透明导电材料的原因. 计算结果与实验数据能较好符合. 关键词： 2:Nb')" href="#">TiO₂:Nb 第一性原理 电子结构 光学性能     

锐钛矿相纳米TiO2晶体生长动力学及生长过程控制

研究了采用溶胶-凝胶法经由前驱物钛酸四异丙酯水解制备纳米TiO₂结构相变及锐钛矿晶体生长动力学过程. 研究结果表明,在酸性条件下水解,由于高压热处理温度的变化导致锐钛矿向金红石相的结构相变,锐钛矿相纳米TiO₂生长活化能在250℃以下和以上分别为(15.8±4.5)kJ/mol和(80.2±1.0)kJ/mol;而在碱性条件下水解的活化能值为(3.5±0.4)kJ/mol. 在不发生结构相变的条件下,酸性水解条件下锐钛矿相纳米TiO₂生长速 关键词： 2')" href="#">纳米TiO₂ 锐钛矿 生长动力学 溶胶-凝胶法     

结构相变对Fe掺杂TiO2薄膜室温铁磁性的影响

采用直流磁控溅射方法在玻璃基底上制备了不同Fe掺杂浓度的TiO₂薄膜, 并对其晶体结构和磁特性进行了研究.在所有掺杂样品中,均观察到了室温铁磁性, 磁性源于Fe离子与其近邻空间分布的空穴相互作用. 在掺杂量为7%的锐钛矿相薄膜中观察到了最大的磁化强度. 随着Fe掺杂浓度的进一步增加, TiO₂的晶体结构逐渐由锐钛矿相向金红石相转变,并且磁性减弱. 不同结构的TiO₂中Ti–O键长不同,导致替代的磁性Fe离子与空穴的作用强度发生改变, 进而使其磁性发生变化. 关键词： 稀磁半导体 结构相变 铁磁性     

O2流量对磁控溅射N掺杂TiO2薄膜成分及晶体结构的影响

利用直流脉冲磁控溅射方法在室温下通过改变O₂流量制备具有不同晶体结构的N掺杂TiO₂薄膜,利用台阶仪、X射线光电子能谱仪、X射线衍射仪、紫外-可见分光光度计等设备对薄膜沉积速率、化学成分、晶体结构、禁带宽度等进行分析.结果表明:所制备的薄膜元素配比约为TiO_1.68±0.06N_0.11±0.01,N为替位掺杂,所有样品退火前后均未形成Ti—N相结构,N掺杂TiO₂薄膜的沉积速率、晶体结构等主要依赖于O₂流量.在O₂流量为2 sccm时,N掺杂TiO₂薄膜沉积速率相对较高,薄膜为非晶态结构,但薄膜内含有锐钛矿(anatase)和金红石(rutile)相晶核,退火后薄膜呈anatase和rutile相混合结构,禁带宽度仅为2.86 eV.随着O₂流量的增加,薄膜沉积速率单调下降,退火后样品禁带宽度逐渐增加.当O₂流量为12 sccm时,薄膜为anatase相择优生长,退火后呈anatase相结构,禁带宽度为3.2 eV.综合本实验的分析结果,要在室温条件下制备晶态N掺杂TiO₂薄膜,需在高O₂流量(＞10 sccn)条件下制备. 关键词： 2薄膜')" href="#">N掺杂TiO₂薄膜 磁控溅射 化学配比 晶体结构     

萤石结构TiO2的电子结构和光学性质

利用第一性原理计算了立方相萤石TiO₂的晶胞参数,能带结构和电子态密度.结果显示萤石TiO₂属于间接带隙半导体材料,其间接禁带宽度(Γ→X)E_g为2.07eV,比常见的金红石和锐钛矿TiO₂的禁带宽度窄.为了更清楚地了解萤石的光学性质,利用Kramers-Kronig色散关系,分别对萤石和金红石TiO₂的复介电常数、吸收率等参数进行了计算,并将二者结果做了 关键词： 2')" href="#">萤石结构TiO₂ 密度泛函理论 能带结构 光学性质     

溅射制备Ge,Nb共掺杂窄光学带隙和低电阻率的TiO2薄膜

采用射频磁控溅射技术制备了Ge,Nb共掺杂的锐钛矿结构TiO₂薄膜,详细探讨了薄膜的结构、电阻率及光学带隙等性质随Ge,Nb掺杂量、溅射功率和热处理温度等参数的变化,发现Ge,Nb共掺杂可以同时调节TiO₂薄膜的光学带隙和电阻率.体积分数约为6%Nb和20%Ge的共掺杂TiO₂薄膜电阻率由10⁴Ω/cm减小至10^-1Ω/cm,光学带隙由3.2 eV减小至1.9 eV.退火后掺杂TiO₂薄膜不仅显示更低的电阻率,还表现出更强的可见-红外光吸收.结果表明,改变Ge,Nb的掺杂量和退火条件能够制备出电阻率和带隙都可调的TiO₂薄膜.     

电场热处理条件下TiO2薄膜的晶化行为研究

利用溶胶-凝胶法和电场热处理工艺在玻璃表面制备出一层TiO₂薄膜，采用DTA ，Raman光 谱，XRD和AFM等测试手段分析了TiO₂薄膜在电场热处理过程中的晶化行为.然后 在理论上 分析了外电场对TiO₂薄膜热处理过程的影响，提出了通过引入外电场促进TiO2薄膜从无 定形到锐钛矿的相转变的方法.通过甲基橙水溶液的光催化降解实验表明：在520℃电场热处 理条件下的TiO₂薄膜的光催化效率高于未引入电场热处理的TiO₂薄 膜. 关键词： 薄膜 晶化 电场 2')" href="#">TiO₂     

阴极电压脉冲占空比对钛合金微弧氧化膜特性的影响

利用自制多功能微弧氧化电源,在保持双极性电压脉冲幅度不变的条件下,研究了阴极电压脉冲占空比（d_c）对钛合金微弧氧化膜特性的影响.结果表明：阴、阳极的峰值电流随处理时间的变化分为几个不同阶段,各阶段的开始和结束时间与d_c密切相关.氧化膜主要由金红石和锐钛矿相TiO₂组成,金红石相TiO₂的相对含量在d_c=50%附近随d_c的 关键词： 微弧氧化 钛合金 占空比     

Influence of growth temperature of TiO2 buffer on structure and PL properties of ZnO films

A series of ZnO films with TiO₂ buffer on Si (1 0 0) substrates were prepared by DC reactive sputtering. Growth temperature of TiO₂ buffer changed from 100 °C to 400 °C, and the influence on the crystal structures and optical properties of ZnO films have been investigated. The XRD results show that the ZnO films with TiO₂ buffer have a hexagonal wurtzite structure with random orientation, and with the increase of growth temperature of TiO₂ buffer, the residual stresses were released gradually. Specially, the UV emission enhanced distinctly and FWHMs (full width half maximum) decreased linearly with the increasing TiO₂ growth temperature. The results all come from the improvement of crystal quality of ZnO films.     

Super-hydrophilic properties of TiO2-DLC nanocomposite films fabricated by the simple electrochemical process

Anatase TiO₂ nanoparticles incorporated DLC films were successfully deposited on single crystalline silicon substrates by the electrolysis of TiO₂-methanol solution under ambient atmospheric pressure and low temperature. Anatase TiO₂ nanoparticles were embedded into amorphous carbon matrix, forming the typical nanocrystalline/amorphous nanocomposite films, confirmed by transmission electron microscopy (TEM). TiO₂ incorporation effectively increased the sp³-hybridized carbon concentration in the composite film, and further regulated the microstructure and surface morphology. Furthermore, the static contact testing completely displayed, TiO₂ incorporation got the composite films super-hydrophilic, which fundamentally improved the wetting ability of DLC film.     

Influence of annealing temperature on the photoluminescence property of ZnO thin film covered by TiO2 nanoparticles

In this work, ZnO thin films covered by TiO₂ nanoparticles (labeled as TiO₂-ZnO thin films) were prepared by electron beam evaporation. The influence of annealing temperature on the photoluminescence property of the samples was studied. The structures and surface morphologies of the samples were analyzed by X-ray diffraction (XRD) and atomic force microscope, respectively. The photoluminescence was used to investigate the fluorescent properties of the samples. The measurement results show that the ultraviolet emission of ZnO thin films is largely enhanced after they are covered by TiO₂ nanoparticles, while the green emission is suppressed. However, when the annealing temperature is relatively high (≥500 °C), the intensity of ultraviolet emission drops off and a violet emission peak along with a blue emission peak appears. This is probably connected with the atomic interdiffusion between TiO₂ nanoparticles and ZnO thin film. Therefore, selecting a suitable annealing temperature is a key factor for obtaining the most efficient ultraviolet emission from TiO₂-ZnO thin films.     

Optical properties of ITO/TiO2 single and double layer thin films deposited by RPLAD

Indium tin oxide (ITO) and titanium dioxide (TiO₂) single layer and double layer ITO/TiO₂ films were prepared using reactive pulsed laser ablation deposition (RPLAD) with an ArF excimer laser for applications in dye-sensitized solar cells (DSSCs). The films were deposited on SiO₂ substrates either at room temperatures (RT) or heated to 200-400 °C. Under optimized conditions, transmission of ITO films in the visible (vis) range was above 89% for films produced at RT and 93% for the ones deposited at higher temperatures. Increasing the substrate temperature from RT to 400 °C enhances the transmission of TiO₂ films in the vis-NIR from about 70% to 92%. High transmission (≈90%) was observed for the double layer ITO/TiO₂ with a transmission cut-off above 900 nm. From the transmission data, the energies gaps (E_g), as well as the refractive indexes (n) for the films were estimated. n ≈ 2.03 and 2.04, respectively for ITO films and TiO₂ film deposited at 400 °C in the visible region. Post-annealing of the TiO₂ films for 3 h at 300 and 500 °C was performed to enhance n. The refractive index of the TiO₂ films increases with the post-annealing temperature. The direct band gap is 3.6, 3.74 and 3.82 eV for ITO films deposited at RT, 200, and 400 °C, respectively. The TiO₂ films present a direct band gap of 3.51 and 3.37 eV for as deposited TiO₂ films and when annealed at 400 °C, respectively. There is a shift of about 0.1 eV between ITO and ITO/TiO₂ films deposited at 200 °C. The shift decreases by half when the TiO₂ film was deposited at 400 °C. Post-annealing was also performed on double layer ITO/TiO₂.     

Preparation of TiO2 thin films from autoclaved sol containing needle-like anatase crystals

A new inorganic sol-gel method was introduced in this paper to prepare TiO₂ thin films. The autoclaved sol with needle-like anatase crystals was synthesized using titanyl sulfate (TiOSO₄) and peroxide (H₂O₂) as starting materials. The transparent anatase TiO₂ thin films were prepared on glass slides from the autoclaved sol by sol-gel dip-coating method. A wide range of techniques such as Fourier transform infrared transmission spectra (FT-IR), X-ray diffraction (XRD), thermogravimetry-differential thermal analysis (TG-DTA), scanning electron microscopes, X-ray photoelectron spectroscopy (XPS) and ultraviolet-visible spectrum were applied to characterize the autoclaved sol and TiO₂ thin films. The results indicate that the autoclaved sol is flavescent, semitransparent and stable at room temperature. The anatase crystals of TiO₂ films connect together to form net-like structure after calcined and the films become uniform with increasing heating temperature. The surface of the TiO₂ films contain not only Ti and O elements, but also a small amount of N and Na elements diffused from substrates during heat treatment. The TiO₂ films are transparent and their maximal light transmittances exceed 80% under visible light region.     

Low-temperature liquid phase deposited TiO2 films on stainless steel for photogenerated cathodic protection applications

The low-temperature synthesis of anatase TiO₂ films was an imperative requirement for their application to corrosion prevention of metals. In this paper, a liquid phase deposition (LPD) technique was developed to prepare TiO₂ films on SUS304 stainless steel (304SS) at a relatively low temperature (80 °C). The as-prepared films were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy and X-ray photon spectroscopy (XPS). It was observed that a dense and crack-free anatase TiO₂ film with a thickness about 300 nm was obtained. The film contained some fluorine and nitrogen elements, and the amounts of these impurities were greatly decreased upon calcination. Under the white light illumination, the electrode potential of TiO₂ coated 304SS rapidly shifted to a more negative direction. Moreover, the photopotential of TiO₂/304SS electrode showed more negative values with increased film thickness. In conclusion, the photogenerated cathodic protection of 304SS was achieved by the low-temperature LPD-derived TiO₂ film.     

Methylene blue photoelectrodegradation under UV irradiation on Au/Pd-modified TiO2 films

In this work TiO₂ thin films were modified with gold/palladium (Au/Pd) bimetallic paticles by sputtering method. TiO₂ films were deposited on ITO (SnO₂:In) by Doctor Blade method and post-anneling. The properties of the films were studied through measurements of XRD (X-ray diffraction) and AFM (atomic force microscopy). The degradation of methylene blue was studied by UV-irradiated pure TiO₂ and Au/Pd-modified TiO₂ in aqueous solution. Langmuir-Hinshelwood model was used to obtain kinetic information. Photocatalytic study indicated that Au/Pd-modified TiO₂ photocatalytic activity was better than TiO₂ pure; the best half-life time for Au/Pd-modified TiO₂ in photodegradation was 2.8 times smaller than TiO₂ pure; finally the efficiency in methylene blue photodegradation was improved from 23% to 43% when Au/Pd-modified TiO₂ films were used.     

Effects of depositing temperatures on structure and optical properties of TiO2 film deposited by ion beam assisted electron beam evaporation

TiO₂, which is high in refractive index and dielectric constant, plays an important role in the fields of optics and electronics. In this work, TiO₂ films were prepared on glass substrates by the technique of ion beam assisted electron beam evaporation. The films were deposited at 50, 150 and 300 °C, respectively. Then the as-deposited TiO₂ films were annealed at 450 °C for 1 h in vacuum atmosphere. Structures and optical properties of TiO₂ films were characterized by XRD, SEM, ellipsometry and spectrophotometer. As a result, the structure and the refractive index of films were improved by both the annealing and the increasing of the deposition temperature. The UV-vis transmittance spectra also confirmed that the deposition temperature has a significant effect on the transparency of the thin films. The highest transparency over the visible wavelength region of spectra was obtained at the deposition temperature of 300 °C. The allowed direct band gap at the deposition temperature ranging from 50 to 300 °C was estimated to be in the range from 3.81 to 3.92 eV.     

Photocatalytic behavior of heavy La-doped TiO2 films deposited by pulsed laser deposition using non-sintered target

We have investigated the control of photocatalytic behavior under deposited conditions of non-sintered target of different molar ratios with TiO₂ and La₂O₃ from 1:0 to 1:2 for heavily La doping, and post-annealing temperature from 600 °C to 1000 °C for crystallizing by pulsed laser deposition. We have successfully crystallized heavily La-doped TiO₂ films with post-annealing temperature over 800 °C and with molar ratio of TiO₂:La₂O₃ over 1:1 on a quartz substrate. Heavily La-doped TiO₂ films are observed the decomposition of methylene blue and a water-splitting reaction in photocatalytic behavior under Xe light irradiation. When stoichiometric La-doped TiO₂ (TiO₂:La₂O₃ = 1: 1) is synthesized with heat-treatment at 900 °C, the best results are obtained under photocatalytic behavior and pure La₂Ti₂O₇ crystalline were obtained.     

Correlation between microstructure and optical properties of nano-crystalline TiO2 thin films prepared by sol-gel dip coating

Titanium dioxide thin films have been prepared from tetrabutyl-orthotitanate solution and methanol as a solvent by sol-gel dip coating technique. TiO₂ thin films prepared using a sol-gel process have been analyzed for different annealing temperatures. Structural properties in terms of crystal structure were investigated by Raman spectroscopy. The surface morphology and composition of the films were investigated by atomic force microscopy (AFM). The optical transmittance and reflectance spectra of TiO₂ thin films deposited on silicon substrate were also determined. Spectroscopic ellipsometry study was used to determine the annealing temperature effect on the optical properties and the optical gap of the TiO₂ thin films. The results show that the TiO₂ thin films crystallize in anatase phase between 400 and 800 °C, and into the anatase-rutile phase at 1000 °C, and further into the rutile phase at 1200 °C. We have found that the films consist of titanium dioxide nano-crystals. The AFM surface morphology results indicate that the particle size increases from 5 to 41 nm by increasing the annealing temperature. The TiO₂ thin films have high transparency in the visible range. For annealing temperatures between 1000 and 1400 °C, the transmittance of the films was reduced significantly in the wavelength range of 300-800 nm due to the change of crystallite phase and composition in the films. We have demonstrated as well the decrease of the optical band gap with the increase of the annealing temperature.