Preparation of rutile and anatase phases titanium oxide film by RF sputtering

Titanium oxide films were prepared by RF magnetron sputtering onto glass substrates. The effects of RF power and deposition temperature on crystalline structure, morphology and energy gap were investigated, which were analyzed by X-ray diffraction, SEM and UV-Vis spectrometer, respectively. Results show that rutile phase is the favored structure during deposition. Applying RF power in the range of 50-250 W, the amorphous, rutile, and both rutile and anatase phases TiO2 films were obtained in sequence, while the content of anatase is similar in the range of 34-37% although the RF power increases. Increasing the deposition temperature, the anatase phase coexists in the rutile phase in the range of 100-200 degrees C, and the content of anatase increases from 20 to 41% with the deposition temperature. In addition, according to the morphology observation, the granulous surface is found in rutile phase while facetted surface in anatase phase when titanium oxide films deposited at various RF powers and substrate temperatures. The band gap energy of titanium oxide evaluated from (alphahv)1/2 versus energy plots show that the energy gap decreases with RF power increasing.     

Controlling the crystallinity and roughness of atomic layer deposited titanium dioxide films

The surface roughness of thin films is an important parameter related to the sticking behaviour of surfaces in the manufacturing of microelectomechanical systems (MEMS). In this work, TiO2 films made by atomic layer deposition (ALD) with the TiCl4-H2O process were characterized for their growth, roughness and crystallinity as function of deposition temperature (110-300 degrees C), film thickness (up to approximately 100 nm) and substrate (thermal SiO2, RCA-cleaned Si, Al2O3). TiO2 films got rougher with increasing film thickness and to some extent with increasing deposition temperature. The substrate drastically influenced the crystallization behaviour of the film: for films of about 20 nm thickness, on thermal SiO2 and RCA-cleaned Si, anatase TiO2 crystal diameter was about 40 nm, while on Al2O3 surface the diameter was about a micrometer. The roughness could be controlled from 0.2 nm up to several nanometers, which makes the TiO2 films candidates for adhesion engineering in MEMS.     

One-dimensional TiO2 nanomaterials: preparation and catalytic applications

This work reports on the syntheses of one-dimensional (1D) H2Ti3O7 materials (nanotubes, nanowires and their mixtures) by autoclaving anatase titania (Raw-TiO2) in NaOH-containing ethanol-water solutions, followed by washing with acid solution. The synthesized nanosized materials were characterized using XRD, TEM/HRTEM, BET and TG techniques. The autoclaving temperature (120-180 degrees C) and ethanol-to-water ratio (V(EtOH)/V(H2O) = 0/60 approximately 30/30) were shown to be critical to the morphology of H2Ti3O7 product. The obtained H2Ti3O7 nanostructures were calcined at 400-900 degrees C to prepare 1D-TiO2 nanomaterials. H2Ti3O7 nanotubes were converted to anatase nanorods while H2Ti3O7 nanowires to TiO2(B) nanowires after the calcination at 400 degrees C. The calcination at higher temperatures led to gradual decomposition of the wires to rods and phase transformation from TiO2(B) to anatase then to rutile. Photocatalytic degradation of methyl orange was conducted to compare the photocatalytic activity of these 1D materials. These 1D materials were used as new support to prepare Au/TiO2 catalysts for CO oxidation at 0 degrees C and 1,3-butadiene hydrogenation at 120 degrees C. For the CO oxidation reaction, Au particles supported on anatase nanorods derived from the H2Ti3O7 nanotubes (Au/W-180-400) were 1.6 times active that in Au/P25-TiO2, 4 times that in Au/Raw-TiO2, and 8 times that on TiO2(B) nanowires derived from the H2Ti3O7 nanotubes (Au/M-180-400). For the hydrogenation of 1,3-butadiene, however, the activity of Au particles in Au/M-180-400 was 3 times higher than those in Au/W-180-400 but similar to those in Au/P25-TiO2. These results demonstrate that the potential of 1D-TiO2 nanomaterials in catalysis is versatile.     

甲烷燃烧法合成纳米二氧化钛的试验研究

以甲烷为燃料、空气为氧化剂、TiC14为原料,采用燃烧法合成了纳米二氧化钛,利用扫描电镜和X射线衍射对制备出的纳米TiO2颗粒产品的颗粒尺寸分布和物相组成进行了表征,通过调节甲烷、空气、载气的流量,并通过热电偶测量火焰温度,制备出不同操作工况下的纳米TiO2产品,讨论了工艺参数对颗粒特性的影响。结果表明,获得的纳米TiO2粒径主要分布在50～70nm,产品中大部分为锐钛矿相,含有少量的金红石相。     

Evaluation of crystallinity in TiO2 films with mixed structures grown on MgO (001) substrates by argon-ion beam sputtering based on infrared reflection-absorption spectra

TiO2 films with thicknesses (d) above 15 nm were grown on optically polished surfaces of MgO (001) substrates held at 400 degrees C by sputtering a Ti target with an argon-ion beam when the partial pressure of O2 was kept at 1.1 x 10(-2) Pa. X-ray diffraction patterns show that TiO2 films with d < 56 nm are composed of an a-axis anatase-type structure, whereas those with d > 56 nm are composed of a mixture of phases with the c-axis parallel to the film surface. The thickness dependence of the infrared reflection-absorption spectra shows that TiO2 films with d < 56 nm are composed of both anatase and amorphous phases, whereas those with d > 56 nm are composed of anatase, rutile, and amorphous phases. The crystallinity in TiO2 films is also evaluated from the infrared reflection-absorption spectra by comparison of the observed and the calculated results determined from the dielectric function of anisotropic TiO2 bulk single crystal.     

添加磷酸根对纳米二氧化钛晶相的控制

以TiCl4为前驱体添加磷酸盐通过水热法制备了纳米TiO2。通过X射线衍射仪、差热分析仪、扫描电子显微镜、比表面仪(BET)和光化学反应器等手段对所制备的TiO2的颗粒晶型、失重、形貌、比表面和降解罗丹明B的能力进行了表征。结果表明,随着磷酸根的添加,TiCl4水解生成的TiO2的晶型由纯金红石型向锐钛矿型转换,且所合成的锐钛矿和金红石的混晶样品的光催化活性明显高于单独晶相的光催化活性。     

气相燃烧合成二氧化钛纳米颗粒

建立了CO气相燃烧合成纳米颗粒材料技术 ,利用TiCl4 气相氧化合成粒度小于 10 0nm纯金红石或锐钛和金红石混合相的TiO2 颗粒。混合温度升高、TiCl4 进料量减小、停留时间缩短时 ,二氧化钛颗粒粒度减小。随混合温度升高、TiCl4 进料增大以及停留时间延长 ,TiO2 颗粒中金红石含量增大。在反应物中加入AlCl3 作为晶型调节剂时 ,金红石含量增大。     

TiO2纳米微晶的RF-PCVD法制备及表征

以TiCl4为原料,采用高频等离子化学气相沉积(RF-PCVD)法制备了TiO2纳米微晶,考察了控制粒径大小及晶相转化的关键操作条件.借助XPS、TEM、XRD、BET等技术对颗粒的化学组成、形貌、晶相结构等进行了表征.研究表明:所得TiO2纳米微晶大部分为球形体颗粒,粒径30～50 nm,单分散性良好;颗粒中锐钛相和金红石相两相共存,结晶完整;金红石相含量在26.7%～53.6%之间可调.     

双微乳液法制备掺杂Fe~(3+)的纳米TiO_2及其光催化性能

为了研究双微乳液法在制备纳米级光催化剂的应用,以TiCl4和NH3.H2O为原料,采用十六烷基三甲基溴化铵-正丁醇-环己烷-水微乳体系制备Fe3+掺杂纳米TiO2,对粉末的晶体结构进行X射线衍射表征,并以其对p-甲酚的降解考察其光催化活性。结果表明,在较小的掺杂量时,Fe3+掺杂量的提高可以提高TiO2的光催化活性,进一步提高掺杂量将引起光催化活性的降低;掺杂Fe3+可导致纳米TiO2的粒径减小;Fe3+的半径较小以及Fe2O3的熔点较低均有利于TiO2从锐钛矿向金红石的相变;当Fe3+掺杂摩尔分数为0.06%,煅烧温度为550℃时,纳米TiO2的光催化活性最高,此时形成TiO2的锐钛矿和金红石相的混晶;乳液中含水量也会影响晶相的组成和粒径大小,随着含水量增加产物中出现了一定比例的金红石相。     

Influence of structure parameters and crystalline phase on the photocatalytic activity of TiO2 nanotube arrays

Titanium oxide nanotube arrays (TiO2-NTAs) with different diameters and lengths are prepared by anodization of titanium foils in a water/ethylene glycol solution (5:95 V/V) containing 0.3 wt% NH4F. The effects of the diameters, lengths and crystalline phases of the NTAs on the photocatalytic (PC) activity are systematically evaluated. Larger pore diameter results in higher PC activity. The PC activity increases initially and then decreases with lengths for TiO2-NTAs and the optimal length that yields the highest PC activity is observed to be 6.2 microm. The crystalline phase and corresponding PC activity depend on the calcination temperature and their relationship is also investigated. The amorphous-to-anatase and anatase-to-rutile phase transitions initially occur at 300 and 500 degrees C, respectively. The PC activity of TiO2-NTAs initially increases with calcination temperature from 250 to 500 degrees C and then decreases at higher calcination temperature. The enhanced PC activity observed from the samples annealed at 250-450 degrees C is attributed to the better anatase crystalline structure at higher calcination temperature. The highest PC activity with regard to photodecomposition of methyl orange is observed from TiO2-NTAs calcined at 500 degrees C, which coincides with the anatse-to-rutile phase transformation. The synergistic effect of the anatase TiO2-NTAs and rutile barrier layers facilitate interfacial electron transfer consequently enhancing the PC activity. Further elevation of the calcination temperatures to 550 and 600 degrees C exhibits diminished PC activity because the NTs become shorter due to conversion of the bottom of anatase NTs into rutile film.     

The effect of substrate temperature on the spray-deposited TiO2 nanostructured films for dye-sensitized solar cells

The nanostructured TiO2 films have deposited on SnO2:F (FTO) coated glass substrate by spray pyrolysis technique at different substrate temperatures of 200-500 degrees C. The structural, surface morphological and optical properties of TiO2 films significantly vary with the substrate temperature. The surface of the TiO2 films deposited at 400 degrees C shows the nanoflakes and short nanorods (approximately 130 nm) like structures while the TiO2 films prepared at 500 degrees C shows only the nanoflakes like structures. The band gap of the TiO2 films prepared at higher temperatures (300-500 degrees C) becomes narrow due to presence the rutile phases in their crystal structure. Ruthenium (II) complex as a dye, KI/I2 as an electrolyte and carbon on FTO glass as a counter electrode has used to fabricate the dye-sensitized solar cell (DSC). The TiO2 film deposited at 400 degrees C has showed the best photovoltaic performance in DSC with the efficiency of 3.81%, the photovoltage of 773 mV, the photocurrent of 8.34 mA/cm2, and the fill factor of 56.17%. The photovoltage of the DSC increases with the increase of substrate temperature during the deposition of TiO2 films. Moreover, all the DSCs exhibit reasonably high fill factor value.     

Ti靶及TiO2靶溅射TiO2薄膜微观形貌、结构及光学性质研究

利用射频磁控溅射技术通过Ti靶及TiO2靶在氩氧气氛中同时溅射制备TiO2薄膜,并对所得的样品进行不同温度的退火处理。采用X射线衍射、扫描电子显微镜、拉曼光谱和吸收谱研究了不同的靶材及退火温度对TiO2薄膜晶体结构、微观形貌及光学性质的影响。结果表明:由于靶材的不同,Ti靶溅射时氧分压较低,造成薄膜中存在大量的氧缺陷,晶相发育不完善,颗粒相比TiO2靶溅射时较小,从XRD和拉曼光谱来看,Ti靶溅射得到的TiO2薄膜更有利于金红石相的形成。薄膜的透过率随退火温度的升高而降低,TiO2靶材溅射的薄膜的光学带隙随温度升高而明显降低,而Ti靶得到的薄膜的光学带隙对退火温度的依赖关系不明显。     

Structural Characteristics of TiO2 Ceramic Coating by Micro-Plasma Oxidation

TiO2 ceramic coatings with thickness of 20 μm were formed on the surface of pure titanium by micro-plasma oxidation. Their micro-structures were investigated by by using X-ray diffraction and their surface images were detected by using scan electronic microscope. There were three kinds of TiO2 coatings, pure anatase type TiO2 phase, mixed phases consisted of rutile type TiO2 phase and anatase type TiO2 phase, pure rutile type TiO2 phase. The coating surface with the pure anatase type TiO2 phase is rough, while the coating surface with the pure rutile type TiO2phase is smooth. The upper coating surface with the mixed type TiO2 phases is anatase type TiO2 structure and the subsurface of the TiO2 coating is rutile type TiO2structure.     

TiO2/SiO2薄膜中的相界扩散及晶化行为研究

本文研究了溶胶一凝胶法制备TiO2／SiO2复合薄膜的晶化行为以及复合薄膜与过渡层的相界扩散采用X-ray衍射分析了50TiO2／50SiO2薄膜中TiO2的析晶特征，研究表明，随热处理温度的升高，薄膜的结构由非晶转变为在SiO2玻璃网络中析出的锐钛矿相，再到锐钛矿和金红石二相共存，最后转变为金红石相，并伴随有磷石英和方石英的析出，且其晶粒尺寸也在逐渐增大．AES分析给出了过渡层的气孔率对复合膜中Ti的扩散能力的影响以及复合膜与过渡层之间碳的分布．SEM及EDS进一步揭示了薄膜表面存在亚微米不均匀区域，在此区域中碳的含量较高．在氧气中，提高热处理温度，可以降低碳的含量.     

Transparent, anatase-free TiO2 nanoparticle dispersions

Preparation of optically transparent dispersions of TiO2 nanoparticles which are free of the anatase polymorph is a challenging process which has been difficult to control to date. Here, we report and discuss the reproducible formation of such dispersions by hydrolysis of TiCl4. Clouding times of the dispersions and the finally resulting crystal modification of TiO2 was found to depend on a number of synthesis parameters, such as the temperature profile during the reaction, the ratio between the starting substances and the rate of TiCl4 addition. A low pH value and moderate reaction temperatures were required to yield rutile particles, which were established to be formed by transformation of initially amorphous particles just prior to clouding occurred. The latter phenomenon was found to be caused by agglomeration, and not by growth of primary nanosized particles.     

超临界流体干燥法制备TiO2/ Fe2O3 和TiO2/ Fe2O3/ SiO2 复合纳米粒子及光催化性能

以TiCl₄ 、Fe (NO₃ )₃·9H₂O 和Na₂SiO₃19H₂O 为原料, 采用溶胶凝胶法结合超临界流体干燥法(SCFD)制备了纳米级TiO₂/ Fe₂O₃ 和TiO₂/ Fe₂O₃/ SiO₂ 复合光催化剂。以光催化降解苯酚对所得催化剂的催化活性进行了评价。结果表明, 纳米TiO₂/ Fe₂O₃ 复合粒子与单组分TiO₂ 比较, 复合粒子光催化活性高于单组分的TiO₂, 6h 苯酚降解率高达95.9 %。SiO₂ 的加入可以抑制纳米粒子粒径的长大和晶相的转变, 增强TiO₂ 纳米粒子的热稳定性。复合光催化剂中Fe₂O₃ 最佳掺入量为0.06 %, SiO₂ 最佳掺入量为10 %(摩尔分数) 。并用XRD、TEM 和FTIR 等手段进行了表征。TiO₂ 以锐钛矿型形式存在, SiO₂ 以无定性形式存在。比较了不同制备方法制得的TiO₂/ Fe₂O₃ 复合光催化剂, 得出超临界干燥法制备的光催化剂具有粒径小、比表面积大、分散性好、光催化活性高等特点。采用超临界流体干燥可直接得锐钛型纳米复合光催化剂。     

Fiber-like TiO2 nanomaterials with different crystallinity phases fabricated via a green pathway

Fiber-like TiO(2) nanomaterials were designed and created, for the first time, by in situ synthesis of TiO(2) nanoparticles in regenerated cellulose fibers in the wet state, followed by calcination at 400-800 °C to remove the cellulose matrix. The cellulose fibers were prepared in an NaOH/urea aqueous system with cooling via an industrial machine. The structure and properties of the fiber-like TiO(2) nanomaterials were characterized with scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and photocatalytic degradation tests. The results revealed that the mean diameter of the fiber-like TiO(2) nanomaterials, which consisted of TiO(2) nanoparticles with a mean size from 21 to 37 nm, was 7-8 μm. The TiO(2) nanomaterials exhibited different crystallinity phases from anatase to rutile, depending on the calcinating temperature. With a decrease in the calcinating temperature from 800 to 400 °C, the surface area of the TiO(2) nanomaterials increased. The photocatalytic activity for the degradation of methyl orange of the anatase T-400 fibers calcined at 400 °C was the highest, compared with that at 600 and 800 °C. This work provided a simple and "green" pathway for the preparation of inorganic nanomaterials with different crystal structures by using porous regenerated cellulose matrix.     

纳米二氧化钛粉体晶相控制实验研究

在水解－沉淀法制备纳米TiO2粉体的过程中，使用不同的沉淀剂获得了晶相不同的纳米TiO2粉体，使用混合沉淀剂，通过控制沉淀剂的比例，制备了晶相组成（金红石与锐钛矿比例）不同的纳米TiO2多晶粉体，采用相同的粉体制备工艺，不同的后续处理工艺，探讨了锐钛矿向金红石转变的相变温度，经分析研究后认为，水解－沉淀法制备的纳米粉体中的锐钛矿向金红石红转变的温度为500－800℃，完全转变的温度在800℃以上；纳米TiO2多晶粉体的晶相组成不仅与沉淀剂的种类，混合沉淀剂中沉淀剂的比例和粉体的煅烧温度有关，而且与粉体的后续处理工艺和粉体表面界面相的稳定性有关。     

Effect of Nb and Sc doping on the phase transformation of sol-gel processed TiO2 nanoparticles

Nb and Sc doped TiO2 nanoparticles were synthesized via sol-gel technique. Dopant concentration of each element was varied from 0.5 to 1.5 atomic%. The effect of metal ion doping and calcination temperatures on anatase to rutile phase transformation has been investigated. Samples were analyzed by various analytical methods such as X-ray diffraction (XRD), Transmission Electron Microscope (TEM), X-ray Photoelectron Spectroscopy (XPS) and Energy Dispersive X-ray Spectroscopy (EDS). XRD analyses showed that Nb and Sc doped samples calcined at 300 degrees C and 350 degrees C, respectively, were crystalline and had an anatase structure. Results showed that anatase was stable up to 700 degrees C annealing temperature for samples doped with 0.5 atomic% Nb. There was a sharp transition from anatase to rutile phase above 700 degrees C and complete rutile structure was obtained at 750 degrees C. However, the transformation from anatase to rutile was not so sharp in samples doped with 1.0 atomic% and 1.5 atomic% Nb. Results indicated that higher concentration of Nb helps to stabilize the anatase phase. For samples doped with 0.5 atomic% Sc, anatase phase is stable up to 650 degrees C. Transformation from anatase to rutile starts at temperature above 650 degrees C and 100% rutile phase was obtained at 800 degrees C while for samples doped with 1.0 atomic% and 1.5 atomic% Sc, the complete transformation from anatase to rutile takes place at an even higher temperature. Results indicate that increasing the calcination time from 0.5 to 2.0 hours at 500 degrees C does not affect the stability of anatase phase. However, TEM and XRD data showed that the increase in the annealing time leads to an increase in particles size. The rutile to anatase concentration ratio increased with temperature above the phase transformation temperature. The activation energy for the phase transformation from anatase to rutile for doped and undoped samples was also measured. There was a general rise in the activation energy with increasing dopant concentration.     

不同晶型纳米TiO2的水热合成及光催化性能

采用水热法制备了TiO2 纳米粉 ,并通过XRD、TEM、激光粒度分析对产物进行表征。结果发现 ,采用不同的钛源 ,不同的加料方式 ,可得到不同晶型的TiO2 纳米粒子。通过系列样品对甲基橙溶液的光催化性能的研究 ,发现混晶相纳米TiO2 的光催化性能最好 ,其次是锐钛矿相 ,金红石相的光催化性能最差。