Photoconductivity studies on amorphous and crystalline TiO<Subscript>2</Subscript> films doped with gold nanoparticles

In this work, amorphous and crystalline TiO₂ films were synthesized by the sol–gel process at room temperature. The TiO₂ films were doped with gold nanoparticles. The films were spin-coated on glass wafers. The crystalline samples were annealed at 100°C for 30 minutes and sintered at 520°C for 2 h. All films were characterized using X-ray diffraction, transmission electronic microscopy and UV-Vis absorption spectroscopy. Two crystalline phases, anatase and rutile, were formed in the matrix TiO₂ and TiO₂/Au. An absorption peak was located at 570 nm (amorphous) and 645 nm (anatase). Photoconductivity studies were performed on these films. The experimental data were fitted with straight lines at darkness and under illumination at 515 nm and 645 nm. This indicates an ohmic behavior. Crystalline TiO₂/Au films are more photoconductive than the amorphous ones.     

Effect of thermal annealing on the structure and microstructure of TiO2 thin films

Nanostructured TiO₂ thin films have been prepared through chemical route using sol-gel and spin coating techniques. The deposited films were annealed in the temperature range 400–1000°C for 1 h. The structure and microstructure of the annealed films were characterized by GAXRD, micro-Raman spectroscopy and AFM. The as-deposited TiO₂ thin films are found to be amorphous. Micro-Raman and GAXRD results confirm the presence of the anatase phase and absence of the rutile phase for films annealed up to 700°C. The diffraction pattern of the film annealed at 800 to 1000°C contains peaks of both anatase and rutile reflections. The intensity of all peaks in micro-Raman and GAXRD patterns increased and their width (FWHM) decreased with increasing annealing temperature, demonstrating the improvement in the crystallinity of the annealed films. Phase transformation at higher annealing temperature involves a competition among three events such as: grain growth of anatase phase, conversion of anatase to rutile and grain growth of rutile phase. AFM image of the asdeposited films and annealed films indicated exponential grain growth at higher temperature.      

有序TiO2纳米管阵列结构的可控生长及其物相研究

分别在HF水溶液、含NH₄F和H₂O的乙二醇有机溶液中对Ti箔进行阳极氧化,得到TiO₂纳米管阵列结构.该结构高度有序、分布均匀、垂直取向,且通过阳极氧化工艺条件(如阳极氧化电压、电解液的选择与配比以及氧化时间等)可实现对其结构参数(如管径、管壁厚度、管密度、管长等)的有效控制.利用XRD研究了TiO₂纳米管阵列的物相结构.结果表明：退火前的TiO₂纳米管阵列为无定形结构;分别在真空和氧气氛中50 关键词： 2纳米管阵列')" href="#">TiO₂纳米管阵列 阳极氧化 可控生长     

Effect of annealing on TiO2 nanoparticles

TiO₂ nanoparticles have been prepared by simple chemical precipitation method and annealed at different temperatures. The as-prepared TiO₂ are amorphous, and they transform into anatase phase on annealing at 450 °C, and rutile phase on annealing at 900 °C. The X-ray diffraction results showed that TiO₂ nanoparticles with grain size in the range of 21–24 nm for anatase phase and 69–74 nm for rutile phase have been obtained. FESEM images show the formation of TiO₂ nanoparticles with small size in structure. The FTIR and Raman spectra exhibited peaks corresponding to the anatase and rutile structure phases of TiO₂. Optical absorption studies reveal that the absorption edge shifts towards longer wavelength (red shift) with increase of annealing temperature.     

Morphology modification of TiO<Subscript>2</Subscript> nanotubes by controlling the starting material crystallite size for chemical synthesis

TiO₂ nanotubes (NTs) were prepared by low-temperature chemical synthesis using anatase TiO₂ particles with different crystallite sizes in a NaOH solution followed by water washing and HCl neutralization. The synthesized TiO₂ NTs showed diverse morphologies depending on the starting materials. The crystallite size of TiO₂ raw materials increased with an increase in annealing temperature, and larger TiO₂ NTs, around 31 nm in diameter, were obtained from large raw powder with a crystallite size of 117 nm. X-ray diffraction and Raman spectroscopy revealed that the obtained TiO₂ NT exhibited lower crystallinity; however, Raman vibration seems to be more likely than a rutile structure.     

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.     

Fabrication and characterization of CdS-sensitized TiO<Subscript>2</Subscript> nanotube photoelectrode

CdS quantum dot (Qd)-sensitized TiO₂ nanotube array photoelectrode is synthesised via a two-step method on tin-doped In₂O₃-coated (ITO) glass substrate. TiO₂ nanotube arrays are prepared in the ethylene glycol electrolyte solution by anodizing titanium films which are deposited on ITO glass substrate by radio frequency sputtering. Then, the CdS Qds are deposited on the nanotubes by successive ionic layer adsorption and reaction technique. The resulting nanotube arrays are characterized by scanning electron microscopy, X-ray diffraction (XRD) and UV–visible absorption spectroscopy. The length of the obtained nanotubes reaches 1.60 μm and their inner diameter and wall thickness are around 90 and 20 nm, respectively. The XRD results show that the as-prepared TiO₂ nanotubes array is amorphous, which are converted to anatase TiO₂ after annealed at 450 °C for 2 h. The CdS Qds deposited on the TiO₂ nanotubes shift the absorption edge of TiO₂ from 388 to 494 nm. The results show that the CdS-sensitized TiO₂ nanotubes array film can be used as the photoelectrode for solar cells.     

Oxygen defect dependent variation of band gap,Urbach energy and luminescence property of anatase,anatase–rutile mixed phase and of rutile phases of TiO2 nanoparticles

TiO₂ nanoparticles are prepared by a sol–gel method and annealed both in air and vacuum at different temperatures to obtain anatase, anatase–rutile mixed phase and rutile TiO₂ nanoparticles. The phase conversion from anatase to anatase–rutile mixed phase and to rutile phase takes place via interface nucleation between adjoint anatase nanocrystallites and annealing temperature and defects take the initiate in this phase transformation. The samples are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV–vis and photoluminescence spectroscopy (PL). Anatase TiO₂ exhibits a defect related absorption hump in the visible region, which is otherwise absent in the air annealed samples. The Urbach energy is very high in the vacuum annealed and in the anatase–rutile mixed phase TiO₂. Vacuum annealed anatase TiO₂ has the lowest emission intensity, whereas an intense emission is seen in its air annealed counterpart. The oxygen vacancies in the vacuum annealed samples act as non-radiative recombination centers and quench the emission intensity. Oxygen deficient anatase TiO₂ has the longest carrier lifetime. Time resolved spectroscopy measurement shows that the oxygen vacancies act as efficient trap centers of electrons and reduce the recombination time of the charge carriers.     

Enhanced photocatalytic performance of TiO2 particles via effect of anatase–rutile ratio

In the present work anatase–rutile transformation temperature and its effect on physical/chemical properties as well as photocatalytic activity of TiO₂ particles were investigated. The characterisation of the synthesised and annealed TiO₂ particles were determined by X-Ray Powder Diffraction (XRD), scanning electron microscope (SEM), dynamic light scattering (DLS) and Brunauer–Emmett–Teller surface area analysis (BET). The refraction in the ultraviolet–visible (UV–vis) range was assessed using a dual-beam spectrophotometer. The photocatalytic performance of the particles was tested on methylene blue solution. The XRD data indicated that the percentage of rutile increased with the annealing temperature and almost 100% of anatase transformed to rutile at 1000 °C. In addition, the phase transformation was a linear function of annealing temperature so phase composition of TiO₂ can be controlled by changing the annealing temperature. The SEM and BET results presented the increase of agglomerate size and the decrease of specific surface area with the increasing annealing temperature. This proved that anatase has smaller particle size and higher surface area than rutile. The photocatalytic activity of the annealed TiO₂ powders reduced with the increase of annealing temperature. The samples annealed at 900 °C and 925 °C with anatase: rutile ratio of 92:8 and 77:23, respectively, showed the best activity. These results suggested that the photocatalytic activity of TiO₂ particles is a function of phase composition. Thus it can be enhanced by changing its phase composition which can be controlled by annealing temperature.     

Effect of TiO2 crystalline composition on the dielectric properties of TiO2/P(VDF‐TrFE) composites

In order to study the effect of the TiO₂ particle crystalline composition (with different proportions of rutile and anatase crystals) on the dielectric properties of the composite, titanium dioxide (TiO₂) particles and TiO₂/poly(vinylidene fluoride‐co‐trifluoroethylene) [P(VDF‐TrFE)] composites were synthesized by a reflux method and the solution route, respectively. The results indicated that the optimum TiO₂ particle crystalline composition is anatase content of 37% and rutile content of 63% for dielectric‐constant modifier applications. Furthermore, a dielectric constant of 25.7 with dielectric loss of 0.17 at 100 Hz at room temperature were obtained in the composite with 40 wt% TiO₂ particles. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electron spin resonance from annealed titania nanotubes

Titania nanotubes were prepared using a hydrothermal method. Hydrogen titanate nanotubes (H-TNTs) with an anatase phase changed to anatase nanocrystals at about 500 °C, and then a rutile structure at ∼800 °C. A sharp and symmetrical electron spin resonance (ESR) signal (g=2.003), attributed to a single-electron-trapped oxygen-vacancy (SETOV), was obtained at the annealed H-TNTs (T<500 °C). The SETOV signal increased and maximized remarkably at about 400–500 °C. Then, the nanotube structure appeared to be demolished. Yet, when the vacuum-heated H-TNTs were sealed in N₂ or Ar ambient, some additional ESR signals appeared besides the SETOV signal. The broad asymmetric ESR signal (g=1.98) was attributed to a surface oxygen vacancy related to the Ti³⁺ sites in a reduced TiO₂ matrix. The vacuum-heated sodium titanate nanotubes (Na-TNTs) showed only the SETOV signal (T<500 °C). PACS 61.46.Fg; 61.72.Ji; 76.30.-v     

Structural study of TiO2 thin films by micro-Raman spectroscopy

The Raman spectroscopy method was used for structural characterization of TiO₂ thin films prepared by atomic layer deposition (ALD) and pulsed laser deposition (PLD) on fused silica and single-crystal silicon and sapphire substrates. Using ALD, anatase thin films were grown on silica and silicon substrates at temperatures 125–425 °C. At higher deposition temperatures, mixed anatase and rutile phases grew on these substrates. Post-growth annealing resulted in anatase-to-rutile phase transitions at 750 °C in the case of pure anatase films. The films that contained chlorine residues and were amorphous in their as-grown stage transformed into anatase phase at 400 °C and retained this phase even after annealing at 900 °C. On single crystal sapphire substrates, phase-pure rutile films were obtained by ALD at 425 °C and higher temperatures without additional annealing. Thin films that predominantly contained brookite phase were grown by PLD on silica substrates using rutile as a starting material.     

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.     

Synthesis and bioactivity of highly ordered TiO2 nanotube arrays

The highly ordered TiO₂ nanotube arrays were fabricated by potentiostatic anodization of Ti foils in fluorinated dimethyl sulfoxide (DMSO). TiO₂ nanotube arrays are formed using a 40 V anodization potential for 24 h, with a length of 12 μm, diameter of 170 nm and aspect ration of about 70. The as-prepared nanotubes are amorphous, but can be crystallized as the heat treatment temperature increases. Anatase phase appears at a temperature of about 300 °C, then transforms to rutile phase at about 600 °C. After heat treatment at 500 °C and soaking in SBF for 14d, a thick apatite layer of about 13 μm covers the whole surface of TiO₂ nanotube arrays, indicating their excellent in vitro bioactivity, which is mainly attributed to their high specific surface area and the anatase phase.     

Charge transport in anodic TiO2 nanotubes studied by terahertz spectroscopy

We report on the photoelectrochemical and terahertz measurements, of the charge transport properties of 1 μm thick self‐organized TiO₂ nanotube layers, prepared by the anodization of titanium. We provide evidence regarding the complexity of electron transport, and dynamics in the nanotubes. Shortly after photoexcitation, charge mobilites in amorphous and crystalline nanotubes are similar, but still lower compared to the bulk anatase. The mobility subsequently decreases due to trapping‐detrapping processes. The recombination rate in anatase nanotubes is much slower than in the amorphous ones, enabling the material to reach an internal photon to electron conversion efficiency exceeding 60%.     

Effect of calcination temperature on the morphology and surface properties of TiO2 nanotube arrays

Well-ordered TiO₂ nanotube arrays were prepared by electrochemical anodization of titanium in aqueous electrolyte solution of H₃PO₄ + NH₄F at a constant voltage of 20 V for 3 h, followed by calcined at various temperatures. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and Photoluminescence (PL) were used to characterize the samples. The results showed that the as-prepared nanotube arrays before being calcined were amorphous and could transform to anatase phase at a heat treatment temperature higher than 400 °C. As the calcination temperatures increased, crystallization of anatase phase enhanced and rutile phase appeared at 600 °C. However, further increasing the calcination temperature would cause the collapse of nanotube arrays. PL intensity of the nanotube arrays annealed at 500 °C was the lowest, which was probably ascribed to better crystallization together with fewer surface defects of the nanotube arrays.     

Efficient solar energy conversion using TiO2 nanotubes produced by rapid breakdown anodization – a comparison

We report on dye‐sensitization of different TiO₂ nanotube layers, their photoelectrochemical response and their efficiency for solar energy conversion. The tubes compared in this study were either grown by controlled Ti anodization in fluoride containing electrolytes or by rapid breakdown anodization (RBA) of Ti in fluoride free electrolytes. After converting the different tube layers to anatase and sensitizing with Ru‐dye (N719), clearly layers consisting of RBA‐NTs show a significantly higher photoresponse and conversion efficiencies than tubes formed under self‐ordering conditions. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Phase transformations and crystallization kinetics in electrospun TiO2 nanofibers in air and argon atmospheres

The effects of atmospheric air and argon environments on thermal-induced phase transformations in electrospun TiO₂ nanofibers have been investigated in situ using synchrotron radiation diffraction. Diffraction results showed that the as-synthesized TiO₂ nanofibers were initially amorphous, but crystallized to form anatase and rutile after thermal annealing in air or argon at elevated temperatures. The crystallization temperature of anatase was delayed by 100 °C in argon relative to in air, and the transformation of anatase into rutile occurs faster in argon atmosphere than in air due to the formation of oxygen vacancies. Non-linear strains formed in both polymorphs and the substantial elevation of rutile thermal expansion pointed to strain anisotropy in the rutile phase and the concomitant fibre breakage.     

Preparation of F-doped titania nanoparticles with a highly thermally stable anatase phase by alcoholysis of TiCl4

Pure anatase is a metastable phase and inclined to (transform) be transformed into rutile structure under heating over than 500 °C, which limits its suitability for high-temperature applications. Hitherto much research efforts have been made to increase the stability temperature of anatase structure. However, metallic doping usually introduced metallic oxides into titania at high temperature, and many nonmetallic doping are not competent for increasing the stability temperature of anatase structure up to 900 °C. In this study, F-doped anatase TiO₂ nanoparticles were conveniently prepared via the alcoholysis of TiCl₄ and the as-prepared product shows very high stability temperature up to 1000 °C before being transformed into rutile structure phase. On the basis of XPS results of F-doped titania annealed at different temperature, it is learned that the F atoms were anchored on the crystal planes of anatase in favor of decreasing the energy faces of anatase and stabilizing the anatase structure till annealed at 1300 °C all the anatase were transformed into rutile phase.     

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.