Effects of deposition rates on laser damage threshold of TiO2/SiO2 high reflectors

TiO₂ single layers and TiO₂/SiO₂ high reflectors (HR) are prepared by electron beam evaporation at different TiO₂ deposition rates. It is found that the changes of properties of TiO₂ films with the increase of rate, such as the increase of refractive index and extinction coefficient and the decrease of physical thickness, lead to the spectrum shift and reflectivity bandwidth broadening of HR together with the increase of absorption and decrease of laser-induced damage threshold. The damages are found of different morphologies: a shallow pit to a seriously delaminated and deep crater, and the different amorphous-to-anatase-to-rutile phase transition processes detected by Raman study. The frequency shift of Raman vibration mode correlates with the strain in film. Energy dispersive X-ray analysis reveals that impurities and non-stoichiometric defects are two absorption initiations resulting to the laser-induced transformation.     

Characterization of TiO2/Au/TiO2 films deposited by magnetron sputtering on polycarbonate substrates

Transparent and conducting TiO₂/Au/TiO₂ (TAuT) films were deposited by reactive magnetron sputtering on polycarbonate substrates to investigate the effect of the Au interlayer on the optical, electrical, and structural properties of the films. In TAuT films, the Au interlayer thickness was kept at 5 nm. Although total thickness was maintained at 100 nm, the stack structure was varied as 50/5/45, 70/5/25, and 90/5/5 nm.In XRD pattern, the intermediate Au films were crystallized, while all TAuT films did not show any diffraction peaks for TiO₂ films with regardless of stack structure. The optical and electrical properties were dependent on the stack structure of the films. The lowest sheet resistance of 23 Ω/□ and highest optical transmittance of 76% at 550 nm were obtained from TiO₂ 90 nm/Au 5 nm/TiO₂ 5 nm films. The work function was dependent on the film stack. The highest work function (4.8 eV) was observed with the TiO₂ 90 nm/Au 5 nm/TiO₂ 5 nm film stack. The TAuT film stack of TiO₂ 90 nm/Au 5 nm/TiO₂ 5 nm films is an optimized stack that may be an alternative candidate for transparent electrodes in flat panel displays.     

TiO2/CdSe多层膜结构的制备及光电化学性能研究

采用电化学方法在导电的ITO/TiO₂ 薄膜上沉积了棕红色CdSe薄膜, 并制得TiO₂/CdSe多层膜体系,研究了多层膜的微结构和光电化学性能. 实验表明, CdSe薄膜沿着(111)方向择优生长, 多层膜结构的厚度和紫外-可见光吸收强度随着沉积层数的增加而增加. 通过测定多层膜电极的光电化学性能表明, 二层膜体系的开路电压和短路电流密度最大,光电化学性能最好.     

The effect of porosity on the laser induced damage threshold of TiO2 and ZrO2 single layer films

Monolayer ZrO₂ and TiO₂ films were prepared on BK7 glass by physical vapor deposition (PVD) and were subsequently annealed for 1 h at 300 °C. By using the transmission spectra of two samples and the envelope method, the refractive index dispersion and extinction coefficients have been calculated. Laser induced damage threshold (LIDT) measurement shows that despite slight differences between the extinction coefficients of the two samples, the LIDT parameter of the ZrO₂ film is greater than that of the TiO₂ film. This fact leads us to consider thermal conductivity as an important parameter for interpreting the LIDT difference. According to our theoretical analysis, as a consequence of increase in the number of thermal barriers along poorer film, its thermal conductivity, and hence LIDT, decreased, which is in agreement with our experimental results. The measured porosity of the two samples shows higher porosity for TiO₂ single layer, which is in agreement with atomic force (AFM) images. The gradual and smooth damage morphology of ZrO₂ observed in optical images implies higher thermal conductivity than TiO₂.     

Synthesis and Characterization of TiO2 Doped ZnO Microtubes

以氯化锌和硫酸钛为原料,通过湿化学法成功制备了钛掺杂氧化锌微米管. 以粉末X射线衍射仪、场发射扫描电子显微镜、光致发光系统对样品进行了表征. 结果表明,未经掺杂的氧化锌微管具有良好的六方中空结构. 在TiO₂/ZnO比率小于5%时,钛掺杂和未掺杂氧化锌管具有相近的尺度,外表光滑,近于圆柱形. 当TiO₂/ZnO比率大于5%时,生成一种由ZnO, Ti₃O₅和TiO组成的多相混合物. 钛掺杂氧化锌在光催化降解甲基橙溶液效果明显.     

Hydrogen shallow donors in ZnO and rutile TiO2

A combined study of IR absorption, photoconductivity, photoluminescence and Raman measurements in ZnO samples supports the theoretical suggestions of a shallow bond-centered hydrogen donor and a shallow hydrogen donor within the oxygen vacancy. In rutile TiO₂ we also identify a shallow hydrogen donor in contrast to recent theoretical predictions. A possible solution to this obvious discrepancy is proposed.     

Light-induced antifungal activity of TiO2 nanoparticles/ZnO nanowires

Antifungal activity of TiO₂/ZnO nanostructures under visible light irradiation was investigated. A simple chemical method was used to synthesize ZnO nanowires. Zinc acetate dihydrate, Polyvinyl Pyrrolidone and deionized water were used as precursor, capping and solvent, respectively. TiO₂ nanoparticles were deposited on ZnO nanowires using an atmospheric pressure chemical vapor deposition system. X-ray diffraction pattern of TiO₂/ZnO nano-composite has represented the diffraction peaks relating to the crystal planes of the TiO₂ (anatase and rutile) and ZnO. TiO₂/ZnO nanostructure antifungal effect on Candida albicans biofilms was studied and compared with the activity of TiO₂ nanoparticles and ZnO nanowires. The high efficiency photocatalytic activity of TiO₂ nanoparticles leads to increased antifungal activity of ZnO nanowires. Scanning electron microscope was utilized to study the morphology of the as prepared nanostructures and the degradation of the yeast.     

Raman spectra of TiO2-II,TiO2-III,SnO2, and GeO2 at high pressure

Raman spectra of the orthorhombic (II) and high pressure (III) phases of titanium dioxide at pressures to 372 kbar and effects of temperature and hydrostatic pressure on Raman spectra of the tetagonal cassiterite-like phases of TiO₂, GeO₂ and SnO₂ are described. At room temperature, the TiO₂ II–III transition is sluggish, and metastable coexistence was observed from 200 to 300 kbar. The Raman spectra of TiO₂-III imply that its primitive cell contains at least four formula units; however, the structure could not be established from the Raman spectra and available powder X-ray diffraction patterns.The temperature and pressure dependences of the spectrum of the tetragonal MO₂ phases together with bulk moduli and thermal expansion data were used to evaluate the pure-volume and pure-temperature contributions to the isobaric temperature dependence of the Raman frequencies. Large anharmonicities in TiO₂ are attributed to hybridization of the oxygen p states with the d states of the Ti ion. GeO₂, where p-electron bonding is involved, is much less Enharmonic.     

Effects of annealing on laser-induced damage threshold of TiO2/SiO2 high reflectors

The mechanism of improving 1064 nm, 12 ns laser-induced damage threshold (LIDT) of TiO₂/SiO₂ high reflectors (HR) prepared by electronic beam evaporation from 5.1 to 13.1 J/cm² by thermal annealing is discussed. Through optical properties, structure and chemical composition analysis, it is found that the reduced atomic non-stoichiometric defects are the main reason of absorption decrease and LIDT rise after annealing. A remarkable increase of LIDT is found at 300 °C annealing. The refractive index and film inhomogeneity rise, physical thickness decrease, and film stress changes from compress stress to tensile stress due to the structure change during annealing.     

Interband optical transition strengths in SiO2, GeO2, SnO2 and TiO2

An analysis of interband optical transition strengths for a series of MO₂ oxides is presented which gives clear evidence for a direct proportionality between transition strengths (as measured by the dispersion energy) and nearest-neighbor cation coordination number. It is also found that neither the extent of O2p orbital delocalization nor the d-electron configuration has a strong influence on transition strengths suggestin that these strengths can be viewed, to a good approximation, as intrinsic properties of valence s,p-electrons which are largely independent of band structure details.     

Investigation of chemical decomposition of CCl4 on TiO2 near room temperature

Dissociative adsorption of CCl₄ on TiO₂ at 35 °C has been studied by Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and electron spin resonance. CCl₄ decompose to form CO, CO₂, and CO₃ on the surface, at such a low temperature, in which CO₂ formation is not from CO oxidation on TiO₂, but CO₃ can be produced by CO and CO₂ adsorption. The Cl generated from CCl₄ decomposition is left on the surface and bonded to titanium ions. Mineralization of CCl₄ on TiO₂ involves the lattice oxygens. Thermodynamical driving force and possible reaction routes for CO and CO₂ formation in the CCl₄ decomposition on TiO₂ are discussed.     

Deposition of Au/TiO2 film by pulsed laser

Au nanoparticles, which were photoreduced by a Nd:YAG laser in HAuCl₄ solution containing TiO₂ colloid and accompanied by the TiO₂ particles, were deposited on the substrate surface. The film consisting of Au/TiO₂ particles was characterized by the absorption spectra, scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis. The adhesion between the film and substrate was evaluated by using adhesive tape test. It was found that the presence of TiO₂ dramatically enhanced the adhesion strength between the film and the substrate, as well as the deposition rate of film. The mechanism for the deposition of Au/TiO₂ film was also discussed.     

Characterization of N,C-codoped TiO2 films prepared by reactive DC magnetron sputtering

Titanium dioxide (TiO₂) films are deposited by codoping nitrogen and carbon on indium tin oxide-coated substrates as visible light (Vis)-enabled catalysts. The X-ray diffraction peak intensity of the preferential orientation in (2 1 1) plane declines when the topmost 1.0 μm layer of the film is ground off. The decrease in the crystallite size and the crystallinity of anatase TiO₂ film is also evidenced by a shift towards the high wave number and broadening of the Raman spectra. Low doping concentrations of N (1.3%) and C (1.8%) are estimated by X-ray photoelectron spectroscopy (XPS) which displays an N 1s peak at 396.8 eV and a C 1s peak at 282.1 eV, respectively. This is attributed to the substitution of the oxygen sites with nitrogen and carbon, which is believed to be responsible for the Vis photocatalytic activity into a wavelength of >500 nm. The cross-sectional transmission electron microscopy images show larger pores at the grain boundaries and in larger columnar crystals than in the undoped TiO₂ film. All of these results indicate that porosity, crystallinity and shift in the preferential orientation are more pronounced close to the surface than close to the bottom of the sample. Wettability upon measurement of the water contact angle, methylene blue degradation and radical formation tests under both ultraviolet and Vis irradiation demonstrate that the topmost surface renders not only a larger reactive surface area but also a better carrier transport route than the rest of the film, improving its photocatalytic activity. These results show that surface porosity of the film is dominant than the tailoring of the photocatalytic activities of N,C-codoped TiO₂ catalysts.     

Femtosecond pulsed laser deposition of nanostructured TiO2 films

Nanostructured deposits of TiO₂ were grown on Si (1 0 0) substrates by laser ablating a TiO₂ sintered target in vacuum or in oxygen using a Ti:sapphire laser delivering 80 fs pulses. The effect of the laser irradiation wavelength on the obtained nanostructures, was investigated using 800, 400 and 266 nm at different substrate temperatures and pressures of oxygen. The composition of the deposits was characterized using X-ray photoelectron spectroscopy (XPS) and the surface morphology was studied by environmental scanning electron microscopy (ESEM) and atomic force microscopy (AFM). Deposits are absent of microscopic droplets in all conditions explored. The best deposits, constituted by nanoparticles of an average diameter of 30 nm with a narrow size distribution, were obtained at the shorter laser wavelength of 266 nm under vacuum at substrate room temperature.     

CdSe infiltrated TiO2 based omnidirectional photonic crystals for visible light control

Control of light emission by engineering the electromagnetic vacuum is important in photonics for fundamental understanding as well as in applications. Omnidirectional photonic crystals such as logpile photonic crystals provide a very interesting system to study such phenomena. Here, we describe the first steps towards achieving systematic and reproducible control of light using titanium dioxide (TiO₂) logpile photonic crystals (PC) with incorporated cadmium chalcogenide (CdSe) quantum dots (QDs) (λ  600 nm) to potentially modify QD photoluminescence (PL). We present a technique for coating a monolayer of the QDs on the PC rods based on 3-mercaptopropyltrimethoxysilanol linkage and measured the resulting PL response. Comparison of the PL spectra to a finite difference time domain model shows the need for further localization of QDs and fabrication of additional PC unit cells to observe PL modification.     

Laser-induced fluorescence of Pb2

Pb₂, which occurs in lead vapor, was studied by the technique of laser-induced fluorescence using single-mode Ar-laser excitation. The fluorescence observed could be classified into the F-X system. Ten progressions involving vibrational quantum numbers v′ = 0?9 and v″ = 0?22 were analyzed. Including collision-induced lines, rotational quantum numbers from J = 25 to J = 300 were observed. The vibrational constants and the numbering of the states had to be reassigned. For the first time rotational constants were determined for the Pb₂ molecule. The internuclear distances of ²⁰⁸Pb₂ in the F and X state are $\text{r = 3.079}\text{A}\text{?}$ and $\text{r}{}_{\mathrm{<mtext>e</mtext>}}\text{= 2.930}\text{A}\text{?}$, respectively. Using the constants derived RKR potentials and Franck-Condon factors were calculated, which confirmed the vibrational assignments and constants.     

From anodic TiO2 nanotubes to hexagonally ordered TiO2 nanocolumns

We report on the formation of hexagonally ordered TiO₂ nanocolumnar layers by electrochemical oxidation in a fluoride containing electrolyte, using self-organizing nanotube formation conditions at elevated potentials and low temperatures. The influence of the substrate temperature on the nanocolumn morphology and composition is investigated and characterized by FE-SEM and EDX. The origin of these nanocolumns can be attributed to a thickening of the inner tube wall of the double wall structure of self-organized TiO₂ nanotubes. Furthermore, a transition from nanocolumnar to nanotubular structure can be established by changing the applied voltage or applying a post-immersion treatment.     

Structural and electrical transport properties of Nb-doped TiO2 films deposited on LaAlO3 by rf sputtering

We have investigated the structural and electrical transport properties of Nb-doped TiO₂ films deposited on (1 0 0) LaAlO₃ substrates by rf magnetron sputtering at temperatures ranging from 873 K to 1073 K. Films deposited below 998 K are anatase, and mixed phases between anatase and rutile exist in the film grown at higher temperatures. We find that films deposited at low temperatures exhibit semiconductor behavior, while metallic conductivity is observed in the most conducting film deposited at 998 K. For this sample, compared to electron-phonon scattering mechanism, electron-phonon-impurity interference effect plays an important role in its electron transport process. Moreover, the temperature coefficient of the resistivity for the film deposited at 1073 K is negative from 2 K to 300 K. The temperature dependence of resistivity for the film is described by ∼exp(b/T)^1/2 at temperatures from 80 K down to 30 K, and by the fluctuation induced tunneling model from 80 K to 300 K.     

丁胺包裹的CdSe量子点敏化的TiO2纳米晶薄膜电子转移机制

利用超快光谱技术系统研究了在丁胺包裹的CdSe量子点敏化的TiO₂纳米晶薄膜起始时刻界面间电子转移动力学。与之前的报道不同,该实验结果表明:CdSe量子点经过表面修饰后,两相电子注入机制--热电子和冷电子注入得以被证实,即:电子能分别从CdSe量子点导带中高的振动能级和导带底转移到TiO₂的导带。该机制详细描绘了电子在纳米界面间转移的图景。进一步研究发现:热电子注入的电子耦合强度(3.6±0.1 meV)比弛豫后的基态电子注入高两个数量级,基于Marcus理论,伴随着0.083 eV的重组能,冷电子注入的耦合强度值为~50 μeV。