Titanium Dioxide Nanomaterials: Synthesis, Properties, Modifications, and Applications

[Yang, Hua Gui; Sun, Cheng Hua; Qiao, Shi Zhang; Liu, Gang; Smith, Sean Campbell; Lu, Gao Qing] Univ Queensland, ARC Ctr Excellence Funct Nanomat, Sch Engn, Brisbane, Qld 4072, Australia. [Yang, Hua Gui; Sun, Cheng Hua; Qiao, Shi Zhang; Liu, Gang; Smith, Sean Campbell; Lu, Gao Qing] Univ Queensland, Australian Inst Bioengn & Nanotechnol, Ctr Computat Mol Sci, Brisbane, Qld 4072, Australia. [Zou, Jin] Univ Queensland, Ctr Microscopy & Microanal, Brisbane, Qld 4072, Australia. [Zou, Jin] Univ Queensland, Sch Engn, Brisbane, Qld 4072, Australia. [Liu, Gang; Cheng, Hui Ming] Chinese Acad Sci, Met Res Inst, Shenyang Natl Lab Mat sci, Shenyang 110016, Peoples R China.;Lu, GQ (reprint author), Univ Queensland, ARC Ctr Excellence Funct Nanomat, Sch Engn, Brisbane, Qld 4072, Australia;s.qiao@uq.edu.au maxlu@uq.edu.au

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Anatase TiO(2) single crystals with a large percentage of reactive facets

The last decade witnessed significant progress in angle-resolved photoemission spectroscopy (ARPES) and its applications. Today, ARPES experiments with 2-meV energy resolution and $0.2\ifmmode^\circ\else\textdegree\fi{}$ angular resolution are a reality even for photoemission on solids. These technological advances and the improved sample quality have enabled ARPES to emerge as a leading tool in the investigation of the high-${T}_{c}$ superconductors. This paper reviews the most recent ARPES results on the cuprate superconductors and their insulating parent and sister compounds, with the purpose of providing an updated summary of the extensive literature. The low-energy excitations are discussed with emphasis on some of the most relevant issues, such as the Fermi surface and remnant Fermi surface, the superconducting gap, the pseudogap and $d$-wave-like dispersion, evidence of electronic inhomogeneity and nanoscale phase separation, the emergence of coherent quasiparticles through the superconducting transition, and many-body effects in the one-particle spectral function due to the interaction of the charge with magnetic and/or lattice degrees of freedom. Given the dynamic nature of the field, we chose to focus mainly on reviewing the experimental data, as on the experimental side a general consensus has been reached, whereas interpretations and related theoretical models can vary significantly. The first part of the paper introduces photoemission spectroscopy in the context of strongly interacting systems, along with an update on the state-of-the-art instrumentation. The second part provides an overview of the scientific issues relevant to the investigation of the low-energy electronic structure by ARPES. The rest of the paper is devoted to the experimental results from the cuprates, and the discussion is organized along conceptual lines: normal-state electronic structure, interlayer interaction, superconducting gap, coherent superconducting peak, pseudogap, electron self-energy, and collective modes. Within each topic, ARPES data from the various copper oxides are presented.

https://arxiv.org/pdf/cond-mat/0208504.pdf

Angle-resolved photoemission studies of the cuprate superconductors

We present an experimental review of the nature of the pseudogap in the cuprate superconductors. Evidence from various experimental techniques points to a common phenomenology. The pseudogap is seen in all high-temperature superconductors and there is general agreement on the temperature and doping range where it exists. It is also becoming clear that the superconducting gap emerges from the normal state pseudogap. The d-wave nature of the order parameter holds for both the superconducting gap and the pseudogap. Although an extensive body of evidence is reviewed, a consensus on the origin of the pseudogap is as lacking as it is for the mechanism underlying high-temperature superconductivity.

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The pseudogap in high-temperature superconductors: an experimental survey

Single crystals of TiO2 anatase containing 0.22% of Al and traces of V, Zr, Nb, and La were grown by chemical transport reactions employing TeCl4 as the transporting agent. Electrodes having the (101) face exposed doped by reduction with hydrogen were employed. The electrochemical and photoelectrochemical behavior of a single crystal of anatase were scrutinized for the first time. Properties were compared to those of single-crystal rutile having the (001) face exposed. Impedance analysis established that the flatband potential of anatase (101) is shifted negatively by 0.2 V with regards to that of rutile (001). Interfacial capacitance measurements under forward bias indicate smaller density of surface states on anatase. Photoelectrochemical oxidation of water occurs on both rutile and anatase with incident photon-to-current conversion efficiencies close to unity at λ = 300 nm. From the comparison of Ufb and Eg, it follows that anatase (101) and rutile (001) electrodes differ mainly in the position of the ...

Electrochemical and photoelectrochemical investigation of single-crystal anatase

Photoemission spectromicroscopy was used to investigate the electronic structure of TiO2 anatase single crystals and polycrystalline thin films The stoichiometry and the degree of oxidation of as-grown crystals, as-deposited films, as well as of thermally annealed samples in different atmospheres, were analyzed, based on the Ti 2p and O 1s core levels, with an energy resolution of 04 eV The experimental density of states (DOS) was found to be in agreement with the theoretical DOS reported in the literature for anatase crystals, and shows some characteristics similar to the experimental DOS reported for rutile crystals In reduced samples, the experimental DOS is characterized by intense emission in the region of O 2p bonding orbitals, and does not exhibit an appreciable density of states in the band gap As-grown crystals exhibit small band gap emission (a few percent of the valence band VB signal) at about 08 eV, which is attributed to Ti3+ (3d) defect states Annealing the crystals at high temperatures in O2 or subsequent thermal reduction in an Ar-H2 Mixture (95%-5%) produces nearly stoichiometric surfaces with smaller or undetectable density of Ti3+ States In addition, some redistribution of the spectral weight is observed in the VB spectra

Electronic-Structure of Anatase Tio2 Oxide

Improved experimental conditions enabled us to increase the signal-to-noise ratio of the photoemission spectra for the superconducting state of Bi2Ca2SrCu2O8, taken with high angular and energy resolution. This also enabled us to reveal a pronounced minimum that separates the two basic features of the spectrum, the narrow quasiparticle excitation peak and the still controversial broad band at lower kinetic energies. The minimum is approximately 3-DELTA below the Fermi level.

Electronic spectrum of the high-temperature superconducting state.

We used the novel experimental technique of photoemission spectromicroscopy to investigate the active area of SnO(x) thin films for gas sensors, deposited by dc sputtering. First, we analyzed the degree of oxidation and the homogeneity of as-deposited films in a high lateral resolution (30 mum) spectromicroscopy mode with an energy resolution of 0.4 eV. This led to a surprising discovery of a large amount of tin monoxide on the film surface. Then we studied the interaction of H-2 and H2O with the surface of polycrystalline SnO2 films used as sensitive layers in actual gas sensor devices. These results have been related to the resistivity changes of the corresponding devices: we found that such changes are primarily due to a reduction process in the film rather than to mere chemisorption.

Photoemission spectromicroscopy: A new insight in the chemistry of SnOx films for gas sensors

We tested the theoretical prediction that the band structures on the opposite sides of a homojunction can be artificially displaced in energy with respect to each other by means of double intralayers of atomiclike thickness, producing band discontinuities of potential interest for practical applications. Evidence of such discontinuities was found when Ga‐As, Al‐As, Ga‐P, or Al‐P intralayers were inserted between Si and Si or Ge and Ge.

Microscopic Manipulation of Homojunction Band Lineups

Valence- and conduction-band offsets can be induced at GaAs(100) polar homojunctions by means of ultrathin Si intralayers. The microscopic interface dipole responsible for the creation of such offsets can be varied by changing the Si intralayer thickness; the consequently variable band discontinuities represent a tunable parameter with potential applications in band-gap engineering. Even though the existence and the direction of these discontinuities are in agreement with theoretical predictions, the existing models overestimate the amount of the offset and cannot explain its dependence on the intralayer thickness. The presence of Si outdiffusion can be a possible explanation for this partial disagreement.

F. Gozzo

Papers

Electronic-Structure of Anatase Tio2 Oxide

Electronic spectrum of the high-temperature superconducting state.

Photoemission spectromicroscopy: A new insight in the chemistry of SnOx films for gas sensors

Microscopic Manipulation of Homojunction Band Lineups

Artificial band discontinuities at GaAs homojunctions.