Optoelectronic properties of rutile (TiO2)

We present here a study of the electronic and optical properties of rutile (TiO₂). An investigation into the energy, pressure and temperature dependence of n_eff and ε_{∞ eff} is presented. Using the calculated values of n_eff and ε_{∞ effs}, we evaluate the Penn gap. The Penn gap thus obtained is shown to be in good agreement with the reflectivity data and also with the value obtained from band structure. In addition, we also show that essentially the Varshni formula explains the temperature dependence of the energy gap for rutile fairly well.     

EPR-spectra of Ga-doped rutile (TiO2)

The EPR spectrum of a trapped hole center in Ga-doped TiO₂ is reported. The electronic structure of the center is discussed in view of the electron configuration of the Ga³⁺ ion.     

Paraelectric resonance of slightly reduced rutile (TiO2)

Paraelectric resonance experiments on slightly reduced, aluminium doped rutile single crystals are reported. In the region 32–37 GHz at reduced He-temperatures a single resonance line is observed which is ascribed to an orientable electric dipole constituted of a multiply localized electron and an interstitial Ti³⁺ ion.     

First-principles study of native defects in rutile TiO2

Native point defects in the rutile TiO₂ are studied via first-principles pseudopotential calculations. Except for the two antisite defects, all the native point defects have low formation energies. Under the Ti-rich growth condition, high concentrations of titanium interstitials and oxygen vacancies would form spontaneously in p-type samples; whereas high concentrations of titanium vacancies would form spontaneously in n-type samples regardless of the oxygen partial pressure.     

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.     

Thermal faceting of the rutile TiO2(001) surface

Temperature dependent faceting of rutile TiO₂ surfaces cut to the (001) plane has been reported [Tait and Kasowski, Phys. Rev. B20 (1979) 5178]. By comparing LEED data to beam positions calculated for various sets of facet planes, the facet planes have been identified. The first ordered structure observed on annealing ion bombarded surfaces is composed of {011} facets with the facet planes in a (2 × 1) reconstruction. The high temperature structure produced on annealing above 1300K is best described as {114} facets; however, there are deviations of the observed LEED pattern from that calculated for {114} facets, possibly because of the presence of related planes. LEED data have now been obtained on the behavior of (110), (100), (011), (114), and (001) surfaces in UHV. The observed stability of TiO₂ surfaces can be related to the Ti ion coordination numbers in the surface plane as derived from stoichiometric terminations of the rutile lattice.     

Formation energies of point defects in rutile (TiO2)

The formation energies for the point defect species Ti⁴⁺ interstitials, Ti_i⁴⁺, and oxygen vacancies with an effective charge of + 2e, Vo²⁺, have been calculated using the polarisable point ion shell model. The formation energy of Ti_i⁴⁺ was found to be a 10.8 eV for occupation of the (0, $\text{1}\text{2}$, $\text{1}\text{2}$) site. The energy of Ti_i⁴⁺ at other sites is somewhat higher than this figure, and allowed the migration energy of Ti_i⁴⁺ parallel to the c axis to be estimated as 2.9 eV. The formation energy of Vo²⁺ was found to be 10.1eV. The variation of these formation energies with dielectric constant was also calculated. It was found that the energy of formation of Ti_i⁴⁺ varied considerably with dielectric constant, while the formation energy of Vo²⁺ was almost independent of dielectric constant. The relevance of these results to the presence of crystallographic shear planes in reduced rutile is considered.     

Surface reconstruction on stishovite SiO2,HfO2 and rutile TiO2 （001）

This paper systematically investigates the surface reconstruction processes and patterns on stishovite SiO 2,HfO 2 and rutile TiO 2 (001) by using classical molecular dynamics.It is found that these three surfaces relax instead of reconstruction at 0 K,and have little possibility to reconstruct below 40 K.Above 40 K,surface reconstructions take place as collective atomic motion which can be speeded by higher temperature or compressed strain.Several reconstruction patterns with approximate surface energies are found,and electrostatic potentials on them are also provided in comparison with possible microscopic results.     

Raman investigation of rutile RuO2

We report the first Raman investigation of the rutile material RuO₂. The four allowed first-order Raman-active phonon modes have been observed and classified. Comparison is made with other rutile materials.     

Raman study of phase transformation of TiO2 rutile single crystal irradiated by infrared femtosecond laser

Titanium dioxide (TiO₂) rutile single crystal was irradiated by infrared femtosecond (fs) laser pulses with repetition rate of 250 kHz and phase transformation of rutile TiO₂ was observed. Micro-Raman spectra show that the intensity of E_g Raman vibrating mode of rutile phase increases and that of A_1g Raman vibrating mode decreases apparently within the ablation crater after fs laser irradiation. With increasing of irradiation time, the Raman vibrating modes of anatase phase emerged. Rutile phase of TiO₂ single crystal is partly transformed into anatase phase. The anatase phase content transformed from rutile phase increased to a constant with increasing of fs pulse laser irradiation time. The study indicates the more stable rutile phase is transformed into anatase phase by the high pressure produced by fs pulse laser irradiation.     

I掺杂金红石TiO$lt;sub$gt;2$lt;/sub$gt;(110)面的第一性原理研究

利用基于密度泛函理论的第一性原理研究了I掺杂金红石TiO₂（110）表面的形成能和电子结构,分析了不同掺杂位置的结构对TiO₂光催化性能的影响. 计算表明,氧化环境下I最容易替代掺杂表面五配位的Ti,而还原环境下最容易替代掺杂表面的桥位氧. I替位Ti或I替位O都能降低禁带宽度,可能使TiO₂吸收带出现红移现象或产生在可见光区的吸收,其中I替位桥位氧的禁带宽度最小. 吸收光谱表明,I掺杂不仅能提高TiO₂可见光响应,同时可增加紫外光的吸收能量,提高其可见光及紫外光下的光催化性能. 关键词： 第一性原理 I掺杂 2(110)')" href="#">金红石相TiO₂(110) 光催化     

EPR study of Mn-implanted single crystal plates of TiO2 rutile

Single crystals of Mn-implanted TiO₂ rutile have been investigated by electron paramagnetic resonance (EPR) technique at room temperature. We have observed an EPR signal on Mn⁴⁺ ions (S=) in the manganese-implanted single crystal TiO₂ plates. Besides, weaker EPR signals due to Fe³⁺(S=, L=0) and Cr³⁺(S=) ions have also been observed. Characteristic six-line splitting of the manganese EPR lines due to hyper-fine interaction with ⁵⁵Mn nuclei (spin I=) has also been observed. Analysis of the EPR spectra shows that the manganese, iron and chromium ions substitute for Ti⁴⁺ ions in the TiO₂ rutile host. Two structurally equivalent groups of the centers have been observed in the EPR spectra in correspondence with two octahedral positions of the Ti ions in the rutile structure. Spin Hamiltonian parameters for the crystal field of orthorhombic symmetry on the Mn⁴⁺, Fe³⁺ and Cr³⁺ centers have been obtained as result of computer modelling.     

Lo phonon-plasmon coupling in non-stoichiometric rutile TiO2

The analysis of the infrared reflectivity spectrum of partially reduced rutile TiO_1.96 reveals a plasmon-LO phonon coupling. Pure-phonon and plasmon frequencies and life times are determined by fit with an appropriate model using the factorized form of the dielectric function for the phonon modes added to a plasmon contribution also derived from the factorized form. Results are compared with data obtained in the insulating stoichiometric rutile.     

Ab initio study of phonons in the rutile structure of TiO2

The local-density approximation is used to find the phonon dispersion relations, total and partial phonon density of states for TiO₂ crystal of rutile structure. For that the Hellmann-Feynman forces were computed and direct method applied. Some thermodynamic quantities are also presented. Calculated results are analyzed and compared with the experimental neutron scattering and optic data. Good agreement has been achieved. A giant LO/TO splitting is observed for A_2u and E_u modes.     

The structure of FeCl2 at high pressures

A full three-dimensional structure determination of FeCl₂ has been performed at hydrostatic pressures up to 6.4 kbar at room temperature. These studies demonstrate the feasibility of four-circle neutron diffraction studies under pressure, and show that above 5.8 kbar FeCl₂ has a structure isomorphous to FeBr₂. The pressure dependence of chlorine position parameter and lattice parameters has been studied over the entire pressure range.     

First-principles study of the electronic and optical properties of rutile TiO2

The electronic, structural properties and optical properties of the rutile TiO₂ have been reported using the full potential linearized augmented plane wave (FP-LAPW) method as implemented in the WIEN2K code. We employed the generalized gradient approximation (GGA), which is based on exchange-correlation energy optimization to calculate the total energy. Also we have used the Engel-Vosko GGA formalism, which optimizes the corresponding potential for band structure calculations. Our results including lattice parameter, bulk modulus, density of states, the reflectivity spectra, the refractive index and band gap are compared with the experimental data. We present calculations of the frequency-dependent complex dielectric function ε(ω) and its zero-frequency limit ε₁(0).     

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.     

Excess electrons in reduced rutile and anatase TiO2

As a prototypical photocatalyst, TiO₂ is a material of scientific and technological interest. In photocatalysis and other applications, TiO₂ is often reduced, behaving as an n-type semiconductor with unique physico-chemical properties. In this review, we summarize recent advances in the understanding of the fundamental properties and applications of excess electrons in reduced, undoped TiO₂. We discuss the characteristics of excess electrons in the bulk and at the surface of rutile and anatase TiO₂ focusing on their localization, spatial distribution, energy levels, and dynamical properties. We examine specific features of the electronic states for photoexcited TiO₂, for intrinsic oxygen vacancy and Ti interstitial defects, and for surface hydroxyls. We discuss similarities and differences in the behaviors of excess electrons in the rutile and anatase phases. Finally, we consider the effect of excess electrons on the reactivity, focusing on the interaction between excess electrons and adsorbates.     

Correlation between defect structures and dielectric constant in gallia-doped rutile (TiO2)

Dielectric constants and a.c. resistivities of rutile (TiO₂) doped with gallia (Ga₂O₃) have been measured as a function of frequency in the range 30–60 kHz at 20°C. The specimens were prepared by heating rutile single crystals on Ga₂O₃ pellets, at 1300°C, in air for various times. The dielectric constants depend on the frequency of measurement. In the c axis, the dielectric constant at low frequencies (30–100 Hz) increases as the sample heating time is extended to 1 week, but it decreases rapidly when the heating time is prolonged over 1 week. However, in the a axis, the dielectric constant does not change from the value of the starting material, being independent of the heating time. Besides dielectric measurements, the defect structures were determined using transmission electron microscopy, which showed that low concentrations of planar faults on {120} planes occur. The changes in dielectric constant are interpreted as being due to space change effects associated with Ga³⁺ ions located in the tunnels which lie parallel to the rutile c axis. Calculations are also included which show why other defects in the crystals have no effect on the value of the dielectric constant compared to pure rutile.     

Electrical conductivity and amorphization of Sc2(WO4)3 at high pressures and temperatures

Impedance spectroscopy measurements and synchrotron X-ray diffraction studies of Sc₂(WO₄)₃ at 400°C have been carried out as a function of pressure up to 4.4 GPa. Ionic conductivity shows normal decrease with increase in pressure up to 2.9 GPa, but then increases at higher pressures. The XRD results show that Sc₂(WO₄)₃ undergoes pressure-induced amorphization at pressures coincident with the reversal in conductivity behavior. The loss of crystal structure at high pressure is consistent with growing evidence of pressure-induced amorphization in negative thermal expansion materials, such as Sc₂(WO₄)₃. The increase in conductivity in the amorphized state is interpreted as the result of an increase in structural entropy and a concomitant reduction of energy barriers for ionic transport.