Thermoelectric power of mixed electronic-ionic conductors III. Case of calcium titanate

The primary purpose of the present work is the determination of the thermopower component related to electronic charge carriers for undoped calcium titanate. The second purpose of this work is establishment of the relationship between this thermopower component and the electronic component of electrical conductivity. An essential part of the present study includes the determination of the thermopower components corresponding to different charge carriers (electrons, electron holes and ions). The determination procedures are based on the following three models:

Symmetrical model. This model assumes consistency between thermopower and electrical conuctivity in terms of the n-p transition (this model assumes that minimum of electrical conductivity corresponds to the electronic component of the thermopower equal zero). It was shown that this model does not apply for CaTiO₃.

The Heikes model. This model is based on Heikes formula and also hopping mechanism of the transport of electrons. It was shown that thermopower of CaTiO₃ cannot be described by this model and, consequently, thermopower vs. electrical conductivity cannot be considered within the Jonker formalism.

General model. This model is based on a general thermopower equation for mixed conductors without any simplifying assumptions. Application of this model indicates that the electronic component of thermopower is not consistent with the minimum of electrical conductivity.

     

Charge transport in polycrystalline titanium dioxide☆

This work reports semiconducting properties of undoped polycrystalline TiO₂ studied using the measurements of the electrical conductivity (EC) and thermopower as a function of oxygen partial pressure and temperature in the ranges of p(O₂) between 10 Pa and 70 kPa and temperature 1173–1273 K. The width of the band gap, determined from the minimum of EC, is equal to 3.055±0.012 eV. It was found that the apparent concentration of negatively charged defects, involving both acceptor-type aliovalent ions and Ti vacancies, increases with temperature from 0.6 at% at 1173 K to the level of 0.9–1.4 at% at 1273 K. This effect is considered in terms of Schottky-type defects. It was observed that the minimum of EC at the n–p transition is lower than that for TiO₂ single crystal thus suggesting that grain boundaries are responsible for the formation of conductivity weak links.     

Proprietes electriques des phases de basse temperature M1, T et M2 dans VO2 dope au chrome et a l'aluminium

The electrical conductivity and thermopower have been measured on Cr and Al doped VO₂ single crystals. The insulating M₁, T and M₂ phases have a similar behaviour with an activation energy E_a ?0.40 eV. The conductivity halves abruptly at the T→M₂ transition but no discontinuity is observed for the thermopower. The ansiotropy of the thermopower may be due to the anisotropic mobility of the holes in the lower quasi one dimensional Hubbard band.     

Half-metallicity and onsite Hubbard interaction on d-electronic states: a case study of Fe2NiZ (Z = Al,Ga, Si,Ge) Heusler systems

DFT-based structural optimisations of Fe₂NiZ (Z?=?Al, Ga, Si, Ge) Heusler compounds confirm the stability of these alloys in F-43m phase. While defining the electronic structure, onsite Hubbard approximation scheme for exchange correlations predicted better results than the generalised gradient approximation. Calculated band structure and densities of states together with spin magnetic moments designate the half-metallic character of these alloys. Indirect band gaps, 1.2?eV for Fe₂NiAl, 0.98?eV for Fe₂NiGa, 1.3?eV for Fe₂NiSi and 1.1?eV for Fe₂NiGe in spin-down states are observed. The ferromagnetic spin moments amount to an integral value of 5μB for (Al, Ga) and 6μB for (Si, Ge) systems with a maximum contribution from transition metal atom (Fe). To forecast the possible turnout of the thermopower, Seebeck coefficients, electrical and thermal conductivities are calculated, which directly hints the thermoelectric response of these materials. This study creates a possibility of these alloys in thermoelectrics and spintronics.     

Physical properties of NxTiO2 prepared by sol–gel route

The compounds N_xTiO₂(x=0, 0.05, 0.1, 0.2) with the anatase structure have been synthesized by Sol–Gel method using Tri-ethyl Amine as nitrogen source and their optical, electrical and electrochemical properties are investigated. The electrical conductivity and thermoelectric power are measured in the temperature rang 300–600 K. The samples exhibit p-type behavior in contrast to TiO₂. The doped-samples exhibit two optical transitions (2.35≤E_h−Vis(eV)≤2.55; 1.97≤E_l−Vis (eV)≤2.06) directly allowed in the visible region, while only one transition is observed in UV region (E_UV∼3.00 eV). Pure TiO₂ shows direct band gap transition of 3.17 eV. The results confirm experimentally the calculations of Di. Valentin et al. [42]. The transitions E_h−Vis and E_l−Vis are attributed respectively to the promotion of electrons from the localized N 2p and π^? N–O bond to the conduction band. In all cases, E_UV is associated to the forbidden band energy. Though that the conductivity is generally improved by doping process, only N_0.05TiO₂ and N_0.1TiO₂ shows an enhanced mobility. The mechanism of conduction takes place by small polaron hopping. The band edge positions of N_xTiO₂ (x=0, 0.05, 0.1, 0.2) at room temperature is predicted from the obtained physical properties. This study proves experimentally the principal role of nitrogen in doping process and permits the electronic states localization associated with N-impurities in TiO₂ anatase.     

Optical properties of anatase and rutile titanium dioxide: Ab initio calculations for pure and anion-doped material

The optical properties of rutile and anatase titanium dioxide (TiO₂) are calculated from the imaginary part of the dielectric function using pseudopotential density functional method within its generalized gradient approximation (GGA) and a scissors approximation. The fundamental absorption edges calculated for the unit cell of both rutile and anatase are consistent with experimentally reported results of single crystal rutile and anatase TiO₂ and with previous theoretical calculations. A significant optical anisotropy is observed in the anatase structure which holds promise for investigating the band gap modification with better visible-light response and provides a reliable foundation for addressing the effect of impurities on the fundamental absorption edge/band gap of anatase TiO₂. Further calculations on the electronic structure and the optical properties of C-, N-, and S-doped anatase TiO₂ are performed. The results are analyzed and discussed in terms of optical anisotropy and scissors approximations.     

Electronic and ionic conductivity in CaTiO3

The present work describes the electrical conductivity of undoped CaTiO₃ in terms of the electrical conductivity components corresponding to electrons, electron holes and ionic charge carriers in the temperature range 973 K — 1323 K and under controlled oxygen partial pressure (10 Pa — 72 kPa). These data are considered in terms of the transference numbers of the respective charge carriers. It appears that the ionic conductivity component assumes maximum at the n-p transition when the ionic transfer number reaches 50% of the total conductivity value at 1323 K. The present study also includes the determination of the activation energy of the conductivity component related to ions (162.1 kJ/mol), electrons (134.2 kJ/mol) and electron holes (86.2 kJ/mol). The data obtained in this work indicate that undoped CaTiO₃ exhibits a substantial level of ionic conduction that cannot be ignored in a quantitative analysis of electrical conductivity data.     

Niveaux d'énergie et spectres de rayons X du rutile

The electronic levels of the complex TiO^?8₆ in the D_2h symmetry are determined according to an extended L. C. A. O. method. The results can explain the X-ray spectra of TiO₂. The absoption L_III and K rays are related to transitions from the 2p_3/2 and 1 s levels to the conduction band levels since the emission L_III and K components are explained by the transitions from the valence band levels to the 2p_3/2 and 1 s states. Interband transitions are related to the components of the optical reflexion spectrum of TiO₂ for the energies 0–20 eV. A comparaison is made with the electronic band structures of SnO₂, TiO₂ and BaTiO₃. At the center of the Brillouin zone, we obtain a forbidden gap of 3,01 eV, the corresponding widths of the valence and conduction band are 4,8 and 2,9 eV.     

Study of trapping and recombination centres in Tl2InGaTe4 chain crystals by dark electrical conductivity and photoconductivity measurements

Dark electrical conductivity and photoconductivity of Tl₂InGaTe₄ single crystals have been measured and analyzed in the temperature region 100–300 K. The dark electrical conductivity measurements revealed an intrinsic- or extrinsic-type of conductivity above or below 210 K, respectively. From intrinsic conductivity data analysis, the energy band gap of Tl₂InGaTe₄ crystals was determined as 0.85 eV. In the extrinsic region, the dark conductivity arises from a donor energy level located at 0.30 eV below the conduction band. The photocurrent increases with increasing illumination intensity. The recombination mechanism in the crystal changes as temperature decreases due to the effect of exponential trapping centres. Two trapping and/or recombination centres located at 89 and 27 meV were determined from the temperature dependence of the photocurrent, which decreased or increased with increasing temperature in the regions above or below 180 K, respectively.     

Thermoelectric power of mixed electronic-ionic conductors I. Basic equations

The present work considers thermopower of oxide materials within n-p transition regime. Specifically, basic equations describing the effect of thermocell reactions on both ionic and electronic component of thermoelectric power are derived. The proposed formalism considers the impact of gas/solid reactions on the relationship between thermopower and electrochemical potential within a system involving a metal oxide of nonstoichiometric composition and a metal (such as Pt) that is applied as a measuring electrode. The derived theoretical model allows the determination of the thermopower components corresponding to different charge carriers, including ions, electrons and electron holes, for metal oxides. The proposed model may be used for derivation of defect chemistry models based on thermopower data that are free of the ionic component.     

Electron transport in Ti1−xNbxO2 solid solutions with x < 4%

By means of conductivity and thermopower measurements in niobium doped rutile TiO₂, we have analysed the electron transport. A previous study made in TiO₂ pointed out the existence of a large polaron transport. Nevertheless, some uncertainties remain as the precise dependence of the mobility with the temperature. The Nb doped TiU₂ studied in the present paper brings some new information: the mobility could follow an optical phonon scattering law. The FHIP model seems to be the more appropriate model to describe the mobility but the lack of theoretical calculation of transport energy does not allow definitive conclusions about the physical processes which occur in the intermediate range of temperature. However, we can say that the ionization activation energy of Nb is found to be close to 14 eV.Moreover, it is found that the localized electrons become mobile by hopping with increasing niobium content. This yields a conductivity composed by electrons which move in the 3d Ti band and localized electrons which hop from site to site. This hopping component and the number of localized electrons increase with niobium content. This leads to the disappearance of the band motion in the conductivity.     

Electrical properties of TiO<Subscript>2</Subscript>: equilibrium vs dynamic electrical conductivity

The present work reports semiconducting properties of high purity TiO₂ determined in the gas/solid equilibrium, as well as during controlled heating and cooling in the range 300–1,273 K. The activation energy of the electrical conductivity is considered in terms of the activation enthalpy of the formation of ionic defects and the activation enthalpy of the mobility of electronic defects. These data, determined from the dynamic electrical conductivity experiments, are compared to the electrical conductivity data determined in equilibrium. It is shown that only the equilibrium electrical conductivity data for high-purity TiO₂ are well defined. It is shown that the activation energy of the electrical conductivity determined in equilibrium differs substantially from that for the dynamic electrical conductivity data during cooling and heating. It is concluded that the formation enthalpy term determined from the dynamic conductivity data is determined by the heating/cooling rate rather than materials’ properties.     

Structural,optoelectronic and thermoelectric properties of antiperovskite compounds Ae3PbS (Ae = Ca,Sr and Ba): A first principles study

In the last years, alkaline-earth based antiperovskite compounds with small semiconductor band gap have been proven to be promising candidate for optoelectronic and thermoelectric applications. In this work, the structural, electronic, optical and thermoelectric properties of Ae₃PbS (Ae = Ca, Sr and Ba) compounds have been predicted using first principles calculations based on the full-potential linearized augmented plane-wave (FP-LAPW) method and semiclassical Boltzmann transport theory. Exchange-correlation effect is treated with the generalized gradient approximation with Perdew–Burke–Ernzerhof scheme (GGA-PBE) and Tran–Blaha modified Becke–Johnson exchange potential. The lattice constant of considered materials increases as Ae goes in order from Ca to Ba and the hardness slightly decreases in this order. Ca₃PbS and Sr₃PbS are semiconductor with direct band gap of 0.199 eV and 0.116 eV, respectively, while Ba₃PbS is nearly metallic. Important optical responses of studied antiperovskites are found in the visible and ultraviolet energy range. Finally, the thermoelectric properties including Seebeck coefficient, electrical conductivity, thermal conductivity, power factor and figure of merit are calculated. Obtained results show that Ca₃PbS and Sr₃PbS could be candidate for applications in thermoelectric generators at low and moderate temperatures due to their high figure of merit values.     

A first-principles calculation on the electronic properties of Si/N-codoped TiO2

To deeply understand the effects of Si/N-codoping on the electronic structures of TiO₂ and confirm their photocatalytic performance, a comparison theoretical study of their energetic and electronic properties was carried out involving single N-doping, single Si-doping and three models of Si/N-codoping based on first-principles. As for N-doped TiO₂, an isolated N 2p state locates above the top of valence band and mixes with O 2p states, resulting in band gap narrowing. However, the unoccupied N 2p state acts as electrons traps to promote the electron-hole recombination. Using Si-doping, the band gap has a decrease of 0.24 eV and the valence band broadens about 0.30 eV. These two factors cause a better performance of photocatalyst. The special Si/N-codoped TiO₂ model with one O atom replaced by a N atom and its adjacent Ti atom replaced by a Si atom, has the smallest defect formation energy in three codoping models, suggesting the model is the most energetic favorable. The calculated energy results also indicate that the Si incorporation increases the N concentration in Si/N-codoped TiO₂. This model obtains the most narrowed band gap of 1.63 eV in comparison with the other two models. The dopant states hybridize with O 2p states, leading to the valence band broadening and then improving the mobility of photo-generated hole; the N 2p states are occupied simultaneously. The significantly narrowed band gap and the absence of recombination center can give a reasonable explanation for the high photocatalytic activity under visible light.     

First-principles studies of structural,mechanical, electronic,optical properties and pressure-induced phase transition of CuInO2 polymorph

Using the first-principles density-functional theory within the generalized gradient approximation (GGA), we have investigated the structural, elastic, mechanical, electronic, and optical properties and phase transition of CuInO₂. Structural parameters including lattice constants and internal parameter, pressure effects and phase transition pressure were calculated. We have obtained the elastic coefficients, bulk modulus, shear modulus, Young's modulus and Poisson's ratio. We find that two phases of CuInO₂ are indirect band gap semiconductors (F–Γ and H–Γ for 3R and 2H, respectively). Optical properties, including the dielectric function, refractive index, extinction coefficient, reflectivity, absorption coefficient, loss function and optical conductivity have been obtained for radiations of up to 30 eV.     

Investigation of electronic structure of Nd-doped TiO2 nanoparticles using synchrotron radiation photoelectron spectroscopy

Doping with transition metal ions in TiO₂ has been found effective to modify the electronic structure of TiO₂ nanoparticles. Application of synchrotron radiation photoelectron spectroscopy (SRPES) to Nd-doped TiO₂ nanoparticles revealed that there existed different peak positions and structure with different doping concentration in the valence band spectra. From the onset of valence band spectrum, it was observed that doping Nd ions alters the electronic structure and makes the band gap of TiO₂ narrow.     

Structural, electrical and optical properties of TiO2 doped WO3 thin films

TiO₂ doped WO₃ thin films were deposited onto glass substrates and fluorine doped tin oxide (FTO) coated conducting glass substrates, maintained at 500 °C by pyrolytic decomposition of adequate precursor solution. Equimolar ammonium tungstate ((NH₄)₂WO₄) and titanyl acetyl acetonate (TiAcAc) solutions were mixed together at pH 9 in volume proportions and used as a precursor solution for the deposition of TiO₂ doped WO₃ thin films. Doping concentrations were varied between 4 and 38%. The effect of TiO₂ doping concentration on structural, electrical and optical properties of TiO₂ doped WO₃ thin films were studied. Values of room temperature electrical resistivity, thermoelectric power and band gap energy (E_g) were estimated. The films with 38% TiO₂ doping in WO₃ exhibited lowest resistivity, n-type electrical conductivity and improved electrochromic performance among all the samples. The values of thermoelectric power (TEP) were in the range of 23-56 μV/K and the direct band gap energy varied between 2.72 and 2.86 eV.     

Hydrostatic pressure driven spin,volume and band gap collapses in SmFeO3: a GGA + U study

The crystal structure, magnetic and electronic properties of SmFeO₃ under hydrostatic pressure have been studied by first-principles calculations within the generalized gradient approximation plus Hubbard U (GGA + U). The iso-structural phase transition with spin, volume and band gap collapses can be induced by a large enough hydrostatic pressure. The high-spin (HS) state of Fe³⁺, with the magnetic moment of ~4 μ_B, is retained at low pressure. The spin crossover occurs at a transition pressure (~68 GPa) with the magnetic moment of Fe³⁺ decreasing to ~1 μ_B in low-spin (LS) state. Meanwhile, the reductions of cell volume (by ~?5.43%) and band gap (from >2 eV to ~1.6 eV) of SmFeO₃ are obtained when the HS–LS transition happens. Finally, the critical pressure of HS–LS transition, magnetic and electronic properties are found to be Hubbard U dependent.     

Luminescence and electrical conductivity of CsSnBr3, and related phases

The black cubic compound CsSnBr₃ shows intense red luminsecene under blue light or electron beam excitation. A second emisssion band occurs in the near IR. This compound shows semiconductor behaviour with a band gap of 0.34 eV up to 303 K when a minor phase transition occurs. As bromide is replaced by chloride the emission band and the absorption edge move to higher energy and the electrical conductivity decreases by a factor of 10⁵. These results are discussed in terms of a possible band structure.