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The purpose of this study is to apply the distribution function formalism to the problem of electronic transport in open systems, and to numerically solve the kinetic equation with a dissipation term. This term is modeled within the relaxation time approximation and contains two parts, corresponding to elastic or inelastic processes. The collision operator is approximated as a sum of the semi-classical energy dissipation term and the momentum relaxation term, which randomizes the momentum but does not change the energy. As a result, the distribution of charge carriers changes due to the dissipation processes, which has a profound impact on the electronic transport through the simulated region discussed in terms of the current–voltage characteristics and their modification caused by the scattering. Measurements of the current–voltage characteristics for titanium dioxide thin layers are also presented, and compared with the results of numerical calculations.

Flower-like TiO2 nanostructures were obtained by chemical oxidation of Ti foil using H2O2 combined with subsequent annealing. This paper offers an analysis of the phase transformation of 3D flower-like titanium dioxide nanostructures. The role of the annealing atmosphere, sample thickness, grain shape, and nanoflower size are discussed. The nanostructures were examined using SEM, XRD, and Raman spectroscopy. Due to the nature of these two processes, the morphology of these nanomaterials is complex, and is obtained through a reaction involving Ti foil and H2O2 at 80°C. A distinction is made between the layer composed of small grains at the substrate/oxide interface, elongated crystal-like structures, and outer spongle-like film. The annealing parameters, such as atmosphere (air or argon) and temperature (450 or 600 °C), affect phase composition. The photoelectrochemical performance of the anode based on flower-like TiO2 has been shown. The thickness and phase composition of the anodes are factors that strongly affect the photocurrent. The multiphase heterojunctions proposed for 3D flower-like TiO2 photoanodes in photoelectrochemical (PEC) cells suppose that the conduction band of anatase should be above rutile. The highest photoelectrochemical performance was obtained for a photoanode composed of 20–40% anatase and an associated thickness of 0.75–1.5 µm. [ABSTRACT FROM AUTHOR]

SnO2@SnS2 multi-core–shell heterostructures were synthesised via chemical conversion of mesoporous raspberry-like SnO2 nanocrystals. In the syntheses, different concentrations of a sulphide precursor (thioacetamide) were applied. The samples were analysed using scanning and high-resolution transmission electron microscopy, X-ray diffraction, Raman spectroscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The results revealed the presence of surface defects (Sn2+, oxygen vacancies) on the raspberry-like surface, which play a crucial role in the chemical conversion reaction. With an increasing amount of thioacetamide, additional redox reactions occurred in the system (Sn4+/Sn2+, S2−/S0). The highest precursor concentration led to the microstructural disintegration and phase composition change. This paper demonstrates the role of defects on the formation of SnO2@SnS2 multi-core–shell heterostructures in mesoporous SnO2 nanomaterials. [ABSTRACT FROM AUTHOR]

Alternating current a.c. measurements enable to understand the physical and chemical processes occurring in semiconductor materials. Impedance spectroscopy has been successfully applied to study the responses of gas sensors based on metal oxides, such as TiO2, SnO2 and TiO2/SnO2 nanocomposites. This work is devoted to dynamic measurements of hydrogen sensor behaviour over the temperature range of 300-450°C. Frequency dependence of the impedance signal gives evidence that 50 mol% TiO2/50 mol% SnO2 nanocomposites should be treated as resistive-type sensors. Temporal evolution of the response to 500 ppm H2 at 320°C indicates a very short response time and much longer recovery. [ABSTRACT FROM AUTHOR]

Recently, transition metal oxides, which exhibit favorable catalytic abilities, have also been investigated as a material for the detection of hydrazine (N2H4). It has been reported that mixed metal oxides usually offer a higher electrochemical activity than binary oxides. In this work, a TiO2-Fe2O3 coupled system is presented as an enhanced material with major applications in electrochemical detectors. The electrochemical behavior of glassy carbon electrodes modified with TiO2-Fe2O3 in the absence and presence of hydrazine was evaluated via cyclic voltammetry (CV). Experimental results also suggest that the formation of the TiO2- Fe2O3 coupled system enhances electrochemical catalytic performance in N2H4 detection. The modification TiO2 + 2 mol% Fe2O3 provides good analytical performance of detection (0.13 mM) and quantification limits (0.39 mM). The presented coupled system provides the premise for a suitable material for a stable and sensitive N2H4 sensor. [ABSTRACT FROM AUTHOR]

The present work deals with nitrogen-doped stoichiometric TiO2:N and non-stoichiometric TiO2−x:N thin films deposited by means of dc-pulsed reactive sputtering for application as photoanodes for hydrogen generation from water, using solar energy. Stoichiometric thin films of TiO2 crystallize as a mixture of anatase and rutile while rutile phase predominates in TiO2:N at higher nitrogen flow rates as shown by X-ray diffraction at grazing incidence, XRD GID. Lack of bulk nitridation of stoichiometric TiO2:N is indicated by valence-to-core X-ray emission spectroscopy, XES, analysis. The energy band gap as well as flat band potential remain almost unaffected by increasing nitrogen flow rate in this case. In contrast to that, non-stoichiometric thin films of TiO2-x:N demonstrate systematic evolution of the structural, morphological, optical and photolectrochemical properties upon increasing level of nitrogen doping. Pronounced changes in the growth pattern of non-stoichiometric TiO2-x:N upon varied nitrogen flow rate, demonstrated by scanning electron microscopy, SEM, can be easily correlated with the crystallographic properties studied by XRD GID. Relative positions of Kβ'' XES lines of the TiO2-x:N thin films, which depend strongly on the nature of the ligands and their local coordination, change with the increasing nitrogen flow. Doping of nonstoichiometric titanium dioxide with nitrogen shifts the absorption spectrum towards the visible range and increases considerably the flat band potential which is beneficial for water photolysis. [ABSTRACT FROM AUTHOR]

Examines the effect of high-temperature treatment on n-p transition in titania (TiO[sub 2]). Derivation of electrical conductivity and Seeback coefficient for TiO[sub 2]; Formation of titanium vacancies; Electrical properties of polycrystalline samples.

The a.c. impedance response of polycrystalline ceramics SnxTi-x1O2 was studied in the air in the temperature range 298–1073 K. The impedance spectra were analyzed in terms of two proposed equivalent circuits involving both resistor and non-Debye constant phase element (CPE). The presence of CPE elements may be interpreted by diffusion phenomena. The results indicate a negligible contribution of grain boundary resistance to the total resistivity of the studied materials. The determined activation energy of the bulk conductivity of TiO2 was compared with literature data. © 2001 Kluwer Academic Publishers [ABSTRACT FROM AUTHOR]

Titanium dioxide photoanodes for hydrogen generation suffer from a profound mismatch between the optical absorption of TiO2 and the solar spectrum. To solve the problem of low solar-to-chemical efficiency, optically active materials are proposed. In this work, TiO2 thin films containing erbium were deposited by radio frequency RF magnetron sputtering under ultrahigh vacuum conditions UHV. Morphology, structural, optical and electronic properties were studied. TiO2:Er thin films are homogenous, with uniform distribution of Er ions and high transparency over the visible VIS range of the light spectrum. However, a profound 0.4 eV blue shift of the fundamental absorption edge with respect to undoped TiO2 was observed, which can be attributed either to the size effect due to amorphization of TiO2 host or to the onset of precipitation of Er2Ti2O7 nanocrystals. Near-infrared NIR to VIS up-conversion is demonstrated upon excitation at 980 nm, while strong green photoluminescence at 525 and 550 nm occurs upon photon absorption at 488 nm. [ABSTRACT FROM AUTHOR]

A TiO2@Cu2O semiconductor heterostructure with better photochemical response compared to TiO2 was obtained using an electrochemical deposition method of Cu2O on the surface of TiO2 nanotubes. The choice of 1D nanotubes was motivated by the possibility of achieving fast charge transfer, which is considered best suited for photochemical applications. The morphology and structural properties of the obtained heterojunction were determined using standard methods —SEM and Raman spectroscopy. Analysis of photoelectrochemical properties showed that TiO2@Cu2O heterostructures exhibit better properties resulting from an interaction with sunlight than TiO2. A close relationship between the morphology of the heterostructures and their photoproperties was also demonstrated. Investigations representing a combination of photoelectrochemical cells for hydrogen production and photocatalysis—photoelectrocatalysis—were also carried out and confirmed the observations on the photoproperties of heterostructures. Analysis of the Mott–Schottky plots as well as photoelectrochemical measurements (Iph-V, Iph-t) showed that TiO2 as well as, unusually, Cu2O exhibit n-type conductivity. On this basis, a new energy diagram of the TiO2@Cu2O system was proposed. It was found that TiO2@Cu2O n-n type heterostructure prevents the processes of photocorrosion of copper(I) oxide contained in a TiO2-based heterostructure. [ABSTRACT FROM AUTHOR]

Upconversion as a modification strategy to enhance the utilization of sunlight in titanium dioxide photoanodes with an internal upconverter was investigated. TiO 2 thin films containing an Er activator and Yb sensitizer were deposited in the magnetron sputtering process on conducting glass, amorphous silica, and silicon. Scanning electron microscopy, energy dispersive spectroscopy, grazing incidence X-ray diffraction, and X-ray absorption spectroscopy allowed assessment of the thin film composition, structure, and microstructure. Optical and photoluminescence properties were measured by means of spectrophotometry and spectrofluorometry. Changing the content of Er 3+ (1, 2, 10 at%) and Yb 3+ (1, 10 at%) ions allowed us to achieve thin film upconverters with a crystallized and amorphous host. Upon 980 nm laser excitation Er 3+ exhibits upconversion with the main emission in green ( 2 H 11/2 → 4 I 15/2 , λ em ≈ 525 nm) and weak emission in red ( 4 F 9/2 → 4 I 15/2 , λ em ≈ 660 nm). For a thin film with a higher ytterbium content (10 at%) a significant increase in red emission and upconversion from NIR to UV was observed. The average decay times of green emission for TiO 2 :Er and TiO 2 :Er,Yb thin films were calculated based on time-resolved emission measurements., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The aim of this research is to study the role of nanocrystalline TiO 2 /SnO 2 n-n heterojunctions for hydrogen sensing. Nanopowders of pure SnO 2 , 90 mol % SnO 2 /10 mol % TiO 2 , 10 mol % SnO 2 /90 mol % TiO 2 and pure TiO 2 have been obtained using flame spray synthesis (FSS). The samples have been characterized by BET, XRD, SEM, HR-TEM, Mössbauer effect and impedance spectroscopy. Gas-sensing experiments have been performed for H 2 concentrations of 1-3000 ppm at 200-400 °C. The nanomaterials are well-crystallized, anatase TiO 2 , rutile TiO 2 and cassiterite SnO 2 polymorphic forms are present depending on the chemical composition of the powders. The crystallite sizes from XRD peak analysis are within the range of 3-27 nm. Tin exhibits only the oxidation state 4+. The H 2 detection threshold for the studied TiO 2 /SnO 2 heterostructures is lower than 1 ppm especially in the case of SnO 2 -rich samples. The recovery time of SnO 2 -based heterostructures, despite their large responses over the whole measuring range, is much longer than that of TiO 2 -rich samples at higher H 2 flows. TiO 2 /SnO 2 heterostructures can be intentionally modified for the improved H 2 detection within both the small (1-50 ppm) and the large (50-3000 ppm) concentration range. The temperature T max at which the semiconducting behavior begins to prevail upon water desorption/oxygen adsorption depends on the TiO 2 /SnO 2 composition. The electrical resistance of sensing materials exhibits a power-law dependence on the H 2 partial pressure. This allows us to draw a conclusion about the first step in the gas sensing mechanism related to the adsorption of oxygen ions at the surface of nanomaterials.