Ti L2 Research Articles

Elemental quantification using electron energy-loss spectroscopy with a low voltage scanning transmission electron microscope (STEM-EELS)

Electron beam damage in electron microscopes is becoming more and more problematic in material research with the increasing demand of characterization of new beam sensitive material such as Li based compounds used in lithium-ion batteries. To avoid radiolysis damage, it has become common practice to use Cryo-EM, however, knock-on damage can still occur in conventional TEM/STEM with a high-accelerating voltage (200–300 keV). In this work, electron energy loss spectroscopy with an accelerating voltage of 30,20 and 10 keV was explored with h-BN, TiB2 and TiN compounds. All Ti L2,3, N K and B K edges were successfully observed with an accelerating voltage as low as 10 keV. An accurate elemental quantification for all three samples was obtained using a multi-linear least square (MLLS) procedure which gives at most a 5 % of standard deviation which is well within the error of the computation of the inelastic partial-cross section used for the quantification. These results show the great potential of using low-voltage EELS which is another step towards a knock-on damage free analysis.

Titanium Self-Intercalation Induced Formation of Orthogonal (1 × 1) Edge/Surface Reconstruction in 1T-TiSe2: Atomic Scale Dynamics and Mechanistic Study.

Edges and surfaces play indispensable roles in affecting the chemical-physical properties of materials, particularly in two-dimensional transition metal dichalcogenides (TMDCs) with reduced dimensionality. Herein, we report a novel edge/surface structure in multilayer 1T-TiSe2, i.e., the orthogonal (1 × 1) reconstruction, induced by the self-intercalation of Ti atoms into interlayer octahedral sites of the host TiSe2 at elevated temperature. Formation dynamics of the reconstructed edge/surface are captured at the atomic level by in situ scanning transmission electron microscopy (STEM) and further validated by density functional theory (DFT), which enables the proposal of the nucleation mechanism and two growth routes (zigzag and armchair). Via STEM-electron energy loss spectroscopy (STEM-EELS), a chemical shift of 0.6 eV in Ti L3,2 is observed in the reconstructed edge/surface, which is attributed to the change of the coordination number and lattice distortion. The present work provides insights to tailor the atomic/electronic structures and properties of 2D TMDC materials.

Determining Quasi-Equilibrium Electron and Hole Distributions of Plasmonic Photocatalysts Using Photomodulated X-ray Absorption Spectroscopy.

Most photocatalytic and photovoltaic devices operate under broadband, constant illumination. Electron and hole dynamics in these devices, however, are usually measured by using ultrafast pulsed lasers in a narrow wavelength range. In this work, we use excited-state X-ray theory originally developed for transient X-ray experiments to study steady-state photomodulated X-ray spectra. We use this method to attempt to extract electron and hole distributions from spectra collected at a nontime-resolved synchrotron beamline. A set of plasmonic metal core-shell nanoparticles is designed as the control experiment because they can systematically isolate photothermal, hot electron, and thermalized electron-hole pairs in a TiO2 shell. Steady-state changes in the Ti L2,3 edge are measured with and without continuous-wave illumination of the nanoparticle's localized surface plasmon resonance. The results suggest that within error the quasi-equilibrium carrier distribution can be determined even from relatively noisy data with mixed excited-state phenomena. Just as importantly, the theoretical analysis of noisy data is used to provide guidelines for the beamline development of photomodulated steady-state spectroscopy.

Enhancement of the Solar Water Splitting Efficiency Mediated by Surface Segregation in Ti-Doped Hematite Nanorods.

Band engineering is employed thoroughly and targets technologically scalable photoanodes for solar water splitting applications. Complex and costly recipes are necessary, often for average performances. Here, we report simple photoanode growth and thermal annealing with effective band engineering results. By comparing Ti-doped hematite photoanodes annealed under nitrogen to photoanodes annealed in air, we found a strongly enhanced photocurrent of more than 200% in the first case. Using electrochemical impedance spectroscopy and synchrotron X-ray spectromicroscopy, we demonstrate that oxidized surface states and increased density of charge carriers are responsible for the enhanced photoelectrochemical (PEC) activity. Surface states are found to be related to the formation of pseudo-brookite clusters by surface Ti segregation. Spectro-ptychography is used for the first time at the Ti L3 absorption edge to isolate Ti chemical coordination arising from pseudo-brookite cluster contribution. Correlated with electron microscopy investigation and density functional theory calculations, the synchrotron spectromicroscopy data unambiguously prove the origin of enhanced PEC activity of N2-annealed Ti-doped hematite nanorods. Finally, we present here a handy and cheap surface engineering method beyond the known oxygen vacancy doping, allowing a net gain in the PEC activity for the hematite-based photoanodes.

Different atomic contrasts in HAADF images and EELS maps of rutile TiO2.

High-angle annular dark-field (HAADF) imaging and elemental mapping at the atomic scale by scanning transmission electron microscopy (STEM) combined with electron energy-loss spectroscopy (EELS) are widely used for material characterization, in which quantitative understanding of the contrast of the image is required. Here, we report an unexpected image contrast in the elemental mapping of rutile TiO2, where the Ti L2,3 map shows an anisotropic elliptical shape that extends along the long axis in the octahedral structure, while the atomic contrast of Ti columns in the HAADF image is almost circular. Multi-slice simulation reveals that unique electron channeling related to the rutile structure and the difference of the potentials between HAADF and EELS cause the different atomic contrasts in the two images.

Effect of annealing temperature on the structural, electronic and magnetic properties of Co doped TiO2 nanoparticles: An investigation by synchrotron-based experimental techniques

The present study examines the effect of annealing temperature on the structural, electronic and magnetic properties of Co-doped TiO2 (TCO) nanoparticles (NPs) synthesized by the sol-gel method. X-ray powder diffractograms of TCO NPs annealed at 400, 600 and 800 °C exhibited the monophasic anatase, diphase (anatase and rutile) and monophasic rutile structures respectively. A morphological investigation using high-resolution scanning electron microscopy (HR-SEM) reveals the presence of nanoparticles with diameters ranging from ∼11 to ∼51 nm. The widening and shifting of the most intense Eg peak in Raman studies and SEM images of TCO NPs suggest Co incorporation in the TiO2 matrix and the formation of oxygen vacancies. Magnetic measurements of TCO at room temperature demonstrate ferromagnetic behaviour which is caused by the existence of oxygen vacancies and the doped Co content. Element specific technique, soft X-ray magnetic circular dichroism (XMCD) was used to study the magnetism in Co doped TiO2 samples. The estimated total magnetic moment by XMCD was in the range of ∼1.3 ± 0.1–2.3 ± 0.2 μB/Co. This huge magnetization was first time observed by the surface-sensitive Total Electron Yield (TEY) mode. The estimated saturation magnetic moment is in the range of 1.0–1.5 μB/Co, also consistent with XMCD analysis and cluster model calculation. The results obtained by XMCD recommend an intrinsic behaviour of ferromagnetism. The X-ray absorption spectra (XAS) of Co-doped TiO2 nanoparticles at Ti L2,3 and Co L2,3 -edge in TEY mode concludes that the valence states of Co and Ti ions are in 2 + and 4 + respectively. Cluster model calculation also confirmed that Co ions are in a 2 + valence state with D2 h high spin crystal-field symmetry at the surface while a random crystal field symmetry in bulk has been observed which is well consistent with experimental data.

XANES and XRR study on phase evolution of TiO2 films developed using HiPIMS

High power impulse magnetron sputtering (HiPIMS) is one of the recent advanced techniques for the development of high quality TiO2 thin films. Due to the formation of high energetic ions in the discharge, HiPIMS can produce various crystalline phases of TiO2 (anatase and rutile) with low roughness as compared to conventional direct current magnetron sputtering (DCMS). This work emphasizes on the effect of oxygen partial pressure in the evolution of phases and oxidation states of TiO2 films deposited using HiPIMS along with a comparative study against DCMS grown films under similar oxygen environment. TiO2 thin films were prepared with DCMS and HiPIMS, as a function of oxygen content in the sputter gas flow. Thickness, density and roughness were calculated using XRR fitting and analysis. It was observed that HiPIMS deposited films were smoother and denser than DCMS grown films. Crystallite sizes of HiPIMS deposited films were significantly lower than DCMS. Phase growth analyses were performed using X-ray diffraction (XRD), Raman and XANES (X-ray absorption near-edge spectroscopy of the Ti L2,3 and O K-edges) spectroscopy. In HiPIMS grown films, the increase in O2 partial pressure changed the phase from rutile to mixed and then to anatase phase whereas only rutile and mixed phases were detected in DCMS grown film under similar oxygen environment. HiPIMS developed films were smooth, uniform free from cracks as observed in FESEM and Atomic Force microscope (AFM) morphological images. Lognormal crystallite size distribution values decreased with increasing O2 partial pressure. Crystal field splitting values of (Δo) between ∼1.9 and 2.2 eV indicate crystalline phase formation by XANES Ti L2,3-edge analysis. These findings point to better crystalline growth TiO2 thin films as compared to DC-MS. HiPIMS grown films shows phase transformation of rutile into mix phase and anatase with increase in oxygen partial pressure.

Atomic-scale characterization of the oxidation state of Ti in meteoritic hibonite: Implications for early solar system thermodynamics

Abstract Calcium-aluminum-rich inclusions (CAIs) in chondritic meteorites are composed of refractory minerals thought to be the first solids to have formed in the solar nebula. Among them, hibonite, nominally CaAl12O19, holds particular interest because it can incorporate significant amounts of Ti into its crystal structure in both Ti3+ and Ti4+ oxidation states. The relative amounts of these cations that are incorporated reflect the redox conditions under which the grain formed or last equilibrated and their measurement can provide insight into the thermodynamic landscape of the early solar nebula. Here we develop a new method for the quantification of Ti oxidation states using electron energy-loss spectroscopy (EELS) in an aberration-corrected scanning transmission electron microscope (STEM) to apply it to hibonite. Using a series of Ti-bearing oxides, we find that the onset intensity of the Ti L2,3 edge decreases with increasing Ti-oxidation state, which is corroborated by simulated Ti-oxide spectra using first-principles density-functional theory. We test the relationship on a set of synthetic hibonite grains with known Ti4+/ΣTi values and apply the developed method on a hibonite grain from a compact type A inclusion in the Northwest Africa (NWA) 5028 CR2 carbonaceous chondrite. The STEM-EELS data show that the chondritic hibonite grain is zoned with a Ti4+/ΣTi ratio ranging from 0.78 ± 0.04 to 0.93 ± 0.04 over a scale of 100 nm between the core and edge of the grain, respectively. The Ti substitution sites are characterized by experimental and calculated high-angle annular-dark-field (HAADF) images and atomic-level EEL spectrum imaging. Simulated HAADF images reveal that Ti is distributed between the M2 and M4 sites while Mg sits on the M3 site. Quantitative energy-dispersive X-ray spectroscopy shows that this grain is also zoned in Al and Ti. The Mg distribution is not well correlated with that of Ti and Ti4+/ΣTi at the nanoscale. The spatial decoupling of the element composition and Ti-oxidation states suggests a multistage evolution for this hibonite grain. We hypothesize that Ti and Mg were incorporated into the structure during condensation at high temperature through multiple reactions. Transient heating, presumably in the solar nebula, adds complexity to the crystal chemistry and potentially redistributed Ti and Mg. Concurrently, the formation of oxygen vacancies as a result of a reducing gas, led to the reduction of Ti4+ to Ti3+. The multiple defect reactions occurring in this single hibonite crystal preclude a simple relationship between the Ti4+/ΣTi and the fO2 of formation. However, moving forward, these measurements are fundamental inputs for modeling of the thermodynamic conditions under which hibonite formed in the early solar nebula.

Electronic structure and physical properties of hybrid heterostructures Sr2CrOsO6/BaTiO3

We report on the electronic structure and magnetic properties of hybrid heterostructures combined the ferromagnetic double perovskite Sr2CrOsO6 (SCOsO) and ferroelectric BaTiO3 (BTO) calculated in the GGA approach using the fully relativistic spin-polarized Dirac LMTO method. The electronic band structure is studied in the BTO and SCOsO oxides as well as in SCOsO/BTO hetero structures with different supercells: (1 × 1 × 1) monolayered, (2 × 2 × 1), and (1 × 1 × 2) SCOsO/BTO heterostructures. The optical and magneto-optical spectra of pure BTO and SCOsO oxides as well as of the SCOsO/BTO heterostructures are investigated theoretically and compared with avaliable experimental data. The element-specific x-ray absorption spectra as well as the x-ray magnetic circular dichroism at the Ti, Ba, and Os L2,3 edges in SCOsO/BTO heterostructures are investigated theoretically. Good agreement with experimental spectra has been found.

Atomic-scale structure and non-stoichiometry of meteoritic hibonite: A transmission electron microscope study

Abstract Hibonite (CaAl12O19) is a common refractory mineral in Ca-Al-rich inclusions (CAIs) in primitive meteorites. Transmission electron microscope (TEM) studies have identified enigmatic planar defects in different occurrences of hibonite in the Allende meteorite that give rise to strong streaking along c* in electron diffraction patterns. Atomic resolution high-angle annular dark-field (HAADF) imaging and energy-dispersive X-ray (EDX) analyses were used to determine the nature and origin of these planar features. HAADF images of hibonite grains reveal lamellar intergrowths of common 1.6 nm spacing, and less commonly 2.0 and 2.5 nm spacings, interspersed in stoichiometric hibonite showing 1.1 nm (002) spacing. Stoichiometric hibonite consists of alternating Ca-containing (“R”) and spinel-structured (“S”) blocks stacked in a sequence RS. In contrast, the 1.6 nm layers result from a doubled S block such that the stacking sequence is RSS, while in the widest defect observed, the stacking sequence is RSSSS. These intergrowths are epitaxial and have coherent, low-strain boundaries with the host hibonite Meteoritic hibonite shows common Ti and Mg substitution for Al in its structure. Atomic-resolution EDX maps of hibonite grains in the Allende CAI confirm the preferred site occupancy of Mg on tetragonal M3 sites in S blocks and of Ti on trigonal bipyramidal M2 and octahedral M4 sites in R blocks. Mg is highly concentrated, but Ti is absent in the planar defects where wider S blocks show Al-rich compositions compared to stoichiometric MgAl2O4 spinel. Therefore, Mg likely played the major role in the formation and metastability of planar defects in hibonite. Electron energy loss spectroscopy data from the Ti L2,3 edge show the presence of mixed Ti oxidation states with ~15–20% of Ti as Ti3+ in hibonite, suggesting a direct substitution of Ti3+ ↔ Al3+ in hibonite. The remaining ~80–85% of Ti is present as Ti4+ and corresponding EDX analyses are consistent with the well-known coupled substitution 2Al3+ ↔ Ti4+ + Mg2+ being the major mechanism for Ti and Mg substitution in hibonite. The formation of planar defects in hibonite occurred during high-temperature nebular condensation or melting/crystallization processes. The occurrence of non-stoichiometric hibonite in the Allende CAI deviates from the mineral formation sequence predicted from equilibrium condensation models. Overall, our atomic resolution TEM observations signify non-equilibrium, kinetic-controlled crystal growth during the high-temperature formation of refractory solids in the early solar nebula.

Multiplet structure for perovskite-type Ba0.9Ca0.1Ti0.9Zr0.1O3 by core–hole spectroscopies

Core–hole spectroscopies such as x-ray photoelectron spectroscopy (XPS) and high-resolution electron energy loss spectroscopy (HR-EELS) in combination with multiplet calculation are important tools to elucidate the electronic structure of transition metal compounds. This work presents a comparison between the electronic structure obtained by XPS and HR-EELS for polycrystalline perovskite-type Ba0.9Ca0.1Ti0.9Zr0.1O3. Raman analysis suggests that Ca2+ cations could partly occupy the Ti4+ cations in the B-site of a perovskite structure with the tetragonal phase. A multiplet structure was determined by XPS for Ti 2p and by HR-EELS for Ca L2,3 and Ti L2,3 edges. Octahedral (Oh) symmetry in the crystal field (CF) effects reproduces the local distortion of TiO6 octahedra. The charge transfer (CT) effects were also considered to reproduce L3-edge EELS shoulders and the satellite in the Ti 2p XPS region. CF and CT parameters, 10 Dq, (charge transfer energy) Δ, and (Coulomb repulsion energy) Udd, are reported for future reference. The broadening of the Ti L2-edge suggests the presence of the Coster–Kronig electron decay process. Multiplet calculation in Oh symmetry for the Ca L2,3-edge could support the Raman interpretation.

Opto-electronic properties of anodized TiO2 nanotube arrays investigated using electron energy loss spectroscopy

A study of the nanoscale crystallinity of anodized TiO2 nanotubes is reported with the aim of demonstrating its influence on the localized optical and electronic properties of the structure. By employing scanning transmission electron microscopy, coupled with electron energy loss spectroscopy, x-ray diffraction and electron energy filtered jump-ratio imaging to probe changes in the electron near edge fine structure of the Ti L3,2 ionization edge, it is found that nanotubes annealed at 450 °C in air for 3 h crystallize in the anatase polymorph along their walls, with the underlying thick oxide barrier layer being predominantly rutile. An increase in annealing temperature to 600 °C results in the co-existence of anatase and rutile along the nanotube length with the nanotube top and bottom showing crystallization in anatase and rutile, respectively. Valence EELS shows that the localized energy band-gap is inconsistent along the nanotube length, deviating between that typically measured for anatase (3.2 eV) and rutile (3.0 eV). The obtained band-gap of 3.21 eV at the nanotube top and 3.44 eV at nanotube bottom is attributed to the co-existence of anatase and rutile phases even at a low annealing temperature of 450 °C.

Axial expansion of Ni-doped TiO2 nanorods grown on carbon nanotubes for favourable lithium-ion intercalation

The serious worldwide competition of energy efficient materials has led the pathway for many materials previously not focused on energy storage applications. In this report, Ni-doped TiO2/MWCNTs (NixTi1−xO2/MWCNTs) nanocomposites were synthesized by surfactant-assisted controlled hydrolysis approach taking advantage of the synergistic interplay between MWCNTs and Ni-doped TiO2 leveraging both the electrode performance and stability. At an optimal 5% doping of Ni the electrode showed 241.3 mAh g−1 capacity at C/10 for 80 cycles, moreover an excellent rate capacity (154.1 mAh g−1) is also demonstrated even at a high rate of 20 C. The lower angle shift and enlargement of TiO2 unit cell from XRD results indicate that Ni is occupying Ti position in TiO2 matrix. The increase in the intensity of t2g and eg bands in O K edge NEXAFS point to the effective hybridization between Ni 3d and O 2p orbitals. Ni and Ti L3,2 edge from NEXAFS spectra clearly reflect 2+ and 4+ valence states of Ni and Ti, respectively. C K edge NEXAFS provides clear evidence for a charge distribution and chemical bonding between NixTi1−xO2 nanorods and MWCNTs. Ex-situ XANES studies of lithiated samples have proved that Ti and Ni K edge shifts to lower energy upon increased doping concentration while ex-situ XRD points towards the lattice expansion upon Li-insertion that seems to be most favoured for Ni0.05Ti0.95O2/MWCNTs sample. This work offers new outlooks for electrode fabrication with a deep insight into structural alterations associated with the charging-discharging behaviour in the nanocomposite electrodes for battery applications.

Evolution of element-specific electronic structures in alkaline titanates

Probing the electron hybridization between alkaline metal and oxygen ions is fundamentally important to understand variable emergent phenomena in alkaline titanates, however, experimental study of which is very limited. In this letter, in order to characterize the evolution of element-specific electronic structures in single crystal alkaline titanates ATiO3 (A = Ca, Sr, Ba), we carried out resonant soft X-ray absorption spectroscopy at Ti L2,3- and O K-edges and performed multiplet calculations. In sharp contrast to analogous Ti electronic structures in ATiO3, the electronic structure of oxygen changes drastically with different A-site metals (Ca, Sr, Ba), indicating the strong hybridization between alkaline metal and oxygen ions. Our work reveals an important role of A-site alkaline metals in determining the electronic structures of oxygens in ATiO3, and paves a way to design novel quantum states (e.g., coexisting ferroelectricity, ferromagnetism, and superconductivity) with oxide interface engineering.

A Ti L3,2 - and K- edge XANES and EXAFS study on Fe3+ - substituted CaCu3Ti4O12

The electronic structures of stoichiometric, single phase, coarse-grained CaCu3-xTi4-xFe2xO12 (x = 0.0, 0.1, 0.3, 0.5 and 0.7) polycrystalline ceramics have been investigated using powerful X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopic measurements, performed near Ti L3,2 and Ti K- edges, registered at 300 K. The absence of pre-edge structures in Ti L3,2 – edge are indicative of a departure from octahedral cubic symmetry, while the observed small increase in the intensity of absorption peaks has been attributed to increasing spin-orbital coupling with increasing Fe-content (x) in the system. The presence of a pre-edge feature in Ti K- edge spectra confirms the presence of octahedrally coordinated Ti4+ ions in the system. The EXAFS spectra measured at Ti K- edge indicate the first shell Ti—O bond distances to be nearly 1.56 Å in the sample without Fe. With the increase in the Fe- concentration (x), the Ti-O distance shows a slight reduction. The second shell Ti-Ca bond distance comes out to be nearly 2.6 Å which decreases with an increase in the Fe - concentration.

Tunable Nonthermal Distribution of Hot Electrons in a Semiconductor Injected from a Plasmonic Gold Nanostructure.

For semiconductors photosensitized with organic dyes or quantum dots, transferred electrons are usually considered thermalized at the conduction band edge. This study suggests that the electrons injected from a plasmonic metal into a thin semiconductor shell can be nonthermal with energy up to the plasmon frequency. In other words, the electrons injected into the semiconductor are still hot carriers. Photomodulated X-ray absorption measurements of the Ti L2,3 edge are compared before and after excitation of the plasmon in Au@TiO2 core-shell nanoparticles. Comparison with theoretical predictions of the X-ray absorption, which include the heating and state-filling effects from injected hot carriers, suggests that the electrons transferred from the plasmon remain nonthermal in the ∼10 nm TiO2 shell, due in part to a slow trapping in defect states. By repeating the measurements for spherical, rod-like, and star-like metal nanoparticles, the magnitude of the nonthermal distribution, peak energy, and number of injected hot electrons are confirmed to be tuned by the plasmon frequency and the sharp corners of the plasmonic nanostructure. The results suggest that plasmonic photosensitizers can not only extend the sunlight absorption spectral range of semiconductor-based devices but could also result in increased open circuit voltages and elevated thermodynamic driving forces for solar fuel generation in photoelectrochemical cells.

Effects of rapid thermal annealing on the local environment, electronic structure and magnetic properties of Mn doped TiO2 thin films

In this report, nanostructure thin films of Ti0.97 Mn0.03 O2−δ were deposited on Si (001) substrate by pulsed laser deposition (PLD) technique, followed by rapid thermal annealing (RTA) in different ambient gases; O2, N2 and Ar. The RTA treatment dramatically affected the surface defects, local environment, electronic structure and magnetic properties of the films, where, annealing of the film in O2 gas recovered the dislocated atoms of oxygen vacancy (Vo) at the surfaces and induced a diamagnetic phase, whereas the annealing of film in N2 gas introduced Vo, reduced the valence state of Ti4+ (TiO2) into Ti3+ (Ti2O3) and induced ferromagnetic (FM) signal. Therefore, the change in the local atomic defects of Vo at the surface texture is likely to be responsible for the magnetic response. The presence of oxygen vacancy has been traced by means of Raman scattering and near edge X-ray absorption fine structure (NEXAFS) spectroscopy measurements. The NEXAFS spectra were carried out in synchrotron facility at Ti/Mn L3,2 and O-K edges. The spectral feature at Ti L3,2 edges revealed the rutile phase of TiO2. The asymmetry of t2g and eg bands at the O-K edge confirmed the formation of Vo and reflected the modification in the O co-ordination around Ti4+cations. The Mn L3,2 edges revealed the incorporation of Mn ions in the TiO2 network with Mn2+ and Mn3+ mixed valence states. This different valance states (Mn2+ and Mn3+) is the basis for the ferromagnetism induced by Stoner spin-splitting of the local density of defects state at Fermi level (EF). The change in the magnetic moment of the films after RTA process is related to the change in the local density of defects band. Crystal field and charge transfer parameters were extracted roughly by using atomic multiplet calculations (theory).

XANES study of vanadium and nitrogen dopants in photocatalytic TiO2 thin films.

We report an X-ray absorption near edge structure (XANES) study of vanadium (V) and nitrogen (N) dopants in anatase TiO2 thin films deposited by radio-frequency magnetron sputtering. Measurements at the Ti K and V K edges were combined with soft X-ray experiments at the Ti L2,3, O K and N K edges. Full potential ab initio spectral simulations of the V, O and N K-edges were carried out for different possible configurations of substitutional and interstitial dopant-related point defects in the anatase structure. The comparison between experiments and simulations demonstrates that V occupies substitutional cationic sites (replacing Ti) irrespective of the film structure and dopant concentration (up to 4.5 at%). On the other hand, N is found both in substitutional anionic sites (replacing O) and as N2 dimers within TiO2 interstices. The dopants' local structures are discussed with reference to the enhanced optical absorption and photocatalytic activity achieved by (co)doping.

Direct Observation of Room-Temperature Stable Magnetism in LaAlO3/SrTiO3 Heterostructures.

Along with an unexpected conducting interface between nonmagnetic insulating perovskites LaAlO3 and SrTiO3 (LaAlO3/SrTiO3), striking interfacial magnetisms have been observed in LaAlO3/SrTiO3 heterostructures. Interestingly, the strength of the interfacial magnetic moment is found to be dependent on oxygen partial pressures during the growth process. This raises an important, fundamental question on the origin of these remarkable interfacial magnetic orderings. Here, we report a direct evidence of room-temperature stable magnetism in a LaAlO3/SrTiO3 heterostructure prepared at high oxygen partial pressure by using element-specific soft X-ray magnetic circular dichroism at both Ti L3,2 and O K edges. By combining X-ray absorption spectroscopy at both Ti L3,2 and O K edges and first-principles calculations, we qualitatively ascribe that this strong magnetic ordering with dominant interfacial Ti3+ character is due to the coexistence of LaAlO3 surface oxygen vacancies and interfacial (TiAl-AlTi) antisite defects. On the basis of this new understanding, we revisit the origin of the weak magnetism in LaAlO3/SrTiO3 heterostructures prepared at low oxygen partial pressures. Our calculations show that LaAlO3 surface oxygen vacancies are responsible for the weak magnetism at the interface. Our result provides direct evidence on the presence of room-temperature stable magnetism and a novel perspective to understand magnetic and electronic reconstructions at such strategic oxide interfaces.

X-ray Diffraction and X-ray Spectroscopy Studies of Cobalt-Doped Anatase TiO2:Co Nanopowders

Co-doped TiO2 is one of the most extensively studied oxides for applying as dilute magnetic semiconductors due to its room temperature magnetism. Here we present results of the studies of Ti0.97Co0.03O2 nanopowders synthesized by hydrothermal method by means of X-ray diffraction, soft X-ray absorption spectroscopy (Ti L2,3 and Co L2,3 spectra), hard X-ray absorption spectroscopy (Co K spectra), and 1s3p resonant inelastic X-ray scattering at the Co K edge. According to X-ray diffraction data and Ti L2,3 X-ray absorption spectra, all the samples before the thermal treatment exhibit anatase structure with substantial amount of amorphous phase. After annealing the Ti0.97Co0.03O2 samples in vacuum or hydrogen at 700oC, the anatase structure persists while amorphous phase contribution is eliminated. Surface sensitive soft X-ray absorption Co L2,3 spectroscopy revealed only Co2+ ions tetrahedrally coordinated by oxygen ions and no sign of metallic Co. Co2+ tetrahedral sites (instead of typical octahedral ones) ...