Electronic structure analysis of Mn- and Fe-codoped In2O3 by photoemission yield measurements

The valence band electronic structures of Mn- and/or Fe-doped In₂O₃, i.e., In₂O₃:Mn, In₂O₃:Fe, and In₂O₃:(Mn, Fe), are investigated by photoemission yield measurements. Significant changes are observed in the threshold energy of photoemission, depending on the doped magnetic ions, which indicates that an additional occupied band appears above the top of the valence band of In₂O₃ owing to doping with Mn and/or Fe ions. It is confirmed that the order of the threshold energies of photoemission, E_PET, is E_PET(In₂O₃:Mn)<E_PET(In₂O₃:(Mn, Fe))<E_PET(In₂O₃:Fe)<E_PET(In₂O₃). To gain a better understanding of these results, first-principles molecular orbital calculations are also carried out, which successfully explain the observed changes in the photoemission threshold energies.     

Optical spectroscopy of Ca3Sc2Si3O12, Ca3Y2Si3O12 and Ca3Lu2Si3O12 doped with Pr

The silicates Ca₃Sc₂Si₃O₁₂, Ca₃Y₂Si₃O₁₂ and Ca₃Lu₂Si₃O₁₂, both undoped and doped with Pr³⁺ ions, have been synthesized by solid-state reaction at high temperature. The luminescence spectroscopy and the excited state dynamics of the materials have been studied upon VUV and X-ray excitation using synchrotron radiation. All doped samples have shown efficient 5d-4f emission upon direct VUV excitation of 5d levels, but only Ca₃Sc₂Si₃O₁₂:Pr³⁺ shows luminescence upon interband VUV or X-ray excitation. The VUV excited emission spectra of Ca₃Y₂Si₃O₁₂:Pr³⁺ and Ca₃Lu₂Si₃O₁₂:Pr³⁺ show features attributed to emission from two distinct sites accommodating the Pr³⁺ dopant. The decay kinetics of the Pr³⁺ 5d-4f emission in Ca₃Sc₂Si₃O₁₂:Pr³⁺ upon VUV excitation across the band gap are characterized by decay times in the range 25-28 ns with no significant rise after the excitation pulse. They appear to be faster upon X-ray irradiation than for VUV excitation. Weak afterglow components are attributed to defect luminescence.     

Structure and surface characterization of ZrO2-Y2O3-Cr2O3 system

3-mol% Y₂O₃ and 0.3 to 3-mol % Cr₂O₃ co-doped ZrO₂ nanopowders were synthesized using co-precipitation technique and investigated by terms of X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy. Structural analysis shows no significant impact of chromium on powders structure except of presence of small amount of m-phase. Surface analysis reveals segregation of yttrium and chromium atoms to the surface along with surface enrichment by oxygen that can be attributed to residual water. Chromium surface atoms present in three oxidation states with catalytically active Cr²⁺ sites possibly controlling m-phase appearance through lattice distortion.     

Photoemission study of the density of valence states of amorphous As2S3 and Sb2S3

The densities of valence states of amorphous As₂S₃ and Sb₂S₃ have been investigated by means of X-ray photoemission and ultraviolet photoemission spectroscopy. The spectra are interpreted on the basis of existing band structure calculations.     

Characterization of interface between CuInSe2 and In2O3

CuInSe₂/In₂O₃ structures were formed by depositing CuInSe₂ films by stepwise flash evaporation onto In₂O₃ films, which were grown by DC reactive sputtering of In target in presence of (Ar+O₂) gas mixture. Phase purity of the CuInSe₂ and In₂O₃ films was confirmed by Transmission Electron Microscopy (TEM) studies. X-ray diffraction (XRD) results on CuInSe₂/In₂O₃/glass structures showed sharp peaks corresponding to (112) plane of CuInSe₂ and (222) plane of In₂O_3. Rutherford Backscattering Spectrometry (RBS) investigations were carried out on CuInSe₂/In₂O₃/Si structures in order to characterize the interface between In₂O₃ and CuInSe₂. The results show that the CuInSe₂ films were near stoichoimetric and In₂O₃ films had oxygen deficient composition. CuInSe₂/In₂O₃ interface was found to include a ∼20 nm thick region consisting of copper, indium and oxygen. Also, the In₂O₃/Si interface showed the formation of ∼20 nm thick region consisting of silicon, indium and oxygen. The results are explained on the basis of diffusion/reaction taking place at the respective interfaces.     

Magnetic and structural studies of Cr2O5 and Cr3O8

The infrared spectra, indexed X-ray powder diffraction patterns, magnetic susceptibilities between 80 and 300 K, and electron paramagnetic resonance spectra at 80 and 300 K are reported for Cr₂O₅ and Cr₃O₈. The results indicate that both oxides are Cr³⁺/Cr⁶⁺ mixed-valence compounds which contain CrO₆ octahedra and CrO₄ tetrahedra in different ratios. The valence formula for Cr₂O₅ is Cr³⁺₂Cr⁶⁺₄O₁₅ and that of Cr₃O₈ is Cr³⁺₂Cr⁶⁺₇O₂₄. The X-ray powder data for Cr₂O₅ and Cr₃O₈ could be indexed on the basis of a monoclinic unit cell $\text{(a = 12.01(2), b = 8.52(1), c = 9.39(1)}\text{A}\text{?}\text{β = 92.0(1)°)}$ and an orthorhombic unit cell $\text{(a = 12.01(7), b = 36.60(7) and c = 3.82(1)}\text{A}\text{?}\text{)}$, respectively.     

Electrical conduction in Fe2O3 and Cr2O3

The influence of some impurities on the conduction properties of Cr₂O₃ and Fe₂O₃ are examined and contrasted. A mechanism is proposed to account for the effect of Ti in Cr₂O₃.     

Structural and optical properties of nanoparticulate Y2O3:Eu2O3 made by microwave plasma synthesis

Nanoparticulate Y₂O₃:Eu₂O₃ with a small, uniform particle size and a well-defined composition was synthesized using a low temperature microwave plasma process. The structural evolution and the luminescence properties were studied in different states of annealing and Eu₂O₃ addition using X-ray diffraction, transmission electron microscopy, and UV-photoluminescence spectroscopy. As synthesized, the samples were amorphous and showed only weak luminescence. Subsequent annealing steps from 500°C to 800°C lead to the formation and growth of cubic Y₂O₃:Eu₂O₃ nanocrystals (5–20 nm) and a concomitant strong increase of the luminescence yield already at small grain sizes in the range of 10 nm. No self-quenching effects were observed up to 11 mol% Eu₂O ₃.     

A close correlation between induced ferromagnetism and oxygen deficiency in Fe doped In2O3

We report on the reversible manipulation of room temperature ferromagnetism in Fe (5%) doped In₂O₃ polycrystalline magnetic semiconductor. The X-ray diffraction and photoemission measurements confirm that the Fe ions are well incorporated into the lattice, substituting the In³⁺ ions. The magnetization measurements show that the host In₂O₃ has a diamagnetic ground state, while it shows weak ferromagnetism at 300 K upon Fe doping. The as-prepared sample was then sequentially annealed in hydrogen, air, vacuum and finally in air. The ferromagnetic signal shoots up by hydrogenation as well as vacuum annealing and bounces back upon re-annealing the samples in air. The sequence of ferromagnetism shows a close inter-relationship with the behavior of oxygen vacancies (V_o). The Fe ions tend to a transform from 3+ to 2+ state during the giant ferromagnetic induction, as revealed by photoemission spectroscopy. A careful characterization of the structure, purity, magnetic, and transport properties confirms that the ferromagnetism is due to neither impurities nor clusters but directly related to the oxygen vacancies. The ferromagnetism can be reversibly controlled by these vacancies while a parallel variation of carrier concentration, as revealed by resistance measurements, appears to be a side effect of the oxygen vacancy variation.     

Vacancy ordering in γ-Fe2O3 small particles

The effect of particle size on the formation of vacancy-ordered superstructure in γ-Fe₂O₃ powders has been investigated by using X-ray, Mössbauer and chemical analyses. Powders of γ-Fe₂O₃ with different average particle size were prepared by chemical precipitation and subsequent heat-treatment. The X-ray diffraction intensity of the superlattice lines decreases with the particle size of γ-Fe₂O₃ and finally disappears at a particle-size between 300-175 Å, possibly around 200 Å. Therefore ordering of the cation vacancies in ultrafine γ-Fe₂O₃ particles is ruled out. Although the vacancies do not form an ordered structure, they do exclusively occupy B-sites.     

Dielectric properties and temperature stability of BaTiO3 co-doped La2O3 and Tm2O3

The influence of La₂O₃ and Tm₂O₃ co-doping on the dielectric properties and the temperature stability of BaTiO₃ was investigated. BaTiO₃ ceramics were prepared with the compositional formula of (Ba_1−xLa_x)(Ti_1-x/4−yTm_y)O₃. La₂O₃ and Tm₂O₃ co-doping in BaTiO₃ mainly had effects on an increase in the dielectric constant and the temperature stability, respectively. The increase of La₂O₃ concentration and the decrease of Tm₂O₃ concentration in BaTiO₃ resulted in a decrease of lattice parameter and tetragonality because La³⁺ ion substituting for Ba site is smaller than Ba²⁺ ion and Tm³⁺ ion substituting for Ti site is larger than Ti⁴⁺ ion. With the increase of La₂O₃ and the decrease of Tm₂O₃, the dielectric constant of BaTiO₃ was enhanced in spite of the reduction of tetragonality. P-E hysteresis measurements revealed that this phenomenon was based on the improvement of remanent polarization with the increase of La₂O₃ concentration. The introduction of excess Tm₂O₃ in BaTiO₃ suppressed the grain growth and BaTiO₃ ceramics showed higher temperature stability due to the stable tetragonal structure and the small grain size with the increase of Tm₂O₃ concentration.     

Influence of Lu2O3 on electrical and microstructural properties of CaCu3Ti4O12 ceramics

In this work, the influence of Lu₂O₃ doped on the dielectric and electrical properties of CaCu₃Ti₄O₁₂ was reported. Lu₂O₃-doped CCTO was prepared by a conventional solid state technique using CuO, TiO₂, and CaCO₃ as starting materials. The samples were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM); dielectric measurements were measured in the 10² Hz–10⁷ Hz frequency range at room temperature; and the nonlinear behavior of all samples was measured. The doping of Lu₂O₃ resulted in an increase in the dielectric constant of CCTO, but decreased the stability of the frequency dependence. Increasing concentrations of Lu₂O₃ resulted in decreasing nonlinear coefficients.     

Growth and characterization of Y2O3 thin films

Y₂O₃ thin films were grown on silicon (1 0 0) substrates by pulsed-laser deposition at different substrate temperatures and O₂ pressures. The structure and composition of films are studied by using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The Y₂O₃ thin films deposited in vacuum strongly oriented their [1 1 1] axis of the cubic structure and the film quality depended on the substrate temperature. The magnitude of O₂ pressure obviously influences the film structure and quality. Due to the silicon diffusion and interface reaction during the deposition, yttrium silicate and SiO₂ were formed. The strong relationship between composition and growth condition was discussed.     

Electronic properties of thin films of laser-ablated Al2O3

Laser ablation coupled to mass quadrupole spectrometry (LAMQS) has been used to prepare thin films of aluminum oxide deposited on Si substrates starting from commercial Al₂O₃ polycrystalline targets. X-ray photoemission (XPS) and reflection electron energy loss spectroscopy (REELS) have allowed the investigation of the electronic properties of the produced films. In particular, it was found that the Al/O atomic ratio assumes a value very near to 0.7 (stoichiometric ratio) only for films deposited normally with respect to the target surface, while films grown at larger deposition angles are more rich in oxygen content.The composition, the mass density, the optical energy gap, the complex dielectric function and refraction index of the films have been calculated and compared with the results obtained from our starting target material and with the literature. The morphology of the deposited samples has been analyzed by the AFM technique.     

Electronic properties of Bi2O3 and MoO3 and relationships to oxidation catalysis

A semiempirical atom superposition and electron delocalization molecular orbital analysis of the bonding and electronic structure of MoO₃, oxygen deficient MoO₃, and the α, β, and δ phases of Bi₂O₃ has been made. It is found that both small — e.g. MoO₆ — and large — e.g. Mo₆O₂₄ — clusters are useful models for cation electronic structure within the theory used. From the calculations, an interpretation is given for all available optical and photoemission data for the oxides. The color, conductivity, and new photoemission peak of oxygen-deficient MoO₃ conducting bronzes are found to be due to the addition of electrons to the lowest of three Mo 5d bands which are empty in MoO₃. Weakly allowed d ← d transitions in the red are responsible for the color. Strongly allowed Mo 5d ← O 2p charge transfer excitations are responsible for the optical absorption above 3.2 eV. For the bismuth oxides, three occupied bands are found showing strong Bi 6s, 6p, 6d and O 2p hybridization. These bands have been seen experimentally. The highest band surprisingly has Bi 6p lone-pair character which is explained in terms of the relative Bi 6s and 6p and O 2p ionization potentials using perturbation theory. Rather similar electronic structures are found for the three phases despite their varying cation coordinations and structures. A charge transfer optical absorption edge at ～ 2.6 eV for the β form agrees well with observations reported in the literature, and similar edges should occur for the other phases. The cubic δ form has an unusual low-lying band suggesting absorption in the infrared. Our results provide insight into the surface properties of these oxides.     

Cu掺杂Ga2O3薄膜的光学性能

采用射频磁控溅射和N₂气氛退火处理制备了多晶Ga₂O₃薄膜和Cu掺杂Ga₂O₃薄膜.用X射线衍射仪、紫外-可见分光光度计、荧光光谱仪对Ga₂O₃薄膜和Cu掺杂Ga₂O₃薄膜的结构和光学性能进行了表征.结果表明,Cu掺杂后Ga₂O₃薄膜的结晶质量变差,透过率明显降低,吸收率增加,光学带隙减小.本征Ga₂O₃薄膜在紫外、蓝光和绿光出现了发光带,Cu掺杂后紫外和蓝光发射增强,且在475 nm 处出现了一个新的发光峰.     

Features of the local structural disorder in Li2O-CaF2-P2O5 glass-ceramics with Cr2O3 as nucleating agent

Li₂O-CaF₂-P₂O₅ glasses mixed with different concentrations of Cr₂O₃ (ranging from 0 to 1.0 mol%) were crystallized. The samples were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy (EDS), differential thermal analysis and conventional spectroscopic techniques. The X-ray diffraction and scanning electron microscopic studies reveal the presence of lithium phosphate, calcium phosphate and chromium phosphate (complexes of Cr³⁺, Cr⁵⁺ and Cr⁶⁺ ions) crystal phases. The study on DTA suggests that the crystallization is predominantly due to the surface crystallization when the concentration of nucleating agent Cr₂O₃ is around 0.8 mol%. The IR and Raman spectral studies of these samples indicate that the sample crystallized with 0.8 mol% Cr₂O₃ is more compact and possesses high rigidity due to the presence of chromium ions largely in tetrahedral positions.     

Electronic structure, magnetic and electrical properties of multiferroic PbFe1/2Ta1/2O3

Structural analysis of the synthesized lead iron tantalate, PbFe_1/2Ta_1/2O₃ (PFT) is performed by the refinement of the X-ray diffraction data at room temperature using the GSAS code. Energy dispersive X-ray spectrometry analysis is done to find out the chemical composition. The electronic structure of PFT is calculated by the first principles full potential linearized augmented plane wave method. The spin polarized density of states shows the insulating nature. The magnetic moment of 4.3 μB per Fe ion is obtained from the electronic structure calculation using the GGA+U method and compared with the available experimental data. The electronic structure of the PFT is verified by X-ray photoemission spectroscopy. The dielectric spectroscopy is applied to investigate the electrical properties of PFT in the frequency range from 100 Hz to 1 MHz and in the temperature range from 183 to 253 K. The frequency dependent electrical data are analyzed by conductivity formalism. The relaxation mechanism is explained using the Cole-Cole approach.     

Chemical quenching of positronium in Fe2O3/Al2O3 catalysts

Fe₂O₃/Al₂O₃ catalysts were prepared by solid state reaction method using α-Fe₂O₃ and γ-Al₂O₃ nano powders. The microstructure and surface properties of the catalyst were studied using positron lifetime and coincidence Doppler broadening annihilation radiation measurements. The positron lifetime spectrum shows four components. The two long lifetimes τ₃ and τ₄ are attributed to positronium annihilation in two types of pores distributed inside Al₂O₃ grain and between the grains, respectively. With increasing Fe₂O₃ content from 3 wt% to 40 wt%, the lifetime τ₃ keeps nearly unchanged, while the longest lifetime τ₄ shows decrease from 96 ns to 64 ns. Its intensity decreases drastically from 24% to less than 8%. The Doppler broadening S parameter shows also a continuous decrease. Further analysis of the Doppler broadening spectra reveals a decrease in the p-Ps intensity with increasing Fe₂O₃ content, which rules out the possibility of spin-conversion of positronium. Therefore the decrease of τ₄ is most probably due to the chemical quenching reaction of positronium with Fe ions on the surface of the large pores.