Luminescence properties of the Mg co–doped Ce:SrHfO3 ceramics prepared by the Spark Plasma Sintering Method

1300 or 1400 °C pre–sintered Al/Ce/Mg:SrHfO₃ and Al/Ce:SrHfO₃ ceramics were prepared by the Spark Plasma Sintering (SPS) in order to search for a new scintillation material with a high–effective atomic number(Z_eff) and good light output. The SrHfO₃ has a high Z_eff of 60, and high gamma–ray detection efficiency is expected. Meanwhile it has a high melting point of over 2500 °C, and single crystal is hard to be grown. On the other hand, high melting materials can be prepared as ceramics, and the SPS method is a simple process to fabricate the ceramics within a few hours. Thus, we prepared the samples using the SPS method, and their optical and scintillation properties were investigated. We found that Al/Ce/Mg:SrHfO₃ and Al/Ce:SrHfO₃ ceramics had an emission wavelength at around 400 nm originating from 5d–4f transition of Ce³⁺. Moreover, Al/Ce/Mg:SrHfO₃ pre-sintered at a temperature of 1400 °C had a light output of approximately 5,000 ph/MeV. In this paper, the light output of Mg-co-doped samples was improved compared with the Mg-free ones. The light output also depends on the pre-sintering temperature.     

Structural,elastic and mechanical properties of orthorhombic SrHfO3 under pressure from first-principles calculations

Structural, elastic and mechanical properties of orthorhombic SrHfO₃ under pressure have been investigated using the plane-wave ultrasoft pseudopotential technique based on the first-principles density functional theory. The calculated equilibrium lattice parameters and elastic constants of orthorhombic SrHfO₃ at zero pressure are in good agreement with the available experimental and calculational values. The lattice parameters, total enthalpy, elastic constants and mechanical stability of orthorhombic SrHfO₃ as a function of pressure were studied. With the increasing pressure, the lattice parameters and volume of orthorhombic SrHfO₃ decrease whereas the total enthalpy increases. Orthorhombic SrHfO₃ is mechanically stable with low pressure (<52.9 GPa) whereas that is mechanically instable with high pressure (>52.9 GPa). The bulk modulus, shear modulus, Young's modulus and mechanical anisotropy of orthorhombic SrHfO₃ as a function of pressure were analyzed. It is found that orthorhombic SrHfO₃ under pressure has larger bulk modulus, better ductility and less mechanical anisotropy than orthorhombic SrHfO₃ at 0 GPa.     

Probing the Ba 5d states in BaTiO3 and BaSO4: A resonant x-ray emission study at the Ba-L3 edge

We have directly probed the Ba 5d states in the ferroelectric barium titanate BaTiO₃ using two bulk-sensitive spectroscopic probes, resonant x-ray emission spectroscopy (RXES) and x-ray absorption spectroscopy in the partial fluorescence mode (PFY-XAS) at the Ba-L₃ edge. The results are compared with those of the non-ferroelectric barium sulfate BaSO₄. While the RXES spectra point to a localized character for the Ba 5d states in both compounds, the main peak of the PFY-XAS spectrum, corresponding to the dipolar transitions from 2p to 5d, is found to be significantly broader for BaTiO₃ than for BaSO₄. On the basis of band structure calculations, this broadening is ascribed to strong hybridization between the unoccupied Ba 5d and O 2p states in the ferroelectric. This suggests that the hybridization between the conduction states of the Ba²⁺ and O^2? ions, and not only Ti⁴⁺ and O^2?, plays a central role in determining the electronic structure of BaTiO₃, and is therefore likely to be indirectly correlated with the occurrence of ferroelectricity in this material.     

Photoluminescence of Pb2+-doped SrHfO3

Pb²⁺ excitation and emission spectra and decay kinetics in SrHfO₃ host are measured within 10–350 K temperature interval. Temperature dependence of decay times is fit by the phenomenological model describing the dynamics of the lowest excited state of Pb²⁺ ion. The best fit provided corresponding quantitative parameters of the model. Suitability of the Pb-doped SrHfO₃ for phosphor and scintillator application is discussed.     

Synthesis and electrical transport of SrHfO3 thin films grown on a SrTiO3 (001) substrate using a pulsed laser deposition

We report the deposition of epitaxial SrHfO₃ thin films on a SrTiO₃ (001) substrate in different substrate temperatures by using a pulsed laser deposition (PLD) method. We carried out X-ray diffraction (XRD), X-ray reflectivity (XRR), reciprocal space mapping (RSM), atomic force microscopy (AFM), resistivity, and Hall measurements to examine the crystallinity, morphology and electrical properties of these films. All films showed smooth and uniform morphology with small root mean square (RMS) roughness. While the SrHfO₃ sample grown at 750 °C is metallic, the films deposited at 600 °C, 650 °C, and 700 °C show an upturn at low temperatures. The temperature dependence of the metallic parts was analyzed based on the parallel resistor model that includes resistivity saturation. On the other hand, the low-temperature upturn was found to be well described by a weak localization mechanism. We also observed the possible emergence of non-Fermi liquid behavior when the upturn disappeared. All SrHfO₃ films have p-type charge carriers.     

Photoluminescence of Lu3Al5O12:Bi and Y3Al5O12:Bi single crystalline films

Single crystalline films of Lu₃Al₅O₁₂:Bi and Y₃Al₅O₁₂:Bi have been studied at 4.2–450 K by the time-resolved luminescence spectroscopy method. Their emission spectrum consists of two types of bands with strongly different characteristics. The ultraviolet band consists of two components, arising from the electronic transitions which correspond to the ³P₁ → ¹S₀ and ³P₀ → ¹S₀ transitions in a free Bi³⁺ ion. At T < 80 K, mainly the lower-energy component with the decay time ～10^?3 s is observed, arising from the metastable ³P₀ level. At T > 150 K, the higher-energy component prevails, arising from the thermally populated emitting ³P₁ level. The visible emission spectrum consists of two dominant strongly overlapped broad bands with large Stokes shifts. At 4.2 K, their decay times are ～10^?5 s and ～10^?4 s and decrease with increasing temperature. Both of the visible emission bands are assumed to be of an exciton origin. The lower-energy band is ascribed to an exciton, localized near a single Bi³⁺ ion. The higher-energy band, showing a stronger intensity dependence on the Bi³⁺ content, is assumed to arise from an exciton, localized near a dimer Bi³⁺ center. The structure of the corresponding excited states is considered, and the processes, taking place in these states, are discussed.     

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.     

β-C3N4,β-Si3N4和β-Ge3N4的能带结构

采用基于密度泛函理论的线性丸盒轨道原子球近似(LMTO-ASA)从头计算方法,研究了β-C₃N₄,β-Si₃N₄和β-Ge₃N₄的能带结构,得到了它们的能隙分别为:4.1751,5.1788和4.0279eV。对于β-C₃N₄,由于N的部分2p电子占据了非键轨道,禁带宽度较窄;对于β-Si₃N_{4关键词：}     

Electronic structure of Cr1−δS (δ=0, 0.17) with NiAs-type crystal structure

Valence-band and conduction-band the electronic structure of the CrS (δ=0) and Cr₅S₆ (δ=0.17) has been investigated by means of photoemission and inverse-photoemission spectroscopies. The bandwidth of the valence bands of Cr₅S₆ (8.5 eV) is wider than that of CrS (8.1 eV), though the Cr 3d partial density of states evaluated from the Cr 3p-3d resonant photoemission spectroscopy is almost unchanged between the two compounds concerning shapes as well as binding energies. The Cr 3d (t_2g) exchange splitting energies of CrS and Cr₅S₆ are determined to be 3.9 and 3.3 eV, respectively.     

A TDDFT study of some dinuclear compounds containing CpM(CO)3 or CpM(CO)2 groups

The electronic structure and spectroscopy of some representative dinuclear compounds containing CpM(CO)₃ and CpM(CO)₂ groups were studied using TDDFT (Time Dependent Density Functional Theory). These compounds contain Cp (cyclopentadienyl) as a ligand, and M can be Cr, Mo or W. Their main electronic transitions were calculated and the results are in good agreement with the experimental data. This allows the assignment of some bands whose origin was not clear. In all the cases, the carbonyls and Cp groups restrict the symmetry. The molecular orbitals that would be involved in M-M bonding interact strongly with the carbonyls and show unusual shapes and occupations. The strongest electronic bands are caused by σ→σ* transitions in most of the molecules containing CpM(CO)₃ groups, whereas in molecules such as Cp(CO)₂M≡M(CO)₂Cp the most intense bands are produced by π→π* transitions. The origin of other bands is now explained. The effect of the solvent on the electronic transitions and the use of EOM-CCSD method in some compounds were also checked.     

Absorption and photoluminescence of Eu2+-doped 1-D CsCdBr3 single crystal

Eu²⁺-doped CsCdBr₃ single crystals are studied by polarized variable-temperature optical absorption and luminescence spectroscopy for different excitation wavelengths. Whereas the low-energy absorption band is assigned to f→d transitions within Eu²⁺ electronic configuration, the high-energy absorption bands are assigned to Eu-trapped exciton due to the proximity of the high-energy d levels to the conduction band.     

First-principles study of structural,electronic, and optical properties of ZnSnO3

The structural, electronic, and optical properties of ZnSnO₃ were investigated using density functional theory within the generalized gradient approximation. The structure parameters obtained agree well with the experimental results. The electronic structures indicate that ZnSnO₃ is a semiconductor with a direct band gap of 1.0 eV. The calculated optical spectra can be assigned to contributions of the interband transitions from valence band O 2p levels to conduction band Sn 5s levels or higher conduction band Zn 3d levels in the low-energy region, and from O 2p to Sn 5p or Zn 4p conduction band in the high-energy region.     

LuI3 闪烁晶体的第一性原理研究

采用基于第一性原理的赝势和平面波方法计算了新型闪烁晶体基质材料 LuI₃的结构特性和电子特性. 计算结果表明: -4.4 eV附近有一个宽度约为0.2 eV的窄带, 主要是Lu的4f态; -3.55–0 eV之间的态组成了价带, 这主要是I的5p态; 2.44–12.35 eV之间的态组成了LuI₃的导带, 这主要来源于Lu的5d态, 其中还含有少量的Lu的6s态的贡献. 在-3.46 eV处, Lu的6s态、4f态和I的5p态同时出现了尖峰, 说明相邻的Lu原子的6s态, 4f态与I原子的5p态之间的相互作用强, 出现了杂化峰. 估算出LuI₃晶体的理论光产额约为100000 ph/MeV, 主要得益于LuI₃合适的带隙和能带结构. 关键词： 3')" href="#">LuI₃ 第一性原理 电子结构     

A comparative study of electronic structure and magnetic properties of SrCrO3 and SrMoO3

A comparative study of electronic structure and magnetic properties of SrCrO₃ and SrMoO₃ has been carried out using FPLAPW method with density-functional theory. The calculated results suggest that both compounds are nonmagnetic (NM) metal in cubic structures at room temperature, and they exhibit very similar band structure and electronic properties except more extend Mo 4d orbitals than Cr 3d electronic states. However, the electronic structure and magnetic properties exhibit remarkable differences between them in the low temperature phases. SrCrO₃ is with a C-AFM ground state with magnetic moment of 1.18μ_B/Cr in the tetragonal structure, while SrMoO₃ is with a NM ground state in the orthorhombic structure. It is assumed that the extend 4d orbitals may be the reason which results in NM solution at low temperature phase of SrMoO₃.     

第一性原理计算XHfO3(X=Ba,Sr)的结构、弹性和电子特性

采用基于密度泛函理论的第一性原理计算方法研究了钙钛矿结构的BaHfO₃和SrHfO₃的基态性质，包括优化后的晶格常数、弹性常数、体弹性模量、剪切模量、态密度、能带结构和电荷密度.计算结果表明BaHfO₃和SrHfO₃具有比较大的体弹性模量，它们都是间接带隙的半导体材料，Ba或Sr原子与HfO₃基团之间形成的化学键主要是离子键，而Hf原子与O原子之间形成的主要是共价键. 关键词： 第一性原理 钙钛矿结构 体弹性模量 价键     

Optical properties and radiation response of Ce:SrHfO3 prepared by the Spark Plasma Sintering Method

SrHfO₃, Ce_0.02Sr_0.98HfO₃ (Ce:SHO) and Ce_0.02Al_0.02Sr_0.96HfO₃ (Ce/Al:SHO) ceramics were prepared by Spark Plasma Sintering (SPS) in order to search for a new material with a high-effective atomic number. Here, SrHfO₃ has high melting point, and single crystal cannot be grown by micro pulling down method (which usually enables growth within less than 1 day) due to its high melting temperature. Since SPS can be used for preparation of the ceramics within roughly 10 h at temperatures lower than the melting point, we use the SPS method for material preparation. Ce:SHO had a low transparency of less than 0.1% below 540-nm, while Ce/Al:SHO had a wider transparent region including the emission wavelength region of Ce³⁺ (∼395 nm). Ce/Al:SHO ceramics had light output of ∼4000 photons/MeV, and decay time of 21.6 ± 0.9 ns.     

Electronic structure of ZrTiO4 and HfTiO4: Self-consistent cluster calculations and X-ray spectroscopy studies

Total and partial densities of states of the constituent atoms of ZrTiO₄ and HfTiO₄ titanates have been calculated using a self-consistent cluster method as incorporated in the FEFF8 code. The calculations reveal the similarity of the electronic structure of both titanates and indicate that the valence band of the compounds under consideration is dominated by contributions of O 2p states. These states contribute throughout the whole valence-band region; however their maximum contributions occur in the upper portion of the band. Other significant contributors in the valence-band region are Ti 3d and Zr 4d states in ZrTiO₄ and Ti 3d and Hf 5d states in HfTiO₄. All the above d-like states contribute throughout the whole valence-band region of the titanates; however maximum contributions of the Ti 3d states occur in the upper portion, whilst those of the Zr 4d (Hf 5d) states are in the central portions of the valence band. The FEFF8 calculations render that the bottom of the conduction band of ZrTiO₄ and HfTiO₄ is dominated by contributions of Ti 3d^? states, with also smaller contributions of Zr 4d^?/Hf 5d^? and O 2p^? states. To verify the above FEFF8 data, the X-ray emission bands, representing the energy distributions of mainly O 2p, Ti 3d and Zr 4d states, were measured and compared on a common energy scale. These experimental data are found to be in agreement with the theoretical FEFF8 results for the electronic structure of ZrTiO₄ and HfTiO₄ titanates. Additionally, X-ray photoelectron valence-band and core-level spectra were recorded for the constituent atoms of the titanates under study.     

SrHfO3和SrTiO3光学特性的第一性原理研究

用全电势线性缀加平面波法(FLAPW)计算了SrTiO₃和SrHfO₃的光学特性，即介电函数虚部ε₂(ω)、光学吸收系数I(ω)和反射率R(ω).对它们光学特性进行了对比分析，给出了它们光学特性的差别，并进行了解释.计算的SrTiO₃光学谱分别在4.4，7.4，8.3和23.6eV处出现峰值，且其在4.4eV处的峰值比较高而尖.计算结果与实验值符合得很好. 关键词： 平面波法计算 光学常量和参数 铁电体     

Mechanistic investigations on emission characteristics from g-C3N4, g-C3N4@Pt and g-C3N4@Ag nanostructures using X-ray absorption spectroscopy

An improved method for the preparation of g-C₃N₄ is described. Currently, heating (>400 C°) of urea is the common method used for preparing the g-C₃N₄. We have found that sonication of melamine in HNO₃ solution, followed by washing with anhydrous ethanol, not only reduce the crystallite size of g-C₃N₄ but also facilitate intriguing electronic structure and photoluminescence (PL) properties. Moreover, loading of metal (Pt and Ag) nanoparticles, by applying the borohydride reduction method, has resulted in multicolor-emission from g-C₃N₄. With the help of PL spectra and local electronic structure study, at C K-edge, N K-edge, Pt L-edge and Ag K-edge by X-ray absorption spectroscopy (XAS), a precise mechanism of tunable luminescence is established. The PL mechanism ascribes the amendments in the transitions, via defect and/or metal states assimilation, between the π* states of tris-triazine ring of g-C₃N₄ and lone pair states of nitride. It is evidenced that interaction between the C/N 2p and metal 4d/5d orbitals of Ag/Pt has manifested a net detraction in the δ*→LP transitions and enhancement in the π*→LP and π*→ π transitions, leading to broad PL spectra from g-C₃N₄ organic semiconductor compound.