First principles study on the ferroelectricity of the perovskite ABO3 ferroelectrics

In order to understand well the different ferroelectric behaviour of quantum paraelectrics and ferroelectrics and the origin of the ferroelectricity of the solid solution KTa0.5Nb0.5O3(KTN),we calculated the electronic structure of CaTiO3,BaTiO3 and KTN by first principles calculation.From total energy analysis,it is shown that,with increasing cell volume,the crystals (CaTiO3,SrTiO3) will have a ferroelectric instability.For BaTiO3,the ferroelectricity will disappear as the cell volume is decreased.From the density of states analysis,it is shown that the hybridization between B d and O p is very important for the ferroelectric stability of ABO3 perovskite ferroelectrics.This is consistent with the analysis of band structure.     

First-principles study of the （001） surface of cubic PbHfO3 and BaHfO3

Using first-principles techniques,we investigate the(001) surfaces of cubic PbHfO3(PHO) and BaHfO3(BHO) terminated with both AO(A=Pb and Ba) and HfO2.Surface structure,partial density of states,band structure,and surface energy are obtained.The BaO surface is found to be similar to its counterpart in BHO.For the HfO2-terminated surface of cubic PHO,the largest relaxation appears on the second-layer atoms but not on the first-layer ones.The analysis of the structure relaxation parameters reveals that the rumpling of the(001) surface for PHO is stronger than that for BHO.The surface thermodynamic stability is explored,and it is found that both the PbO-and the BaO-terminated surfaces are more stable than the HfO2-terminated surfaces for PHO and BHO,respectively.The surface energy calculations show that the(001) surface of PHO is more easily constructed than that of BHO.     

X-ray study of structural phase transitions in nanocrystalline LaMnO3+δ perovskite

The nanocrystalline LaMnO_3+δ perovskite was synthesized by the microwave-assisted glycothermal method and calcined at several temperatures up to 1500°C. The prepared samples were examined by the X-ray powder diffraction with the aim to show that LaMnO_3+δ exhibits the size-induced structural phase transitions. The as-received nanocrystals of LaMnO_3+δ are of tetragonal, pseudo-cubic symmetry not known for bulk material. The samples calcined at temperatures 750–1100°C have trigonal symmetry known from the high-temperature phase of LaMnO₃ single crystal. The samples calcined from 1200°C to 1500°C have two phases: trigonal and orthorhombic. Thus, the observed phase sequence is inverted with respect to that of the bulk material, which is the characteristic of the size-induced mechanism of phase transitions in the nanocrystals. The critical crystallite sizes for both structural transitions were evaluated as 20 and 100?nm.     

EPR and optical spectroscopy of the Yb3+ cubic center in β-PbF2

Optical spectroscopy and EPR are employed to study a β-PbF₂ crystal doped with Yb³⁺ ions. The presence of only one paramagnetic center, the Yb³⁺ ion with cubic symmetry, is established. Its optical lines are identified, the empirical system of energy levels is constructed, and the phenomenological crystal field potential is determined. The information on the phonon spectrum of the β-PbF₂ crystal is obtained from the electron-vibrational structure of the optical absorption and luminescence spectra.     

Temperature dependence of magnetic properties and change of specific heat in perovskite ErCrO3 chromites

In this paper, the temperature dependence of magnetic properties and specific heat are systematically investigated for perovskite ErCrO₃ chromites. The results show that there exists a strong temperature dependence of magnetic ordering and phase coexistence in the region of low temperature. Specifically, ErCrO₃ possesses the long-range antiferromagnetic ordering and the appearance of weak ferromagnetism, occurring at T _N =133 K. In the range of higher temperature, above 133.0 K, the reciprocal of magnetic susceptibility χ ⁻¹ behaves linearly, indicating a typical Curie–Weiss behavior fitted. The effective magnetic moment μ _eff=10.57μ _B and asymptotic paramagnetic Curie temperature T _cw=−30 K, which suggests the predominance of antiferromagnetic interactions in ErCrO₃ chromites. Around T _SR≈22 K, ErCrO₃ undergoes a spin reorientation from \varGamma ₄(G_x,A_y,F_z;F^R_z)\varGamma _{4}(G_{x},A_{y},F_{z};F^{R}_{z}) to \varGamma ₁(A_x,G_y,C_z;C^R_z)\varGamma _{1}(A_{x},G_{y},C_{z};C^{R}_{z}) or Γ ₁(0). Also, the stability of the ferromagnetic Γ ₄ phase increases with increasing applied field. Furthermore, the ac susceptibilities exhibit frequency-independent anomalies near 133 K and the coexistence of the magnetic configuration \varGamma ₂(F_x,G_y,C_z;F^R_x,C^R_y)\varGamma _{2}(F_{x},G_{y},C_{z};F^{R}_{x},C^{R}_{y}) and Γ ₄. Combining the magnetic properties and the specific-heat measurements, this current magnetization can be interpreted from the interaction between C ^r3+–Cr³⁺, Cr³⁺–Er³⁺ and Er³⁺–Er³⁺.     

Electronic structures and optical properties of Si-and Sn-doped β-Ga_2O_3: A GGA+U study

The electronic structures and optical properties of β-Ga_2O_3 and Si-and Sn-doped β-Ga_2O_3 are studied using the GGA + U method based on density functional theory. The calculated bandgap and Ga 3d-state peak of β-Ga_2O_3 are in good agreement with experimental results. Si-and Sn-doped β-Ga_2O_3 tend to form under O-poor conditions, and the formation energy of Si-doped β-Ga_2O_3 is larger than that of Sn-doped β-Ga_2O_3 because of the large bond length variation between Ga–O and Si–O. Si-and Sn-doped β-Ga_2O_3 have wider optical gaps than β-Ga_2O_3, due to the Burstein–Moss effect and the bandgap renormalization effect. Si-doped β-Ga_2O_3 shows better electron conductivity and a higher optical absorption edge than Sn-doped β-Ga_2O_3, so Si is more suitable as a dopant of n-type β-Ga_2O_3, which can be applied in deep-UV photoelectric devices.     

Effect of 100 MeV swift Si8+ ions on structural and thermoluminescence properties of Y2O3:Dy3+nanophosphor

Nanoparticles of Y₂O₃:Dy³⁺ were prepared by the solution combustion method. The X-ray diffraction pattern of the 900°C annealed sample shows a cubic structure and the average crystallite size was found to be 31.49?nm. The field emission scanning electron microscopy image of the 900°C annealed sample shows well-separated spherical shape particles and the average particle size is found to be in a range 40?nm. Pellets of Y₂O₃:Dy³⁺ were irradiated with 100?MeV swift Si⁸⁺ ions for the fluence range of 3?×?10^11_3?×?10¹³ ions cm^?2. Pristine Y₂O₃:Dy³⁺ shows seven Raman modes with peaks at 129, 160, 330, 376, 434, 467 and 590?cm^?1. The intensity of these modes decreases with an increase in ion fluence. A well-resolved thermoluminescence glow with peaks at ～414?K (T_m1) and ～614?K (T_m2) were observed in Si⁸⁺ ion-irradiated samples. It is found that glow peak intensity at 414?K increases with an increase in the dopant concentration up to 0.6?mol% and then decreases with an increase in dopant concentration. The high-temperature glow peak (614?K) intensity linearly increases with an increase in ion fluence. The broad TL glow curves were deconvoluted using the glow curve deconvoluted method and kinetic parameters were calculated using the general order kinetic equation.     

Influence of γ-radiation on photoluminescence properties of YPO4:Eu3+,Ce3+ and YPO4:Dy3+,Ce3+ phosphors

Hexagonal YPO₄ phosphors doped with Eu³⁺/Dy³⁺ and co-doped with Ce³⁺ were synthesized by a hydrothermal route assisted using lauric acid as a capping agent. The prepared phosphors were characterized by transmission electron microscopy, infrared spectroscopy, powder X-ray diffraction and photoluminescence spectra. YPO₄: Eu³⁺ gives two red emission peaks at 587 and 610?nm corresponding to ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transitions, respectively. YPO₄: Dy³⁺ exhibits two emission peaks at 485?nm (blue) and 575?nm (yellow) corresponding to ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transitions, respectively. Ce³⁺ ions enhanced the emission intensity as a co-dopant in both phosphors. Moreover, the effect of γ-radiation in the dose range 5–300?kGy on the photoluminescence behaviour of YPO₄:Eu³⁺,Ce³⁺ and YPO₄:Dy³⁺,Ce³⁺ was also investigated. Quenching of emission intensity, after irradiation at 5 and 300?kGy, was observed in both the phosphors due to loss of excess energy through a non-radiative relaxation process.     

Up-conversion and optical storage properties of SrS: Eu, Sm in PMMA

An erasable and rewritable optical-storage material SrS: Eu,Sm synthesized. Optical emission and excitation spectra of this material were measured. Using the SrS: Eu, Sm-PMMA film, the image-recording experiment was performed.     

The charge states’ conversion of the activator ions in CaF2:Eu nanophosphors

According to stationary X-ray-excited luminescence spectra and thermally stimulated luminescence spectra of CaF₂:Eu nanophosphors, it was found that Eu³⁺?→?Eu²⁺ conversion can occur during thermal annealing of fine-grained (d?=?25?nm) nanoparticles in the 200–800°C range, which is accompanied by an increase in their size within 40–189?nm. An important role of the exciton mechanism of Eu²⁺ luminescence excitation was revealed according to the temperature dependence of X-ray-excited luminescence spectra of CaF₂:Eu nanoparticles of 114?nm size. The maximum of the X-ray-excited luminescence light output of CaF₂:Eu nanophosphors in the Eu²⁺ ions’ emission band was traced out at 400–500°C annealing temperature and at the size of nanoparticles of 114–180?nm. The subsequent growth of the annealing temperatures, particularly in the 800–1000°C range, causes the reduction of X-ray-excited luminescence light output because of the increment of lattice defects’ concentration due to a sharp increase in the size of nanoparticles and their agglomeration.     

The TL and room temperature OSL properties of the glow peak at 110 °C in natural milky quartz: A case study

The LM–OSL signal of quartz, while measured at room temperature, is dominated by an intermediate, broad and intense OSL component, so that its contribution and general characteristics are derived very accurately. Through a series of dose–response, bleaching and thermal decay at room temperature experiments, in conjunction with curve fitting studies, a component resolved analysis is carried out studying the correlation between this specific component, termed as LM–OSL component C₂ and the 110 °C TL glow peak in quartz. The dose–response of these two luminescence components behaves exactly similar being linear at low doses and saturating at almost 100 Gy. Both signals decay exponentially under illumination, providing identical optical detrapping cross-section values. Residual of both luminescence signals after thermal decay at room temperature follows an exponential law, yielding similar mean half-lives. All previous luminescence features provide strong evidence for the electron trap being the same for both the 110 °C TL trap and the LM–OSL component C₂. The results of the present work are very promising and clearly support the possibility of extrapolating the TL pre-dose methodology to the OSL pre-dose effect using only the LM–OSL component C₂.     

The power and limits of the Judd—Ofelt theory: a case of Pr3+ and Tm3+ acetates and dipicolinates

Electronic absorption spectra of crystals and solutions of praseodymium and thulium acetates and dipicolinates are reported. The influence of spectral properties of both ligands on intensities of the f—f transitions in the crystals studied is discussed. In the near-IR region, overtone vibrations of ligands are strongly coupled with the f—f transitions, particularly with the hypersensitive ones. In the UV spectral range, absorption bands of the π → π?, n → π? and possible charge transfer of metal ? ligand transitions affect f—f transitions and should also be taken into account. The phenomenological Judd—Ofelt parameters evaluated for praseodymium complexes in solution and crystals are meaningless, because no set of intensities unbiased by ligand transitions and/or neighbouring f-d configurations is available. For Tm³⁺ compounds the Judd-Ofelt analysis has given quite good results, however no significant influence of the metal ion environment changes on the Ωλ parameters can be observed.     

Preparation of Sm3+–Eu3+ coactivating red-emitting phosphors and improvement of their luminescent properties by charge compensation

By charge compensating, a series of red-emitting phosphors Ca_0.54Sr_0.16Ca_0.54Sr_0.31Eu_0.08Sm_0.02(MoO₄)_0.6(WO₄)_0.4 were synthesized. Two approaches to charge compensation were used: (a) 2Ca²⁺/Sr²⁺→Eu ³⁺/Sm³⁺+M ⁺, where M⁺ is a monovalent cation like Li⁺, Na⁺ or K⁺; (b) Ca²⁺/Sr²⁺→Eu ³⁺/Sm³⁺+N ^?, where N⁺ is a monovalent anion like F^?, Cl^?, Br^?, or I^?. One red LED was made by combining the phosphor and 390–405 nm emitting LED chip under 20 mA forward-bias current, the color purity, chromaticity coordinates and the luminous intensity of which were 99.5%, x=0.66, y=0.33, 5600 mcd, respectively.     

The use of 3D-laser scanning in assessing the safety of masonry vaults—A case study on the church of Saint-Jacobs

Safety and stability of historical structures are of key importance when dealing with a restoration project. The stability of masonry vaults very much depends on its overall geometry and the analysis results strongly depend on the accuracy in which this geometry can be measured in practice. To obtain an accurate estimate of the geometry of the vaults, 3D-laser scanning was performed. Based on the 3D-point cloud, a 3D-model of the vaults allows determining the lines of thrust in the structure as well as the reaction forces (application point and magnitude) at the abutments. This contribution gives a critical appraisal of the process used in the preliminary research phase: gathering the point clouds, 3D-modelling, structural analysis calculating thrust lines and the consolidation requirements that are obtained. The focus is on the added value of the methodology, its applicability, cost-effectiveness, overall advantages and drawbacks.