NTCR behavior of Sm-substituted barium zirconium titanate nanocrystalline solid solution

Ceramic solid solution of nanocrystalline barium zirconium titanate in the form of Ba(Zr_0.52Ti_0.48)O₃ substituted by samarium (Sm³⁺) was prepared using the conventional solid state reaction method. The phase assemblage analyzed by the X-ray diffraction technique was fitted for cubic-crystal-symmetry. The change in the grain size depicted the influence of Sm³⁺ ions on the microstructure. The electrical behavior was studied in the temperature range from 323 to 773 K. The sintered samples exhibited a negative temperature coefficient of resistance (NTCR) and superior semiconducting behavior above 513 K. Addition of Sm³⁺ increased the room temperature resistivity of Ba(Zr_0.52Ti_0.48)O₃ solid solution. The results obtained from the thermoelectric power measurement confirm electrons as the majority charge carriers.     

Anomalous behavior of the dielectric response of quantum paraelectric CaTiO3 with iron impurities

We report on the studies of lattice dynamics and crystal structure of natural perovskite with the general formula CaTiO₃:0.01Fe by dielectric spectroscopy and X-ray diffraction in a wide temperature range. In contrast to the “chemically pure” synthetic perovskite, the lattice dynamics of the Fe-containing natural sample exhibits a structural instability in the vicinity of 240 K. Our studies of the behavior of magnetic moment of CaTiO₃:0.01Fe demonstrate that in the temperature region from 4.3 to 300 K this material is paramagnetic. No changes in the crystal symmetry have been observed in the structural studies, which can be explained by the small degree of lattice distortions, as has been observed previously for isotopically substituted SrTiO ₃ ¹⁸ . Conductivity measurements and analysis of the dielectric response dispersion of CaTiO₃:0.01Fe have shown that the dispersion is due to the Maxwell–Wagner mechanism and can be attributed to oxygen vacancies present in the mineral.     

Synthesis of micro-FeTi powders by direct electrochemical reduction of ilmenite in CaCl2-NaCl molten salt

Micro-ferrotitanium powders have been prepared by molten salt electrolysis via directly electrochemical reduction of solid ilmenite in eutectic CaCl₂-NaCl melt at 973 K. In the direct electrochemical reduction process, the reduction of FeTiO₃ first gives rise to the formation of Fe and CaTiO₃, which as intermediates will be further deoxidized at the interface of iron metals, solid CaTiO₃ matrix, and electrolyte to directly form ferrotitanium alloy powders in porous structure. Furthering the electrolytic time can promote the dense structure of ilmenite pellet turn to be more porous, indicating pores inside the pellet are sufficient for the diffusion of oxygen ions. Based on the reduction behavior of partially reduced powders in metallic cavity electrode during the cathodic potentiostatic electrolysis, it shows that the slow deoxidization rate is mainly caused by the more and more difficult reduction of CaTiO₃ than that of FeTiO₃.

     

Effects of Zn impurities on the electronic properties of Pr doped CaTiO3

Microcosmic investigations of weak red-emitting materials are crucial for their further development and application. In this work, we have focused on the band structures and electronic properties of Pr mono- and (Zn, Pr) co-doped CaTiO₃ using density functional theory. Zn substitution for Ca or Ti tends to form clusters energetically with Pr substituting for Ca in CaTiO₃. In Pr mono-doped CaTiO₃, the O_2p→Ti_3d transition in CaTiO₃ host corresponds to the centered 330 nm excitation spectra. The gap states above the valence band of ∼1.30 eV and ∼2.06 eV are hybridized by Pr_4f, O_2p and Ti_3d orbitals. They are mainly due to Pr_4f orbitals in CaTiO₃:Pr. The former gap level is related to red emission at 614 nm due to ¹D₂→³H₄ transition of Pr³⁺ activator. The latter is related to the excitation spectra centered at 380 nm due to the low-lying Pr-to-mental intervalence charge transfer transitions (Pr³⁺-O²⁻-Ti⁴⁺?Pr⁴⁺-O²⁻-Ti³⁺). The band structures of (Zn, Pr) co-doped CaTiO₃ keep the similar gap levels to those in Pr mono-doped CaTiO₃. The incorporation of Zn brings out the two stronger localized gap states, which are hybridized by Pr_4f, O_2p and Ti_3d orbitals, in comparison with those in Pr mono-doped CaTiO₃. Therefore, when Zn impurities are added into Pr doped CaTiO₃, the present calculations visualize the two enhanced levels and the distorted structures around Pr.     

退火诱导亚稳态Fe80Cu20合金固溶体的结构相变

利用扩展x射线吸收精细结构和x射线衍射研究了机械合金化制备的体心立方(bcc)的亚稳态Fe₈₀Cu₂₀合金固溶体的结构随退火温度的变化特点.结果表明，在300—873 K温度范围内，随着退火温度的升高，bcc结构物相的晶格常数近于线性降低，这主要是由于Cu原子从bcc结构Fe₈₀Cu₂₀合金固溶体中逐渐偏析出来，生成面心立方(fcc)结构的Cu物相所致.经603K退火后，Cu原子的平均键长R_Cu—Cu增加了0.003 nm左右，大约有50%的Cu原子从bcc结构的Fe₈₀Cu₂₀合金固溶体中偏析出来.在773 K退火后，bcc结构Fe_８０Cu₂₀合金固溶体近于完全相分离，生成了bcc结构的α-Fe与fcc结构的Cu物相. 关键词： 扩展x射线吸收精细结构 x射线衍射 ８０Cu₂₀合金')" href="#">Fe_８０Cu₂₀合金 机械合金化     

Ferroelectricity in SrTiO3 nanocrystalline disks

SrTiO₃ and CaTiO₃ conventional bulk materials are incipient ferroelectrics. In this note, we report for the first time that ferroelectricity could occur in SrTiO₃ nanocrystalline disks even at room temperature. The peak in the temperature dependence of permittivity for a CaTiO₃ nanocrystalline disk at a low temperature is also observed. The observed ferroelectricity (or permittivity peak) in SrTiO₃ (or CaTiO₃) nanocrystalline disks could be attributed to the strain effect.     

0.5NdAlO3-0.5CaTiO3电子结构及光学性质的第一性原理计算

采用基于第一性原理密度泛函理论的平面波赝势方法,对0.5NdAlO₃-0.5CaTiO₃晶体进行结构优化,并对其能带结构,态密度和光学性质进行了理论计算.结构优化后晶格参数与实验数据相符合,误差小于1%;能带计算结果表明0.5NdAlO₃-0.5CaTiO₃为间接带隙,带隙值为0.52eV;费米面附近的能带由Nd-4f,O-2p,Nd-4p,Al-3p,Ti-4d层的电子态密度确定.同时也计算了该结构的介电函数,反射率和复折射率等光学性质.     

Native defects and Pr impurities in orthorhombic CaTiO3 by first-principles calculations

Formation energies of native defects and Pr impurities in orthorhombic CaTiO₃ are explored using the first-principles calculations. The Ca vacancy (V_Ca), Ti vacancy (V_Ti) and Ca antisite (Ca_Ti) are found to be energetically preferable. The Ti antisite (Ti_Ca) and O vacancy (V_O) are not energetically favorable in the wide range of Fermi level. In Pr-doped CaTiO₃, Pr substituting for Ca (Pr_Ca) is likely to form under condition A in which CaTiO₃ is in equilibrium with CaO and O₂. Under condition B (TiO₂, CaTiO₃ and O₂ are in equilibrium), Pr_Ti defect is energetically preferable depending on the Fermi levels. Several native defects and the two sites of Pr impurities in CaTiO₃ are coincided with several different defects in Pr-doped CaTiO₃ reported in the literature. Based on the present calculations, we can elucidate that the Ca deficiency design of the traditional formula Ca_1−xV_Ca(x/2)Pr_xTiO₃ is not the best for efficient red photoluminescence, which is realized via the experimental measurements.     

Structural phase transitions in Cu2–x Te crystals (x = 0.00, 0.10, 0.15, 0.20, 0.25)

Structural phase transitions in Cu_2–x Te crystals have been investigated by high-temperature X-ray diffraction.

At room temperature Cu₂Te and Cu_1.90Te specimens are two-phased, i.e. they consist of an orthohombic phase with a = 7.319, b = 22.236, c = 36.458 Å and a hexagonal phase with a = 4.150, c = 7.188 Å. The changes in both compounds take place generally in the hexagonal phase with increasing temperature. At 821, 873 K they transform to a FCC phase. Monocrystals of the other compounds at room temperature crystallize in the hexagonal system and at 673, 773, 723 K, respectively, they transform to a FCC phase. It is determined that as the cation deficiency increases the crystal quality becomes better.     

Chemical diffusion in calcium titanate

This work reports the gas/solid equilibration kinetics for the O₂/CaTiO₃ system. The electrical conductivity measurement was applied for monitoring the kinetics in the ranges of temperature 973-1323 K and oxygen partial pressure 10 Pa-72 kPa. It was found that the gas/solid equilibration kinetics for the polycrystalline CaTiO₃ specimen in the above experimental conditions is determined by bulk diffusion rather than by grain boundary conditions. The obtained data of the electrical conductivity vs. time were used for the determination of the chemical diffusion coefficient as a function of temperature at low and high p(O₂), respectively:

(1)     

Doping effects of Nb5+ on red long afterglow phosphor CaTiO3:Pr3+

A series of Nb5+ codoped red long afterglow phosphors CaTi1 xNbxO3:Pr03.+002 (0 ≤ x ≤ 0.05) is prepared by a solid state reaction method. Their photoluminescence, phosphorescence and thermoluminescence are investigated. The results indicate that codoping Nb5+ can improve the photoluminescence and phosphorescence property of CaTiO3:Pr3+ significantly. When 3-mol% Nb5+ is codoped, the emission intensity of CaTiO3:Pr3+ is enhanced twice, while the afterglow time is extended from 10 min to about 40 min. Thermoluminescence results reveal that the trapping level of CaTiO3:Pr3+ is reduced from 0.82 eV to 0.62 eV by codoping Nb5+. The effect of Nb5+ doping on enhancing the photoluminescence intensity and afterglow time of CaTiO3:Pr3+ is discussed.     

Improved photoluminescence and afterglow in CaTiO3:Pr with addition of nanosized SiO2

Enhancement of the ¹D₂-³H₄ red emission in CaTiO₃:Pr³⁺ with addition of nanosized SiO₂ fabricated by a solid state reaction method is reported. The dynamical processes for the improvement of red emission were systematically investigated using photoluminescence (PL) and PL excitation spectra, and diffused reflectance spectra as well as time decay patterns of PL and persistent afterglow. Higher efficiency of energy transfer from CaTiO₃ host to the activator Pr³⁺ due to the improvement of crystallinity by SiO₂ addition was discussed in comparison with that of the SiO₂ free sample. The enhancement of persistent afterglow after the cessation of excitation in SiO₂ added CaTiO₃:Pr³⁺ was also analyzed by theoretically fitted results.     

Microstructure characterization and phase transformation kinetic study of ball-milled m-ZrO2–30 mol% a-TiO2 mixture by Rietveld method

High-energy ball milling of monoclinic ZrO₂–30 mol% anatase TiO₂ mixture at different durations results in the formation of m-ZrO₂–a-TiO₂ solid solution from which the nucleation of nanocrystalline cubic (c) ZrO₂ polymorphic phase sets in. Post-annealing of 12 h ball-milled sample at different elevated temperatures for 1 h results in almost complete formation of c-ZrO₂ phase. Microstructure of the unmilled, all the ball milled and annealed samples has been characterized by Rietveld's X-ray powder structure refinement method. Particle size, rms lattice strain, change in lattice parameters and phase content of individual phases have been estimated from Rietveld analysis, and are utilized to interpret the results. In course of milling, (1 1 1) of cubic lattice became parallel to () plane of monoclinic lattice due to the orientation effect and cubic phase may have been formed on the (0 0 1) of the m-ZrO₂–a-TiO₂ solid solution lattice. A comparative study of microstructure and phase transformation kinetics of ZrO₂–10, 20 and 30 mol% a-TiO₂ ball-milled and post-annealed samples reveals that rate of phase transformation m→c-ZrO₂ increases with increasing a-TiO₂ concentration and 30 mol% of nanocrystalline c-ZrO₂ phase can be obtained within 4 h of milling time in the presence of 30 mol% of a-TiO₂. The post-annealing treatment at 773, 873 and 973 K for 1 h duration each reveals that rate of c-ZrO₂ formation with increasing temperature is retarded with increasing a-TiO₂ concentration but the amount of c-ZrO₂ becomes almost equal (95 mol%) at 973 K. It suggests that almost fully stabilized nanocrystalline c-ZrO₂ can be formed by adding a tetravalent solute to m-ZrO_2.     

First-principles study of the pressure-induced phase transition in CaTiO3

An investigation into the phase stabilities of CaTiO₃ under high pressure was conducted using first-principles calculations based on density functional theory. We have identified three candidate structures of CaTiO₃, Pbnm, Pm3m and Cmcm, respectively. Our results demonstrate that a phase transition from orthorhombic (Pbnm) to cubic (Pm3m) is impossible for CaTiO₃ under high pressure at ambient temperature, and further predict that Pbnm-CaTiO₃ will transform to post-perovskite phase (Cmcm) at enough temperature and pressure.     

Aluminium-based amorphous and nanocrystalline alloys with Fe impurity

Aluminium-based rapidly quenched alloys of nominal composition of Al₉₀Fe₇Nb₃ and Al₉₄Fe₂V₄ were studied by Mössbauer spectroscopy. Samples annealed up to 573K showed amorphous structure represented by quadrupole-split doublets. From the corrected spectra areas, the values of f-factor and Debye temperature were calculated for both samples in the as-cast state. In the case of AlFeNb sample, f-factor was estimated to be f = 0.26 and for AlFeV, f = 0.31. High-temperature annealing at 773K and 873K induced a formation of nano-and microcrystalline structures. Mössbauer spectra of both compositions (with vanadium as well as with niobium) annealed at 773K showed superposition of crystalline phases with dominant contribution of Al₃Fe alloy. During annealing at 873K, phases with large grains and a small amount of the FeAl metastable phase were developed.     

Observation of ferroelectricity induced by defect dipoles in the strain-free epitaxial CaTiO3 thin film

CaTiO₃ is a well-known incipient ferroelectric material that does not undergo a ferroelectric phase transition in spite of the intriguing dielectric constant behavior. Especially, unlike a prototypical incipient ferroelectric SrTiO₃, the paraelectric state of CaTiO₃ cannot be easily destroyed by small perturbations, including cation doping and epitaxial strain. We present that a nearly strain-free epitaxial CaTiO₃ film grown at a low oxygen partial pressure exhibits polarization–voltage hysteresis loops and the distinct difference of piezoresponse force microscopy phase signals, implying that a ferroelectric phase is induced. Such results are shown even at room temperature. We suggest that the observed ferroelectric behavior in CaTiO₃ film comes from the defect dipoles composed of vacancies inside the film. Using electron-probe microanalysis and optical absorption spectra measurements, we found that CaTiO₃ film has considerable Ca and O vacancies, forming the localized defect state in electronic structure. This work highlights the importance of vacancies and their clusters, such as defect dipoles, in understanding the electronic properties of perovskite oxide thin films, including ferroelectricity.     

Characterization of chemically deposited ZnSe/SnO2/glass films: Influence of annealing in Ar atmosphere on physical properties

The Zinc Selenide (ZnSe) thin films have been deposited on SnO₂/glass substrates by a simple and inexpensive chemical bath deposition (CBD). The structural, optical and electrical properties of ZnSe films have been characterized by X-ray diffraction (XRD), Energy Dispersive X-ray Analysis (EDAX), optical absorption spectroscopy, and four point probe techniques, respectively. The films have been subjected to different annealing temperature in Argon (Ar) atmosphere. An increase in annealing temperature does not cause a complete phase transformation whereas it affects the crystallite size, dislocation density and strain. The optical band gap (E_g) of the as-deposited film is estimated to be 3.08 eV and decreases with increasing annealing temperature down to 2.43 eV at 773 K. The as-deposited and annealed films show typical semiconducting behaviour, dρ/dT > 0. Interestingly, the films annealed at 373 K, 473 K, and 573 K show two distinct temperature dependent regions of electrical resistivity; exponential region at high temperature, linear region at low temperature. The temperature at which the transition takes place from exponential to linear region strongly depends on the annealing temperature.     

Work function of indium sesquioxide thin film

This paper reports surface electrical properties of thin film of indium sesquioxide, In₂O₃, during oxidation and reduction at elevated temperatures (298 K and 873 K). The studies involved monitoring of surface potential during oxidation and reduction experiments using work function measurements. The obtained experimental data are considered in terms of the effect of temperature on reactivity between oxygen and In₂O₃, involving chemisorption and oxygen incorporation. The reactivity in the range 298 – 773 K is limited to chemisorption resulting in the formation of surface dipoles exhibiting positive surface charge. Oxidation at 873 K results in slow oxygen incorporation.     

Highly luminescent red light phosphor CaTiO3:Eu under near-ultraviolet excitation

The Eu-doped CaTiO₃ particles with a good crystallinity were prepared via sol-gel method. The phosphors showed a strong red emission corresponding to ⁵D₀→⁷F₂ (618 nm) of Eu³⁺ under the near-ultraviolet excitation (400 nm). X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM), photoluminescent (PL) analysis and Brunauer-Emmett-Teller (BET) specific surface area measurement were utilized to characterize the CaTiO₃:Eu³⁺ particles. The concentration quenching and thermal quenching of the samples were discussed as well. The optimal concentration and the calcination temperature were 16 mol% of Eu³⁺ and 1400 °C for these phosphors, and the possible reason was discussed as well. CaTiO₃:Eu³⁺ is a promising red phosphor under near-ultraviolet excitation for various applications.     

Electronic and ionic conductivity in CaTiO3

The present work describes the electrical conductivity of undoped CaTiO₃ in terms of the electrical conductivity components corresponding to electrons, electron holes and ionic charge carriers in the temperature range 973 K — 1323 K and under controlled oxygen partial pressure (10 Pa — 72 kPa). These data are considered in terms of the transference numbers of the respective charge carriers. It appears that the ionic conductivity component assumes maximum at the n-p transition when the ionic transfer number reaches 50% of the total conductivity value at 1323 K. The present study also includes the determination of the activation energy of the conductivity component related to ions (162.1 kJ/mol), electrons (134.2 kJ/mol) and electron holes (86.2 kJ/mol). The data obtained in this work indicate that undoped CaTiO₃ exhibits a substantial level of ionic conduction that cannot be ignored in a quantitative analysis of electrical conductivity data.