Effects of cerium doping on dielectric properties and defect mechanism of barium strontium titanate glass-ceramics

The effect of cerium content on phase evolution, dielectric properties and defect mechanism has been investigated in (Ba,Sr)TiO₃ glass-ceramics. Cerium mainly acts as an isovalent dopant in the B-site of ABO₃ perovskite structure at low content (1 mol%) and then cerium substitution gradually occurs in the A-site with increasing cerium content. A compensation mechanism related to variation in oxygen vacancy concentration has been identified. When cerium content increased to 2 mol%, the maximum values of dielectric constant and energy storage density were simultaneously achieved. The impedance spectra revealed the highest conductivity. It is due to the increase in the concentration of charge carriers accompanied by the decrease in the activation energy of oxygen vacancy migration. With a further addition of cerium to 3 mol%, the opposite trend was observed. The result is related to the presence of more cation vacancies, which, in turn, limits the diffusion rate of oxygen vacancy.     

Effect of high-content Yttria on the thermal expansion behaviour and ionic conductivity of a stabilised cubic Hafnia

The needs for space propulsion thruster induce the development of new designs and material compositions able to withstand 3000 K of flame combustion temperature. Cubic-stabilised hafnia appears as one of the most promising candidates to protect refractory materials in such conditions. Here, the influence of dopant content on the thermal expansion (473−1823 K) and ionic conductivity (600−1150 K) in highly doped-hafnia (12−33 mol% Y₂O₃) with disordered cubic systems is reported. The composition and the homogeneity of the samples were carefully checked using crystallographic, chemical and spectroscopy analyses. Finally, the study of thermal and oxygen conductivity properties highlighted their dependence on the amount of dopant. The average thermal expansion coefficient was lowered from 11.3 to 10.9 10⁻⁶/K and the ionic conductivity decreased by two decades with 33 mol% of Y₂O₃ by using the optimised substitution ratio. Interactions and local ordering of oxygen vacancies can explain this behaviour.     

Synthesis and characterization of Gd-doped SnO2 nanostructures and their enhanced gas sensing properties

In the present work, we report the influence of Gd-doping on structural, optical and gas sensing properties of SnO₂ nanoparticles. X-ray diffraction (XRD) and Raman spectroscopy studies confirmed formation of tetragonal rutile type structure of both undoped and Gd-doped SnO₂ nanoparticles. The crystallite size has been found to decrease with increase in dopant concentration which was confirmed from XRD and TEM techniques. It has been observed that Raman surface modes are directly related to the surface area of nanoparticles. Photoluminescence (PL) spectroscopy confirmed large number of oxygen vacancies in 3% Gd-doped SnO₂ nanoparticles. It has been observed that 3% doped sensor displayed exceptionally large sensor response towards ethanol which is about 27 times larger than that of undoped sensor. The optimum operating temperature of doped sensors has reduced as compared to undoped sensor. The enhanced sensor response of Gd-doped nanoparticles has been attributed to small crystallite size, large number of oxygen vacancies, high surface basicity and increased contribution of Raman surface modes. Moreover, it has been observed that 3% Gd doped SnO₂ nanoparticle sensor is highly selective towards ethanol.     

Size and Lone Pair Effects on the Multiferroic Properties of Bi0.75A0.25FeO3−δ (A = Sr,Pb, and Ba) Ceramics

The work presents a comparative study of the effects of divalent Ba, Sr, and Pb substituents on the multiferroic properties of BiFeO₃. The multiferroic properties of Bi_0.75A_0.25FeO₃ (A = Sr, Pb, Ba) solid solution have been explained taking into account the effects of size differences and electronic configuration differences between the host element (Bi) and the substituent. X‐ray diffraction studies revealed that Sr and Pb substitution at Bi‐site transforms the rhombohedral phase (R3c) to cubic phase (Pm3m), whereas the Ba‐substituted sample exhibited the presence of both rhombohedral and cubic phases (R3c + Pm3m). Electronic structure studies through XPS revealed that charge imbalance induced by divalent substitution was being compensated by the formation of oxygen vacancies, while the Fe ions exist in Fe²⁺ and Fe³⁺ states. Replacement of volatile Bi by Sr, Pb, and Ba reduces the concentration of oxygen vacancies (V_O²⁺) and helps to improve the dielectric properties. Strong magnetization enhancement was observed in the substituted compositions and was seen to be consistent with the suppression of cycloid spin structure due to structural transformation as well as possible changes in Fe–O local environment leading to local lattice distortion effects. Furthermore, the observed decrease in the values of magnetic coercivity at low temperature in all the substituted samples is explained in terms of reduced effective single ion anisotropy, originating in the magnetoelectric coupling and being a particularly stronger effect in the case of the lone pair dopant Pb, consistent with theoretical predictions. The lone pair substituent Pb leads to the largest dielectric constant, enhanced magnetization, and large effects on the low‐temperature hysteresis.     

掺杂的阳离子缺陷型磷灰石 La9.33－2x/3MxSi6O26 (M=Mg,Sr,Ca)的合成及离子导电特性

Apatite-type lanthanum silicate with special conduction mechanism via interstitial oxygen has attracted considerable interest in recent years. In this work, pure powder of La9.33－2x/3MxSi6O26 (M＝Mg, Ca, Sr) is prepared by the sol-gel method with sintering at 1000°C. The powder is characterized by X-ray diffraction (XRD) and scan-ning electron micrograph (SEM). The apatite can be obtained at relatively low temperature as compared to the con-ventional solid-state reaction method. The measurements of conductivity of a series of doped samples La9.33－2x/3MxSi6O26 (M＝Ca, Mg, Sr) indicate that the type of dopant and the amount have a significant effect on the conductivity. The greatest decrease in conductivity is observed for Mg doping, following the Ca and the Sr doped apatites. The effect is ultimately attributed to the amount of oxygen interstitials, which is affected by the crystal lat-tice distortion arising from cation vacancies.     

Thermal and chemical induced expansion of La0.3Sr0.7(Fe,Ga)O3−δ ceramics

The linear thermal expansion coefficients (TECs) of perovskite-type La_0.3Sr_0.7Fe_1−xGa_xO_3−δ (x=0–0.4), determined by dilatometric and high-temperature X-ray diffraction techniques, are in the range (19–41)×10⁻⁶ K⁻¹ at 770–1170 K, decreasing when the oxygen partial pressure or gallium concentration increases. At oxygen pressures from 10⁻⁴ to 1 atm, the isothermal chemically induced expansion of La_0.3Sr_0.7Fe(Ga)O_3−δ ceramics is a linear function of the oxygen nonstoichiometry. The magnitude of changes in δ and, thus, chemical expansion both are reduced by gallium doping. The ratio between isothermal chemical strain and nonstoichiometry variations, (ε_C/Δδ), follows an Arrhenius-type dependence on temperature and varies in the range (1.7–5.9)×10⁻². The drastic increase in the thermal expansion at temperatures above 700 K, typical for ferrite-based ceramics, was shown to be mainly apparent, resulting from the chemically-induced expansion of the lattice due to oxygen losses. The TEC values, corrected for the chemical strain on heating, are close to the TECs at low temperatures and increase with gallium content. The observed correlations between the thermal and chemical expansion and ionic conductivity of La_0.3Sr_0.7Fe_1−xGa_xO_3−δ are discussed in terms of their relationships with the oxygen deficiency and cation composition.     

Significantly enhanced breakdown field in Ca1-xSrxCu3Ti4O12 ceramics by tailoring donor densities

Significantly enhanced breakdown field of 24.52 kV cm^?1 as well as noteworthy nonlinear coefficient of 8.11 and low dielectric loss of 0.077 were obtained in Ca_0.6Sr_0.4Cu₃Ti₄O₁₂ ceramic. It was proved from impedance spectra that improved breakdown field was attributed to enhanced grain boundary resistance and elevated Schottky barrier height, which was further found resulting from reduced donor densities in C-V measurements. In addition, it was found that the activation energy originated from oxygen vacancies was increased, indicating the generation of oxygen vacancies was suppressed. Since oxygen vacancies acted as donors in depletion layers, it is reasonable to deduce that the reduced donor density was mainly ascribed to the decreased oxygen vacancies. In conclusion, maximum integrated action of strong solid solution effect and weak Sr-stretching effect was achieved when Sr/Ca ratio is 40/60, leading to greatly elevated potential barrier height and enhanced breakdown field consequently.     

Effects of rare-earth doping on the ionic conduction of CeO2 in solid oxide fuel cells

Rare-earth-doped CeO₂ have been found to enhance the ionic conductivity of ceria-based electrolytes in solid oxide fuel cells (SOFCs) because trivalent rare-earth cations can spontaneously induce oxygen vacancies. Experimentally, it has been shown that the rare-earth elements La, Nd, Sm, Gd, Tb, Dy, and Er are likely candidates for electrolyte doping. However, the performances differ for the trivalent cations, suggesting that rare-earth doping plays multiple roles instead of only increasing the oxygen vacancies. First-principles calculations are performed on a series of rare-earth-doped CeO₂ systems to study the doping effects on the ionic conductivity. It is found that the migration barriers of the oxygen ions are significantly different for the different dopants and depend on the dopant's radius. Gd-, Dy-, Er-, and Tb-doping results in small migration barriers and enhances the ionic conductivity. We also calculate the formation energies (E_vac) of the intrinsic oxygen vacancies due to thermal excitation. It is found that the Sm- and Gd-doped ceria systems have the smallest E_vac values. The electronic structures indicate that the band gaps are not sensitive to the dopant elements but are very sensitive to the fluctuations in the oxygen content.     

Role of a low level of La2O3 dopant on the tetragonal-to-monoclinic phase transformation of ceria-yttria co-stabilized zirconia

Yttria, yttria-ceria and yttria-ceria-lanthana stabilized zirconia powders were prepared by coprecipitation. Their tetragonal-to-monoclinic phase (t→m) transformation was investigated by calcining the powders in a temperature range of 400–1400 °C for 2 h. The results show that after doping with 0.1 to 0.3 mol.% La₂O₃ and calcining at 1400 °C in air, unusual redox behaviours of cerium were detected in the 1.5 mol.% Y₂O₃+5.5 mol.% CeO₂ co-stabilized zirconia. Grain refinement and a sharp reduction in oxygen vacancy concentration were observed simultaneously. The t→m transition was not found in the 0.1 mol.% La₂O₃ doped zirconia but appeared in the cases with a higher dopant content. The changes are discussed with regards to the grain size, valence change of cerium, presence of oxygen vacancies, and segregation of the dopants at grain boundaries.     

(Ba,Sr)TiO3 solid solutions sintered from sol-gel derived powders: An insight into the composition and temperature dependent dielectric behavior

Single-phase Ba_1-xSr_xTiO₃ (BST) perovskite ceramics with 0.3 ≤ x ≤ 0.4 were prepared from powders synthesized via sol-gel route. The compositions have the ferroelectric-paraelectric phase transition close to room temperature. At 20 ^°C the BST ceramics are ferroelectric for 0.3 ≤ x ≤ 0.35 and paraelectric for x = 0.375 and x = 0.40. The study follows the relation between the structural changes produced when increasing the Sr content and the dielectric properties at low intensity electric fields. It is found that the grain size and tetragonality decreases as the Sr content increases. Analyses of complex permittivity and impedance spectroscopy reveal the temperature and frequency dependencies of the dielectric properties. The phase transitions seem to be of first order for all compositions, with a thermal hysteresis that decreases with increasing the Sr content, fact attributed to the corresponding increase of the grain boundaries weight allowing a more efficient stress relaxation in the structure during the change of the symmetry from cubic to tetragonal. The diffusiveness degree during the phase transition is increasing with Sr content, suggesting some relaxor-type contribution attributed to smaller grain size. The ac conductivity follows the universal Jonscher law, with an ac component having the power parameter s independent of Sr content, and a dc component that it is thermally activated with an activation energy of about 0.7–0.77 eV attributed to oxygen vacancies acting as donor-like defects. The fit of impedance spectra at different temperatures and frequencies is obtained by using an equivalent circuit accounting the grains, grain boundaries, electrode interfaces and the local contributions produced by reorientation of defect dipoles or defect clusters. All the component circuits have significant variations around phase transitions. These are discussed in relation to structural changes occurring during transition and considering the changes in the distribution of various charges when polarization vanishes.     

Excess oxygen-vacancy formed by FAST regime of direct-current electric field during flash sintering for 3 mol%–10 mol% Y2O3-doped ZrO2

The amount of excess oxygen vacancies that are generated during FAST regime of direct-current flash sintering was estimated semi-quantitatively for 3 mol%–10 mol% Y₂O₃-doped ZrO₂ (3–10YSZ) using the temperature dependence of the electrical conductivity. For the estimation, the electrical conductivity in the temperature range, where shrinkages are below a few percent, was used to avoid the effect of large microstructural changes on the electric conductivity. For all Y₂O₃ contents except 3YSZ, the amount of excess oxygen vacancies increased above a compact temperature of approximately 840 °C, which depended on Y₂O₃ content, and was highest in 8YSZ. Approximately 0.13% excess oxygen vacancy was generated by direct-current flashing in 8YSZ in the present electric field condition. In contrast, the increase in the excess oxygen vacancies is negligible in 3YSZ. The dependence of the amount of excess oxygen vacancies on the Y₂O₃ content was related possibly to the dependence of the electrode overvoltage on the Y₂O₃ content.     

Thermally stimulated depolarization current measurements on degraded lead zirconate titanate films

Charge transport mechanisms governing DC resistance degradation in ferroelectric films are influenced by defects, particularly oxygen vacancies. This paper demonstrates that oxygen vacancies migrate in lead zirconate titanate (PZT) films under a DC bias field and contribute to resistance degradation. Model PZT thin films were developed in which the concentration and distribution of oxygen vacancies were controlled via (a) changing the dopant type and concentration from 1%–4% Mn (acceptor) to 1%–4% Nb (donor) or (b) annealing undoped PZT films at varying partial pressures of PbO. The presence of associated (immobile) and dissociated (mobile) oxygen vacancies was distinguished by thermally stimulated depolarization current (TSDC) measurements. The impact of mobile oxygen vacancies on local defect chemistry and associated charge transport mechanisms was explored by electron energy loss spectroscopy (EELS). For Mn-doped PZT films, following resistance degradation, TSDC studies revealed only one depolarization peak with an activation energy of 0.6–0.8 eV; this peak was associated with ionic space charge presumably due to migration of oxygen vacancies. The magnitude of the depolarization current peak increased with increasing degradation times. A similar depolarization current peak attributed to the existence of mobile oxygen vacancies was also observed for undoped and Nb-doped PZT films; the magnitude of this peak decreased as the Nb or PbO contents in PZT films increased. An additional TSDC peak associated with polaron hopping between Ti³⁺ and Ti⁴⁺ was found in both Nb-doped PZT films and undoped PZT films annealed under low PbO partial pressure. Degraded Nb-doped samples exhibited a chemical shift in the TiL_2,3 peak to lower energy losses and the appearance of shoulders on the t_2g and e_g peaks, implying a reduction of Ti cations in regions near the cathode.     

Influence of Fe3+-doping on optical properties of CeO2−y nanopowders

Ce_1?xFe_xO_2?y (0≤x≤0.05) nanopowders were synthesized using hydrothermal method at low calcination temperature and low doping regime. Structural and morphological characterization has been carried out by the X-ray diffraction method and non-contact atomic force microscopy. Vibrational properties were investigated by Raman spectroscopy. It was observed that the content of oxygen vacancies increased significantly with Fe doping up to 3 mol%. For higher dopant concentration, phase separation was detected. The optical properties of pure and Fe³⁺-doped CeO_2?y samples were investigated by spectroscopic ellipsometry. Several analytical models were applied to analyze the optical absorption onset of ceria defective structure. It was found that, Cody–Lorentz model most suitably described the sub-band gap region of CeO_2?y nanopowders and consequently gave more accurate band gap values, which are closer to the direct band gap transitions than to the indirect ones. The increased content of localized defect states in the ceria gap and corresponding shift of the optical absorption edge towards visible range in Fe-doped samples can significantly improve the optical activity of nanocrystalline ceria.     

Flame synthesis of titania particles from titanium tetraisopropoxide in premixed flames

An experimental investigation of flame synthesis of titania particles was conducted in premixed flames. The titanium precursor and silicon dopant used in this study were titanium tetraisopropoxide (TTIP) and hexamethyldisiloxane (HMDS), respectively. The objective of this study was to investigate the influence of flame condition, TTIP concentration, and HMDS on the phase composition and particle morphology of titania synthesized in flames. It was found that the anatase content of titania particles made in flames was appreciably increased by the increase of oxygen concentration in the oxidizer. The increase of flame temperature results in the decrease of anatase content. A significant increase in rutile content of titania particles was observed by increasing the particle residence time at high temperatures. The doping of HMDS in flames inhibits the transformation of anatase to rutile phase and, therefore, reduces the rutile content of product particles. Under the flame doped with low concentrations of HMDS, titania particles with SiO₂ particle agglomerates attached were produced. Further increase of the HMDS concentration up to the Si to Ti molar ratio equal to 0.375 results in the formation of a large amount of SiO₂ agglomerates in the product.     

Effect of cobalt doping on the sintering mechanisms of the lead-free piezoceramic (Bi0.5Na0.5)TiO3

In the search for lead-free piezoelectric ceramics, such as potassium sodium niobate, (K_0.5Na_0.5)NbO₃ (KNN), and bismuth sodium titanate (Bi_0.5Na_0.5)TiO₃ (BNT), high sintering temperatures and the associated volatilization of cations represent a major obstacle to achieve well performing materials. In this study, we investigated the effect of cobalt on the sintering behavior of BNT using in situ thermo-optical dilatometry. The addition of cobalt significantly reduced the sintering temperature at which fully dense ceramic bodies are obtained. This is accomplished by a dual effect of the dopant which facilitates oxygen diffusion: a fraction of the available Ti forms a secondary cobaltous phase. Instead of Ti, some Co is incorporated into BNT at the Ti site, causing oxygen vacancies for charge balancing. To a small degree, the dopant induces liquid phase sintering. At high sintering temperatures, swelling was observed, which was attributed to oxygen release caused by the valence transition from Co³⁺ to Co²⁺.     

In-situ immobilization of Sr radioactive isotope using nanocrystalline hydroxyapatite

Hydroxyapatite was used as the inert matrix for in-situ immobilization of strontium (Sr) radioactive isotopes at room temperature. A nano-emulsification method was applied to synthesize Sr-substituted calcium hydroxyapatite (Ca_1?xSr_x)₁₀(PO₄)₆(OH)₂. The concentration of incorporated Sr was in the range of 0 ≤ x ≤ 1. Immobilization of Sr was evaluated using a stable isotope instead of radioactive isotope. The effect of strontium concentration on the crystal structure was studied and the results have showed that in the whole concentration range, Sr forms solid solutions with the host hydroxyapatite crystal structure. Powders comprised of nanometre sized particles were obtained and their properties, such as crystallite and particle size, changes in lattice parameters as function of dopant content and thermal stability, were further examined. It was found that the crystal structure of obtained powders is thermally stable at high temperatures. No secondary phases were formed in as-prepared powders or during calcination. The results in this study showed that nano-emulsion strategy provides a simple pathway for synthesis of a single-phase Sr-substituted hydroxyapatite, which can be used for immobilization of Sr radioactive isotopes.     

Aging-induced change of photoluminescence in yttria-fully-stabilized ZrO2 with Sc2O3 or In2O3 doping

We report on the photoluminescence properties of Sc₂O₃- or In₂O₃-doped yttria-fully-stabilized zirconia (YSZ) by sub-bandgap photo-excitation to localized electronic states of oxygen vacancies, in order to clarify the mechanism for the aging-induced decrease of ionic conductivity via vacancies known in YSZ and suppressed by such doping. A new band emerged at 2.70 eV and remained even after the aging for the Sc₂O₃-doped samples at the doping concentration whereof the conductivity decrease was suppressed. On the other hand, a sharp and singular increase of the photoluminescence intensity was observed for the In₂O₃-doped samples at the range of the dopant concentration wherein a singular conductivity drop was observed and the suppression of conductivity decrease started. It is suggested that the suppression mechanism is different between Sc₂O₃-doped YSZ (Sc-YSZ) and In₂O₃-doped YSZ (In-YSZ).     

Structure and the enhanced ferromagnetism in single phase Sr4Fe5CoO13-δ ceramic

Oxides with superstructure have attracted special attention for their great tolerance in structure and composition regulation, which enables them to have great potential in energy conversion devices, electromagnetic regulation devices, spintronic devices, and so on. Here, we successfully prepared a superstructure oxide Sr₄Fe₅CoO_13-δ via combustion method. X-ray photoelectron spectroscopy (XPS) and soft X-ray absorption spectra (XAS) analysis suggest that Co dopant could improve the amount of oxygen vacancies in oxides. Unlike the thermal activated electrical conducting behavior of Sr₄Fe₆O_13-δ, Sr₄Fe₅CoO_13-δ demonstrates an electrical behavior in line with the Mott's variable range hopping (VRH) model at low temperatures, implying the localization of electrons. Sr₄Fe₅CoO_13-δ shows a ferromagnetic property with a high Curie temperature of 771 K, which should be attributed to the new formed Dzyaloshinskii-Moriya (D-M) interaction of Fe–O–Co, the increased lattice distortion and the increased amount of oxygen vacancies induced by Co dopant. These properties render it a broadened working temperature range and may contribute to explore high temperature spintronic devices.     

Co and Fe co-doping influence on functional properties of SrTiO3 for use as oxygen transport membranes

Perovskite-structured powders of SrTi_1-xCo_xO_3-δ (STC-x) with nominal stoichiometry of x?=?0–0.75 as well as SrTi_0.75Co_0.25-yFe_yO_3-δ (STCF-y) where y?=?0–0.25 were synthesized using the Pechini method. Thermal/chemical expansion behaviour, total electrical conductivities, and oxygen permeation rates were investigated. The substitution of Ti with Co leads to an increase in both electronic and ionic conductivities and, therefore, oxygen permeability. Thermal and chemical expansions also increase slightly. The optimum Co content was found to be 25–35% due to the trade-off between phase stability and permeability. The oxygen permeation rate of STC35 is comparable to that of state-of-the-art (La,Sr)(Co,Fe)O_3-δ, whereas the expansion coefficients are lower. Co-doping in STCF-y did not produce any significant differences in oxygen permeability at both high temperature and sample thickness (1.0?mm), i.e. in a solid-state diffusion-limited regime. At lower temperatures (<800?°C), STC25 exhibits higher permeability than STF25 due to the higher catalytic activity of Co compared to Fe.     

Towards the fabrication of La0.98−xSrxCo0.2Fe0.8O3−δ perovskite-type oxygen transport membranes

La_0.98−xSr_xCo_0.2Fe_0.8O_3−δ (LSCF) is a candidate material for use as an oxygen transport membrane (OTM). In this work, fabrication-relevant properties (sintering behaviour, thermal and chemical expansion) of LSCF (x = 0.2, 0.4, 0.6, 0.8) were investigated in order to select the preferred composition for fabricating a thin-film supported membrane able to withstand the thermochemical stresses encountered during manufacturing and operation with simultaneously high oxygen permeation flux.Partial substitution of La by Sr ions in LSCF is beneficial for increasing the oxygen permeation rate, but it causes drawbacks regarding manufacturing and operation. A Sr content of x ≥ 0.6 results in a swelling of the material during sintering, which complicates the manufacturing of thin, leak-free membranes. This swelling is related to oxygen release during heating, combined with the formation of a liquid phase above 1200 °C. Furthermore, an increase in total strain with Sr content is observed. This is caused by the chemical expansion, while there is no significant change in thermal expansion with increasing Sr content.The compositions x = 0.4 and x = 0.6 showed tolerable expansion coefficients as well as adequate sintering behaviour and were therefore selected for the fabrication of thin supported membranes. These supported membranes with a thickness of 30 μm were manufactured by sequential tape casting and characterised regarding microstructure and oxygen flux.