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Rare-earth titanate oxides are believed to be prospective functional materials for photocatalytic and photoluminescent applications because of their excellent optical properties and thermal stability of their physical properties. However, the relationships between optical properties and photoelectron trapping mechanisms are unclear. Herein, the structure, electronic, and optical properties of pyrochlore-structure Re2Ti2O7 (Re = Sm and Eu) were investigated using the first-principles approach with the Hubbard parameter U (GGA + U). The calculated bandgap is 2.5 eV for Sm2Ti2O7 and 2.4 eV for Eu2Ti2O7, which is in good agreement with the experimental observation. The results indicate that the strongly localized f states at the top of valence band are charge-trapping sites for photoexcitation of Re2Ti2O7, where electrons can absorb photon energy and transfer from the valence band to the conduction band, resulting in the photocatalytic and/or fluorescent effects in the visible and early UV regions. The important optical parameters, dielectric function ε (ω) , refractive index n (ω) , extinction coefficient k (ω) , reflectivity R (ω) , absorption coefficient I (ω) , optical conductivity σ (ω) , and electron energy-loss L (ω) were studied in detail, indicating that these optical parameters of Sm2Ti2O7 and Eu2Ti2O7 are insensitive to the ultra-violet (UV) radiation, but both Sm2Ti2O7 and Eu2Ti2O7 exhibit excellent optical properties in the visible and early UV regions. This work provides a clear understanding on the photoelectron trapping mechanism of pyrochlore-structure Re2Ti2O7, which will help to improve the photocatalytic and photoluminescent performance of Re2Ti2O7 and broaden their applications. [ABSTRACT FROM AUTHOR]

Adding excessive metal oxide doping to a powder batch is a known way to compensate for the loss of volatile cation species during high temperature sintering. An important case in the piezoelectric ceramics is the bismuth oxide in the lead-free ferroelectric ceramic bismuth sodium titanate (BNT). Building from the earlier knowledge about excessive bismuth oxide's influences on the properties of BNT, we further note that varying the sintering temperature can both control the distribution of excessive Bi3+ and impact the relaxor/normal ferroelectric behaviors and corresponding phase transition. In addition to the nature of polarization, the sintering temperature also significantly manipulates the electrical conductivity. A hypothetical mechanism for the resistive grain boundary is proposed, based on inferences from electrical—microstructure—processing relations in 85% Bi0.5Na0.5TiO3-15% BaTiO3 with batched Bi2O3 excess and acceptor Mg2+ in a co-doped strategy. [ABSTRACT FROM AUTHOR]

Whispering gallery mode resonators (WGMRs) have garnered significant interest due to their potential applications in the fields of electro-optic modulation and microwave to optical photon conversion. In this study, we have leveraged an electro-optic crystal, lead indium niobate-lead magnesium niobate-lead titanate (PIN-PMN-PT), to fabricate a high-quality WGMR. Our investigation revealed that the crystal composition used in this work is 0.24PIN-0.45PMN-0.31PT, and each element of the whole sample is homogeneously distributed. The dielectric properties of the sample revealed the necessity of limiting the temperature and external electric field frequency to below 100 °C and 106 Hz, respectively. The obtained optical quality factor value (Q value) of the resonator is ∼0.7 × 105. Impressively, our resonator could be conveniently tuned by exploiting the enormous inverse piezoelectric effect d31 of the crystal, thereby alleviating the need for precise fabrication. Furthermore, a theoretical analysis of our resonator revealed that a calculated resonance wavelength shift is within a broad range of 2.16 nm. Intriguingly, if the surface roughness of the resonator is reduced tenfold, we can increase the calculated Q value dependent on surface scattering by 104. Our finding showcases the tremendous potential of the PIN-PMN-PT crystal-based WGMR as versatile building blocks for a variety of applications in the burgeoning field of photonic technology. [ABSTRACT FROM AUTHOR]

Rare-earth titanate pyrochlores have attracted significant attention for their unique magnetic frustration; however, research on the origin of low-temperature dielectric dispersion and the relationship between dielectric properties and structure lags far behind. Here, by systematically investigating the dielectric properties of representative rare-earth titanates R2Ti2O7 (R = La, Nd, Sm, Er, Yb, and Lu), we demonstrate that R2Ti2O7 with a cubic pyrochlore structure exhibits low-temperature dielectric dispersion behavior, while the other compounds with a monoclinic perovskite-like layered structure possess no dispersion behavior but excellent temperature-stable dielectric property. The dielectric dispersion in cubic pyrochlores arises from the structural distortion. Furthermore, the existence of structural distortion is affirmed by the anomalous phonon softening of A1g Raman mode around the dielectric dispersion temperature, and the origin of the structural distortion is attributed to anharmonic phonon–phonon interactions induced by intrinsic vacant oxygen at Wyckoff 8a sites. In addition, with increasing ionic radius from R = Lu to Sm, the increased lattice parameter leads to varied bond length and bond angle of Ti-O(1)-Ti, which strengthens the local lattice distortion of TiO(1)6 octahedra and thus enhances diffusion degree of dielectric dispersion. On the other hand, the absence of intrinsic vacant oxygen site hardly gives rise to the local structural distortion and thus no dielectric dispersion in monoclinic R2Ti2O7. Our work not only clarifies the mechanism of dielectric dispersion but also gives a comprehensive perspective on the structure–property relationship of rare-earth titanates R2Ti2O7, and thus lays a solid foundation for further work on related materials. [ABSTRACT FROM AUTHOR]

Sub-micrometer-sized (0.33 μm) polycrystalline powders of calcium copper titanate (CCTO) were synthesized via the solgel method. Compacted calcined powders were sintered at 900 °C/2h to obtain porous (<80% density) pellets. Subsequently, ZnO or SnO2 pastes (∼10 μm grain size) were smeared on either side of the pellets and sintered at 1100 °C/15 h, which yielded dense (>95% density) ceramics. X-ray structural investigations revealed the presence of ZnO or SnO2 traces in the bulk of the CCTO ceramics. Scanning electron microscopy and energy dispersive spectroscopic studies confirmed the diffusion and the segregation of these oxides at the grain boundaries. The dielectric and varistor properties of the ZnO or SnO2 diffused samples were found to be superior to that of pristine CCTO ceramics. For instance, the dielectric constant (ɛ′) of ZnO diffused ceramics exhibited a value as high as 2.4 × 104 (1 kHz, at room temperature) and a dielectric loss (D) of 0.059. Similarly, SnO2 diffused ceramics exhibited a dielectric constant of 2.7 × 104 (1 kHz, at room temperature) associated with a dielectric loss of 0.047. The figure of merit of varistor performance, i.e., nonlinear coefficient (α = 10.6), of the SnO2 diffused sample is significantly higher than that of ZnO diffused (α = 7.4) and pristine CCTO (α = 4.5) ceramics. The dielectric data obtained for both the pristine and ZnO or SnO2 diffused ceramics were rationalized by invoking Cole–Cole analysis. The thermal activation energy was estimated from the temperature-dependent dielectric data besides current (I)–voltage (V) characteristics. Equivalent circuit modeling of the Nyquist plots demonstrated that the inclusion of ZnO and SnO2 layers in CCTO ceramics remarkably improved the grain boundary resistance (Rgb) by 5-fold and 20-fold, respectively, which resulted in making CCTO a better dielectric. This methodology of fabricating ceramics via interfacial engineering could pave the way for obtaining superior CCTO ceramics associated with exotic functional properties. [ABSTRACT FROM AUTHOR]

Structurally correlated ferroelectric phase transitions induced by temperature are reported for the solid solution Pb0.6Ca0.4TiO3 compound. Such phase transitions were analyzed by considering different parameters, such as lattice parameters, microstrain, dielectric properties, and thermal analysis. Synchrotron x-ray diffraction and Rietveld refinement studies revealed a tetragonal symmetry from room temperature up to ∼550 K and uniaxial microstrain from room temperature to ∼400 K. The first thermally driven phase transition observed was from displacive ferroelectric tetragonal symmetry to another non-displacive tetragonal symmetry. The next phase transition was from the tetragonal to cubic. The electric permittivity as a function of temperature for frequency from 1 kHz to 1 MHz and the differential scanning calorimetry report features typical of ferroelectric–paraelectric phase transition only around 400 K, and no other abrupt change in properties is observed at 550 K, indicating the sequence of first- and then second-order phase transition. [ABSTRACT FROM AUTHOR]

Single crystals of undoped and Nb doped sodium and potassium-bismuth titanate at the morphotropic phase boundary (MPB) composition [(Na0.41K0.09Bi0.50)TiO3: NKBT] were grown from high temperature solutions. The effect of Nb doping on the electronic property of NKBT was investigated by optical transmission and photoelectron spectroscopy (PES). The optical absorption shows that the bandgap having the lowest energy is indirect in nature and increases with the increase in the Nb concentration in the lattice. The estimated Urbach energy increases with the increase of Nb concentration signifying an increase in the disorder in the lattice on Nb doping. The PES revealed that the valence band maxima (VBM) exhibit red shift on Nb doping. It also revealed the presence of in-gap states probably due to Ti3+ defect and oxygen vacancy. Moreover, inline with the optical measurement, the PES showed that there is a decrease in the energy gap between the VBM and defect state with the Nb doping. Furthermore, the angle resolved PES measurement confirmed the presence of both the direct and indirect bandgaps in the crystal. [ABSTRACT FROM AUTHOR]

Uniformly acceptor doped Pb(Zr0.48Ti0.52)O3 (PZT) films with 2 mol. % Mg or Fe prepared by chemical solution deposition exhibited decreased dielectric constants and remanent polarizations relative to undoped PZT. For highly accelerated lifetime testing (HALT) at 200 °C and an electric field of 300 kV/cm in the field up direction, the HALT lifetimes (t50) for undoped, Mg-doped, and Fe-doped PZT films were shortened from 2.81 ± 0.1 to 0.21 ± 0.1 and 0.54 ± 0.04 h, respectively. Through thermally stimulated depolarization current measurement, significant V O ∙ ∙ electromigration was found in homogeneously Mg-doped PZT thin films, a major factor in their short HALT lifetime. Because the concentration of oxygen vacancies increases with uniform acceptor doping, the lifetime decreases. In contrast, when a thin layer of Mg-doped or Fe-doped PZT was deposited on undoped PZT or Nb-doped PZT (PNZT), the HALT lifetimes were longer than those of pure PZT or PNZT films. This confirms prior work on PNZT films with a Mn-doped top layer, demonstrating that the HALT lifetime increases for composite films when a layer with multivalent acceptors is present near the negative electrode during HALT. In that case, the compensating electrons are trapped, presumably on the multivalent acceptors, thus increasing the lifetime. [ABSTRACT FROM AUTHOR]

Although a large electric-induced strain has been obtained in sodium bismuth titanate (Bi0.5Na0.5TiO3, BNT)-based ceramics using chemical modifications, the effect of initial BNT-based ceramic's polarity on modulating strain properties was rarely reported. Herein, we comparatively studied the effect of tantalum (Ta) doping on two BNT-based ceramics with different ferroelectric polarities, namely, (Bi0.5Na0.5)0.935Ba0.065TiO3–0.7%Bi2FeCrO6 and (Bi0.98Gd0.02)0.5Na0.5TiO3. The former locates at the morphotropic phase boundary (MPB), whereas the latter is close to pristine BNT ceramics. An effective critical point, located at the crossover between ferroelectric and relaxor, is constructed in the former ceramic and significantly enhances strain properties, whereas a useless one is found in the latter ceramic due to the retention of a non-ergodic relaxor and has merely limited ability to promote strain properties. Our results demonstrate that the ferroelectric polarity of the initial BNT-based ceramic matrix also plays an important role in pursuing high strain properties. [ABSTRACT FROM AUTHOR]

The micrometer-sized nickelate–titanate heterojunctions with LaNiO3 (LNO) electrode have been fabricated to investigate the dominant current transport mechanisms under positive and negative bias. The LNO/SmNiO3 (SNO)/Nb:SrTiO3 (NSTO) heterojunction exhibits a highly rectifying feature with a very low leakage in a broad temperature region (from 200 to 425 K), which is attributed to the formation of a Schottky-like barrier at the SNO/NSTO interface. In addition, it is found that the trap defects (i.e., oxygen vacancies) play an essential role in determining the current density (J)–voltage (V) characteristics irrespective of the voltage polarity. The leakage current at low electric fields (<0.25 MV/cm) is dominated by temperature-enhanced trap assisted tunneling process, which is caused by the interface oxygen vacancy induced states. Further analysis suggests that, at high fields (>1.2 MV/cm), the leakage is ascribed to the bulk-limited field enhanced thermal ionization of trapped carriers in the SNO film (i.e., Poole–Frenkel emission). Specially, the oxygen vacancy redistribution near the SNO/NSTO heterointerface driven by a high temperature (425 K) or high electrical field (>3.8 MV/cm) stress is emphasized to account for the transition from the Schottky contact limited to bulk-limited conduction mechanism (i.e., space charge limited conduction). This work will benefit the further analysis of the resistive switching phenomena in nickelate-based devices, showing a potential for nonvolatile memory applications. [ABSTRACT FROM AUTHOR]

Rare earth and barium titanates are useful as ferroelectric, dielectric, and optical materials. Measurements of their thermophysical properties in the liquid state can help guide melt processing technologies for their manufacture and advance understanding of fragile liquids' behavior and glass formation. Here, we report the density, thermal expansion, viscosity, and surface tension of molten BaTi2O5, BaTi4O9, and 83TiO2-17RE2O3 (RE = La or Nd). Measurements were made using electrostatic levitation and droplet oscillation techniques in microgravity, which provide access to quiescent liquid droplets and deep supercooling of 510–815 K below the equilibrium melting points. Densities were measured over 900–2400 K. Viscosities were similar for all four compositions, increasing from ∼10 mPa s near 2100 K to ∼30 mPa s near 1750 K. Surface tensions were 450–490 dyn cm−1 for the rare earth titanates and 383–395 dyn cm−1 for the barium titanates; surface tensions of all compositions had small or negligible temperature dependence over 1700–2200 K. For solids recovered after melt quenching, x-ray microtomography revealed the fracture mechanics in crystalline products and minimal internal porosity in glass products, likely arising from entrapped gas bubbles. Internal microstructures were generally similar for products processed either in microgravity or in a terrestrial aerodynamic levitator. [ABSTRACT FROM AUTHOR]

This contribution provides a thorough examination of the structural characteristics of pyrochlore-type lanthanide titanates and zirconates Ln2Ti2O7 and Ln2Zr2O7, across various length scales. This paper also examines their processing, interesting physical properties (electrical, magnetic, and thermal characteristics), and responses to high pressure and ion irradiation. Brief sections on the elemental oxides' crystal chemistry, pertinent phase diagrams, and energetics of defect formation are also provided. Pyrochlore-type Ln2Ti2O7 and Ln2Zr2O7 stand out as truly multifunctional materials. Moreover, they have emerged as fascinating materials due to magnetic geometrical frustration, arising from the ordering of magnetic Ln3+ and non-magnetic Ti4+ (or Zr4+) cations into separate, interpenetrating lattices of corner-sharing tetrahedra. This results in a diverse array of exotic magnetic ground states, such as spin-ice (e.g., Dy2Ti2O7 or Ho2Ti2O7) or quantum spin ice (e.g., Tb2Ti2O7), observed at both low and room temperatures. They also exhibit varied electrical and electrochemical characteristics. Some members such as Gd2Zr2O7, function as fast ion conductors with a conductivity (σ) of ≈10−2 S·cm−1 at 800 °C and activation energy (Ea) ranging from 0.85 to 1.52 eV, depending on the degree of structural disorder. Others, such as Gd2TiMoO7, are mixed ionic-electronic conductors with σ ≈ 25 S·cm−1 at 1000 °C, making them promising candidate materials for applications in energy conversion and storage devices and oxygen separation membranes. Their exceptionally low thermal conductivity (e.g., κ ∼ 1.1–1.7 W·m−1·K−1 between 700 and 1200 °C for Ln2Zr2O7), close to the glass-like lower limit of highly disordered solids, positions them as valuable materials for thermal barrier coatings. They can also effectively accommodate actinides (e.g., Pu, Np, Cm, Am) in solid solutions and sustain prolonged exposure to radiation due to alpha-decay events, while preserving the integrity of the periodic atomic structure. Proposed as major components in actinide-bearing ceramics, they contribute to the long-term immobilization and disposal of long-lived waste radionuclides from nuclear programs. Some of these properties are displayed simultaneously, opening avenues for new applications. Despite the wealth of data available in the literature, this review highlights the need for a better understanding of order/disorder processes in pyrochlore-type materials and the influence of the structural length scale on their physical and chemical properties. Recent experimental evidence has revealed that pyrochlore short-range structure is far more complex than originally thought. Moreover, pyrochlore local structure is now believed to include short-range, lower symmetry, ordered domains, such as the orthorhombic weberite-type of structure. Notably, short- and long-range structures appear decoupled across different length scales and temperature regimes, and these differences persist even in well-ordered samples. We believe that the pyrochlore structure offers a unique opportunity for examining the interplay between chemical composition, defect chemistry, and properties. [ABSTRACT FROM AUTHOR]

The bulk photovoltaic effect observed in ferroelectric materials can enable photovoltaic performance beyond the Shockley–Queisser limit of efficiency. This requires the use of ferroelectrics with strong polarization and low bandgap (Eg) that are typically contradictory in the common perovskite oxides ferroelectrics. Here, we use first-principles calculations to study the KNbO3–K(Ti0.5Mo0.5)O3 (KNTM) solid solutions as possible narrow-gap ferroelectric materials. KTM, the end-member of the recently discovered KNTM solid solution system, maintains a ferroelectric polarization similar to that of other K-based systems due to its d0 configuration at the B-site. The substitution of Nb in KTM reduces Eg from 2.9 of KTM to 1.83 eV for an unstrained system and 1.7 eV for a compressively strained system, while maintaining ferroelectricity. The combination of narrow Eg, strong ferroelectricity, low toxicity, and abundance of the constituent elements make Nb-substituted KTM a promising candidate material for photoferroelectric applications. [ABSTRACT FROM AUTHOR]

Lanthanum titanate glasses (17 La2O3-83 TiO2) are fabricated via aerodynamic levitation melting. Nonlinear refraction and absorption were measured with the Z scan technique using ∼ 550 ps optical pulses at 532 nm wavelength with peak intensities in the range of 0.25–2.5 GW/cm2. The two-photon absorption coefficient (β) and the effective nonlinear refraction coefficient ( n 2 eff ) are found to be, respectively, 2.19 cm/GW and 152 × 10−16 cm2/W (85 × 10−13 esu). The Raman gain is measured to be 106 × 10−11 cm/W. The nonlinearity strength is found to be nearly 60 times larger in lanthanum titanate glasses relative to silica. [ABSTRACT FROM AUTHOR]

Lithium lanthanum titanate (Li3xLa2/3−xTiO3, abbreviated as LLTO, where x = 0.08, 0.1, 0.12, 0.14, 0.16, and 0.167) is prepared using a conventional solid-phase method, and its crystal structure, phase composition, microstructure, and electrical properties are investigated. Experimental results indicate that when the Li content is low (x = 0.8), there exist tetragonal, cubic, and orthogonal phases in LLTO. As the Li content increases (x ≥ 0.1), the orthogonal phase disappears, and there are changes in the phase composition of tetragonal and cubic phases. When the occupancy rates of Li and La are low, the number of A-site vacancies increases, as does the electrical conductivity of LLTO. At room temperature, the ionic conductivity of LLTO increases and then decreases. The Li0.30La0.56TiO3 ceramic electrolyte exhibits the highest total ionic conductivity of 7.22 × 10−5 S/cm, a minimum activation energy of 0.31 eV, and an electrical conductivity of 6.26 × 10−11 S/cm. This paper provides a theoretical basis for subsequent research on solid Li3xLa2/3−xTiO3 electrolytes. [ABSTRACT FROM AUTHOR]

Lithium lanthanum titanate (Li3xLa2/3−xTiO3, abbreviated as LLTO, where x = 0.08, 0.1, 0.12, 0.14, 0.16, and 0.167) is prepared using a conventional solid-phase method, and its crystal structure, phase composition, microstructure, and electrical properties are investigated. Experimental results indicate that when the Li content is low (x = 0.8), there exist tetragonal, cubic, and orthogonal phases in LLTO. As the Li content increases (x ≥ 0.1), the orthogonal phase disappears, and there are changes in the phase composition of tetragonal and cubic phases. When the occupancy rates of Li and La are low, the number of A-site vacancies increases, as does the electrical conductivity of LLTO. At room temperature, the ionic conductivity of LLTO increases and then decreases. The Li0.30La0.56TiO3 ceramic electrolyte exhibits the highest total ionic conductivity of 7.22 × 10−5 S/cm, a minimum activation energy of 0.31 eV, and an electrical conductivity of 6.26 × 10−11 S/cm. This paper provides a theoretical basis for subsequent research on solid Li3xLa2/3−xTiO3 electrolytes. [ABSTRACT FROM AUTHOR]

Frustrated rare-earth pyrochlore titanates, Yb 2 Ti 2 O 7 and Tb 2 Ti 2 O 7 , have been proposed as promising candidates to realize quantum spin ice (QSI). Multiple exotic quantum phases, including Coulombic ferromagnet, quantum valence bond solid, and quadrupolar ordering, have been predicted to emerge in the QSI state upon the application of a (111)-oriented external magnetic field. Here, we report on the successful layer-by-layer growth of thin films of the frustrated quantum pyrochlores, R 2 Ti 2 O 7 (R = Er , Yb, and Tb), along the (111) direction. We confirm their high crystallinity and proper chemical composition by a combination of methods, including in situ RHEED, x-ray diffraction, reciprocal space mapping, and x-ray photoelectron spectroscopy. The availability of large area (111)-oriented QSI structures with planar geometry offers a new complementary to the bulk platform to explore the strain and the magnetic field-dependent properties in the quasi-2D limit. [ABSTRACT FROM AUTHOR]

We report a systematic investigation of individual and multisite Hubbard-U corrections for the electronic, structural, and optical properties of the metal titanate oxide d0 photocatalysts SrTiO3 and rutile/anatase TiO2. Accurate bandgaps for these materials can be reproduced with local density approximation and generalized gradient approximation exchange-correlation density functionals via a continuous series of empirically derived Ud and Up combinations, which are relatively insensitive to the choice of functional. On the other hand, lattice parameters are much more sensitive to the choice of Ud and Up, but in a systematic way that enables the Ud and Up corrections to be used to qualitatively gauge the extent of self-interaction error in the electron density. Modest Ud corrections (e.g., 4 eV–5 eV) yield the most reliable dielectric response functions for SrTiO3 and are comparable to the range of Ud values derived via linear response approaches. For r-TiO2 and a-TiO2, however, the Ud,p corrections that yield accurate bandgaps fail to accurately describe both the parallel and perpendicular components of the dielectric response function. Analysis of individual Ud and Up corrections on the optical properties of SrTiO3 suggests that the most consequential of the two individual corrections is Ud, as it predominately determines the accuracy of the dominant excitation from O-2p to the Ti-3d t2g/eg orbitals. Up, on the other hand, can be used to shift the entire optical response uniformly to higher frequencies. These results will assist high-throughput and machine learning approaches to screening photoactive materials based on d0 photocatalysts. [ABSTRACT FROM AUTHOR]

In this paper, domain switching induced by applied stress and thermal treatment was compared in (Na0.5Bi0.5)TiO3−xBaTiO3 (NBT-BT) solid solutions and the monolithic components by Raman spectroscopy. Despite possessing a Ti-O6 structure, the titanate materials exhibit quite different patterns of switching upon indentation generation, which might be associated with the presence of distinct stable polarizations. Significant stress induced a→c domain switching occurs around the indentation print and along the cracks for stress relaxation during crack propagation in the case of BT, while for NBT and related solution, remnant domains exist and a switching of the domains to other polarization, e.g., <110> may occur, showing a dependence on the BT addition content. Thermal treatments at temperatures above the Curie point were found to show different influences on domain patterns due to distinct changes in the microstructure in the presence of residual stress fields, suggesting the possibility of a combinatory effect of thermal treatment and residual stress for domain controls. [ABSTRACT FROM AUTHOR]

The electrocaloric response of bulk monodomain BaZrxTi(1−x)O3 (BZT) under modest electrical fields at room temperature has been evaluated using a Landau theory thermodynamic model as a function of the zirconium content x. The computations show that increasing x changes the nature of the ferroelectric phase transitions of BZT. There are potentially three ferroelectric phases in BZT for zirconium contents 0 < x < 0.30. For 0 < x < 0.15, the cubic paraelectric phase transitions successively into the tetragonal, orthorhombic, and rhombohedral phases with decreasing temperature. For x > 0.15, the rhombohedral phase becomes the sole ferroelectric phase upon cooling from the cubic paraelectric state. The magnitude of the polarization discontinuity at the phase transition decreases with increasing x as it approaches a continuous, second order transition. We show here that these phase changes have a significant effect on electrocaloric and pyroelectric properties of BZT. The room temperature adiabatic temperature change was calculated for compositions of BZT with 0 < x < 0.30, revealing a maximum temperature change of ΔTad = 1.25 °C for an electric field difference of 100 kV/cm for x = 0.20 near room temperature. [ABSTRACT FROM AUTHOR]

A series of Au@Void@TiO2 yolk-shell structures were synthesized and characterized, and their catalytic activity was tested for the oxidation of carbon monoxide. The target of this work was to evaluate the effects of (1) the crystallinity of the TiO2 shell and (2) the presence of titanate phases. Transmission electron microscopy and X-ray diffraction data show that increasing calcination temperatures, from 850 to 1250 K, leads to the formation of larger titania crystallites. These crystallites are typically in the form of anatase, but some rutile is also made at high temperatures. The general yolk-shell nanostructures retain their basic characteristics upon calcination and upon treatment with HCl (used to remove the titanate phases), but a few structural and chemical changes do take place: (1) the void-space diameter is reduced by approximately 10% when going from TCalc = 850 K to TCalc = 1250 K, a change that is accompanied by a decrease in the surface area (estimated from N2 adsorption-desorption isotherms); (2) the shell thickness remains unaffected by either calcination or HCl treatment; (3) the pore volume also remains approximately constant with increasing calcination temperature in the catalysts free of titanates but diminishes significantly in the samples with titanate phases; (4) the mesoporosity is minimal in all yolk-shell nanostructures but more noticeable with the pure TiO2 shells; (5) the titanates have high Na content (measured by X-ray photoelectron spectroscopy), but that Na is fully removed upon treatment with HCl; (6) no Ti3+ was detectable in any of the samples, but silica, together with C and (minor amounts of) N, was present in all; (7) all Au is in metallic form; (8) two temperature regimes were observed for the catalytic oxidation of CO, as reported for other similar samples in the past, an Arrhenius regime around or above room temperature, and a cryogenic range going to temperatures as low as 120 K; (9) the latter regime is only seen with the samples containing titanate phases; (10) the titanates seem to also aid in the oxidation at higher temperatures; and (11) in general, increasing titania crystallinity leads to a decrease the catalytic activity. [ABSTRACT FROM AUTHOR]

We present here a comprehensive analysis of the effect of thermal stresses on the functional properties of ferroelectric oxides on metal substrates. We use a Landau-Devonshire formalism to quantitatively assess the role of in-plane thermal strains that arise from the coefficient of thermal expansion (CTE) mismatch between lead zirconate titanate [PbZrxTi1–xO3, PZT x/(1 – x)] films and Al, Cu, Fe, Ni, and Ti-based substrates. Specifically, we compute Curie transition temperatures, spontaneous polarizations, dielectric permittivities, piezoelectric coefficients, and pyroelectric responses of tetragonal PZT compositions as a function of the growth/processing temperature. To provide a rapid evaluation, we also develop Ashby diagrams of property coefficients as a function of PZT composition, processing temperature, and CTE of the substrate. Our results show that thermal strains in PZT may significantly alter the ferroelectric transition temperature, dielectric, piezoelectric, and pyroelectric properties. For example, for PZT 50/50 films on Ni-based superalloys processed/annealed at 700 °C, we predict monodomain intrinsic dielectric, piezoelectric, and pyroelectric responses to be 234, 152 pC/N, and 0.021 μC cm−2 °C−1, respectively, compared to bulk PZT 50/50 values of 381, 326 pC/N, and 0.045 μC cm−2 °C−1. These are substantial variations which show that thermal strains must be considered in the design and development of built-in functionality obtained through ferroelectric films in structural, aerospace components. [ABSTRACT FROM AUTHOR]

The influence of donor (L a 3 +) and acceptor (S c 3 +) dopant on structural and electrical properties of lead-free B i 0.5 N a 0.5 Ti O 3 (BNT) ceramics system was investigated. Both donor and acceptor substitutions induced a structural transformation of pure BNT ceramics from a rhombohedral to a pseudocubic structure. Splitting of the (111) p c peak in pure BNT was considered symmetry identification for a rhombohedral structure. A micrometer level grain size (1.70 μm–2.81 μm), dense microstructure with good ferroelectric and piezoelectric performance (d 33 = 56 − 45 pC / N) was obtained. The 3% La content BNT ceramic shows an improved dielectric property. The Curie temperature increases from 355 °C for pure BNT to 365 °C for donor-doped and 370 °C for acceptor-doped BNT. The donor doping created cationic vacancies; acceptor doping induces oxygen vacancies that stabilized the polarization level. Maximum remnant polarization (P r) value has been obtained for 3% La-doped (P r = 27 μ C / c m 2) and 5% Sc-doped (P r = 20 μ C / c m 2) BNT system. Bipolar strain increased with the increase in donor dopant concentration resulting in a large electrostrictive coefficient (Q11 ∼ 0.0122%–0.045%) has been obtained. Electric field-induced unipolar strain value was enhanced to its maximum value (Smax = 0.14%) for 3% La content with normalized strain d 33 ∗ = 209 pm / V and Smax = 0.13% for 5% Sc with normalized strain d 33 ∗ = 155 pm / V at an applied electric field of 70 kV/cm and 50 kV/cm, respectively. The enhanced strain was considered to be associated with low internal bias field and maximum polarization level. In terms of capacitive response, 5% Sc holds a maximum current (∼0.017 mA) during polarization switching. [ABSTRACT FROM AUTHOR]

The ability of Au/TiO2 catalysts to promote the oxidation of carbon monoxide at cryogenic temperatures was probed by using diffuse-reflectance infrared absorption spectroscopy (DRIFTS). The focus of this work was to identify correlations between the catalytic activity and both the nature of the titania support and the size of the Au nanoparticles (NPs). Two key intermediates were identified: an initial CO adsorbed on defect sites within the titania support with a 2175 cm−1 C–O stretching frequency signature, and a second species with a DRIFTS peak at 2163 cm−1 associated with the intermediate at Au–TiO2 interfacial sites that incorporates atomic oxygen to produce CO2. CO adsorption at the low temperatures associated with this process (120 K) appears to require defective sites, possibly titanate-type surface species: an amorphous (and NaOH-treated) support showed higher activity than crystalline titania. In addition, the catalytic activity peaks at an Au NP average size of about 3 nm, which, in turn, correlates with the population of the second CO intermediate mentioned above. The mechanism that explains this cryogenic oxidation reaction is different than that extensively reported for the room-temperature processes, but both appear to display similar dependence on Au NP diameter. [ABSTRACT FROM AUTHOR]

Artificial superlattice thin films of lead zirconate titanate (PZT) were epitaxially grown on silicon substrates, and the influence of superlattice strain on their piezoelectric properties was investigated. The c-axis oriented PZT superlattice thin film consists of two different PZT layers, Pb(Zr0.65Ti0.35)O3 (PZT-65) and Pb(ZrxTi1−x)O3 (PZT-X: x = X/100 = 0.3–0.9), with a 4 nm period. Satellite peaks were clearly observed in x-ray diffraction patterns, and cross-sectional composition measurements confirmed the superlattice structure with good interfaces, showing an alternate change in Zr and Ti compositions. Ferroelectric properties varied significantly depending on the PZT-X composition, and in particular, the PZT-65/PZT-30 superlattice thin film showed nearly the same ferroelectricity as the tetragonal phase under a large compressive strain of PZT-65 from the PZT-30 layer. For the PZT-65/PZT-X (X = 30–58) superlattice thin films, the PZT-65 layers received a compressive strain, and a relatively large piezoelectric coefficient, which did not depend on the PZT-X composition, was obtained. However, a decrease in piezoelectricity was observed in PZT-65/PZT-X (X = 70 and 90), where the PZT-65 layers experienced tensile strain. This result indicates that the piezoelectric properties of PZT superlattice thin films can be controlled by the interlayer strain. [ABSTRACT FROM AUTHOR]

The main method to expand the operating bandwidth of the transducer is by exciting multi-order vibration modes, which develop from the earliest excitation of odd-order modes to the excitation of multi-order continuous modes. However, no detailed theoretical characterization of the excitation mechanism and electroacoustic properties of continuous-order modes has been given. In this paper, the excitation mechanism of continuous-order modes for one-dimensional thickness vibration is studied in detail. From the perspective of analytical characterization, the mathematical and physical conditions of mode excitation are analyzed and extended to continuous-order modes. Partial 1–3 piezocomposite consists of two parts; one part is complete lead zirconate-titanate and the other part is 1–3 composite, which is helpful for exciting continuous-order modes. Based on the excitation mechanism of continuous-order modes, a design method of broadband transducer used of partial 1–3 piezocomposite is proposed, and large bandwidth and good pulse response are obtained. The excitation mechanism of continuous-order modes proposed in this paper provides an idea for the theoretical analysis and design of multi-resonant broadband transducers. [ABSTRACT FROM AUTHOR]

We experimentally investigated the photo-induced direct current (DC) drift of a lead lanthanum zirconate titanate (PLZT) Mach-Zehnder modulator with large optical input power. We clarify the mechanism by which short-term and long-term DC drifts arise and discuss each case of DC drift. We reveal that short-term DC drift can be reduced by adjusting the buffer-layer resistivity of the PLZT modulator. We also found that the impurity level of the buffer layer affects long-term DC drift. [ABSTRACT FROM AUTHOR]

Integration of high-performance lead zirconate titanate (PZT) piezoelectric films onto (111) Si substrates is beneficial for the development of piezoelectric micro-electro-mechanical systems (Piezo-MEMS) because of (111) Si's isotropic mechanical properties and desirable etching characteristics. These features will greatly reduce complications in micro-device fabrication and patterning of PZT/Si heterostructures. However, piezoelectric performance of a PZT film is usually dominated by its preferred crystalline orientation, with (001) being superior than (110) and (111). Such a vectorial dependence seriously restricts applications of PZT films grown on (111) Si, which are usually not (001)-textured. In this work, highly (001)-oriented PZT thick films (∼1.5 μm) with a 53/47 Zr/Ti ratio were prepared on (111) Si substrates via a multi-layer buffering technique, i.e., through the use of a (111)Pt/Ti bi-layer and a LaNiO3 buffer layer. The PZT films were sputter-deposited at a low temperature (350 °C) and then crystallized in a (001) texture via a rapid thermal annealing (RTA). The e31,f transverse piezoelectric coefficient was up to ∼11.6 C/m2 for PZT films with a RTA time of 2 minutes. Such an e31,f value is comparable to that of PZT films grown on (100) Si. This work opens up many possibilities for Piezo-MEMS by demonstrating the desirable combination of a large piezoelectricity in (001) PZT with a good patternability of (111) Si. [ABSTRACT FROM AUTHOR]

Crack initiation stresses for different lead zirconate titanate (PZT) film compositions were investigated. PZT/Pt/TiO2/SiO2/Si stacks with 2.0 μm thick {100} oriented PZT films at the morphotropic phase boundary (MPB) showed a characteristic strength of 1137 MPa, and the film thickness served as the limiting flaw size for failure of the film/substrate stack. In contrast, for Zr/Ti ratios of 40/60 and 30/70, the characteristic stack strength increased while the Weibull modulus decreased to values typical for that of Si. This difference is believed to be due to toughening from ferroelasticity or phase switching. X-ray diffraction showed that the volume fraction of c-domains increased in Ti-rich compositions. This would allow for more switching from c to a-domains under biaxial tensile stress. Zr/Ti concentration gradients were present for all compositions, which contributed to the observation of a rhombohedral phase off the MPB. Due to the reduced tendency toward cracking, off-MPB compositions are potentially of interest in actuators, albeit with the trade-off of needing a high actuation voltage. [ABSTRACT FROM AUTHOR]

Phase pure PbZr0.52Ti0.48O3 (PZT) films with up to 13 mol. % Nb were prepared on Pt-coated Si substrates using chemical solution deposition; charge compensation for Nb was accomplished by reducing the concentration of lead in the film. For high Nb doping levels, (1) superoxidation of the PZT film surface makes the PZT/Pt interface more p-type and, hence reduces electron injection over the Schottky barrier, (2) the bulk charge transport mechanism changes from electron trapping by Ti4+ to hole migration between lead vacancies, and (3) the ionic conductivity due to migration of oxygen vacancies decreases. For ≤ 6 mol. % Nb, electrical degradation was controlled via field-induced accumulation of oxygen vacancies near the cathode, which, in turn, leads to Schottky barrier lowering and electron trapping by Ti4+. In phase pure 13 mol. % Nb doped PZT films, on the other hand, the increase in the leakage current during electrical degradation was dominated by hole migration between lead vacancies ( 2 [ V P b ″ ] ∼ [ h • ]). A much lower lifetime and drastic increase in the leakage current upon electrical degradation was observed in mixed phase PNZT films, which was attributed to (1) a more electrically conductive pyrochlore phase and (2) a high concentration of lead vacancies. [ABSTRACT FROM AUTHOR]

Calcium Copper Titanate ceramics (CaCu3Ti4O12) doped with Yb were prepared by the traditional solid–state reaction method. It is found by x-ray diffraction, scanning electron microscopy, energy dispersive spectrometry, and X-ray photoelectron spectroscopy that Yb prefers to locate at the A site as a donor, which gives rise to the inhibition of oxygen vacancies in the grains and the segregation of Cu to the grain boundaries. Dielectric properties of the samples and electronic structure at grain boundary were investigated further by dielectric spectroscopy and specific impedance spectroscopy, respectively. It is revealed that medium frequency dielectric relaxation is restrained obviously for the decrease of oxygen vacancy, while giant dielectric permittivity (higher than 104) is maintained for the decrease of depleted layer thickness after donor doping. Therefore, the research of this paper offers an effective way to improve the dielectric properties of CaCu3Ti4O12 based on the modulation of intrinsic point defects. [ABSTRACT FROM AUTHOR]

We outline a method to synthesize (ATiO3)nAO Ruddlesden–Popper phases with high-n, where the A-site is a mixture of barium and strontium, by molecular-beam epitaxy. The precision and consistency of the method described is demonstrated by the growth of an unprecedented (SrTiO3)50SrO epitaxial film. We proceed to investigate barium incorporation into the Ruddlesden–Popper structure, which is limited to a few percent in bulk, and we find that the amount of barium that can be incorporated depends on both the substrate temperature and the strain state of the film. At the optimal growth temperature, we demonstrate that as much as 33% barium can homogeneously populate the A-site when films are grown on SrTiO3 (001) substrates, whereas up to 60% barium can be accommodated in films grown on TbScO3 (110) substrates, which we attribute to the difference in strain. This detailed synthetic study of high n, metastable Ruddlesden–Popper phases is pertinent to a variety of fields from quantum materials to tunable dielectrics. [ABSTRACT FROM AUTHOR]

Practical pyroelectric materials require excellent pyroelectric performance, high depolarization temperature, and good temperature stability. In this work, the microstructure, ferroelectric, dielectric, and pyroelectric properties were studied systematically in (Bi0.5Na0.5)TiO3–0.1%MnCO3 (BNT–Mn) lead-free ceramics. It is observed that the pyroelectric coefficient p reaches 2.90 × 10−4 C m−2 K−1 at room temperature in the samples. Due to the low dielectric constant (291) and dielectric loss (0.010), the figures of merit (FoMs) Fi, Fv, and FD are as high as 1.03 × 10−10 m/V, 4.05 × 10−2 m2/C, and 1.86 × 10−5 Pa−1/2, measured at 1 kHz. With the increase in temperature, the p and FoMs change slightly, showing good temperature stability. More importantly, a relatively high depolarization temperature of 205 °C is achieved, which should help deliver reliable operation in practice. In general, all performances reveal that BNT–Mn ceramics are expected to pave the way for uncooled infrared detector applications. [ABSTRACT FROM AUTHOR]

We report on the structural, magnetic, optical, and electrical properties of iron titanate thin films prepared using a spin-coating technique having nominal compositions of FeTiO3 and Fe1.4Ti0.6O3. X-ray diffraction measurements show clear evidence for the presence of both ilmenite and pseudobrookite crystal structures, which is confirmed using Raman spectroscopy. X-ray photoemission spectroscopy studies indicate that Fe is present mainly in the 2+ valence state, with some Fe3+ present on the more heavily oxidized surface of the films. The as-prepared samples exhibit weak ferromagnetism at room temperature. While the valence state of Fe is not significantly affected by vacuum annealing, the saturation magnetization is increased dramatically, reaching nearly 220 emu mole−1 for the Fe-rich film. The optical band gap was found to be roughly 2.0 eV for all samples, with negligible changes on vacuum annealing. [ABSTRACT FROM AUTHOR]

Temperature dependent diffuse reflectance spectroscopy measurements were carried out on polycrystalline samples of BaTiO3 across the tetragonal to cubic structural phase transition temperature (TP). The values of various optical parameters such as band gap (Eg), Urbach energy (Eu), and Urbach focus (E0) were estimated in the temperature range of 300 K to 480 K. It was observed that with increasing temperature, Eg decreases and shows a sharp anomaly at TP. First principle studies were employed in order to understand the observed change in Eg due to the structural phase transition. Near TP, there exist two values of E0, suggesting the presence of electronic heterogeneity. Further, near TP, Eu shows metastability, i.e., the value of Eu at temperature T is not constant but is a function of time (t). Interestingly, it is observed that the ratio of Eu (t=0)/Eu (t = tm), almost remains constant at 300 K (pure tetragonal phase) and at 450 K (pure cubic phase), whereas this ratio decreases close to the transition temperature, which confirms the presence of electronic metastability in the pure BaTiO3. The time dependence of Eu, which also shows an influence of the observed metastability can be fitted with the stretched exponential function, suggesting the presence of a dynamic heterogeneous electronic disorder in the sample across TP. First principle studies suggest that the observed phase coexistence may be due to a very small difference between the total cohesive energy of the tetragonal and the cubic structure of BaTiO3. The present work implies that the optical studies may be a sensitive probe of disorder/heterogeneity in the sample. [ABSTRACT FROM AUTHOR]

The dynamic hysteresis and scaling behavior of unpoled 0.96(Bi0.5Na0.5)TiO3-0.04BiAlO3 lead-free relaxor ceramics were investigated through the evolution of the hysteresis loops at a wide frequency (f) and electric-field amplitude (Eo) range. The variation of the hysteresis area (A) and remanent polarization Pr clearly suggested three stages of polarization reversal with increasing external electric fields. It was found that the dynamic hysteresis area in the low-Eo and high-Eo regions followed the power law relationships: (A) α f –0:14Eo3:30 (Eo ≤ 5.0 kV/mm) and (A) α f 0:064Eo–0:6Eo1:65 (Eo ≥ 6.2 kV/mm), respectively. Those power-law functions did not fit in the second stage (5.0 kV/mm < Eo < 6.2 kV/mm), where different numbers of polar nanoregions or nanodomains can be activated and transformed into macrodomains. The polarization mechanisms of above mentioned three stages were ascribed to the domain wall motion, then the formation of microdomains within the disordered nanodomains or polar nanoregions, followed by the induced macrodomains aligning parallel to the applied electric field. [ABSTRACT FROM AUTHOR]

The accurate evaluation of ferroelectric thin films operated with interdigitated electrodes is quite a complex task. In this article, we show how to correct the electric field and the capacitance in order to obtain identical polarization and CV loops for all geometrical variants. The simplest model is compared with corrections derived from Schwartz-Christoffel transformations, and with finite element simulations. The correction procedure is experimentally verified, giving almost identical curves for a variety of gaps and electrode widths. It is shown that the measured polarization change corresponds to the average polarization change in the center plane between the electrode fingers, thus at the position where the electric field is most homogeneous with respect to the direction and size. The question of maximal achievable polarization in the various possible textures, and compositional types of polycrystalline lead zirconate titanate thin films is revisited. In the best case, a soft (110) textured thin film with the morphotropic phase boundary composition should yield a value of 0.95Ps, and in the worst case, a rhombohedral (100) textured thin film should deliver a polarization of 0.74Ps. [ABSTRACT FROM AUTHOR]

This manuscript examines the mechanism of strain-coupling in a multiferroic composite of mesoporous cobalt ferrite (CFO), conformally filled with lead zirconate titanate (PZT). We find that when the composites are electrically poled, remanent strain from the piezoelectric PZT layer can be transferred to the magnetostrictive CFO layer. X-ray diffraction shows that this strain transfer is greatest in the most porous samples, in agreement with magnetometry measurements, which show the greatest change in sample saturation magnetization in the most porous samples. Strain analysis shows that porosity both accommodates greater lattice strain and mitigates the effects of substrate clamping in thin film strain-coupled composites. [ABSTRACT FROM AUTHOR]

This manuscript examines the mechanism of strain-coupling in a multiferroic composite of mesoporous cobalt ferrite (CFO), conformally filled with lead zirconate titanate (PZT). We find that when the composites are electrically poled, remanent strain from the piezoelectric PZT layer can be transferred to the magnetostrictive CFO layer. X-ray diffraction shows that this strain transfer is greatest in the most porous samples, in agreement with magnetometry measurements, which show the greatest change in sample saturation magnetization in the most porous samples. Strain analysis shows that porosity both accommodates greater lattice strain and mitigates the effects of substrate clamping in thin film strain-coupled composites. [ABSTRACT FROM AUTHOR]

Publisher's Note: "Unveiling the strain and structural ferroelectric phase transition induced by temperature in lead titanate perovskite modified with 40% of calcium" [J. Appl. Phys. Equation (3) is correct as it appears below: HT ht (3) AIP Publishing apologizes for this error. This article was originally published online on 22 December 2022 with an error in Eq. (3). [Extracted from the article]

A direct quantification of a structural in-depth composition in the lead zirconate titanate Pb(Zr,Ti)O3 thin films of morphotropic composition has been conducted using the newly available X-ray nano-pencil beam (i.e., beam size of 100 nm ×1 μm) diffraction approach. We tested two samples with different Zr/Ti chemical gradients. Here, we demonstrate the presence of a significant microstructural gradient between the rhombohedral and tetragonal phases through PbZrxTi1-xO3 (PZT) films with a 100 nm in-depth resolution. The phase gradient extends over around 350 nm, and it is repeated through the PZT film three times, which corresponds to the number of thermal annealings. Moreover, this microstructural gradient is in agreement with the Zr/Ti chemical gradient observed by the secondary ion mass spectroscopy (SIMS). Indeed, the quantity of tetragonal phases rises in the Ti-rich zones as revealed by SIMS, and the quantity of rhombohedral phases rises in the Zr-rich zones. We also demonstrated a huge difference in the in-depth phase variation between the two tested samples. The gradient free sample still contains 4.7% of phase variation through the film and the amplified gradient contains 9.6% of phase variation through the film. Knowing that the gradient free sample shows better electric and piezoelectric coefficients, one can draw a correlation between the chemical composition, crystallographic homogeneity, and electromechanical properties of the film. The more close the film is to the morphotropic composition and the more it is crystallographically homogeneous, the higher the piezoelectric coefficients of the PZT are. Finally, the adequate knowledge of phase variation and its relation to the fabrication technique are crucial for the enhancement of the PZT electro-mechanical properties. Our methodology and findings open up new perspectives in establishing a relevant quantitative feedback to reach an ultimate electro-mechanical coupling in the sol-gel PZT thin films. [ABSTRACT FROM AUTHOR]