Evaluation of ferroelectricity in a distorted wurtzite-type structure of Sc-doped LiGaO2.

Since the discovery of ferroelectricity in a wurtzite-type structure, this structural type has gathered much attention as a next-generation ferroelectric material due to its high polarization value combined with its high breakdown strength. However, the main targets of wurtzite-type ferroelectrics have been limited thus far to simple nitride/oxide compounds. The investigation of new ferroelectric materials with wurtzite-type structures is important for understanding ferroelectricity in such structures. We therefore focus on ß-LiGaO2 in this study. Although AlN and ZnO possess well-known wurtzite-type structures (P63mc), ß-LiGaO2 has a distorted wurtzite-type structure (Pna21), and there are no reports of ferroelectricity in LiGaO2. In this study, we have revealed that LiGaO2 exhibits relatively high barrier height energy for polarization switching, however, Sc doping effectively reduces that energy. Then, we conducted thin film preparation and evaluation for Sc-doped LiGaO2 to observe its ferroelectric properties. We successfully observed ferroelectric behavior by using piezoresponse force microscopy measurements for LiGa0.8Sc0.2O2/SrRuO3/(111)SrTiO3.

Atomic scale symmetry and polar nanoclusters in the paraelectric phase of ferroelectric materials.

The nature of the "forbidden" local- and long-range polar order in nominally non-polar paraelectric phases of ferroelectric materials has been an open question since the discovery of ferroelectricity in oxide perovskites, ABO3. A currently considered model suggests locally correlated displacements of B-site atoms along a subset of <111> cubic directions. Such off-site displacements have been confirmed experimentally; however, being essentially dynamic in nature they cannot account for the static nature of the symmetry-forbidden polarization implied by the macroscopic experiments. Here, in an atomically resolved study by aberration-corrected scanning transmission electron microscopy complemented by Raman spectroscopy, we reveal, directly visualize and quantitatively describe static, 2-4 nm large polar nanoclusters in the nominally non-polar cubic phases of (Ba,Sr)TiO3 and BaTiO3. These results have implications on understanding of the atomic-scale structure of disordered materials, the origin of precursor states in ferroelectrics, and may help answering ambiguities on the dynamic-versus-static nature of nano-sized clusters.

Suppression Mechanisms of the Solid-Electrolyte Interface Formation at the Triple-Phase Interfaces in Thin-Film Li-Ion Batteries.

Side reactions of the charge/discharge in Li-ion batteries (LIBs) generate a solid-electrolyte interface (SEI) onto an electrode surface, resulting in the degradation of the lifetime of a cell. The suppression of SEI formations has attracted much attention for achieving longer cyclable LIBs. Our research group has previously reported that few SEI were observed at triple-phase interfaces (TPIs) consisting of BaTiO3, LiCoO2, and electrolyte interfaces in LIBs with excellent cyclability and ultrahigh-speed chargeability. An investigation on the suppression mechanisms of SEI formations at TPIs should yield important information on understanding the undesirable side reactions. Therefore, we have explored the suppression mechanisms of SEI formations by preparing epitaxial thin films and evaluating the surface of the samples after the electrochemical treatment. The results of X-ray photoelectron spectroscopy and scanning electron microscopy with energy-dispersive X-ray analysis measurements suggested that the decomposition of LiPF6 was suppressed at TPIs, implying that the generation of PF5 via the decomposition of LiPF6 contributed to SEI formation.

Visible-light-driven dry reforming of methane using a semiconductor-supported catalyst.

Dry reforming of methane (DRM) is an attractive reaction that consumes two major greenhouse gases while producing the industrially important components of syngas. In this study, various semiconductors were examined as light-harvesting support materials to promote catalytic DRM reaction under mild conditions. Among the metal-loaded catalysts, rhodium-loaded tantalum oxynitride (Rh/TaON) drove the DRM reaction even under visible light irradiation (>400 nm), and its activity exceeded the thermal catalyst limit. According to our spectroscopic analysis and the surface temperature measurement, the bandgap excitation of TaON dominantly promotes the DRM reaction in addition to its photo-thermal effect.

Transparent semiconducting SrTiO3 crystal fabricated by heating treatment with gaseous ammonia and CeO2 powder.

A transparent semiconducting SrTiO3 single crystal with a resistivity of the order of 103 Ω·cm was fabricated by heating a SrTiO3 single crystal with gaseous ammonia and CeO2 powder. Conductive atomic force microscope (C-AFM) measurement revealed that micro-sized voids were formed and the high conductivity was exhibited only at around the voids. It is considered that the micro-sized voids were caused by the concentrated SrO planar defects, and TiO2-terminated structure with oxygen vacancies contributed to the two-dimensional conduction. In the heating process, the CeO2 powder acted as an oxygen source, and radicals such as NH2 and NH were generated by the reaction of oxygen and ammonia. The radicals may have contributed to the formation of three-dimensional network of the conductive paths consisting of SrO planar defects without the reduction of the bulk components. The electrons were localized on the TiO2-terminated structure, and the volume content of the conductive paths was small compared to the insulating bulk component. Therefore, the crystal was optically transparent and semiconducting.

Analysis of vibration waveforms of electromechanical response to determine piezoelectric and electrostrictive coefficients.

We developed a possible method to determine both coefficients of piezoelectricity (d) and electrostriction (M) at the same time by a waveform analysis of current and vibration velocity in the resonance state. The waveforms of the current and vibration velocity were theoretically described using the equations of motion and piezoelectric constitutive equations, considering the dissipation effect. The dissipation factor of the d coefficient and M coefficient is dielectric loss tangent tan δ. The waveforms measured in all of the ceramics, such as Pb(Zr,Ti)O(3) (PZT), Pb(Mg,Nb)O(3) (PMN), and 0.8Pb(Mg(1/3)Nb2/3)O(3)-0.2PbTiO(3) (PMN-PT), were well fitted with the calculated waveform. This fitting produced both the d and M coefficients, which agreed with those determined via the conventional methods. Moreover, the respective contributions of both piezoelectricity and electrostriction to the d value determined in the resonance-antiresonance method were clarified.

Analysis of nonlinear transient responses of piezoelectric resonators.

The electric transient response method is an effective technique to evaluate material constants of piezoelectric ceramics under high-power driving. In this study, we tried to incorporate nonlinear piezoelectric behaviors in the analysis of transient responses. As a base for handling the nonlinear piezoelectric responses, we proposed an assumption that the electric displacement is proportional to the strain without phase lag, which could be described by a real and constant piezoelectric e-coefficient. Piezoelectric constitutive equations including nonlinear responses were proposed to calculate transient responses of a piezoelectric resonator. The envelopes and waveforms of current and vibration velocity in transient responses observed in some piezoelectric ceramics could be fitted with the calculation including nonlinear responses. The procedure for calculation of mechanical quality factor Q(m) for piezoelectric resonators with nonlinear behaviors was also proposed.

Effect of material constants on power output in piezoelectric vibration-based generators.

A possible power output estimation based on material constants in piezoelectric vibration-based generators is proposed. A modified equivalent circuit model of the generator was built and was validated by the measurement results in the generator fabricated using potassium sodium niobate-based and lead zirconate titanate (PZT) ceramics. Subsequently, generators with the same structure using other PZT-based and bismuth-layered structure ferroelectrics ceramics were fabricated and tested. The power outputs of these generators were expressed as a linear functions of the term composed of electromechanical coupling coefficients k(sys)(2) and mechanical quality factors Q*(m) of the generator. The relationship between device constants (k(sys)(2) and Q*(m)) and material constants (k(31)(2) and Q(m)) was clarified. Estimation of the power output using material constants is demonstrated and the appropriate piezoelectric material for the generator is suggested.

Analysis of polarization behavior in relaxation of BaTiO3-based ferroelectrics using wideband dielectric spectroscopy.

Wideband dielectric spectra from the kilohertz to terahertz range are discussed for BaTiO3-based ferroelectrics. Ceramics of BaTiO3 (BT), Ba(0.6)Sr(0.4)TiO3 (BST-0.6), and BaZr(0.25)Ti(0.75)O3 (BZT-0.25) were selected as normal ferroelectrics, ferroelectrics with diffuse phase transition (DPT ferroelectrics), and relaxor ferroelectrics, respectively. The variation of ionic polarization in both BT and BST-0.6 ceramics with temperature could be explained by the softening of the soft phonon mode. In BZT-0.25, a permittivity anomaly at the dielectric maximum temperature (T(m)) at low frequencies is not attributed to the softening of the soft phonon mode, but originates from the permittivity derived from the dipole polarization (ϵ(dipole)). Relaxor behavior in BZT-0.25 is derived from the increase in the depression of ϵ(dipole) on cooling across the T(m) with increasing frequency. In dipole polarization, BT, BST- 0.6, and BZT-0.25 all exhibited a similar tendency of ϵ(dipole) above the Curie temperature (T(c)) and T(m). However, behavior of ϵ(dipole) below the T(c) can be explained by the ferroelectric domains in BT, whereas the variation of ϵ(dipole) below the Tm could be explained by growth process of polar nanoregions (PNRs) in BST-0.6 and BZT-0.25. Regarding this, BT can be distinguished from BST-0.6 and BZT-0.25. Relaxation in BT could be interpreted as successive change in polarization mechanism from normal ferroelectrics to relaxor ferroelectrics via DPT ferroelectrics.

Size effect of barium titanate and computer-aided design of multilayered ceramic capacitors.

The size effect of BaTiO3 (BTO) is the most important issue to design multilayer ceramic capacitors (MLCCs) with high capacitance. In the size effect of BTO particles, the size dependence of dielectric permittivity related with the complex structure in BTO nano-particles. The grain size dependence of dielectric permittivity in BTO ceramics was due to the domain wall contribution. The core-shell structure played an important role in the size effect of dielectric layers in X7R-MLCCs. Computer simulation technique was developed to predict the limit of capacitance density of MLCCs produced by the current technology. Dielectric properties of MLCCs with different particle size of BTO were measured, and the data were analyzed using B-SPLINE fitting to predict dielectric permittivity at arbitrary temperatures and AC-fields. The dielectric properties of barium titanate grains smaller than 100 nm were predicted using least squares fitting of the B-SPLINE coefficients. It was found from the simulation that the use of barium titanate grains smaller than 80 nm did not give an advantage to increase the capacitance density as well as temperature stability of the MLCCs. The maximum capacitance was predicted for the 1608 (mm) chip size.

Preparation of barium titanate nanoparticle sphere arrays and their dielectric properties.

Barium titanate (BaTiO(3)) nanoparticles from 27 to 192 nm were prepared by the 2-step thermal decomposition method from barium titanyl oxalate nanoparticles. These particles were dispersed well into 1-propanol, and dense BaTiO(3); nanoparticle sphere arrays without stress-field were prepared by the meniscus method. Temperature dependence of dielectric properties was successfully measured using these dense nanoparticle sphere arrays, and size effect on dielectric properties was discussed.