Electrochemical and microstructural analysis of LiNi1/3Mn1/3Co1/3O2 cathode composites prepared using the SEED method.

Cathode composites were fabricated using the nuclear growth (SEED) method. Compared to mortar mixing, the SEED method demonstrated higher cycle stability, with a 90LiNi1/3Mn1/3Co1/3O2-10Li7P2S8I composite retaining 99.7% discharge capacity after six cycles compared to 66.1%. Cross-sectional SEM-EDX images suggest that the solid electrolyte was more uniformly distributed in the cathode composite prepared using the SEED method. This study opens up the potential for higher cathode-active material loading ratios.

Magnetic Phase Transition-Induced Modulation of Ferroelectric Properties in Hexagonal RFeO3 (R = Tb and Ho).

Hexagonal rare-earth iron oxides (h-RFeO3) exhibit spontaneous magnetization and room-temperature ferroelectricity simultaneously. However, achieving a large magnetoelectric coupling necessitates further exploration. Herein, we report the impact of the magnetic phase transition on the ferroelectric properties of epitaxial h-RFeO3 (R = Tb and Ho) films prepared by pulsed laser deposition. The metastable h-RFeO3 phase is successfully stabilized with high crystallinity and low leakage current due to the ITO buffer layer, making it possible to investigate the ferroelectric properties. The h-TbFeO3 film exhibits a magnetic-field-induced transition from antiferromagnetic (AFM) to weak ferromagnetic (wFM) phases below 30 K, while also exhibiting ferroelectricity at 300 K. The dielectric constants change with the magnetic phase transition, demonstrating hysteresis in the magnetocapacitance. In contrast, the h-HoFeO3 film exhibits antiferroelectric-like behavior and an AFM-wFM phase transition. Notably, the h-HoFeO3 film shows a rapid increase in the remnant polarization during the AFM-wFM phase transition accompanied by an increase in the ferroelectric component. Considering the strong connection between the antiferroelectric behavior in the h-RFeO3 system and the ferroelectric domain wall motion, this considerable modification of ferroelectric properties during the magnetic phase transition is probably due to the faster movement of the ferroelectric domain walls in the wFM phase induced by the clamping effect. Our findings indicate the effectiveness of magnetic phase transitions in enhancing the magnetoelectric coupling, particularly when utilizing domain wall clamping properties.

Chemical design of a new displacive-type ferroelectric.

Since the discovery of the ferroelectric perovskite-type oxide BaTiO3 in 1943, numerous materials have been surveyed as candidates for new ferroelectrics. Perovskite-type materials have played a leading role in basic research and applications of ferroelectric materials since the last century. Experimentalists and theoreticians have developed a new materials design stream for post-perovskite materials. In this stream, we have mainly focused on the role of covalency in the evolution of ferroelectricity for displacive-type ferroelectrics in oxides. This perspective surveys the following topics: (1) crossover from quantum paraelectric to ferroelectric through a ferroelectric quantum critical point, (2) the role of cation-oxygen covalency in ferroelectricity and the crossover to quantum paraelectric in perovskite-type compounds, (3) off-center-induced ferroelectricity in perovskites, (4) second-order Jahn-Teller effect enhancement of ferroelectricity in lithium-niobate-type oxides, (5) the presence of four ferroelectric phases and structural transitions of phases of AFeO3 with decreasing radius of A (A = La-Al), (6) tetrahedral ferroelectrics of perovskite-related Bi2SiO5 and wurtzites, (7) a rare type of polarization switching system in which the coordination number of ions in κ-Al2O3 systems changes between 4 and 6, and (8) lone-pair-electron-induced ferroelectrics in langasite-type compounds.

Room-Temperature Antiferroelectricity in Multiferroic Hexagonal Rare-Earth Ferrites.

The antiferroelectric (AFE) phase, in which nonpolar and polar states are switchable by an electric field, is a recent discovery in promising multiferroics of hexagonal rare-earth manganites (ferrites), h-RMn(Fe)O3. However, this phase has so far only been observed at 60-160 K, which restricts key investigations into the microstructures and magnetoelectric behaviors. Herein, we report the successful expansion of the AFE temperature range (10-300 K) by preparing h-DyFeO3 films through epitaxial stabilization. Room-temperature scanning transmission electron microscopy reveals that the AFE phase originates from a nanomosaic structure comprising AFE P3̅c1 and ferroelectric P63cm domains with small domain sizes of 1-10 nm. The nanomosaic structure is stabilized by a low c/a ratio derived from the large ionic radius of Dy3+. Furthermore, weak ferromagnetism and magnetocapacitance behaviors are observed. Below 10 K, the film exhibits an M-shaped magnetocapacitance versus magnetic field curve, indicating unusual magnetoelectric coupling in the AFE phase.

Skewed electronic band structure induced by electric polarization in ferroelectric BaTiO3.

Skewed band structures have been empirically described in ferroelectric materials to explain the functioning of recently developed ferroelectric tunneling junction (FTJs). Nonvolatile ferroelectric random access memory (FeRAM) and the artificial neural network device based on the FTJ system are rapidly developing. However, because the actual ferroelectric band structure has not been elucidated, precise designing of devices has to be advanced through appropriate heuristics. Here, we perform angle-resolved hard X-ray photoemission spectroscopy of ferroelectric BaTiO3 thin films for the direct observation of ferroelectric band skewing structure as the depth profiles of atomic orbitals. The depth-resolved electronic band structure consists of three depth regions: a potential slope along the electric polarization in the core, the surface and interface exhibiting slight changes. We also demonstrate that the direction of the energy shift is controlled by the polarization reversal. In the ferroelectric skewed band structure, we found that the difference in energy shifts of the atomic orbitals is correlated with the atomic configuration of the soft phonon mode reflecting the Born effective charges. These findings lead to a better understanding of the origin of electric polarization.

Modulating the Structure and Magnetic Properties of ε-Fe2O3 Nanoparticles via Electrochemical Li+ Insertion.

ε-Fe2O3, a metastable phase of iron oxide, is widely known as a room-temperature multiferroic material or as a superhard magnet. Element substitution into ε-Fe2O3 has been reported in the literature; however, the substituted ions have a strong site preference depending on their ionic radii and valence. In this study, in order to characterize the crystal structure and magnetic properties of ε-Fe2O3 in the Fe2+/Fe3+ coexisting states, Li+ was electrochemically inserted into ε-Fe2O3 to reduce Fe3+. The discharge and charge of Li+ into/from ε-Fe2O3 revealed that Li+ insertion was successful. X-ray magnetic circular dichroism results indicated that the reduced Fe did not exhibit site preference. Increasing the Li+ content in ε-Fe2O3 resulted in decreased saturation magnetization and irregular variation of the coercive field. We present a comprehensive discussion of how magnetic properties are modified with increasing Li+ content using transmission electron microscopy images and considering the Li+ diffusion coefficient. The results suggest that inserting Li+ into crystalline ε-Fe2O3 is a useful tool for characterizing crystal structure, lithiation limit, and magnetic properties in the coexistence of Fe2+/Fe3+.

Layer matching epitaxy of NiO thin films on atomically stepped sapphire (0001) substrates.

Thin-film epitaxy is critical for investigating the original properties of materials. To obtain epitaxial films, careful consideration of the external conditions, i.e. single-crystal substrate, temperature, deposition pressure and fabrication method, is significantly important. In particular, selection of the single-crystal substrate is the first step towards fabrication of a high-quality film. Sapphire (single-crystalline α-Al2O3) is commonly used in industry as a thin-film crystal-growth substrate, and functional thin-film materials deposited on sapphire substrates have found industrial applications. However, while sapphire is a single crystal, two types of atomic planes exist in accordance with step height. Here we discuss the need to consider the lattice mismatch for each of the sapphire atomic layers. Furthermore, through cross-sectional transmission electron microscopy analysis, we demonstrate the uniepitaxial growth of cubic crystalline thin films on bistepped sapphire (0001) substrates.