Ferroelectric BaTaO2N Crystals Grown in a BaCN2 Flux.

Perovskite-type oxynitride BaTaO2N has been attracting attention for its large dielectric constant, which is almost independent of the temperature by measurements on its ceramics. Its dielectric characteristics are attributed to polar nanoregions (PNRs) in the average cubic crystal structure. Polarization saturation to produce a butterfly-like piezoresponse force microscopy (PFM) signal was observed on BaTaO2N crystals in the present study. Reddish crystallites of BaTaO2N of up to 3.1 µm in size were grown using a BaCN2 flux. Grain growth proceeded through the formation of a Ruddlesden-Popper-type oxynitride from the reaction between BaTaO2N powder and molten BaCN2. Their electrical property was studied using PFM with special care because of the small size of the crystals. They were found to be much more highly insulating than its ceramics. Ferroelectricity with complete phase inversion was observed on an oxynitride perovskite crystal for the first time. A large coercivity of 50-60 V was observed in the measurement. Such ferroelectricity is ascribed to the PNRs induced by the polar linkages between cis-type TaO4N2 octahedra.

Advanced humidity sensing properties of CuO ceramics.

This research explores the capacitive humidity sensing properties of CuO ceramic, selected for its simplicity as an oxide and ease of fabrication, in addition to its remarkable dielectric properties. The CuO sample was fabricated by sintering at 980 °C for 5 h. A microstructure with a relative density of 88.9% was obtained. X-ray diffraction confirmed the formation of a pure CuO phase. Broadband dielectric spectroscopy revealed that the observed giant dielectric properties at room temperature (RT) were attributed to extrinsic effects, including the internal barrier layer capacitor and sample-electrode contact effects. A key focus of this study was to examine the giant dielectric properties of CuO ceramic as a function of relative humidity (RH) at RT and frequencies of 102 and 103 Hz. It was observed that the capacitance of CuO continuously increased with rising RH levels, ranging from 30 to 95%. Notably, the maximum hysteresis errors were constrained to 2.3 and 3.3% at 102 and 103 Hz, respectively. Additionally, the CuO ceramic demonstrated very fast response and recovery times, approximately 2.8 and 0.95 min, respectively. The repeatability of the humidity response of the capacitance was also established. Overall, this research highlights the high potential of CuO as a giant dielectric material for application in humidity sensors.

Pioneering dielectric materials of Sn-doped Nb0.025Ti0.975O2 ceramics with excellent temperature and humidity stability for advanced ceramic capacitors.

In this study, the rutile TiO2 system, widely acclaimed for its superior properties, was enhanced through co-doping with isovalent Sn4+ ions and 2.5% Nb5+ donor ions, diverging from traditional acceptor doping practices. This novel doping strategy was implemented by employing a conventional solid-state reaction method, resulting in the synthesis of Sn-doped Nb0.025Ti0.975O2 (Sn-NTO) ceramics. These ceramics demonstrated remarkable dielectric characteristics, with a high dielectric constant (ε') ranging from ∼27 000 to 34 000 and an exceptionally low loss tangent between 0.005 and 0.056 at ∼25 °C and 1 kHz. Notably, the temperature coefficient of ε', , aligned with the stringent specifications for X7/8/9R capacitors. Furthermore, the Sn-NTO ceramics exhibited a stable Cp response across various frequencies within a humidity range of 50 to 95% RH, with ΔCp (%) values within ±0.3%, and no hysteresis loop was detected, suggesting the absence of water molecule adsorption and desorption during humidity assessments. This behavior is primarily attributed to the effective suppression of oxygen vacancy formation by the Sn4+ ions, which also affects the grain growth diffusion process in the Sn-NTO ceramics. The observed heterogeneous electrical responses between semiconducting grains and insulating grain boundaries in these polycrystalline ceramics are attributed to the internal barrier layer capacitor effect.

Mechanisms of enhanced performance in Zr4+/Ta5+ codoped rutile-TiO2 ceramics via broadband dielectric spectroscopy.

Aliovalent dopant codoped rutile-TiO2 materials have garnered attention due to their excellent performance properties, characterized by low loss tangent (tanδ), high dielectric permittivity (ε'), and stable ε' over a broad temperature range. This performance is primarily due to the electron-pinned defect-dipoles (EPDDs) of the complex defects [Formula: see text]Ti3+-[Formula: see text]Ti3+BTi. Notably, the excellent dielectric properties in ZrxTa2.5%Ti0.975-xO2 (Zr-TTO) ceramics can be achieved using the traditional mixed oxide method without the EPDDs, due to the absence of A3+ (acceptor doping ions). Instead, the existence of localized free electrons and oxygen vacancies ([Formula: see text]) in Zr-TTO structures, due to doping ions and the sintering process, was confirmed by X-ray photoelectron and Raman spectroscopies. These ceramics exhibited ε'~ 2 × 104 and tanδ < 0.03 at 1 kHz and 25 °C in the 2.5-10%Zr-TTO samples. Moreover, all ceramics demonstrated a maximum ε' change (∆ε') of less than ±15% over the temperature range suitable for X7R and X8R type ceramic capacitors. Significantly, the change in ε' related to relative humility was calculated to be less than ±0.5% over the range of 50-95% RH, indicating the environmental stability of the dielectric properties, which is essential for capacitor applications. Investigations suggested that at least four mechanisms contributed to this system: the intrinsic effect of ionic polarization, Ti4+ · e- -[Formula: see text]- Ti4+ · e- and Ti4+ · e- - [Formula: see text] defects, interfacial polarization at insulating grain boundaries, and non-Ohmic contact between the surface sample and the metal electrode.

High-Performance Giant Dielectric Properties of Cr3+/Ta5+ Co-Doped TiO2 Ceramics.

The effects of the sintering temperature on microstructures, electrical properties, and dielectric response of 1%Cr3+/Ta5+ co-doped TiO2 (CrTTO) ceramics prepared using a solid-state reaction method were studied. The mean grain size increased with an increasing sintering temperature range of 1300-1500 °C. The dielectric permittivity of CrTTO ceramics sintered at 1300 °C was very low (ε' ∼198). Interestingly, a low loss tangent (tanδ ∼0.03-0.06) and high ε' (∼1.61-1.9 × 104) with a temperature coefficient less than ≤ ±15% in a temperature range of -60 to 150 °C were obtained. The results demonstrated a higher performance property of the acceptor Cr3+/donor Ta5+ co-doped TiO2 ceramics compared to the Ta5+-doped TiO2 and Cr3+-doped TiO2 ceramics. According to a first-principles study, high-performance giant dielectric properties (HPDPs) did not originate from electron-pinned defect dipoles. By impedance spectroscopy (IS), it was suggested that the giant dielectric response was induced by interfacial polarization at the internal interfaces rather than by the formation of complex defect dipoles. X-ray photoelectron spectroscopy (XPS) results confirmed the existence of Ti3+, resulting in the formation of semiconducting parts in the bulk ceramics. Low tanδ and excellent temperature stability were due to the high resistance of the insulating layers with a very high potential barrier of ∼2.0 eV.