Low-temperature synthesis of K0.5Na0.5NbO3 ceramics in a wide temperature window via cold-sintering assisted sintering method and enhanced electrical properties

High temperatures (≥ 1100 °C) and narrow temperature window (～ 20 °C) for sintering dense K_0.5Na_0.5NbO₃ ceramics always deteriorate their electrical properties. Here, via cold-sintering assisted sintering method, dense K_0.5Na_0.5NbO₃ ceramics were obtained in a wide temperature span between 800 °C and 1000 °C. An aqueous solution of NaOH and KOH mixture was used as transient liquid. Effects of liquid content (LC), molar concentration (MC) of liquid, cold-sintering temperature (T_CS), and post-annealing temperature (T_AN) on densification and electrical properties of the ceramics were investigated in detail. The ceramics prepared using LC = 10 wt%, MC = 10 mol/L, T_CS = 350 °C, and T_AN = 900 °C exhibit excellent electrical properties with d₃₃ = 123 pC/N, ε_r = 609, tanδ = 0.021, P_r = 28.0 μC/cm², P_m = 39.2 μC/cm², and E_c = 20.3 kV/cm. Compared to the ceramics with same or similar compositions via conventional solid-state sintering, the present K_0.5Na_0.5NbO₃ ceramics exhibit excellent electrical properties. The study endows the cold-sintering assisted sintering the successful method to prepare K_0.5Na_0.5NbO₃ ceramics at low temperatures and in a wide temperature window.     

Impact of microwave sintering on dielectric properties of screen printed Ba0.6Sr0.4TiO3 thick films

The influence of 30 GHz microwave sintering compared to conventional sintering has been investigated on polycrystalline Ba_0.6Sr_0.4TiO₃ (BST60) thick films with respect to an application as tunable dielectrics. The BST thick films were prepared as metal–insulator–metal (MIM) capacitors on alumina substrates. The average grain size (440 nm) and the porosity (approx. 30%) of the sintered films are only little affected by the sintering method. However, permittivity, dielectric loss and tunability have been influenced substantially. The dielectric improvement by microwave sintering is interpreted in terms of an increased crystal quality (ξ_S) and/or a decrease of defect concentrations. It is assumed that microwave sintering preferably heats up parts of the film where an increased defect density exists and therefore causes a selective heating process. This may heal up charged defects, inhomogeneities, and structural defects.     

Modulations in relaxor nature due to Sr2+ doping in 0.68PMN-0.32PT ceramic

Substitution of alkali earth metal ion of Sr²⁺, in the Pb²⁺ site of Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ is expected to induce functional modulations in the system. Doping of 4 at.% of Sr²⁺ in 0.68PMN-0.32PT was carried out to lower the transition temperature, and to investigate the intended ferroelectric and dielectric variations. Excellent relaxor property was observed in the doped sample without appreciable reduction in remnant polarization. Doping with Sr²⁺ led to a reduction in transition temperature from 165 °C to 117 °C. Doped sample exhibited remnant polarization P_r = 16.2 μC/cm², Squareness factor (Rsq) = 1.05 and Relaxor exponent (γ) around 2. Modulation in the functional response was exhibited by the doped composition, having low transition temperature, and its prospect in electrocaloric applications was analyzed.     

Effects of reoxidation on the dielectric and energy storage properties of Ce-doped (Ba,Sr)TiO3 ceramics prepared by hot-pressed sintering

Fully densified Ba_0.6Sr_0.34Ce_0.04TiO₃ ceramics with small grain microstructure (0.3−0.8 μm) and high insulation (∼10¹⁴Ω cm) could be successfully obtained by hot-pressed sintering (HPS) coupled with subsequent thermal annealing in oxygen atmosphere. The effects of annealing on the microstructure, dielectric, electric and energy storage properties were investigated with scanning electron microscope, X-ray photoelectron spectroscope, impedance and ferroelectric analyzers. The preferential oxidation of grain boundaries to gains resulted in the formation of electrically inhomogeneous microstructure, which could be much improved by increasing O₂ pressure during annealing process. The reduction of Ti⁴⁺ in the as-sintered HPS sample could be decreased with increasing the annealing temperature up to 1200 °C in flowing O₂ gas, leading to the decrease in dielectric relaxation and corresponding permittivity/loss above room temperature. Maximum energy density of 1.75 J/cm³ could be obtained under the field of 235 kV/cm with the efficiency of 85 %.     

Preparation of Na0.5Bi0.5TiO3 ceramics by hydrothermal-assisted cold sintering

A recently proposed novel technique, termed “cold sintering process” (CSP), can provide dense ceramic solids at remarkably low temperatures around 180?°C. In a recent work, we successfully obtained dense Na_0.5Bi_0.5TiO₃ ceramics by this method. Bismuth titanate sodium nanoparticles were prepared as the raw material powder by the hydrothermal synthesis route. A hydrothermal precursor solution was used as the transient solvent for cold sintering. Under the combined action of pressure and temperature, the Na_0.5Bi_0.5TiO₃ green body was densified by dissolution-precipitation, and a preliminary densified ceramic sheet was obtained. The amorphous phase in the ceramic sheet was then transformed into a crystalline phase by annealing. Finally, densified Na_0.5Bi_0.5TiO₃ ceramic sheets were obtained, with density of up to 99%, relative permittivity of 681, and dielectric loss of 0.08 at 10?kHz and room temperature. The piezoelectric coefficient d₃₃ of the sample was 52.5?pC/N. The properties of the prepared ceramics were comparable to those of the conventional sintered ceramics.     

Tailoring structural and electrical properties of A-site non-stoichiometric Na0.5Bi0.5TiO3 ceramic at different sintering temperature

Na/Bi stoichiometry plays crucial role in determining various properties of sodium bismuth titanate-based system. In this work, we have synthesised lead free (Na_0.5Bi_0.5)_1+x TiO₃ (x?=?0, 0.02 and 0.05) ceramics by sol-gel method and systematically presented structural, dielectric and ferroelectric properties at different sintering temperature. Single phase perovskite structure with rhombohedral symmetry (R3c) is obtained for all compositions from low (850°C) to maximum (1150°C) sintering temperature. The shifting of x-ray diffraction peaks and characteristic perovskite metal-oxide vibrational band (～627?cm^?1) in Fourier Transform Infra-red spectra suggests compression or expansion of crystal lattice with Na/Bi non-stoichiometry. Excess of Na/Bi comprises dense crystal growth as compared to pure Na_0.5Bi_0.5TiO₃ composition suggesting compensation of volatile elements loss during heat treatment whose impact has also been observed in dielectric as well as ferroelectric properties. It is observed that Na_0.51Bi_0.51TiO₃ sample with x?=?0.02 exhibits better structural, dielectric and ferroelectric properties in whole range of sintering temperature.     

Grain size-driven effect on the functional properties in Ba0.6Sr0.4TiO3 ceramics consolidated by spark plasma sintering

Dense fine-grained Ba_0.6Sr_0.4TiO₃ ceramics with submicronic grains sizes (GS) have been prepared using nanopowders synthesized via sol-gel route and consolidated by Spark Plasma Sintering (SPS). By changing SPS parameters, the GS was reduced from 214 nm to 74 nm. Diffuse ferroelectric-paraelectric phase transitions and low values of dielectric permittivity (<1000) at the Curie temperature (T_C ∼280 K) were revealed by Impedance Spectroscopy in all sintered ceramics. The GS reduction from submicron to nanoscale range reflects in a gradually diminishment of dielectric constant, tunability, polarisation and storage energy properties. Raman spectroscopy investigations pointed out the presence of polar nanoclusters above the T_C. The short-range polar order is affected by the GS decrease, but becomes more thermally stable. The observed properties of Ba_0.6Sr_0.4TiO₃ nanostructured ceramics are interpreted by considering the interplay between the GS reduction, the role of low-permittivity grain boundaries and the diffuse character of the ferroelectric-to-paraelectric transformation.     

Remarkably enhanced energy storage properties of lead-free Ba0.53Sr0.47TiO3 thin films capacitors by optimizing bottom electrode thickness

The lead-free Ba_0.53Sr_0.47TiO₃ (BST) thin films buffered with La_0.67Sr_0.33MnO₃ (LSMO) bottom electrode of different thicknesses were fabricated by pulsed laser deposition method on a (001) SrTiO₃ substrate. It was found that the roughness of electrode decreases and substrate stress relaxes gradually with the increase of LSMO thickness, which is beneficial for weakening local high electric field and achieving higher E_b. Therefore, the recoverable energy density (W_rec) of BST films can be greatly improved up to 67.3 %, that is, from 30.6 J/cm³ for the LSMO thickness of 30 nm up to 51.2 J/cm³ for the LSMO thickness of 140 nm after optimizing the LSMO thickness. Furthermore, the thin film capacitor with a 140 nm LSMO bottom electrode shows an outstanding thermal stability from 20 °C to 160 °C and superior fatigue resistance after 10⁸ electrical cycles with only a slightly decrease of W_rec below 1.6 % and 3.7 %, respectively. Our work demonstrates that optimizing bottom electrodes thickness is a promising way for enhancing energy storage properties of thin-film capacitors.     

Critical role of CuO doping on energy storage performance and electromechanical properties of Ba0.8Sr0.1Ca0.1Ti0.9Zr0.1O3 ceramics

CuO doped Ba_0.8Sr_0.1Ca_0.1Ti_0.95Zr_0.05O₃ (BSCTZ) ceramics were prepared by a modified mechano-chemical activation technique with the aim of improving energy storage properties for ceramic capacitor applications. CuO can effectively improve the microstructural characteristics along with a transformation of BSCTZ from classical ferroelectric to relaxor, which is the prime requirement for obtaining high discharge energy density and energy efficiency. The effect of CuO doping on the microstructural, ferroelectric, dielectric, and piezoelectric properties have been systematically studied. The study reveals that an appropriate amount of CuO doping can significantly enhance the morphological properties along with improvement in material density, which is very beneficial in a material for attaining improved energy storage performance. The BSCTZ sample with 3 mol% CuO doping has shown a highly dense microstructure, high saturation polarization (33.01 μC/cm²), low remnant polarization (6.74 μC/cm²), ultrahigh discharge energy density (1.81 J/cm³) and high energy efficiency (81.9%). The CuO doping in BSCTZ has also led to a slight improvement in breakdown strength and electromechanical properties compared to pure BSCTZ ceramics, which is mainly attributed to excellent density and optimum grain size of the material.     

Modulation of electrical transport in calcium cobaltite ceramics and thick films through microstructure control and doping

Ca₃Co₄O₉ is a promising p-type thermoelectric oxide material having intrinsically low thermal conductivity. With low cost and opportunities for automatic large scale production, thick film technologies offer considerable potential for a new generation of micro-sized thermoelectric coolers or generators. Here, based on the chemical composition optimized by traditional solid state reaction for bulk samples, we present a viable approach to modulating the electrical transport properties of screen-printed calcium cobaltite thick films through control of the microstructural evolution by optimized heat-treatment. XRD and TEM analysis confirmed the formation of high-quality calcium cobaltite grains. By creating 2.0 at% cobalt deficiency in Ca_2.7Bi_0.3Co₄O_9+δ, the pressureless sintered ceramics reached the highest power factor of 98.0 μWm^?1 K^-2 at 823 K, through enhancement of electrical conductivity by reduction of poorly conducting secondary phases. Subsequently, textured thick films of Ca_2.7Bi_0.3Co_3.92O_9+δ were efficiently tailored by controlling the sintering temperature and holding time. Optimized Ca_2.7Bi_0.3Co_3.92O_9+δ thick films sintered at 1203 K for 8 h exhibited the maximum power factor of 55.5 μWm^?1 K^-2 at 673 K through microstructure control.     

Rutile TiO2 microwave dielectric ceramics prepared via cold sintering assisted two step sintering

In this work, a sintering route named cold sintering assisted two step sintering process (CSP-TS) is presented to prepare rutile TiO₂ ceramics with submicron grain sizes. Cold sintering process at 300 °C with tetrabutyl titanate and water as the liquid phase yields a ‘green body’ with a relatively high density of ～80 %, and finally dense (98.5–99.8 %) rutile TiO₂ ceramics with grain sizes of ～600 nm can be obtained in the second sintering process at 950?1000 °C. The microstructural analysis with SEM and TEM indicates that the CSP-TS samples sintered at 950 °C have an obvious phenomenon of recrystallization, accompanying by a decrease of amorphous phases and a formation of clear grain boundaries. Besides, the rutile TiO₂ ceramics prepared by CSP-TS possess excellent microwave dielectric properties with relative permittivity of 92.0–98.4 and Q × f values of 27,800?31,900 GHz. Therefore, it is feasible to utilize CSP-TS to prepare ceramics with small grain sizes at low sintering temperatures.     

Influence of K0.5Bi0.5TiO3 on the structure,dielectric and ferroelectric properties of (Ba,Ca)(Zr,Ti)O3 ceramics

A new lead-free ferroelectric solid solution between (Ba,Ca)(Zr,Ti)O₃ (BCZT) and K_0.5Bi_0.5TiO₃ (KBT) has been systematically investigated in terms of its phase transformations, microstructure, dielectric and ferroelectric properties. The incorporation of KBT into BCZT was found to enhance the sintering behavior, although secondary phases of K₄Ti₃O₈ and BaBi₄Ti₄O₁₅ were detected at high KBT contents. Chemical heterogeneity was also observed in the form of core-shell grain structures comprising tetragonal ferroelectric BCZT-rich cores with pseudo-cubic relaxor ferroelectric KBT-rich shell regions. Temperature-dependent dielectric property measurements revealed that the BCZT-KBT ceramics exhibited both normal and relaxor ferroelectric behaviour simultaneously, associated directly with the core-shell structure. Ferroelectric hysteresis measurements indicated that the remanent polarisation and coercive field were strongly dependent on KBT content. In common with other lead-free relaxor ferroelectrics, increasing temperature led to the formation of constricted polarisation-electric field hysteresis loops, indicating the occurrence of a reversible electric field-induced nanopolar to long-range ordered ferroelectric state.     

Influence of microwave sintering on electrical properties of BCTZ lead free piezoelectric ceramics

Barium titanate doped with calcium and zirconium (BCTZ) could be used at low temperature to replace lead based piezoelectric ceramics (PZT). The classical way to obtain BCTZ is the solid-state route coupled with conventional sintering, but this step is time-consuming. To reduce the duration of this process, microwave heating was used for sintering. It is a fast sintering method and the heating rate was around 200 °C/min in this study. Slightly better electrical properties with finer microstructures (d₃₃* = 706 pm/V, grain size about 42.1 ± 14.2 μm) were obtained for samples sintered by microwave heating during 50 min compared to the conventional sintering (d₃₃* = 622 pm/V, 22.6 ± 4.4 μm). The main result of this study is that by using microwave heating, the sintering step duration (including heating, dwell time and cooling) was drastically reduced: 1.5 h for microwave sintering against 12.5 h for conventional sintering.     

Effects of Mn doping on dielectric properties and energy-storage performance of Na0.5Bi0.5TiO3 thick films

Lead-free Na_0.5Bi_0.5Ti_1−xMn_xO₃ (NBTMn_x, x=0, 0.01, 0.03 and 0.05) ferroelectric thick films have been fabricated on LaNiO₃/Si(100) substrate by using a polyvinylpyrrolidone-modified sol-gel method and the effects of Mn content on their microstructure, dielectric properties and energy-storage performance were investigated. Compared with the pure Na_0.5Bi_0.5TiO₃ (NBT) thick films, NBTMn_x thick films exhibited a large enhancement in dielectric properties and energy-storage performance. Particularly, a giant recoverable energy-storage density (W) of 30.2 J/cm³ and the corresponding efficiency (η) of 47.7% were obtained in NBTMn_0.01 thick film at 2310 kV/cm. Moreover, the NBTMn_0.01 thick film displayed good energy-storage stability over a large temperature range at different frequency.     

Dielectric and energy storage properties of Mn-doped Ba0.3Sr0.475 La0.12Ce0.03TiO3 dielectric ceramics

Microstructure, temperature and frequency dependent dielectric and energy storage properties of Ba_0.3Sr_0.475La_0.12Ce_0.03Ti_1−xMn_xO₃(x = 0 − 0.005) have been investigated with X-ray diffractometer, and scanning electron microscope, broad band dielectric spectrometer and ferroelectric analyzer. The doping of Mn substantially decreased the dielectric loss, but made some of Ce³⁺ be oxidized to Ce⁴⁺ entering into B-site, which resulted in the formation secondary phases. For the Mn-doped composition, extremely low dielectric loss (10⁻⁵ order of magnitude at 10 kHz) could be obtained at room temperature. The relaxation mechanism at low temperature is of the dipole type for the undoped composition and that at high temperature (>500 K) is governed by the trap controlled ac conduction, respectively. The energy storage properties were improved by the doping with Mn due to the increase of insulation. Maximum energy density of 0.953 J/cm³ could be obtained for x = 0.003 composition with the BDS of 247 kV/cm and efficiency of 93%.     

Cold sintering optimized SrF2 microwave dielectric ceramics for the development of dielectric resonator antenna at 5G millimeter-wave band

SrF₂ is a promising low-ε_r fluoride with outstanding microwave dielectric properties, while densification of SrF₂ ceramics is challenging via traditional thermal sintering (TTS). In this work, dense SrF₂ ceramics with 93.4%–97.2% relative density have been obtained via cold sintering (300 MPa–900 MPa, 150 °C, 1 h) and subsequent post-annealing at 950 °C/3 h. The pretreated cold sintering process is beneficial for microstructure optimization, where the maximum Qf value (62,037 GHz) is obtained at 750 MPa, nearly three times higher than the TTS sample (21,080 GHz). An ultra-low dielectric constant (ε_r) of 5.94 is simultaneously obtained, together with a temperature coefficient of resonant frequency τ_f = ?78.26 ppm/°C. Good chemical compatibility between SrF₂ ceramics and silver is verified, indicating great promise for their use in LTCC technology. Moreover, the low-ε_r and high Qf values of the cold sintering optimized SrF₂ ceramics suggest great potential in the 5G millimeter-wave antenna systems. A SrF₂-based dielectric resonator antenna is designed and fabricated, which resonates at the desired 24.5 GHz and exhibits an outstanding S₁₁ of ?43.95 dB and a broad bandwidth of 4.51 GHz.     

Microstructure and electrical properties of Mn/Y codoped Ba0.67Sr0.33TiO3 ceramics

Pure and Mn/Y codoped Ba_0.67Sr_0.33TiO₃ (BST) ceramics were fabricated via the citrate–nitrate combustion technique, and the microstructure and electrical properties of BST ceramics were mainly investigated. The Mn/Y codoping concentration has a strong influence on the microstructure and electrical properties of BST ceramics. All BST ceramics possess a pure polycrystalline structure. The density, dielectric loss, leakage current, and ferroelectric properties are improved by codoping 0.5 mol% Mn and 1.0 mol% Y to BST. The relative density of 0.5 mol% Mn/1.0 mol% Y-codoped BST (BST0510) ceramics reaches 97.5% of the theoretical value. BST0510 ceramics have the lowest dielectric loss (tanδ < 0.0073 at 1 kHz) among all BST ceramics. BST0510 ceramics also demonstrate a low leakage current density (1.23 × 10^?7 A/cm²) at an applied field of 10 kV/cm, and excellent ferroelectric properties with a remanent polarization of 2P_r = 15.327 μC/cm² and a coercive field of 2E_c = 3.456 kV/cm. Therefore, the Mn and Y with optimum content help improve the electrical properties of BST materials.     

Preparation and properties of LiF transparent ceramics by cold sintering process

The development of optoelectronic devices depends on the development of optoelectronic materials such as transparent ceramics. LiF transparent ceramics are photoelectronic ceramics with excellent photoelectric properties. Still, the traditional preparation of LiF transparent ceramics generally needs a high temperature or high-pressure environment, and the cost is high. This paper adopts a cold sintering process to prepare high-density LiF transparent ceramics at low temperatures to reduce the preparation conditions. The effects of different cold sintering temperatures on microstructure, density, hardness, visible and near-infrared transmittance, and electrical properties of transparent ceramics were studied. The results show that using LiOH solution as the solvent, the relative density of LiF ceramics can reach up to 99.64% under the sintering condition of 375 °C/470 MPa, and the Vickers hardness is 1.34 GPa. Vickers hardness is 1.34 GPa. The transmittance in the visible and near-infrared regions is 60.45% and 85.31%, respectively. The dielectric constant and dielectric loss of 13 GHz are 4.36 and 1.11 × 10⁻³, respectively.     

Ba0.64Sr0.36TiO3薄膜的介电与热释电性能的研究

应用溶胶-凝胶工艺在Pt/SiO2/Si(100)衬底上制备了Ba0.64Sr0.36TiO3薄膜,研究了薄膜的结构与电学性能.实验结果表明Ba0.64*Sr0.36TiO 3薄膜经700 ℃热处理1h,薄膜呈现出钙钛矿结构.当测试频率为200 Hz 时, 薄膜的介电常数和损耗因子分别为592和0.028.在40 ℃时,Ba0.64Sr0.36TiO 3薄膜存在一扩散铁电-顺电相变.在室温(25 ℃)、100 kHz条件下测试薄膜的C-V 特性得到一"蝶形"曲线,表明Ba0.64Sr0.36TiO3薄膜在室温下处于铁电相, 且当直流偏压从-5 V增至+5 V期间, 薄膜电容由495 pF增至1 108pF.热释电性能测试结果表明室温下Ba0.64Sr0.36TiO3薄膜的热释电系数为1 860μC/(m2*K), 材料的优值为37.4 μC/(m3*K), 这些结果表明应用溶胶-凝胶工艺制备的Ba0.64Sr0.36TiO3薄膜完全能满足红外探测器和热成像应用的需要.