Center for Dielectrics & Piezoelectrics

Research on sintering of dense ceramic materials has been very active in the past decades and still keeps gaining in popularity. Although a number of new techniques have been developed, the sintering process is still performed at high temperatures. Very recently we established a novel protocol, the “Cold Sintering Process ( CSP )”, to achieve dense ceramic solids at extraordinarily low temperatures of <300°C. A wide variety of chemistries and composites were successfully densified using this technique. In this article, a comprehensive CSP tutorial will be delivered by employing three classic ferroelectric materials ( KH 2 PO 4 , Na NO 2 , and BaTiO 3 ) as examples. Together with detailed experimental demonstrations, fundamental mechanisms, as well as the underlying physics from a thermodynamics perspective, are collaboratively outlined. Such an impactful technique opens up a new way for cost‐effective and energy‐saving ceramic processing. We hope that this article will provide a promising route to guide future studies on ultralow temperature ceramic sintering or ceramic materials related integration.

This study demonstrates that antiferroelectricity can be stabilized in NaNbO(3) (NN) based ceramics by lowering the tolerance factor. Through consideration of the crystal chemistry via the Goldschmidt tolerance factor and polarizability, we show that simultaneous substitution of Zr(4+) and Ca(2+) ions in the Nb and Na sites, respectively, lowers the polarizability and tolerance factor of the (Na(1-x)Ca(x))(Nb(1-x)Zrx)O(3) (CZNN100x) solid solution, while maintaining charge neutrality. Structural investigations using both X-ray diffraction and transmission electron microscopy (TEM) indicated an enhancement of antiferroelectric (AFE) superlattice peaks with CaZrO(3) substitution. The TEM domain analysis revealed that only AFE domains existed in the CZNN4 and CZNN5 ceramics; in contrast, normal NN ceramics displayed coexistence of AFE and ferroelectric (FE) domains at room temperature. The CZNN100x (0.02 ≤x≤ 0.05) ceramics showed double polarization hysteresis loops, characteristic of reversible AFE↔FE phase transition switching. The field-induced polarization decreased drastically with increasing substitution, an effect of the decreases in tolerance factor. In addition, the AFE switching field was increased by the chemical substitution. First principles calculations are performed to obtain insights into the relative stability and coexistence of the AFE and FE phases in single domains. The large decrease of polarization in the CZNN system is explained by a modification of the relative stability of the relevant structures, which favours nonpolar-to-polar AFE transitions over polar-to-polar FE domain switching.

Abstract Cold sintering process ( CSP ) is an extremely low‐temperature sintering process (room temperature to ~200°C) that uses aqueous‐based solutions as transient solvents to aid densification by a nonequilibrium dissolution‐precipitation process. In this work, CSP is introduced to fabricate microwave and packaging dielectric substrates, including ceramics (bulk monolithic substrates and multilayers) and ceramic‐polymer composites. Some dielectric materials, namely Li 2 MoO 4 , Na 2 Mo 2 O 7 , K 2 Mo 2 O 7 , and (LiBi) 0.5 MoO 4 ceramics, and also (1− x )Li 2 MoO 4 − x PTFE and (1− x )(LiBi) 0.5 MoO 4 − x PTFE composites, are selected to demonstrate the feasibility of CSP in microwave and packaging substrate applications. Selected dielectric ceramics and composites with high densities (88%‐95%) and good microwave dielectric properties (permittivity, 5.6‐37.1; Q × f , 1700‐30 500 GH z) were obtained by CSP at 120°C. CSP can be also used to potentially develop a new co‐fired ceramic technology, namely CSCC . Li 2 MoO 4 −Ag multilayer co‐fired ceramic structures were successfully fabricated without obvious delamination, warping, or interdiffusion. Numerous materials with different dielectric properties can be densified by CSP , indicating that CSP provides a simple, effective, and energy‐saving strategy for the ceramic packaging and microwave device development.

Tetragonal tungsten bronzes (TTBs), an important class of oxides known to exhibit ferroelectricity, undergo complex distortions, including rotations of oxygen octahedra, which give rise to either incommensurately or commensurately modulated superstructures. Many TTBs display broad, frequency-dependent relaxor dielectric behavior rather than sharper frequency-independent normal ferroelectric anomalies, but the exact reasons that favor a particular type of dielectric response for a given composition remain unclear. In this contribution the influence of incommensurate/commensurate displacive modulations on the onset of relaxor/ferroelectric behavior in TTBs is assessed in the context of basic crystal-chemical factors, such as positional disorder, ionic radii and polarizabilities, and point defects. We present a predictive crystal-chemical model that rationalizes composition–structure–properties relations for a broad range of TTB systems.

Abstract The recently developed technique of cold sintering process (CSP) enables densification of ceramics at low temperatures, i.e., <300°C. CSP employs a transient aqueous solvent to enable liquid phase‐assisted densification through mediating the dissolution‐precipitation process under a uniaxial applied pressure. Using CSP in this study, 80% dense Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) electrolytes were obtained at 120°C in 20 minutes. After a 5 minute belt furnace treatment at 650°C, 50°C above the crystallization onset, Li‐ion conductivity was 5.4 × 10 −5 S/cm at 25°C. Another route to high ionic conductivities ~10 −4 S/cm at 25°C is through a composite LAGP ‐ (PVDF‐HFP) co‐sintered system that was soaked in a liquid electrolyte. After soaking 95, 90, 80, 70, and 60 vol% LAGP in 1 M LiPF 6 EC‐DMC (50:50 vol%) at 25°C, Li‐ion conductivities were 1.0 × 10 −4 S/cm at 25°C with 5 to 10 wt% liquid electrolyte. This paper focuses on the microstructural development and impedance contributions within solid electrolytes processed by (i) Crystallization of bulk glasses, (ii) CSP of ceramics, and (iii) CSP of ceramic‐polymer composites. CSP may offer a new route to enable multilayer battery technology by avoiding the detrimental effects of high temperature heat treatments.

This paper describes a cold sintering process for Pb(Zr,Ti)O3 ceramics and the associated processing-property relations. Pb(Zr,Ti)O3 has a very small, incongruent solubility that is a challenge during cold sintering. To circumvent this, a Pb(NO3)2 solution was used as the transient liquid phase. A bimodal lead zirconate titanate powder was densified to a relative density of 89% by cold sintering at 300 °C and 500 MPa. After the cold sintering step, the permittivity was 200, and the dielectric loss was 2.0%. A second heat-treatment involving a 3 h anneal at 900 °C increased the relative density to 99%; the resulting relative dielectric permittivity was 1300 at room temperature and 100 kHz. The samples showed well-defined ferroelectric hysteresis loops, having a remanent polarization of 28 μC/cm2. On poling, the piezoelectric coefficient d33 was ∼200 pC/N. With a 700 °C 3 h post-annealing, samples show a lower room temperature relative permittivity (950 at 100 kHz), but a 24 h hold time at 700 °C produces ceramics where there is an improved relative dielectric constant (1050 at 100 kHz).

High dielectric permittivity and low dielectric loss of CCTO–Fe₃O₄/PI composites were obtained at low filler loading induced by magnetic field.

Conventional thermal sintering of ceramics is generally accomplished at high temperatures in kilns or furnaces. We have recently developed a procedure where the sintering of a ceramic can take place at temperatures below 200°C, using aqueous solutions as transient solvents to control dissolution and precipitation and enable densification (i.e., sintering). We have named this approach as the “Cold Sintering Process” because of the drastic reduction in sintering temperature and time relative to the conventional thermal process. In this study, we fabricate basic monolithic capacitor array structures using a ceramic paste that is printed on nickel foils and polymer sheets, with silver electrodes. The sintered capacitors, using a dielectric Lithium Molybdenum Oxide ceramic, were then cold sintered and tested for capacitance, loss, and microstructural development. Simple structures demonstrate that this approach could provide a cost‐effective strategy to print and densify different materials such as ceramics, polymers, and metals on the same substrate to obtain functional circuitry.

We demonstrated a new CaHfO3-NaNbO3 solid solution system that allows stable antiferroelectric (AFE) (P) phase to exist under ambient conditions. Based on crystal chemistry viewpoint of relative change of the Goldschmidt tolerance factor (t) and polarizability, two new solid solutions were fabricated using the perovskite end member CaHfO3. It was found that the CaHfO3 effectively stabilized the antiferroelectric (AFE) P phase in NaNbO3. In this article, electrical properties and transmission electron microscopy experiments were conducted to verify the stabilization and enhancement of antiferroelectric behavior over the various solid solutions, where both structural signature of ¼{010} superlattice diffraction reflections and electrical characteristic of double polarization-electric (P-E) hysteresis were observed.

Polymer composites filled with conductive fillers can demonstrate ultrahigh effective dielectric permittivity, which is generally attributed to an enhanced Maxwell–Wagner–Sillars interfacial polarization associated with the formation of microcapacitor networks. Here, we explore a composite of the ethylene–propylene–diene elastomer with carbon-black (CB) nanofillers and investigate its dielectric response over wide ranges of temperature and frequency. The dielectric relaxation exhibits atypical (counter-Arrhenius) temperature dependence, contradicting the widely assumed interfacial polarization mechanisms. It is shown that the relaxation/polarization is actually determined by electron displacement─primarily via e-conduction and tunneling within CB clusters─and that the composites’ dielectric response can be quantitatively correlated with the CB cluster morphology via a set of scaling laws. Considering the selected composite as a paradigmatic system, the physical origins of the dielectric relaxation and the associated scaling relations seem to be generally applicable and expected to also pertain to other dielectric polymer/conductive-filler composites near percolation.

We previously reported various solid solution systems that demonstrated the stabilized antiferroelectric (P) phases in NaNbO3 through lowering the tolerance factor. However, all those reported modifications were achieved by adding A2+B4+O3 type solid solutions. A lead-free antiferroelectric (AFE) solid solution xBiScO3-(1-x)NaNbO3 was rationalized by adopting the tolerance factor design rule. Specifically, adding BiScO3 was found to effectively stabilize the AFE phase without changing the crystal symmetry of NaNbO3. Microstructure and electron zone axis diffraction patterns from transmission electron microscopy revealed the stabilized AFE (P) phase in this solid solution. Besides, the electric-field-induced polarization with a double-hysteresis loop was observed. The present results pointed out that the strategy could also be applied while adding A3+B3+O3 type solid solutions. In addition, it expanded the compositional design that can be applied to antiferroelectric materials.

Low‐temperature conductivity mechanisms were identified in acceptor‐doped SrTiO 3 single crystals quenched from high temperatures under reducing conditions. Impedance spectroscopy measurements made on samples of the prototypical perovskite structure doped with iron provided a framework for creating a complete conductivity model for a well‐defined point defect system. The dominant conductivity mechanism in the room‐temperature range was identified as being controlled by oxygen vacancy hopping. The activation energy for oxygen vacancy migration, an often debated value in the perovskite community, is determined to lie within the range of 0.59–0.78 eV for the iron‐doped system with the bottom of this range approaching the intrinsic value for oxygen vacancy hopping in an undoped single crystal. At low temperatures, oxygen vacancies form defect complexes with iron impurities, and the observed range of activation energies is explained and modeled in terms of an oxygen vacancy trapping mechanism.

KNN-based crystals with ultrahigh piezoelectric coefficients (<italic>d</italic>₃₃ = 1050 pC N⁻¹, and <italic>d</italic>₃₃* = 2290 pm V⁻¹) were fabricated.

A Li and Ta modified (Na, K)NbO 3 piezoelectric ceramic has been successfully co‐fired with inner copper electrodes in a reduced atmosphere. Highly dense NKN ceramics (95% relative density, 4.64 g/cm 3 ) were obtained by sintering the samples in a low oxygen partial pressure (low p O 2 ) atmosphere at 1050°C. The poly(propylene carbonate) binder system was used to permit a clean burnout at low temperature in N 2 atmosphere, and also prevent the electrode copper particles from undergoing any oxidation. No interdiffusion of copper, chemical reactions, and/or carbon residues were observed in the grains, grain boundaries, or at the electrode–ceramic interface of the co‐fired samples from a detailed transmission electron microscopy ( TEM ) analysis. Dielectric and piezoelectric properties were characterized from those co‐fired prototyped samples. The samples displayed high relative dielectric permittivity above 800, with low dielectric loss about 3.6%. A normalized strain coefficient (max. strain/max. electric field) of = 220 pm/V was obtained under unipolar converse electromechanical measurement at 20 kV/cm. This paper presents the feasibility of co‐firing a Cu inner electrode with NKN ceramics toward multilayer lead‐free piezoelectric applications, providing an engineering route to narrow the performance differences between soft lead‐based piezoelectrics and lead‐free materials.

nano-crystalline ceramic (n-NITO) synthesized by a low-temperature spark plasma sintering (SPS) technique. The dielectric properties of the n-NITO were not largely affected by the metal electrode contacts. Huge dielectric relaxation was observed at a very low temperature below 35 K. Both the activation energy and relaxation time suggested that the electronic hopping motion is the underlying mechanism responsible for the colossal dielectric permittivity (CP) and its relaxation, instead of the internal barrier layer effect or a dipolar relaxation. With Havriliak-Negami (H-N) fitting, a relaxation time with a large distribution of dielectric relaxations was revealed. The broad distributed relaxation phenomena indicated that Nb and In were involved, controlling the dielectric relaxation by modifying the polarization mechanism and localized states. The associated distribution function is calculated and presented. The frequency-dependent a.c. conductance is successfully explained by a hopping conduction model of the localized electrons with the distribution function. It is demonstrated that the dielectric relaxation is strongly correlated with the hopping electrons in the localized states. The CP in SPS n-NITO is then ascribed to a hopping polarization.

Large Na 0.5 K 0.5 NbO 3 ( NKN ) piezoelectric single crystals were obtained by seed‐free solid‐state crystal growth method, which is a traditional sintering grain growth process, with LiBiO 3 used as a sintering aid. The largest dimension of the single crystals obtained was 11 mm × 9 mm × 3 mm. In addition to the LiBiO 3 doping content, temperature, and time effect of the crystal growth process was systematically investigated and considered from the kinetics point of view. With the assistance of Avrami analysis, parameters relevant to the crystal growth process were determined. Laue diffraction and transmission electron microscopy suggested an orthorhombic symmetry for the single crystalline structure. Dielectric‐frequency‐temperature measurements revealed an orthorhombic‐tetragonal and tetragonal‐cubic phase transition at 155°C and 405°C, respectively, both of which are typical of first‐order transitions, and have a well‐defined thermal hysteresis. Rayleigh analysis was performed regarding to the extrinsic reversible and nonreversible piezoelectric properties, and the result suggested a dominant intrinsic reversible piezoelectric contribution of 91.5% under E 0 = 1 kV/cm AC amplitude. Such a single crystal growth process route is low cost and a relative simple preparation process.

A self-powered, ultraviolet-visible perovskite photodetector based on TiO₂ nanorods/CH₃NH₃PbI₃ heterojunction was reported.

OBJECTIVE: Among older adults, the ability to stand or walk while performing cognitive tasks (ie, dual-tasking) requires coordinated activation of several brain networks. In this multicenter, double-blinded, randomized, and sham-controlled study, we examined the effects of modulating the excitability of the left dorsolateral prefrontal cortex (L-DLPFC) and the primary sensorimotor cortex (SM1) on dual-task performance "costs" to standing and walking. METHODS: Fifty-seven older adults without overt illness or disease completed 4 separate study visits during which they received 20 minutes of transcranial direct current stimulation (tDCS) optimized to facilitate the excitability of the L-DLPFC and SM1 simultaneously, or each region separately, or neither region (sham). Before and immediately after stimulation, participants completed a dual-task paradigm in which they were asked to stand and walk with and without concurrent performance of a serial-subtraction task. RESULTS: tDCS simultaneously targeting the L-DLPFC and SM1, as well as tDCS targeting the L-DLPFC alone, mitigated dual-task costs to standing and walking to a greater extent than tDCS targeting SM1 alone or sham (p < 0.02). Blinding efficacy was excellent and participant subjective belief in the type of stimulation received (real or sham) did not contribute to the observed functional benefits of tDCS. INTERPRETATION: These results demonstrate that in older adults, dual-task decrements may be amenable to change and implicate L-DPFC excitability as a modifiable component of the control system that enables dual-task standing and walking. tDCS may be used to improve resilience and the ability of older results to walk and stand under challenging conditions, potentially enhancing everyday functioning and reducing fall risks. ANN NEUROL 2021;90:428-439.

Defect dipoles are significant point defects in perovskite oxides as a result of their impact on oxygen vacancy dynamics. Electron paramagnetic resonance (EPR) was used to investigate the local defect structure of single crystal BaTiO3 doped with manganese. These results, along with a re-analysis of literature data, do not support the conclusion that transition metal-oxygen vacancy nearest neighbor defect dipoles (MnTi″−VO••)× in ferroelectric BaTiO3 are majority defect centers as previously reported. Local symmetry analysis of the zero-field splitting term of the spin Hamiltonian supports the assignment of fully coordinated defect centers as opposed to defect dipoles for resonance signals at geff ∼ 2. A newly discovered defect center with g⊥ ∼ 6 is observed in the manganese doped system, and it is argued that this defect center belongs to an associated defect complex or defect dipole. This newly reported strong axial defect center, however, is present in small, minor concentrations compared to the well-known Mn2+ center with zero-field splitting of D ∼ 645 MHz. In regard to relative concentration, it is concluded that the dominant point defect related to the Mn2+ ion doped in BaTiO3 corresponds to B-site substitution with six nearest neighbor anions in octahedral coordination.

A series of A-site defective scheelite (Ca_1−3xBi_2xΦ_x)MoO₄compositions were formed as a solid solution, and their local structures indicate that Bi–O polyhedrons become more distorted with<italic>x</italic>value.