skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Lead-free Zr-doped ceria ceramics with low permittivity displaying giant electrostriction
Abstract Electrostrictors, materials developing mechanical strain proportional to the square of the applied electric field, present many advantages for mechanical actuation as they convert electrical energy into mechanical, but not vice versa. Both high relative permittivity and reliance on Pb as the key component in commercial electrostrictors pose serious practical and health problems. Here we describe a low relative permittivity (<250) ceramic, ZrxCe1-xO2(x < 0.2), that displays electromechanical properties rivaling those of the best performing electrostrictors: longitudinal electrostriction strain coefficient ~10−16m2/V2; relaxation frequency ≈ a few kHz; and strain ≥0.02%. Combining X-ray absorption spectroscopy, atomic-level modeling and electromechanical measurements, here we show that electrostriction in ZrxCe1-xO2is enabled by elastic dipoles produced by anharmonic motion of the smaller isovalent dopant (Zr). Unlike the elastic dipoles in aliovalent doped ceria, which are present even in the absence of an applied elastic or electric field, the elastic dipoles in ZrxCe1-xO2are formed only under applied anisotropic field. The local descriptors of electrostrictive strain, namely, the cation size mismatch and dynamic anharmonicity, are sufficiently versatile to guide future searches in other polycrystalline solids.  more » « less
Award ID(s):
2312690
PAR ID:
10474179
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ; ;
Publisher / Repository:
Nature Publishing Group
Date Published:
Journal Name:
Nature Communications
Volume:
14
Issue:
1
ISSN:
2041-1723
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Advances in creating polar structures in atomic‐layered hafnia‐zirconia (HfxZr1−xO2) films not only augurs extensive growth in studying ferroelectric nanoelectronics and neuromorphic devices, but also spurs opportunities for exploring novel integrated nanoelectromechanical systems (NEMS). Design and implementation of HfxZr1−xO2NEMS transducers necessitates accurate knowledge of elastic and electromechanical properties. Up to now, all experimental approaches for extraction of morphological content, elastic, and electromechanical properties of HfxZr1−xO2are based on solidly mounted structures, highly stressed films, and electroded architectures. Unlike HfxZr1−xO2layers embedded in electronics, NEMS transducers require free‐standing structures with highly contrasted mechanical boundaries and stress profiles. Here, a nanoresonator‐based approach for simultaneous extraction of Young's modulus and residual stress in free‐standing ferroelectric Hf0.5Zr0.5O2films is presented. High quality factor resonance modes of nanomechanical resonators created in predominantly orthorhombic Hf0.5Zr0.5O2films are measured using nondestructive optical transduction. Further, the evolution of morphology during creation of free‐standing Hf0.5Zr0.5O2structures is closely mapped using X‐ray diffraction measurements, clearly showing transformation of ferroelectric orthorhombic to nonpolar monoclinic phase upon stress relaxation. The extracted Young's modulus of 320.0 ± 29.4 GPa and residual stress ofσ = 577.4 ± 24.1 MPa show the closest match with theoretical calculations for orthorhombic Hf0.5Zr0.5O2
    more » « less
  2. Abstract Next‐generation electronics and energy technologies can now be developed as a result of the design, discovery, and development of novel, environmental friendly lead (Pb)‐free ferroelectric materials with improved characteristics and performance. However, there have only been a few reports of such complex materials’ design with multi‐phase interfacial chemistry, which can facilitate enhanced properties and performance. In this context, herein, novel lead‐free piezoelectric materials (1‐x)Ba0.95Ca0.05Ti0.95Zr0.05O3‐(x)Ba0.95Ca0.05Ti0.95Sn0.05O3, are reported, which are represented as (1‐x)BCZT‐(x)BCST, with demonstrated excellent properties and energy harvesting performance. The (1‐x)BCZT‐(x)BCST materials are synthesized by high‐temperature solid‐state ceramic reaction method by varyingxin the full range (x= 0.00–1.00). In‐depth exploration research is performed on the structural, dielectric, ferroelectric, and electro‐mechanical properties of (1‐x)BCZT‐(x)BCST ceramics. The formation of perovskite structure for all ceramics without the presence of any impurity phases is confirmed by X‐ray diffraction (XRD) analyses, which also reveals that the Ca2+, Zr4+, and Sn4+are well dispersed within the BaTiO3lattice. For all (1‐x)BCZT‐(x)BCST ceramics, thorough investigation of phase formation and phase‐stability using XRD, Rietveld refinement, Raman spectroscopy, high‐resolution transmission electron microscopy (HRTEM), and temperature‐dependent dielectric measurements provide conclusive evidence for the coexistence of orthorhombic + tetragonal (Amm2+P4mm) phases at room temperature. The steady transition ofAmm2crystal symmetry toP4mmcrystal symmetry with increasingxcontent is also demonstrated by Rietveld refinement data and related analyses. The phase transition temperatures, rhombohedral‐orthorhombic (TR‐O), orthorhombic‐ tetragonal (TO‐T), and tetragonal‐cubic (TC), gradually shift toward lower temperature with increasingxcontent. For (1‐x)BCZT‐(x)BCST ceramics, significantly improved dielectric and ferroelectric properties are observed, including relatively high dielectric constantεr≈ 1900–3300 (near room temperature),εr≈ 8800–12 900 (near Curie temperature), dielectric loss, tanδ≈ 0.01–0.02, remanent polarizationPr≈ 9.4–14 µC cm−2, coercive electric fieldEc≈ 2.5–3.6 kV cm−1. Further, high electric field‐induced strainS≈ 0.12–0.175%, piezoelectric charge coefficientd33≈ 296–360 pC N−1, converse piezoelectric coefficient ≈ 240–340 pm V−1, planar electromechanical coupling coefficientkp≈ 0.34–0.45, and electrostrictive coefficient (Q33)avg≈ 0.026–0.038 m4C−2are attained. Output performance with respect to mechanical energy demonstrates that the (0.6)BCZT‐(0.4)BCST composition (x= 0.4) displays better efficiency for generating electrical energy and, thus, the synthesized lead‐free piezoelectric (1‐x)BCZT‐(x)BCST samples are suitable for energy harvesting applications. The results and analyses point to the outcome that the (1‐x)BCZT‐(x)BCST ceramics as a potentially strong contender within the family of Pb‐free piezoelectric materials for future electronics and energy harvesting device technologies. 
    more » « less
  3. Accurate characterization of chemical strain is required to study a broad range of chemical–mechanical coupling phenomena. One of the most studied mechano-chemically active oxides, nonstoichiometric ceria (CeO 2−δ ), has only been described by a scalar chemical strain assuming isotropic deformation. However, combined density functional theory (DFT) calculations and elastic dipole tensor theory reveal that both the short-range bond distortions surrounding an oxygen-vacancy and the long-range chemical strain are anisotropic in cubic CeO 2−δ . The origin of this anisotropy is the charge disproportionation between the four cerium atoms around each oxygen-vacancy (two become Ce 3+ and two become Ce 4+ ) when a neutral oxygen-vacancy is formed. Around the oxygen-vacancy, six of the Ce 3+ –O bonds elongate, one of the Ce 3+ –O bond shorten, and all seven of the Ce 4+ –O bonds shorten. Further, the average and maximum chemical strain values obtained through tensor analysis successfully bound the various experimental data. Lastly, the anisotropic, oxygen-vacancy-elastic-dipole induced chemical strain is polarizable, which provides a physical model for the giant electrostriction recently discovered in doped and non-doped CeO 2−δ . Together, this work highlights the need to consider anisotropic tensors when calculating the chemical strain induced by dilute point defects in all materials, regardless of their symmetry. 
    more » « less
  4. Abstract We report on the structure and dielectric properties of ternary A6B2O17(A = Zr; B = Nb, Ta) thin films and ceramics. Thin films are produced via sputter deposition from dense, phase‐homogenous bulk ceramic targets, which are synthesized through a reactive sintering process at 1500°C. Crystal structure, microstructure, chemistry, and dielectric properties are characterized by X‐ray diffraction and reflectivity, atomic force microscopy, X‐ray photoelectron spectroscopy, and capacitance analysis, respectively. We observe relative permittivities approaching 60 and loss tangents <1 × 10−2across the 103–105 Hz frequency range in the Zr6Nb2O17and Zr6Ta2O17phases. These observations create an opportunity space for this novel class of disordered oxide electroceramics. 
    more » « less
  5. Abstract A traditional composite cathode for proton‐conducting solid oxide fuel cells (H‐SOFCs) is typically obtained by mixing cathode materials and proton conducting electrolyte of BaCe0.7Y0.2Zr0.1O3–δ(BZCY), providing chemical and thermal compatibility with the electrolyte. Here, a series of triple‐conducing and cobalt‐free iron‐based perovskites as cathodes for H‐SOFCs is reported. Specifically, BaCexFe1–xO3–δ(x = 0.36, 0.43, and 0.50) shows various contents of two single phase perovskites with an in situ heterojunction structure as well as triple conductivity by tailoring the Ce/Fe ratios. The cell performance with the optimized BaCe0.36Fe0.64O3–δ(BCF36) cathode composition reaches 1056 mW cm−2at 700 °C. Moreover, a record cell performance of 1525 mW cm−2at 700 °C is obtained by modifying the BCF36 cathode microstructure through a spraying method, demonstrating high promise with Co‐free cathodes for H‐SOFCs. 
    more » « less