Julian Walker

Domain-wall conduction in ferroelectric BiFeO3 controlled by accumulation of charged defects

Mobile charged defects, accumulated in the domain-wall region to screen polarization charges, have been proposed as the origin of the electrical conductivity at domain walls in ferroelectric materials. Despite theoretical and experimental efforts, this scenario has not been directly confirmed, leaving a gap in the understanding of the intriguing electrical properties of domain walls. Here, we provide atomic-scale chemical and structural analyses showing the accumulation of charged defects at domain walls in BiFeO3. The defects were identified as Fe4+ cations and bismuth vacancies, revealing p-type hopping conduction at domain walls caused by the presence of electron holes associated with Fe4+. In agreement with the p-type behaviour, we further show that the local domain-wall conductivity can be tailored by controlling the atmosphere during high-temperature annealing. This work has possible implications for engineering local conductivity in ferroelectrics and for devices based on domain walls.

Dual strain mechanisms in a lead-free morphotropic phase boundary ferroelectric

Electromechanical properties such as d33 and strain are significantly enhanced at morphotropic phase boundaries (MPBs) between two or more different crystal structures. Many actuators, sensors and MEMS devices are therefore systems with MPBs, usually between polar phases in lead (Pb)-based ferroelectric ceramics. In the search for Pb-free alternatives, systems with MPBs between polar and non-polar phases have recently been theorized as having great promise. While such an MPB was identified in rare-earth (RE) modified bismuth ferrite (BFO) thin films, synthesis challenges have prevented its realization in ceramics. Overcoming these, we demonstrate a comparable electromechanical response to Pb-based materials at the polar-to-non-polar MPB in Sm modified BFO. This arises from ‘dual’ strain mechanisms: ferroelectric/ferroelastic switching and a previously unreported electric-field induced transition of an anti-polar intermediate phase. We show that intermediate phases play an important role in the macroscopic strain response, and may have potential to enhance electromechanical properties at polar-to-non-polar MPBs.

Temperature dependent piezoelectric response and strain–electric-field hysteresis of rare-earth modified bismuth ferrite ceramics

The rare-earth (RE)-modified bismuth ferrite (BiFeO3 or BFO) family of ferroelectrics have uncomplicated lead-free chemistries and simple perovskite structures. Due to the high Curie transition temperature of the parent BiFeO3 perovskite (∼830 °C), they are promising piezoelectric materials for use at elevated temperatures. However, the influence of the specific RE species on the electromechanical behavior at high temperatures and above the coercive electric-field is not widely reported. Here, structural analysis over multiple length scales using X-ray diffraction, transmission electron microscopy and piezoresponse force microscopy is coupled with a high electric-field cycling study and in situ converse d33 measurements up to 325 °C for three RE–BFO ceramic compositions, Bi0.86Sm0.14FeO3, Bi0.88Gd0.12FeO3 and Bi0.91Dy0.09FeO3. The ceramics exhibit different phase assemblages with varying amounts of polar rhombohedral R3c and intermediate antipolar orthorhombic Pbam phases as a function of the RE species. During electric-field cycling at electric-fields with amplitudes of 160 kV cm−1, peak-to-peak strains of 0.23–0.27% are reached for all three compositions. However, there are qualitative differences in the field-induced strain and electric current behavior as a function of electric-field cycling and the materials exhibit an electrical-history dependent behavior. Bi0.91Dy0.09FeO3 possesses an improved d33 stability as a function of temperature relative to the parent BFO perovskite and the highest depolarization temperature among the three RE–BFO compositions, with a stable d33 of ∼22 pC N−1 up to 325 °C.

Piezoelectric response of BiFeO3 ceramics at elevated temperatures

The high Curie temperature (TC ∼ 825 °C) of BiFeO3 has made this material potentially attractive for the development of high-TC piezoelectric ceramics. Despite significant advances in the search of new BiFeO3-based compositions, the piezoelectric behavior of the parent BiFeO3 at elevated temperatures remains unexplored. We present here a systematic analysis of the converse, longitudinal piezoelectric response of BiFeO3 measured in situ as a function of temperature (25–260 °C), driving-field frequency, and amplitude. Earlier studies performed at room temperature revealed that the frequency and field dependence of the longitudinal response of BiFeO3 is dominated by linear and nonlinear piezoelectric Maxwell-Wagner mechanisms, originating from the presence of local conductive paths along domain walls and grain boundaries within the polycrystalline matrix. This study shows that the same mechanisms are responsible for the distinct temperature dependence of the piezoelectric coefficient and phase angle and thus...

Dielectric relaxation and charged domain walls in (K,Na)NbO3-based ferroelectric ceramics

The influence of domain walls on the macroscopic properties of ferroelectric materials is a well known phenomenon. Commonly, such “extrinsic” contributions to dielectric permittivity are discussed in terms of domain wall displacements under external electric field. In this work, we report on a possible contribution of charged domain walls to low frequency (10–106 Hz) dielectric permittivity in K1-xNaxNbO3 ferroelectric ceramics. It is shown that the effective dielectric response increases with increasing domain wall density. The effect has been attributed to the Maxwell-Wagner-Sillars relaxation. The obtained results may open up possibilities for domain wall engineering in various ferroelectric materials.

Quantitative phase separation in multiferroic Bi0.88Sm0.12FeO3 ceramics via piezoresponse force microscopy

BiFeO3 (BFO) is a classical multiferroic material with both ferroelectric and magnetic ordering at room temperature. Doping of this material with rare-earth oxides was found to be an efficient way to enhance the otherwise low piezoelectric response of unmodified BFO ceramics. In this work, we studied two types of bulk Sm-modified BFO ceramics with compositions close to the morphotropic phase boundary (MPB) prepared by different solid-state processing methods. In both samples, coexistence of polar R3c and antipolar Pbam phases was detected by conventional X-ray diffraction (XRD); the non-polar Pnma or Pbnm phase also has potential to be present due to the compositional proximity to the polar-to-non-polar phase boundary. Two approaches to separate the phases based on the piezoresponse force microscopy measurements have been proposed. The obtained fractions of the polar and non-polar/anti-polar phases were close to those determined by quantitative XRD analysis. The results thus reveal a useful method for qua...

Solid-state reaction in Pd/ZnSe thin film contacts

We report on solid‐state reactions in Pd thin film contacts on ZnSe at temperatures below 500 °C. We found that a solid‐state reaction was initiated at the Pd/ZnSe interface by thermal annealing at 200 °C. A tetragonal ternary phase, Pd5+xZnSe, consisting of highly oriented grains was formed as a result of this reaction. This phase is found to be stable up to an annealing temperature of 400 °C. The crystallography and morphology of this ternary Pd–ZnSe phase was studied by x‐ray diffraction and transmission electron microscopy and has similarities to the analogous ternary Pd–GaAs phase formed in the Pd/GaAs contact structure. The Pd/ZnSe interface is found to be thermally more stable than the corresponding Pd/GaAs and Pd/Si structures. Comparisons are made between the systematics of Pd/semiconductor interfacial phenomena on the three semiconductors.

Lynx Mission concept status

Lynx is a concept under study for prioritization in the 2020 Astrophysics Decadal Survey. Providing orders of magnitude increase in sensitivity over Chandra, Lynx will examine the first black holes and their galaxies, map the large-scale structure and galactic halos, and shed new light on the environments of young stars and their planetary systems. In order to meet the Lynx science goals, the telescope consists of a high-angular resolution optical assembly complemented by an instrument suite that may include a High Definition X-ray Imager, X-ray Microcalorimeter and an X-ray Grating Spectrometer. The telescope is integrated onto the spacecraft to form a comprehensive observatory concept. Progress on the formulation of the Lynx telescope and observatory configuration is reported in this paper.

Failure of the threaded region of rockbolts in underground coal mines

Abstract HSAC 840 steel rockbolts were examined, all of which had failed in service through the threaded region exterior to the rock face by brittle fracture transverse to the bolt axis. The bolts had been in service in an Australian coal mine in which the groundwater had a pH of 7·5–8·5 and a relatively high bicarbonate level of 515–2200 mg l−1. All failures had occurred within the region comprising the domed washer and the end plate. The majority of the bolts showed a small thumbnail-shaped discoloured region 1.5-4.5 mm in length at the fracture origin, as is characteristic of stress corrosion cracking (SCC) in rockbolts. In half of these bolts, SCC had initiated immediately at the root of the thread, but in the other half of the bolts, SCC had initiated from a small pre-existing crack that had been produced in the thread as a result of a prior bending load.

Design and fabrication of adjustable x-ray optics using piezoelectric thin films

Piezoelectric adjustable optics are being developed for high throughput, high resolution, low mass Xray mirror assemblies. These optics require robust piezoelectric thin films and reproducible lithographic patterning on curved glass substrates. This work details the cleaning of Corning Eagle XG glass substrates for thin shell X-ray mirrors by a three stage acid and solvent cleaning procedure before a 0.02 μm Ti adhesion layer and a 0.1 μm Pt bottom electrode layer was deposited using DC magnetron sputtering. Piezoelectric Pb(Zr0.52Ti0.48)0.99Nb0.01O3 thin films with a thickness of 1.5 μm were then deposited by radio frequency magnetron sputtering in three 0.5 µm layers with intermittent annealing steps in a rapid thermal annealing furnace at 650°C for 60 seconds. Defects observed in the piezoelectric thin films were linked to residue remaining on the glass after cleaning. 112 piezoelectric cells and 100 μm wide conductive Pt traces were patterned using bilayer photolithography. The photoresist layers were deposited using spin coating at 2000 and 4000 RPM to achieve uniform 1 μm thick layers, resulting in reproducibly resolved features with limiting resolutions of approximately >25 μm. The resulting mirror pieces achieved a 100% yield, with average relative permittivity of 1270, dielectric loss 0.047, coercive field 30 kV/cm and remanent polarization of 20 μC/cm2 . While the defects observed in the films appeared to have not influence on the electrical properties, additional cleaning steps using DI water were proposed to further reduce their presence.