Ferroelectric-Ferroelastic Transitions in (Na0.5Bi0.5)TiO3-BaTiO3 Single Crystals.

The comprehensive understanding of (Na0.5Bi0.5)TiO3-BaTiO3 (NBT-BT) lattice structure is highly desired to develop lead-free ferroelectric materials. However, most of the previous studies focused on the improvement of piezoelectric properties at room temperature, and many structural puzzles are left unclear. In this work, the lattice structure of a ferroelastic phase and the ferroelectric-ferroelastic transitions in both rhombohedral NBT and tetragonal NBT-8%BT single crystals are investigated in detail. Our results illustrate the complex process of the ferroelectric-ferroelastic transition of NBT. The variation of Ti-O modes and oxygen octahedra modes clearly indicates the gradual change of lattice symmetry from R3c to P4bm during a wide temperature range between 170 and 350 °C. A ferroelectric-ferroelastic transition is also confirmed in tetragonal NBT-8BT for the first time, and the lattice symmetry of P4bm is found to be maintained during the ferroelastic stage. This work reveals the lattice evolutions of the ferroelectric-ferroelastic transition of NBT-BT crystals and provides new insights for understanding the ferroelasticity and the evolution of phonon modes in a lead-free relaxor.

Formation of Head/Tail-to-Body Charged Domain Walls by Mechanical Stress.

Domain walls (DWs) in ferroelectric materials are interfaces that separate domains with different polarizations. Charged domain walls (CDWs) and neutral domain walls are commonly classified depending on the charge state at the DWs. CDWs are particularly attractive as they are configurable elements, which can enhance field susceptibility and enable functionalities such as conductance control. However, it is difficult to achieve CDWs in practice. Here, we demonstrate that applying mechanical stress is a robust and reproducible approach to generate CDWs. By mechanical compression, CDWs with a head/tail-to-body configuration were introduced in ultrathin BaTiO3, which was revealed by in-situ transmission electron microscopy. Finite element analysis shows strong strain fluctuation in ultrathin BaTiO3 under compressive mechanical stress. Molecular dynamics simulations suggest that the strain fluctuation is a critical factor in forming CDWs. This study provides insight into ferroelectric DWs and opens a pathway to creating CDWs in ferroelectric materials.

Giant electric field-induced strain in lead-free piezoceramics.

Piezoelectric actuators are indispensable over a wide range of industries for their fast response and precise displacement. Most commercial piezoelectric actuators contain lead, posing environmental challenges. We show that a giant strain (1.05%) and a large-signal piezoelectric strain coefficient (2100 picometer/volt) are achieved in strontium (Sr)-doped (K,Na)NbO3 lead-free piezoceramics, being synthesized by the conventional solid-state reaction method without any post treatment. The underlying mechanism responsible for the ultrahigh electrostrain is the interaction between defect dipoles and domain switching. The fatigue resistance, thermal stability, and strain value (0.25%) at 20 kilovolt/centimeter are comparable with or better than those of commercial Pb(Zr,Ti)O3-based ceramics, showing great potential for practical applications. This material may provide a lead-free alternative with a simple composition for piezoelectric actuators and a paradigm for the design of high-performance piezoelectrics.

A very low frequency (VLF) antenna based on clamped bending-mode structure magnetoelectric laminates.

As the development of wireless communication devices tends to be highly integrated, the miniaturization of very low frequency (VLF) antenna units has always been an unresolved issue. Here, a novel VLF mechanical communication antenna using magnetoelectric (ME) laminates with bending-mode structure is realized. ME laminates combines magnetostrictive Metglas amorphous ribbons and piezoelectric 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3single crystal plates. From the simulation, we confirmed that the ME laminates can reduce the resonance peak from 18 kHz to 7.5 kHz by bending-mode structure. Experiment results show the resonance frequency can be farther reduced to 6.3 kHz by clamping one end of the ME antenna. The ME laminate exhibits a giant converse ME coefficient of 6 Oe cm V-1at 6.3 kHz. The magnetic flux density generated by the ME antenna has been tested along with distance ranging from 0 to 60 cm and it is estimated that a 1 fT flux could be detected around 100 m with an excitation power of 10 mW.

Power Batteries Health Monitoring: A Magnetic Imaging Method Based on Magnetoelectric Sensors.

With the popularity of electric vehicles, the ever-increasing demand for high-capacity batteries highlights the need for monitoring the health status of batteries. In this article, we proposed a magnetic imaging technique (MIT) to investigate the health status of power batteries nondestructively. This technique is based on a magnetic sensor array, which consists of a 16-channel high-performance magnetoelectric sensor, and the noise equivalent magnetic induction (NEB) of each channel reaches 3-5 pT/Hz1/2@10 Hz. The distribution of the magnetic field is imaged by scanning the magnetic field variation of different positions on the surface. Therefore, the areas of magnetic anomalies are identified by distinguishing different magnetic field abnormal results. and it may be possible to classify the battery failure, so as to put forward suggestions on the use of the battery. This magnetic imaging method expands the application field of this high-performance magnetoelectric sensor and contributes to the battery's safety monitoring. Meanwhile, it may also act as an important role in other nondestructive testing fields.

Optimization of Ferroelectric Ordering and Thermal Stability in Na1/2Bi1/2TiO3-Based Lead-Free Single Crystal through Defect Engineering.

Environmentally friendly lead-free piezoelectric materials have been attracting significant attention in recent years. Na1/2Bi1/2TiO3-based relaxor ferroelectrics have found acceptance for application in promising lead-free transducers in high-power ultrasonic devices. However, their low thermal stability, i.e., their relatively low ferroelectric-relaxor transition temperature (TF-R), hinders their practical application. Herein, a thermal-quenching approach is applied on a Na1/2Bi1/2TiO3 (NBT)-based single crystal, which yields a large increase in TF-R and dramatic enhancement of its ferroelectric ordering, leading to excellent thermal stability of its dielectric, ferroelectric, and piezoelectric properties. This behavior is mainly attributed to quenching-induced domain evolution as well as its octahedral tilt, which is linked to the increased oxygen vacancies. The substitution of long-range ordered ferroelectric domains for short-range polar nanodomains contributes to its increased coherence length and, consequently, enhancement of TF-R. This work provides an approach to the optimization of the ferroelectric ordering and thermal stability of NBT as well as an in-depth understanding of the quenching effect on the local structure, which could be applied to other relaxor-based ferroelectrics for optimization of their macroscopic properties.

Reporting Excellent Transverse Piezoelectric and Electro-Optic Effects in Transparent Rhombohedral PMN-PT Single Crystal by Engineered Domains.

Transparent ferroelectric crystals with high piezoelectricity are challenging to build because of their complex structure and disordered domains in rhombohedral relaxor ferroelectrics. There are eight domains along the <111> direction, which cause light scattering. In this study, perfect transparency is achieved along the [110] and [001] directions in [110]-poled rhombohedral 0.72Pb(Mg1/3 Nb2/3 )O3 -0.28PbTiO3 (PMN-PT) crystals, which have a high d31 value of 1700 pC N-1 and a high electro-optic coefficient γ33 of 320 pm V-1 . This implies that the [110]-oriented rhombohedral PMN-0.28PT crystal can realize the mode of transverse modulation, whereas the [001]-oriented PMN-0.28PT crystal is more suitable for the longitudinal mode. Through piezoresponse force microscopy (PFM), it is confirmed that the [110]-poled rhombohedral PMN-PT crystals form 71° layered domains, which are similar to the 109° layered domains of the [001]-oriented transparent crystal. Combined with PFM and birefringence microscopy, the degradation of domains and thickness dependence of piezoelectricity provide clear evidence for the relationship between the engineered domain structures and piezoelectric properties, which should be considered in the design of piezoelectric or electro-optic devices with excellent performance. This work enriches the research on ferroelectric domain engineering for excellent transparency and high piezoelectricity to provide new ideas for photoacoustic devices.

Manipulating ferroelectric behaviors via electron-beam induced crystalline defects.

Ferroelectric nanoplates are attractive for applications in nanoelectronic devices. Defect engineering has been an effective way to control and manipulate ferroelectric properties in nanoscale devices. Defects can act as pinning centers for ferroelectric domain wall motion, altering the switching properties and domain dynamics of ferroelectrics. However, there is a lack of detailed investigation on the interactions between defects and domain walls in ferroelectric nanoplates due to the limitation of previous characterization techniques, which impedes the development of defect engineering in ferroelectric nanodevices. In this study, we applied in situ biasing transmission electron microscopy to explore how dislocation loops, which were judiciously introduced into barium titanate nanoplates via electron beam irradiation, affect the motion of ferroelectric domain walls. The results show that the motion was dramatically suppressed by these localized defects, because of the local strain fields induced by the defects. The pinning effect can be further enhanced by multiple domain walls embedded with defect arrays. These results indicate the possibility of manipulating domain switching in ferroelectric nanoplates via the electron beam.

Search for Axionlike Dark Matter Using Solid-State Nuclear Magnetic Resonance.

We report the results of an experimental search for ultralight axionlike dark matter in the mass range 162-166 neV. The detection scheme of our Cosmic Axion Spin Precession Experiment is based on a precision measurement of ^{207}Pb solid-state nuclear magnetic resonance in a polarized ferroelectric crystal. Axionlike dark matter can exert an oscillating torque on ^{207}Pb nuclear spins via the electric dipole moment coupling g_{d} or via the gradient coupling g_{aNN}. We calibrate the detector and characterize the excitation spectrum and relaxation parameters of the nuclear spin ensemble with pulsed magnetic resonance measurements in a 4.4 T magnetic field. We sweep the magnetic field near this value and search for axionlike dark matter with Compton frequency within a 1 MHz band centered at 39.65 MHz. Our measurements place the upper bounds |g_{d}|<9.5×10^{-4} GeV^{-2} and |g_{aNN}|<2.8×10^{-1} GeV^{-1} (95% confidence level) in this frequency range. The constraint on g_{d} corresponds to an upper bound of 1.0×10^{-21} e cm on the amplitude of oscillations of the neutron electric dipole moment and 4.3×10^{-6} on the amplitude of oscillations of CP-violating θ parameter of quantum chromodynamics. Our results demonstrate the feasibility of using solid-state nuclear magnetic resonance to search for axionlike dark matter in the neV mass range.

Direct observation of nanoscale dynamics of ferroelectric degradation.

Failure of polarization reversal, i.e., ferroelectric degradation, induced by cyclic electric loadings in ferroelectric materials, has been a long-standing challenge that negatively impacts the application of ferroelectrics in devices where reliability is critical. It is generally believed that space charges or injected charges dominate the ferroelectric degradation. However, the physics behind the phenomenon remains unclear. Here, using in-situ biasing transmission electron microscopy, we discover change of charge distribution in thin ferroelectrics during cyclic electric loadings. Charge accumulation at domain walls is the main reason of the formation of c domains, which are less responsive to the applied electric field. The rapid growth of the frozen c domains leads to the ferroelectric degradation. This finding gives insights into the nature of ferroelectric degradation in nanodevices, and reveals the role of the injected charges in polarization reversal.

Giant tuning of ferroelectricity in single crystals by thickness engineering.

Thickness effect and mechanical tuning behavior such as strain engineering in thin-film ferroelectrics have been extensively studied and widely used to tailor the ferroelectric properties. However, this is never the case in freestanding single crystals, and conclusions from thin films cannot be duplicated because of the differences in the nature and boundary conditions of the thin-film and freestanding single-crystal ferroelectrics. Here, using in situ biasing transmission electron microscopy, we studied the thickness-dependent domain switching behavior and predicted the trend of ferroelectricity in nanoscale materials induced by surface strain. We discovered that sample thickness plays a critical role in tailoring the domain switching behavior and ferroelectric properties of single-crystal ferroelectrics, arising from the huge surface strain and the resulting surface reconstruction. Our results provide important insights in tuning polarization/domain of single-crystal ferroelectric via sample thickness engineering.

A Two-Step Annealing Method to Enhance the Pyroelectric Properties of Mn:PIMNT Chips for Infrared Detectors.

Mn:0.15Pb(In1/2Nb1/2)O3-0.55Pb(Mg1/3Nb2/3)O3-0.30PbTiO3 (Mn:PIMNT) pyroelectric chips were prepared by a two-step annealing method. For the two steps, annealing temperatures dependence of microstructure, defects, surface stress, surface roughness, dielectric properties and pyroelectric properties were studied comprehensively. The controlling factors influencing the pyroelectric properties of the Mn:PIMNT crystals were analyzed and the optimum annealing temperature ranges for the two steps were determined: 600-700 °C for the first step and 500-600 °C for the second step. The pyroelectric properties of the thin Mn:PIMNT chips were significantly enhanced by the two-step annealing method via tuning oxygen vacancies and eliminating surface stress. Based on Mn:PIMNT pyroelectric chips annealed at the most favorable conditions (annealed at 600 °C for the first step and 500 °C for the second step), infrared detectors were prepared with specific detectivity D* = 1.63 × 109 cmHz1/2W-1, nearly three times higher than in commercial LiTaO3 detectors.

FEM simulation and comparison of PMN-PT single crystals based phased array ultrasonic transducer by alternating current poling and direct current poling.

The Finite element modeling (FEM) simulation and comparison of electroacoustic properties for alternating current poling (ACP) phased arrays and direct current poling (DCP) phased arrays were investigated. The simulated electrical impedance reveals that the effective working bandwidth of ACP phased arrays is wider than that of DCP phased arrays as a whole. Besides, the ACP phased arrays have a higher effective electromechanical coupling coefficient keff compared to DCP arrays, which indicates that higher electromechanical conversion capacity is obtained. The average value of the ratio of longitudinal displacement Rdisp for ACP phased arrays is larger than that of DCP arrays, indicating that the longitudinal transmission efficiency of acoustic energy can be enhanced by using the ACP method. The simulation results of crosstalk are consistent with the results of vibration modal analysis. The coupling effect of transverse vibration for ACP phased arrays is weaker than that of DCP arrays, leading to reduce the interaction between the adjacent elements. The crosstalk of the ACP arrays is -11.87 dB, 0.91 dB lower than that of DCP arrays. The pulse-echo response of ACP phased arrays is 7.2% broader -6 dB bandwidth, 0.79 dB higher relative sensitivity compared to the DCP phased arrays, which prove that the longitudinal resolution and penetration depth of the ultrasonic imaging can be improved by using the ACP arrays. Besides, the consequences of the beam profile illustrate that the maximum acoustic pressure of ACP arrays is 13.8% higher than that of DCP arrays and the directivity of ACP array is slightly better than that of DCP arrays.

Giant tunability of upconversion photoluminescence in Er3+-doped (K, Na)NbO3 single crystals.

Perovskite oxides with luminescent ions hold great promise in optoelectronic devices because of their outstanding thermal stabilities and electro-optic performance. As one typical perovskite upconversion (UC) host material, lead-free potassium sodium niobate ((K, Na)NbO3/(KxNa1-x)NbO3 or KNN) has attracted much attention in recent years. In the present work, a novel routine was developed to tune the upconversion photoluminescence (UC PL) performance by controlling the oxygen vacancy concentration in the KNN matrix, based on the 0.1% Er3+-doped KNN (Er-KNN) single crystals grown for the first time. UC PL properties, conductivity and defect chemistry of the single crystals were systematically investigated. The UC PL intensity of the as-grown Er-KNN material could be enhanced by 20 times after oxygen atmosphere annealing at 800 °C and fully quenched after vacuum annealing. What's more, by annealing under an oxygen atmosphere and vacuum, the conductivity of the Er-KNN sample was successfully tuned for more than 8 orders of magnitude. The super-wide range tunability of UC PL performance and conductivity could be explained by oxygen vacancies which gave rise to Nb5+-Nb4+ valence alternation. Because of the modulated photoluminescence properties and conductivity, our grown Er-KNN single crystals have great potential for use in multifunctional devices.

Nonvolatile Control of the Electronic Properties of In2-xCrxO3 Semiconductor Films by Ferroelectric Polarization Charge.

A series of Cr-doped In2-xCrxO3 (ICO) semiconductor thin films were epitaxially grown on (111)-oriented 0.71Pb(Mg1/3Nb2/3)O3-0.29PbTiO3 (PMN-0.29PT) single-crystal substrates by the pulsed laser deposition. Upon the application of an electric field to the PMN-0.29PT substrate along the thickness direction, we realized in situ, reversible, and nonvolatile control of the electronic properties and Fermi level of the films, which are manifested by abundant physical phenomena such as the n-type to p-type transformation, metal-semiconductor transition, metal-insulator transition, crossover of the magnetoresistance (MR) from negative to positive, and a large nonvolatile on-and-off ratio of 5.5 × 104% at room temperature. We also strictly disclose that both the sign and the magnitude of MR are determined by the electron carrier density of ICO films, which could modify the s-d exchange interaction and weak localization effect. Our results demonstrate that the ferroelectric gating approach using PMN-PT can be utilized to gain deeper insight into the carrier-density-related electronic properties of In2O3-based semiconductors and provide a simple and energy efficient way to construct multifunctional devices which can utilize the unique properties of composite materials.

Comment on "Giant electromechanical coupling of relaxor ferroelectrics controlled by polar nanoregion vibrations".

Manley et al. (Science Advances, 16 September 2016, p. e1501814) report the splitting of a transverse acoustic phonon branch below T C in the relaxor ferroelectric Pb[(Mg1/3Nb2/3)1-x Ti x ]O3 with x = 0.30 using neutron scattering methods. Manley et al. argue that this splitting occurs because these phonons hybridize with local, harmonic lattice vibrations associated with polar nanoregions. We show that splitting is absent when the measurement is made using a different neutron wavelength, and we suggest an alternative interpretation.

Nonvolatile and Reversible Ferroelectric Control of Electronic Properties of Bi2Te3 Topological Insulator Thin Films Grown on Pb(Mg1/3Nb2/3)O3-PbTiO3 Single Crystals.

Single-phase (00 l)-oriented Bi2Te3 topological insulator thin films have been deposited on (111)-oriented ferroelectric 0.71Pb(Mg1/3Nb2/3)O3-0.29PbTiO3 (PMN-PT) single-crystal substrates. Taking advantage of the nonvolatile polarization charges induced by the polarization direction switching of PMN-PT substrates at room temperature, the carrier density, Fermi level, magnetoconductance, conductance channel, phase coherence length, and quantum corrections to the conductance can be in situ modulated in a reversible and nonvolatile manner. Specifically, upon the polarization switching from the positively poled Pr+ state (i.e., polarization direction points to the film) to the negatively poled Pr- (i.e., polarization direction points to the bottom electrode) state, both the electron carrier density and the Fermi wave vector decrease significantly, reflecting a shift of the Fermi level toward the Dirac point. The polarization switching from Pr+ to Pr- also results in significant increase of the conductance channel α from -0.15 to -0.3 and a decrease of the phase coherence length from 200 to 80 nm at T = 2 K as well as a reduction of the electron-electron interaction. All these results demonstrate that electric-voltage control of physical properties using PMN-PT as both substrates and gating materials provides a simple and a straightforward approach to realize reversible and nonvolatile tuning of electronic properties of topological thin films and may be further extended to study carrier density-related quantum transport properties of other quantum matter.

Integration of Oxide Semiconductor Thin Films with Relaxor-Based Ferroelectric Single Crystals with Large Reversible and Nonvolatile Modulation of Electronic Properties.

We report the fabrication of 0.71Pb(Mg1/3Nb2/3)O3-0.29PbTiO3 (PMN-0.29PT)-based ferroelectric field effect transistors (FeFETs) by the epitaxial growth of cobalt-doped tin dioxide (SnO2) semiconductor thin films on PMN-0.29PT single crystals. Using such FeFETs we realized in situ, reversible, and nonvolatile manipulation of the electron carrier density and achieved a large nonvolatile modulation of the resistance (∼330%) of the SnO2:Co films through the polarization switching of PMN-0.29PT at 300 K. Particularly, combining the ferroelectric gating with piezoresponse force microscopy, X-ray diffraction, Hall effect, and magnetoresistance (MR), we rigorously disclose that both sign and magnitude of the MR are intrinsically determined by the electron carrier density, which could modify the s-d exchange interaction of the SnO2:Co films. Furthermore, we realized multilevel resistance states of the SnO2:Co films by combining the ferroelectric gating with ultraviolet light illumination, demonstrating that the FeFETs have potential applications in multistate resistive memories and electro-optical devices.

Acoustic Anomalies and Phase Transition Behaviors of Lead-Free Piezoelectric (Na1/2Bi1/2)TiO3-xBaTiO3 Single Crystals as Revealed by Brillouin Light Scattering.

The elastic properties of unpoled and prepoled (Na1/2Bi1/2)TiO3-xBaTiO3 (NBT-xBT) single crystals near the morphotropic phase boundary were investigated as a function of temperature using Brillouin light scattering. The acoustic mode frequency and the related acoustic damping of unpoled NBT-xBT showed very broad minimum and maximum, respectively, consistent with typical relaxor behaviors. The frequency softening of the longitudinal acoustic mode together with the increase in acoustic damping was largest along the <100> direction, indicating that polarization fluctuations were most substantial along this crystallographic direction. The difference in acoustic behaviors between the unpoled NBT-xBTs with x = 0.05 and 0.08 were negligible, which means that the NBT-xBT system exhibits typical relaxor properties over a certain composition range of at least 5~8%. The obtained relaxation time of polar nanoregions in the paraelectric phase showed a gradual slowing-down character without any critical divergent behavior. The prepoling of NBT-xBT along the <100> direction induced drastic changes in both mode frequency and damping at ~110 °C when the poling field was larger than 1.4 kV/mm, corresponding to the depoling process from macroscopic/mesoscopic ferroelectric order to ergodic relaxor state upon heating. Phase coexistence of ferroelectric and relaxor states was observed at the intermediate poling field of 1.4 kV/mm.