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At least 55 records · Page 3

High temperature sensor/microphone development for active noise control

The industrial and scientific communities have shown genuine interest in electronic systems which can operate at high temperatures, among which are sensors to monitor noise, vibration, and acoustic emissions. Acoustic sensing can be accomplished by a wide variety of commercially available devices, including: simple piezoelectric sensors, accelerometers, strain gauges, proximity sensors, and fiber optics. Of the several sensing mechanisms investigated, piezoelectrics were found to be the most prevalent, because of their simplicity of design and application and, because of their high sensitivity over broad ranges of frequencies and temperature. Numerous piezoelectric materials are used in acoustic sensors today; but maximum use temperatures are imposed by their transition temperatures (T(sub c)) and by their resistivity. Lithium niobate, in single crystal form, has the highest operating temperature of any commercially available material, 650 C; but that is not high enough for future requirements. Only two piezoelectric materials show potential for use at 1000 C; AlN thin film reported to be piezoactive at 1150 C, and perovskite layer structure (PLS) materials, which possess among the highest T(sub c) (greater than 1500 C) reported for ferroelectrics. A ceramic PLS composition was chosen. The solid solution composition, 80% strontium niobate (SN) and 20% strontium tantalate (STa), with a T(sub c) approximately 1160 C, was hot forged, a process which concurrently sinters and renders the plate-like grains into a highly oriented configuration to enhance piezo properties. Poled samples of this composition showed coupling (k33) approximately 6 and piezoelectric strain constant (d33) approximately 3. Piezoactivity was seen at 1125 C, the highest temperature measurement reported for a ferroelectric ceramic. The high temperature piezoelectric responses of this, and similar PLS materials, opens the possibility of their use in electronic devices operating at temperatures up to 1000 C. Concurrent with the materials study was an effort to define issues involved in the development of a microphone capable of operation at temperatures up to 1000 C; important since microphones capable of operation above 260 C are not generally available. The distinguishing feature of a microphone is its diaphragm which receives sound from the atmosphere: whereas, most other acoustic sensors receive sound through the solid structure on which they are installed. In order to gain an understanding of the potential problems involved in designing and testing a high temperature microphone, a prototype was constructed using a commercially available lithium niobate piezoelectric element in a stainless steel structure. The prototype showed excellent frequency response at room temperature, and responded to acoustic stimulation at 670 C, above which temperature the voltage output rapidly diminished because of decreased resistivity in the element. Samples of the PLS material were also evaluated in a simulated microphone configuration, but their voltage output was found to be a few mV compared to the 10 output of the prototype.

Shrout, Thomas R.↗

Constructing Polymorphic Nanodomains in BaTiO 3 Films via Epitaxial Symmetry Engineering

Ferroelectric materials owning a polymorphic nanodomain structure usually exhibit colossal susceptibilities to external mechanical, electrical, and thermal stimuli, thus holding huge potential for relevant applications. Despite the success of traditional strategies by means of complex composition design, alternative simple methods such as strain engineering have been intensively sought to achieve a polymorphic nanodomain state in lead-free, simple-composition ferroelectric oxides in recent years. Here, a nanodomain configuration with morphed structural phases is realized in an epitaxial BaTiO3 film grown on a (111)-oriented SrTiO3 substrate. Using a combination of experimental and theoretical approaches, it is revealed that a threefold rotational symmetry element enforced by the epitaxial constraint along the [111] direction of BaTiO3 introduces considerable instability among intrinsic tetragonal, orthorhombic, and rhombohedral phases. Such phase degeneracy induces ultrafine ferroelectric nanodomains (1-10 nm) with low-angle domain walls, which exhibit significantly enhanced dielectric and piezoelectric responses compared to the (001)-oriented BaTiO3 film with uniaxial ferroelectricity. Therefore, the finding highlights the important role of epitaxial symmetry in domain engineering of oxide ferroelectrics and facilitates the development of dielectric capacitors and piezoelectric devices.

36 MATERIALS SCIENCE↗

Giant piezoelectricity in oxide thin films with nanopillar structure

High-performance piezoelectric materials are critical components for electromechanical sensors and actuators. For more than 60 years, the main strategy for obtaining large piezoelectric response has been to construct multiphase boundaries, where nanoscale domains with local structural and polar heterogeneity are formed, by tuning complex chemical compositions. We used a different strategy to emulate such local heterogeneity by forming nanopillar regions in perovskite oxide thin films. We obtained a giant effective piezoelectric coefficient d 33 , f * of ~1098 picometers per volt with a high Curie temperature of ~450°C. Our lead-free composition of sodium-deficient sodium niobate contains only three elements (Na, Nb, and O). The formation of local heterogeneity with nanopillars in the perovskite structure could be the basis for a general approach to designing and optimizing various functional materials.

Science & Technology - Other Topics↗

Simulating the non-monotonic strain response of nanoporous multiferroic composites under electric field control

In this work, we simulate and analyze the mechanical response of a class of multiferroic materials consisting of a templated porous nanostructure made out of cobalt ferrite (CFO) partially filled by atomic layer deposition (ALD) with a ferroelectric phase of lead zirconate titanate (PZT). The strain in the device is measured when an electric field is applied for varying ALD thicknesses, displaying a non-monotonic dependence with a maximum strain achieved for a coating thickness of 3 nm. To understand this behavior, we apply finite element modeling to the smallest repeatable unit of the nanoporous template and simulate the mechanical response as a function of PZT coating thickness. We find that this non-monotonic response is caused by the interplay between two driving forces opposing one another. First, increased porosity works toward increasing the strain due to a reduced system stiffness. Second, decreased porosity involves a larger mass fraction of PZT, which drives the electro-mechanical response of the structure, thus leading to a larger strain. The balance between these two driving forces is controlled by the shear coupling at the CFO/PZT interface and the effective PZT cross section along the direction of the applied electric field. Here, our numerical results show that considering a nonlinear piezoelectric response for PZT leads to an improved agreement with the experimental data, consistent with ex situ poling of the nanostructure prior to magnetic measurements.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Structure-Property Study of Piezoelectricity in Polyimides

High performance piezoelectric polymers are of interest to NASA as they may be useful for a variety of sensor applications. Over the past few years research on piezoelectric polymers has led to the development of promising high temperature piezoelectric responses in some novel polyimides. In this study, a series of polyimides have been studied with systematic variations in the diamine monomers that comprise the polyimide while holding the dianhydride constant. The effect of structural changes, including variations in the nature and concentration of dipolar groups, on the remanent polarization and piezoelectric coefficient is examined. Fundamental structure-piezoelectric property insight will enable the molecular design of polymers possessing distinct improvements over state-of-the-art piezoelectric polymers including enhanced polarization, polarization stability at elevated temperatures, and improved processability.

Ounaies, Zoubeida↗

Novel vertically aligned nanocomposite of Bi 2 WO 6 -Co 3 O 4 with room-temperature multiferroic and anisotropic optical response

A review of a new vertically aligned nanocomposite (VAN) structure based on two-dimensional (2D) layered oxides has been designed and self-assembled on both LaAlO 3 (001) and SrTiO 3 (001) substrates. The new VAN structure consists of epitaxially grown Co 3 O 4 nanopillars embedded in the Bi 2 WO 6 matrix with a unique 2D layered structure, as evidenced by the microstructural analysis. Physical property measurements show that the new Bi 2 WO 6 -Co 3 O 4 VAN structure exhibits strong ferromagnetic and piezoelectric response at room temperature as well as anisotropic permittivity response. This work demonstrates a new approach in processing multifunctional VANs structure based on the layered oxide systems towards future nonlinear optics, ferromagnets, and multiferroics.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

High performance high-power textured Mn/Cu-doped PIN-PMN-PT ceramics

Piezoelectric ceramics with combinatory soft and hard characteristics are highly desired for high-power applications. However, it remains grand challenge to achieve simultaneous presence of hard (e.g. high coercive field, E c ; high mechanical quality factor, Q m ) and soft (e.g. high piezoelectric constant, d; high electromechanical coupling factor, k) piezoelectric properties in piezoelectric ceramics since the mechanism controlling the hard behavior (pinned domain walls) will significantly reduce the soft behavior. Here, we address this grand challenge and demonstrate <001> textured MnO 2 and CuO co-doped Pb(In 1/2 Nb 1/2 )O 3- Pb(Mg 1/3 Nb 2/3 )O 3- PbTiO 3 (PIN-PMN-PT) ceramics exhibiting ultrahigh combined soft and hard piezoelectric properties (d 33 = 713 pC N –1 , k 31 = 0.52, Q m ≈950, E c = 9.6 kV cm –1 , tan δ = 0.45%). The outstanding electromechanical properties are explained by considering composition/phase selection, crystallographic anisotropy and defect engineering. Phase-field model in conjunction with high resolution electron microscopy and diffraction techniques is utilized to delineate the contributions arising from intrinsic piezoelectric response, domain dynamics, and local structural heterogeneity. Furthermore, these results will have significant impact in the development of high-power transducers and actuators.

36 MATERIALS SCIENCE↗

High field dielectric response in κ-Ga 2 O 3 films

κ-Ga 2 O 3 has been predicted to be a potential ferroelectric material. In this work, undoped Ga 2 O 3 films were grown by either plasma-enhanced atomic layer deposition (PEALD) or metal organic chemical vapor deposition (MOCVD) on platinized sapphire substrates. 50 nm thick PEALD films with a mixture of κ-Ga 2 O 3 and β-Ga 2 O 3 had a relative permittivity of ~27, a loss tangent below 2%, and high electrical resistivity up to ~1.5 MV/cm. 700 nm thick MOCVD films with predominantly the κ-Ga 2 O 3 phase had relative permittivities of ~18 and a loss tangent of 1% at 10 kHz. Neither film showed compelling evidence for ferroelectricity measured at fields up to 1.5 MV/cm, even after hundreds of cycles. Here, piezoresponse force microscopy measurements on bare κ-Ga 2 O 3 showed a finite piezoelectric response that could not be reoriented for electric fields up to 1.33 MV/cm.

36 MATERIALS SCIENCE↗

Anomalous polarization reversal in strained thin films of CuIn⁢P 2 ⁢S 6

Strain-induced transitions of polarization reversal in thin films of a ferrielectric CuIn⁢P 2 ⁢S 6 (CIPS) with ideally conductive electrodes are explored using the Landau-Ginzburg-Devonshire approach with an eighth-order free energy expansion in polarization powers. Due to multiple potential wells, the height and position of which are temperature and strain dependent, the energy profiles of CIPS can flatten in the vicinity of the nonzero polarization states. Thereby, we reveal an unusually strong effect of a mismatch strain on the out-of-plane polarization reversal, hysteresis loop shape, dielectric susceptibility, and piezoelectric response of CIPS films. By varying the sign of the mismatch strain and its magnitude in a fairly narrow range, quasistatic hysteresisless paraelectric curves can transform into double, triple, and other types of pinched and single hysteresis loops. The strain effect on the polarization reversal is opposite, i.e., anomalous, in comparison with many other ferroelectric films, for which the out-of-plane remanent polarization and coercive field increase strongly for tensile strains and decrease or vanish for compressive strains. For definite values of temperature and mismatch strain, the low-frequency hysteresis loops of polarization may exhibit negative slope in a relatively narrow range of external field amplitude and frequency. The low-frequency susceptibility hysteresis loops, which correspond to the negative slope of polarization loops, contain only positive values, which can be giant in the entire range of field changes. In conclusion, the corresponding piezoresponse also reaches giant values, being maximal near coercive fields.

Dielectric properties↗

Freestanding BaTiO 3 ‐Au Vertically Aligned Nanocomposite toward Flexible Multi‐Sensing Platform

Abstract Flexible and wearable sensors show enormous potential for personalized healthcare devices by real‐time monitoring of an individual's health. Typically, a single functional material is selected for one sensor to sense a particular physical signal while multiple materials will be selected for multi‐mode sensing. Vertically aligned nanocomposites (VANs) have recently demonstrated various material combinations and novel coupled multifunctionalities that are hard to achieve in any single‐phase material alone, including multiphase multiferroics, magneto‐optic coupling, and strong magnetic and optical anisotropy. Integrating these novel VANs into wearable sensors shows enormous potential in multi‐mode sensing owing to their multifunctional nature. In this work, the transfer of VANs onto polydimethylsiloxane as a novel flexible chemical and pressure sensor is demonstrated. For this demonstration, the classical BaTiO 3 ‐Au VAN with combined plasmonic and piezoelectric properties is used to demonstrate a multi‐sensing mechanism. A thin water‐soluble buffer of Sr 3 Al 2 O 6 serves as a buffer layer for the epitaxial growth and transfer process. The electrical output based on the piezoelectric responses and identifying 4‐mercaptobenzoic acid by surface‐enhanced Raman spectroscopy reveal great potential for free‐standing VANs in a wearable multifunctional sensing platform.

Tsai, Benson Kunhung [School of Materials Engineer↗

Ferroelectricity in Atomic Layer Deposited Wurtzite Zinc Magnesium Oxide Zn 1– x Mg x O

Conformal deposition of wurtzite ferroelectrics, which is needed for their use in scaled nonvolatile memories, is challenging using current physical vapor deposition techniques. To overcome the conformality barrier, this work demonstrates ferroelectricity in wurtzite Zn 1− x Mg x O thin films prepared by plasma-enhanced atomic layer deposition, which is a non-line-of-sight deposition method. Films ranging in composition from x = 0.00 to x = 0.58 are predominantly wurtzite phase and exhibit a (0001)-texture. Increasing the magnesium content decreases the c/a ratio, increases the optical bandgap energy, increases the piezoelectric response, and enables polarization reversal. Clear polarization switching is demonstrated in 50 nm thick Zn 1− x Mg x O films by piezoresponse force microscopy in compositions containing x = 0.46 and x = 0.58.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanoscale Control of Polar Surface Phases in Layered van der Waals CuInP 2 S 6

Antiferroelectric (AFE) materials, in which alternating dipole moments cancel out to a zero net macroscopic polarization, can be used for high-density energy storage and memory applications. The AFE phase can exist in bulk CuInP 2 Se 6 , CuBiP 2 S 6 , and a few other transition-metal thiophosphates below 200 K. The required low temperature poses challenges for practical applications. In this work, we report the coexistence of ferrielectric (FE) states and a stable surface phase that does not show piezoelectric response (“zero-response phase”) in bulk CuInP 2 S 6 at room temperature. Using piezoresponse force microscopy (PFM) tomographic imaging together with density functional theory, we find that direct and alternating voltages can locally and stably convert FE to zero-response phases and vice versa. While PFM loops show pinched hystereses reminiscent of antiferroelectricity, PFM tomography reveals that the zero-response areas form only on top of the FE phase in which the polarization vector is pointing up. Theoretical calculations suggest that the zero-response phase may correspond to AFE ordering where stacked CuInP 2 S 6 layers have alternating polarization orientations thereby leading to a net-zero polarization. Consistent with experimental findings, theory predicts that the FE polarization pointing down is robust up to the top surface, whereas FE polarization pointing up energetically favors the formation of an AFE surface layer, whose thickness is likely to be sensitive to local strains. AFE order is likely to be more robust against detrimental size effects than polar order, therefore providing additional opportunities to create multifunctional heterostructures with 2D electronic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Piezoelectric domain walls in van der Waals antiferroelectric CuInP2Se6

Polar van der Waals chalcogenophosphates exhibit unique properties, such as negative electrostriction and multi-well ferrielectricity, and enable combining dielectric and 2D electronic materials. Using low temperature piezoresponse force microscopy, we revealed coexistence of piezoelectric and non-piezoelectric phases in CuInP2Se6, forming unusual domain walls with enhanced piezoelectric response. From systematic imaging experiments we have inferred the formation of a partially polarized antiferroelectric state, with inclusions of structurally distinct ferrielectric domains enclosed by the corresponding phase boundaries. The assignment is strongly supported by optical spectroscopies and density-functional-theory calculations. Enhanced piezoresponse at the ferrielectric/antiferroelectric phase boundary and the ability to manipulate this entity with electric field on the nanoscale expand the existing phenomenology of functional domain walls. At the same time, phase-coexistence in chalcogenophosphates may lead to rational strategies for incorporation of ferroic functionality into van der Waals heterostructures, with stronger resilience toward detrimental size-effects.

36 MATERIALS SCIENCE↗

Ultrahigh-power-density flexible piezoelectric energy harvester based on freestanding ferroelectric oxide thin films

Flexible piezoelectric nanogenerators are emerging as a promising solution for powering next-generation flexible electronics by converting mechanical energy into electrical energy. However, traditional ferroelectric ceramics, despite their excellent piezoelectric properties, lack flexibility; while piezoelectric polymers, although highly flexible, have low piezoelectricity. The quest to develop materials that combine high piezoelectricity with exceptional flexibility has thus become a research focus. Herein, we present a breakthrough in this field with the fabrication of freestanding (111)-oriented PbZr 0.52 Ti 0.48 O 3 single crystalline thin films, which exhibit remarkable flexibility and a high converse piezoelectric coefficient (~585 pm/V). This is achieved through water-soluble sacrificial layer to relieve substrate clamping and controlling the crystal orientation to further enhance the piezoelectric response. Our nanogenerators, constructed using these freestanding nanoscale membranes, demonstrate a record-high output power density (~63.5 mW/cm 3 ), excellent flexibility (with a strain tolerance >3.4%), and superior mechanical stability in cycling tests (>60,000 cycles). These advancements pave the way for high-performance, flexible electronic devices utilizing ferroelectric oxide thin films.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Influence of doping and thickness on domain avalanches in lead zirconate titanate thin films

In undoped lead zirconate titanate films of 1–2 μm thick, domain walls move in clusters with a correlation length of approximately 0.5–2 μm. Band excitation piezoresponse force microscopy mapping of the piezoelectric nonlinearity revealed that niobium (Nb) doping increases the average concentration or mobility of domain walls without changing the cluster area of correlated domain wall motion. In comparison, manganese (Mn) doping reduces the contribution of mobile domain walls to the dielectric and piezoelectric responses without changing the cluster area for correlated motion. In both Nb and Mn doped films, the cluster area increases and the cluster density drops as the film thickness increases from 250 to 1250 nm. This is evident in spatial maps generated from the analysis of irreversible to reversible ratios of the Rayleigh coefficients.

36 MATERIALS SCIENCE↗

Photoinduced patterning of oxygen vacancies to promote the ferroelectric phase of Hf 0.5 Zr 0.5 O 2

Photoinduced reductions in the oxygen vacancy concentration were leveraged to increase the ferroelectric phase fraction of Hf 0.5 Zr 0.5 O 2 thinfilms. Modest ( ~ 2 — 77 pJ=cm 2 ) laser doses of visible light (488 nm, 2.54 eV) spatially patterned the concentration of oxygen vacancies as monitored by photoluminescence imaging. Local, tip-based, near-field, nanoFTIR measurements showed that the photoinduced oxygen vacancy concentration reduction promoted formation of the ferroelectric phase (space group Pca2 1 ), resulting in an increase in the piezoelectric response measured by piezoresponse force microscopy. Photoinduced vacancy tailoring provides, therefore, a spatially prescriptive, postsynthesis, and low-entry method to modify phase in HfO 2 -based materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optical and electronic functionality arising from controlled defect formation in nanoscale complex oxide lateral epitaxy

Epitaxial crystallization of complex oxides provides the means to create materials with precisely selected composition, strain, and orientation, thereby controlling their functionalities. Extending this control to nanoscale three-dimensional geometries can be accomplished via a three-dimensional analog of oxide solid-phase epitaxy, lateral epitaxial crystallization. The orientation of crystals within laterally crystallized SrTiO 3 systematically changes from the orientation of the SrTiO 3 substrate. This evolution occurs as a function of lateral crystallization distance, with a rate of approximately 50° μm -1 . The mechanism of the rotation is consistent with a steady-state stress of tens of megapascal over a 100–nanometer scale region near the moving amorphous/crystalline interface arising from the amorphous-crystalline density difference. Second harmonic generation and piezoelectric force microscopy reveal that the laterally crystallized SrTiO 3 is noncentrosymmetric and develops a switchable piezoelectric response at room temperature, illustrating the potential to use lateral crystallization to control the functionality of complex oxides.

36 MATERIALS SCIENCE↗

Charge Generation and Propagation in Igneous Rocks

Various electrical phenomena have been reported prior to or concurrent with earthquakes such as resistivity changes, ground potentials, electromagnetic (EM), and luminous signals. Doubts have been raised as to whether some of these phenomena are real and indeed precursory. One of the reasons for uncertainty is that, despite decades of intense work, there is still no physically coherent model. Using low- to medium-velocity impacts to measure electrical signals with microsecond time resolution, it has now been observed that when dry gabbro and diorite cores are impacted at relatively low velocities, approximately 100 m/s, highly mobile charge carriers are generated in a small volume near the impact point. They spread through the rocks, causing electric potentials exceeding +400 mV, EM, and light emission. As the charge cloud spreads, the rock becomes momentarily conductive. When a dry granite block is impacted at higher velocity, approximately 1.5 km/s, the propagation of the P and S waves is registered through the transient piezoelectric response of quartz. After the sound waves have passed, the surface of the granite block becomes positively charged, suggesting the same charge carriers as observed during the low-velocity impact experiments, expanding from within the bulk. During the next 2-3 ms the surface potential oscillates, indicating pulses of electrons injected from ground and contact electrodes. The observations are consistent with positive holes, e.g., defect electrons in the O(2-) sublattice, traveling via the O 2p-dominated valence band of the silicate minerals. Before activation, the positive holes lay dormant in the form of electrically inactive positive hole pairs (PHP), chemically equivalent to peroxy links, O3X/OO\XO3, with X=Si(4+), Al(3+), etc. PHPs are introduced into the minerals by way of hydroxyl,O3X-OH, which all nominally anhydrous minerals incorporate when crystallizing in H2O-laden environments. The fact that positive holes can be activated by low-energy impacts, and their attendant sound waves, suggests that they can also be activated by microfracturing. Depending on where in the stressed rock volume the charge carriers are activated, they will form rapidly moving or fluctuating charge clouds that may account for earthquake-related electrical signals and EM emission. Wherever such charge clouds intersect the surface, high fields are expected, causing electric discharges and earthquake lights.

Freund, Friedemann↗