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At least 1,027 records · Page 57

Towards Scalable 3D Integration of 2T-nC FeRAM with Hundreds of Layer Stacking

In this article, we study the limits of the number of capacitors and read history dependence in a 2T-nC ferroelectric random-access memory (FeRAM) cell, paving the way for its high-density integration toward hundreds of stacked layers. Through a comprehensive experimental and simulation study on the scaling behavior of the 2T-nC FeRAM architecture, we demonstrate: (i) successful fabrication of 2T-64C cells with robust memory operation and clearly distinguishable ‘0’ and ‘1’ states, even in 64- capacitor configurations; (ii) that the parasitic capacitance of the floating node originates predominantly from the linear component of the ferroelectric capacitor, and its impact on n-scaling—due to degraded sense margin—can be mitigated by floating unselected capacitors with enough TΩ isolation; (iii) that sharing write and read transistors among n capacitors introduces a read history dependence issue due to fluctuating floating node voltage (VFN); and (iv) that a proposed FN discharge scheme can effectively eliminate read-sequence dependence, at the cost of reduced read endurance.

36 MATERIALS SCIENCE↗

Manipulating chiral spin transport with ferroelectric polarization

A magnon is a collective excitation of the spin structure in a magnetic insulator and can transmit spin angular momentum with negligible dissipation. This quantum of a spin wave has always been manipulated through magnetic dipoles (that is, by breaking time-reversal symmetry). Here we report the experimental observation of chiral spin transport in multiferroic BiFeO 3 and its control by reversing the ferroelectric polarization (that is, by breaking spatial inversion symmetry). The ferroelectrically controlled magnons show up to 18% modulation at room temperature. The spin torque that the magnons in BiFeO 3 carry can be used to efficiently switch the magnetization of adjacent magnets, with a spin-torque efficiency comparable to the spin Hall effect in heavy metals. Utilizing such controllable magnon generation and transmission in BiFeO 3 , an all-oxide, energy-scalable logic is demonstrated composed of spin-orbit injection, detection and magnetoelectric control. In conclusion, our observations open a new chapter of multiferroic magnons and pave another path towards low-dissipation nanoelectronics.

36 MATERIALS SCIENCE↗

Direct processing of PbZr 0.53 Ti 0.47 O 3 films on glass and polymeric substrates

This work reports on direct crystallization of PbZr 0.53 Ti 0.47 O 3 (PZT) thin films on glass and polymeric substrates, using pulsed thermal processing (PTP). Specifically, xenon flash lamps deliver pulses of high intensity, short duration, broadband light to the surface of a chemical solution deposited thin film, resulting in the crystallization of the film. Structural analysis by X-ray diffraction (XRD) and transmission electron microscopy show the existence of perovskite structure in nano-sized grains (≤5 nm). Local functional analysis by band excitation piezoelectric spectroscopy and electrostatic force microscopy confirm the presence of a ferroelectric phase and retention of voltage-written polarization for multiple days. Based on structural and functional analyses, strategies are discussed for optimization of pulse voltage and duration for the realization of crystalline ferroelectric thin films. For ~200 nm-thick PZT films on glass substrates, 500 μs-long pulses were required for crystallization, starting with 100 pulses at 350 V, 10 or 25 pulses at 400 V and in general lower number of pulses at higher voltages (resulting in higher radiant energy). Overall power densities of >6.4 kW/cm 2 were needed for appearance of peaks corresponding to the perovskite phase in the XRD. Films on glass processed at 350–400 V had a higher degree of 111-oriented perovskite grains. Higher applied radiant energy (through increased pulse voltage or count) resulted in more random and/or partially 001-oriented films. For ~1 μm-thick PZT films on polymeric substrates, 10 to 25 250 μs-long pulses at voltages ranging between 200 to 250 V, corresponding to power densities of ~2.8 kW/cm 2 , were optimal for maximized perovskite phase crystallization, while avoiding substrate damage.

36 MATERIALS SCIENCE↗

Magnetic state switching in FeGa microstructures

This work demonstrates that magnetoelectric composite heterostructures can be designed at the length scale of 10µms that can be switched from a magnetized state to a vortex state, effectively switching the magnetization off, using electric field induced strain. This was accomplished using thin film magnetoelectric heterostructures of Fe 81.4 Ga 18.6 on a single crystal (011) [Pb(Mg 1/3 Nb 2/3 )O 3 ] 0.68 -[PbTiO 3 ] 0.32 (PMN-32PT) ferroelectric substrate. Here, the heterostructures were tripped from a multi-domain magnetized state to a flux closure vortex state using voltage induced strain in a piezoelectric substrate. FeGa heterostructures were deposited on a Si-substrate for superconducting quantum interference device magnetometry characterization of the magnetic properties. The magnetoelectric coupling of a FeGa continuous film on PMN-32PT was characterized using a magneto optical Kerr effect magnetometer with bi-axial strain gauges, and magnetic multi-domain heterostructures were imaged using x-ray magnetic circular dichroism—photoemission electron microscopy during the transition to the vortex state. The domain structures were modelled using MuMax 3 , a micromagnetics code, and compared with observations. The results provide considerable insight into designing magnetoelectric heterostructures that can be switched from an ‘on’ state to an ‘off’ state using electric field induced strain.

36 MATERIALS SCIENCE↗

Manipulating Ferroelectric Topological Polar Structures with Twisted Light

Abstract The dynamic control of non‐equilibrium states represents a central challenge in condensed matter physics. While intense terahertz fields drive metal‐insulator transitions and ferroelectricity via soft phonon modes, recent theory suggests that twisted light with orbital angular momentum (OAM) offers a distinct route to manipulate ferroelectric order and stabilize topological excitations including skyrmions, vortices, and Hopfions. Control of ferroelectric polarization in quasi‐2D CsBiNb 2 O 7 (CBNO) is demonstrated using non‐resonant twisted ultra‐violet (UV) light (375 nm, 800 THz). Combining in situ X‐ray Bragg coherent diffractive imaging (BCDI), twisted optical Raman spectroscopy, and density functional theory (DFT), three‐dimensional (3D) ionic displacements, strain fields, and polarization changes are resolved in single crystals. Operando measurements reveal light‐induced strain hysteresis under twisted light–a hallmark of nonlinear, history‐dependent ferroelastic switching driven by OAM. Discrete, irreversible domain transitions emerge as the topological charge ℓ is cycled, stabilizing non‐trivial domain textures including vortex‐antivortex pairs, Bloch/anti‐Bloch points, and merons. These persist after OAM removal, indicating a memory effect. Competing mechanisms are discussed, including multiphoton absorption, strain‐mediated polarization switching, and defect‐wall interactions. The findings establish structured light as a tool for deterministic, reversible control of ferroic states, enabling optically reconfigurable non‐volatile devices.

Chemistry↗

Predicting the formation of fractionally doped perovskite oxides by a function-confined machine learning method

Abstract Fractionally doped perovskites oxides (FDPOs) have demonstrated ubiquitous applications such as energy conversion, storage and harvesting, catalysis, sensor, superconductor, ferroelectric, piezoelectric, magnetic, and luminescence. Hence, an accurate, cost-effective, and easy-to-use methodology to discover new compositions is much needed. Here, we developed a function-confined machine learning methodology to discover new FDPOs with high prediction accuracy from limited experimental data. By focusing on a specific application, namely solar thermochemical hydrogen production, we collected 632 training data and defined 21 desirable features. Our gradient boosting classifier model achieved a high prediction accuracy of 95.4% and a high F1 score of 0.921. Furthermore, when verified on additional 36 experimental data from existing literature, the model showed a prediction accuracy of 94.4%. With the help of this machine learning approach, we identified and synthesized 11 new FDPO compositions, 7 of which are relevant for solar thermochemical hydrogen production. We believe this confined machine learning methodology can be used to discover, from limited data, FDPOs with other specific application purposes.

08 HYDROGEN↗

Structural phase diagram for Sm-substituted BiFeO 3 multiferroics

The structural evolution of Sm substituted BiFe⁢O 3 is studied by total x-ray scattering and structure modeling. It is shown that the crystal structure changes from polar to antipolar and then to nonpolar when the Sm to Bi ratio in the material approaches 20% and 40%, respectively, with no intermixing between the structure types. The evolution is driven by lattice strain induced by the difference in the size of Sm and Bi atoms, leading to changes in the pattern of octahedral tilts and Bi off-centering, which, in turn, induce changes in the multiferroic properties. Furthermore, the substitution ratio at which the different structure types emerge appears to be tied up with the average radius of the atomic species occupying the Bi sites in the perovskite lattice and volume occupied by a formula unit, rendering both quantities useful predictor variables for guiding computational searches for substituted BiFe⁢O 3 multiferroics with improved functional properties.

Ferroelectricity↗

Energy conversion and storage via photoinduced polarization change in non-ferroelectric molecular [CoGa] crystals

To alleviate the energy and environmental crisis, in the last decades, energy harvesting by utilizing optical control has emerged as a promising solution. Here we report a polar crystal that exhibits photoenergy conversion and energy storage upon light irradiation. The polar crystal consists of dinuclear [CoGa] molecules, which are oriented in a uniform direction inside the crystal lattice. Irradiation with green light induces a directional intramolecular electron transfer from the ligand to a low-spin Co III centre, and the resultant light-induced high-spin Co II excited state is trapped at low temperature, realizing energy storage. Additionally, electric current release is observed during relaxation from the trapped light-induced metastable state to the ground state, because the intramolecular electron transfer in the relaxation process is accompanied with macroscopic polarization switching at the single-crystal level. It demonstrates that energy storage and conversion to electrical energy is realized in the [CoGa] crystals, which is different from typical polar pyroelectric compounds that exhibit the conversion of thermal energy into electricity.

25 ENERGY STORAGE↗

Domain wall motion across microstructural features in polycrystalline ferroelectric films

This paper describes the effect of microstructural features such as grain boundaries and triple points on the pinning of domain wall motion in perovskite Pb(Zr 0.52 Ti 0.48 )O 3 (PZT) films on polycrystalline SrRuO 3 /SrTiO 3 substrates. Here, spatial variability in the collective domain wall dynamics was assessed using non-linearity mapping via Band Excitation Piezoresponse Force Microscopy (BE-PFM). Collocating the non-linearity maps with triple point locations (as visualized by EBSD) allowed for exploration of the effects that local microstructure (e.g., grain boundary) have on domain wall motion. It was found that the extrinsic behavior varied with both the misorientation angle and the proximity to the grain boundary. The width of influence of individual grain boundaries on the motion of domain walls was a function of the character of the grain boundary; random grain boundaries exhibit deeper minima in α d /d 33,initial and larger widths of influence (up to 905 nm) compared to coincident site lattice (CSL) boundaries (up to 572 nm). Additionally, triple points containing larger numbers of random boundaries exhibited non-Rayleigh behavior to greater distances, suggesting that the triple point provides either a deep potential minimum or a region where domain wall motion is unfavorable.

36 MATERIALS SCIENCE↗

Polymer Coats Leads on Implantable Medical Device

Langley Research Center s Soluble Imide (LaRC-SI) was discovered by accident. While researching resins and adhesives for advanced composites for high-speed aircraft, Robert Bryant, a Langley engineer, noticed that one of the polymers he was working with did not behave as predicted. After putting the compound through a two-stage controlled chemical reaction, expecting it to precipitate as a powder after the second stage, he was surprised to see that the compound remained soluble. This novel characteristic ended up making this polymer a very significant finding, eventually leading Bryant and his team to win several NASA technology awards, and an "R&D 100" award. The unique feature of this compound is the way that it lends itself to easy processing. Most polyimides (members of a group of remarkably strong and incredibly heat- and chemical-resistant polymers) require complex curing cycles before they are usable. LaRC-SI remains soluble in its final form, so no further chemical processing is required to produce final materials, like thin films and varnishes. Since producing LaRC-SI does not require complex manufacturing techniques, it has been processed into useful forms for a variety of applications, including mechanical parts, magnetic components, ceramics, adhesives, composites, flexible circuits, multilayer printed circuits, and coatings on fiber optics, wires, and metals. Bryant s team was, at the time, heavily involved with the aircraft polymer project and could not afford to further develop the polymer resin. Believing it was worth further exploration, though, he developed a plan for funding development and submitted it to Langley s chief scientist, who endorsed the experimentation. Bryant then left the high-speed civil transport project to develop LaRC-SI. The result is an extremely tough, lightweight thermoplastic that is not only solvent-resistant, but also has the ability to withstand temperature ranges from cryogenic levels to above 200 C. The thermoplastic s unique characteristics lend it to many commercial applications; uses that Bryant believed would ultimately benefit industry and the Nation. "LaRC-SI," he explains, "is a product created in a government laboratory, funded with money from the tax-paying public. What we discovered helps further the economic competitiveness of the United States, and it was our goal to initiate the technology transfer process to ensure that our work benefited the widest range of people." Several NASA centers, including Langley, have explored methods for using LaRC-SI in a number of applications from radiation shielding and as an adhesive to uses involving replacement of conventional rigid circuit boards. In the commercial realm, LaRC-SI can now be found in several commercial products, including the thin-layer composite unimorph ferroelectric driver and sensor (THUNDER) piezoelectric actuator, another "R&D 100" award winner (Spinoff 2005).

Source record↗

Investigation into the crystal structure–dielectric property correlation in barium titanate nanocrystals of different sizes

For high capacitance multilayer ceramic capacitors, high dielectric constant and lead-free ceramic nanoparticles are highly desired. However, as the particle size decreases to a few tens of nanometers, their dielectric constant significantly decreases, and the underlying mechanism has yet to be fully elucidated. Herein, we report a systematic investigation into the crystal structure–dielectric property relationship of combustion-made BaTiO 3 (BTO) nanocrystals. When the nanocrystal size was 100 nm and below, a metastable paraelectric cubic phase was found in the as-received BTO (denoted as arBTO) nanocrystals based on an X-ray diffraction (XRD) study. A stable ferroelectric tetragonal phase was present when the nanocrystal size was above 200 nm. Notably, the cubic arBTO (particle size ≤100 nm) exhibited tetragonal fluctuations as revealed by Raman spectroscopy, whereas the tetragonal arBTO (particle size ≥200 nm) contained ~10% cubic fraction according to the Rietveld fitting of the XRD profiles. Thermal annealing of the multi-grain tetragonal arBTO at 950 °C yielded single crystals of annealed BTO (denoted as anBTO), whose dielectric constants were higher than those of arBTO. However, the single crystalline anBTO prevented the formation of 90° domains; therefore, they exhibited a low dielectric constant of ~300. Although X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy could not identify the exact structural defects, our study revealed that surface and bulk defects formed during synthesis affect the final crystal structures and thus the dielectric properties of BTO nanocrystals with different sizes. Finally, the understanding obtained from this study will help us design high dielectric constant perovskite nanocrystals for next-generation multilayer ceramic capacitor applications.

36 MATERIALS SCIENCE↗

SnSe 1-x S x Alloys: Anisotropic Van der Waals Semiconductors with Tunable Bandgaps

Alloying is one of the main tools of bandgap engineering, allowing the tuning of crystal structure, lattice parameters, and electronic structure of 3D and 2D/layered semiconductors. Among the latter, it can play a key role in tailoring the properties of tin monochalcogenides, a class of van der Waals semiconductors of interest for optoelectronics, thermoelectrics, ferroelectrics, and valleytronics. Here, the study investigates the synthesis and properties of large flakes of the anion substitution alloys SnSe 1-x S x . Alloy flakes across a wide range of compositions are obtained systematically by repeated growth from the same mixed (SnS, SnSe) powder precursor. Combined experiment and theory show full miscibility for all compositions, along with tunable lattice constants, bandgaps, and vibrational modes. Atomic resolution imaging demonstrates the accumulation of S and Se in alternating layers in the SnSe 1-x S x unit cell, attributed to growth kinetics. Polarized Raman spectroscopy confirms anisotropic vibrational modes; the calculated and measured band structure shows systematic changes in the band edge energies and anisotropic electronic structure due to the anisotropic in-plane lattice of the monochalcogenides. Cathodoluminescence, finally, indicates that a unique configuration of two non-degenerate, direct valleys along orthogonal k-space directions persists all the way from SnS to SnSe, making SnSe 1-x S x alloys interesting for valleytronics.

36 MATERIALS SCIENCE↗

Origins of Electrostriction in Poly(vinylidene fluoride)-Based Ferroelectric Polymers

Although electrostriction is ubiquitous for dielectric polymers, giant electrostriction has not been observed until relaxor ferroelectric (RFE) poly(vinylidene fluoride) (PVDF)-based polymers are achieved. However, the exact origin for giant electrostriction in these polymers has not been fully understood. By studying the electrostriction in the uniaxially stretched films of a ferroelectric poly(VDF-co-trifluoroethylene) [P(VDF-TrFE)] random copolymer and an RFE poly(VDF-co-TrFE-co-chlorotrifluoroethylene) [P(VDF-TrFE-CTFE)] random terpolymer in this work, we confirmed that ferroelectric switching with large hysteresis, such as in the case of P(VDF-TrFE), was not genuine electrostriction. By decreasing large ferroelectric domains to the nanometer scale (i.e., 2–3 nm), such as in the case of the P(VDF-TrFE-CTFE) terpolymer, electrostriction with low hysteresis could be achieved. Here, two origins of the large electrostriction in these polymers were identified. The first was the mechano-electrostriction due to the poling field-induced conformation transformation of oriented polymer chains. The second was the electric repulsion of electrically aligned nanodomains. These effects could occur in both crystals and the oriented amorphous fraction, which links between the nanocrystals and the isotropic amorphous fraction. When the poling field was relatively low (e.g., <40 MV/m), the mechano-electrostriction was the major contribution and the electric repulsion effect was a minor contribution to electrostriction. Meanwhile, a strong temperature dependence of the low-field electrostriction coefficient was observed. Finally, we found an empirical inverse relationship between the electrostriction coefficient and the product of Young’s modulus and dielectric constant. The knowledge obtained from this study provides an insightful understanding of the electrostriction mechanism in PVDF-based electroactive polymers, which will find potential applications in sensors and actuators for wearable electronics and soft robotics.

36 MATERIALS SCIENCE↗

Metal–insulator transition tuned by oxygen vacancy migration across TiO2/VO2 interface

Abstract Oxygen defects are essential building blocks for designing functional oxides with remarkable properties, ranging from electrical and ionic conductivity to magnetism and ferroelectricity. Oxygen defects, despite being spatially localized, can profoundly alter global properties such as the crystal symmetry and electronic structure, thereby enabling emergent phenomena. In this work, we achieved tunable metal–insulator transitions (MIT) in oxide heterostructures by inducing interfacial oxygen vacancy migration. We chose the non-stoichiometric VO 2-δ as a model system due to its near room temperature MIT temperature. We found that depositing a TiO 2 capping layer on an epitaxial VO 2 thin film can effectively reduce the resistance of the insulating phase in VO 2 , yielding a significantly reduced R OFF /R ON ratio. We systematically studied the TiO 2 /VO 2 heterostructures by structural and transport measurements, X-ray photoelectron spectroscopy, and ab initio calculations and found that oxygen vacancy migration from TiO 2 to VO 2 is responsible for the suppression of the MIT. Our findings underscore the importance of the interfacial oxygen vacancy migration and redistribution in controlling the electronic structure and emergent functionality of the heterostructure, thereby providing a new approach to designing oxide heterostructures for novel ionotronics and neuromorphic-computing devices.

36 MATERIALS SCIENCE↗

Low-voltage magnetoelectric coupling in membrane heterostructures

Strain-mediated magnetoelectric (ME) coupling in ferroelectric (FE)/ferromagnetic (FM) heterostructures offers a unique opportunity for both fundamental scientific research and low-power multifunctional devices. Relaxor-FEs, such as (1-x)Pb(Mg 1/3 Nb 2/3 )O 3 -(x)PbTiO 3 (PMN-xPT), are ideal FE layer candidates because of their giant piezoelectricity. However, thin films of PMN-PT suffer from substrate clamping, which substantially reduces piezoelectric in-plane strains. Here, we demonstrate low-voltage ME coupling in an all-thin-film heterostructure that uses the anisotropic strains induced by the (011) orientation of PMN-PT. We completely remove PMN-PT films from their substrate and couple with FM Ni overlayers to create membrane PMN-PT/Ni heterostructures showing 90° Ni magnetization rotation with 3 V PMN-PT bias, much less than the bulk PMN-PT ~100-V requirement. Scanning transmission electron microscopy and phase-field simulations clarify the membrane response. These results provide a crucial step toward understanding the microstructural behavior of PMN-PT thin films for use in piezo-driven ME heterostructures.

36 MATERIALS SCIENCE↗

Phase-Shifting Liquid Crystal Point-Diffraction Interferometry

Microgravity fluid physics experiments frequently measure concentration and temperature. Interferometers such as the Twyman Green illustrated have performed full-field measurement of these quantities. As with most such devices, this interferometer uses a reference path that is not common with the path through the test section. Recombination of the test and reference wavefronts produces interference fringes. Unfortunately, in order to obtain stable fringes, the alignment of both the test and reference paths must be maintained to within a fraction of the wavelength of the light being used for the measurement. Otherwise, the fringes will shift and may disappear. Because these interferometers are extremely sensitive to bumping, jarring and transmitted vibration, they are typically mounted on optical isolation tables. Schlieren deflectometers or the more recent Shack-Hartmann wavefront sensors also measure concentration and temperature in laboratory fluid flows. Ray optics describe the operation of both devices. In a schlieren system, an expanded, collimated beam passes through a test section where refractive index gradients deflect rays. A lens focuses the beam to a filter placed in the rear focal plane of the decollimating lens. In a quantitative color schlieren system, gradients in the index of refraction appear as colors in the field of view due to the action of the color filter. Since sensitivity is a function of the focal length of the decollimating lens, these systems are rather long and filter fabrication and calibration is rather difficult. A Shack-Hartmann wavefront sensor is an array of small lenslets. Typical diameters are on the order of a few hundred microns. Since these lenslets divide the test section into resolution elements, the spatial resolution can be no smaller than an individual lenslet. Such a device was recently used to perform high-speed tomography of heated air exiting a 1.27 cm diameter nozzle. While these wavefront sensors are very compact, the limited spatial resolution and the methods required for data reduction suggest that a more useful instrument needs to be developed. The category of interferometers known as common path interferometers can eliminate much of the vibration sensitivity associated with traditional interferometry as described above. In these devices, division of the amplitude of the wavefront following the test section produces the reference beam. Examples of these instruments include shearing and point diffraction interferometers. In the latter case, shown schematically, a lens focuses light passing through the test section onto a small diffracting object. Such objects are typically either a circle of material on a high quality glass plate or a small sphere in a glass cell. The size of the focused spot is several times larger than the object so that the light not intercepted by the diffracting object forms the test beam while the diffracted light generates a spherical reference beam. While this configuration is mechanically stable, phase shifting one beam with respect to the other is difficult due to the common path. Phase shifting enables extremely accurate measurements of the phase of the interferogram using only gray scale intensity measurements and is the de facto standard of industry. Mercer and Creath 2 demonstrated phase shifting in a point diffraction interferometer using a spherical spacer in a liquid crystal cell as the diffracting object. By changing the voltage across the cell, they were able to shift the phase of the undiffracted beam relative to the reference beam generated by diffraction from the sphere. While they applied this technology to fluid measurements, the device shifted phase so slowly that it was not useful for studying transient phenomena. We have identified several technical problems that precluded operation of the device at video frame rates and intend to solve them to produce a phase-shifting liquid crystal point-diffraction interferometer operating at video frame rates. The first task is to produce high contrast fringes. Since the diffracted beam is much weaker than the transmitted beam, interferograms have poor contrast unless a dye is added to the liquid crystal to reduce the intensity of the undiffracted light. Dyes previously used were not rigorously characterized and suffered from hysteresis in both the initial alignment state of the device and the electro-optic switching characteristics. Hence, our initial effort will identify and characterize dyes that do not suffer from these difficulties and are readily soluble in the liquid crystal host. Since the ultimate goal of this research is to produce interferometers capable of phase shifting at video frame rates, we will quantify the difference in switching times between ferroelectric and nematic liquid crystals. While we have more experience with nematic crystals, they typically switch more slowly than ferroelectric cells. As part of that effort, we will investigate the difference in the modulation of the interferograms as a function of the type of liquid crystal in the cell. Because the temporal switching response of a liquid crystal cell is directly related its thickness, we intend to explore techniques required to produce cells that are as thin as possible. However, the cells must still produce a total phase shift of two pi radians.

Griffin, DeVon W.↗

Comparison of the dielectric and magnetocaloric properties of bulk and film of GdFe 0.5 Cr 0.5 O 3

Here, we report a comparison of the magnetic, magnetocaloric, and dielectric properties of 50% iron substituted GdCrO 3 (GdFe 0.5 Cr 0.5 O 3 ) bulk pellet and 960 nm thick film of GdFe 0.5 Cr 0.5 O 3 (GFCO). The 960 nm film was synthesized on a platinized-silicon substrate by chem. soln. deposition and spin-coating methods. The X-ray diffraction scans of the bulk sample and the film as well as the morphology of the film as examined by the field-emission scanning electron microscope indicate phase-pure and polycrystalline nature of these samples. XPS was used to deermine the valence states of Gd, Fe, and Cr. The temp. dependence of the dielectric const. from 225 to 700 K shows peaks at T C = 525 K for the bulk and ≈450 K for the film due to ferroelectric to paraelectric transitions, since elec. polarization vs elec. field hysteresis loops are observed. at room temp. The dielectric studies in the bulk GFCO for T > T C indicate a relaxor-like behavior. The measurements of the magnetization (M) of the samples as a function of temp. (5-350 K) and magnetic field (H) up to 7 T (=70 kOe) depict hysteresis behavior at low temps. due to the canted antiferromagnetic order of Fe 3+ /Cr 3+ below the Néel temp. of ≈275 K. The M vs H isotherms at various temps. are used to det. and compare the magnetic entropy change (-ΔS) and relative cooling power (RCP) of the two samples, yielding (-ΔS) = 30.7 J/kg K (18.8 J/kg K) and RCP = 566.5 J/kg (375 J/kg) for the bulk (960 nm film) samples of GFCO at 7 K and 7 T, resp. The plot of RCP vs T shows that magnetic cooling for this system is most effective for T < 30 K. Comparatively smaller magnitudes of (-ΔS) and RCP for the film vis-a-vis the bulk sample of GFCO scale with its reduced magnetization. This suggests that further improvements in the quality of the films are needed to improve their magnetization and hence their magnetocaloric properties, possibly making them useful for on-chip cooling in miniaturized devices.

36 MATERIALS SCIENCE↗

Unexpected Giant Microwave Conductivity in a Nominally Silent BiFeO 3 Domain Wall

Nanoelectronic devices based on ferroelectric domain walls (DWs), such as memories, transistors, and rectifiers, have been shown in recent years. Practical high-speed electronics, on the other hand, usually demand operation frequencies in the gigahertz (GHz) regime, where the effect of dipolar oscillation is important. Herein, an unexpected giant GHz conductivity on the order of 10 3 S m -1 is observed in certain BiFeO 3 DWs, which is about 100 000 times greater than the carrier-induced direct current (dc) conductivity of the same walls. Surprisingly, the nominal configuration of the DWs precludes the alternating current (ac) conduction under an excitation electric field perpendicular to the surface. Theoretical analysis reflects that the inclined DWs are stressed asymmetrically near the film surface, whereas the vertical walls in a control sample are not. The resultant imbalanced polarization profile can then couple to the out-of-plane microwave fields and induce power dissipation, which is confirmed by the phase-field modeling. Since the contributions from mobile-carrier conduction and bound-charge oscillation to the ac conductivity are equivalent in a microwave circuit, the research on local structural dynamics may open a new avenue to implement DW nano-devices for radio-frequency applications.

36 MATERIALS SCIENCE↗