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At least 127 records · Page 7

New examples of ferroelectric nematic materials showing evidence for the antiferroelectric smectic-Z phase

Abstract We present a new ferroelectric nematic material, 4-((4′-((trans)-5-ethyloxan-2-yl)-2′,3,5,6′-tetrafluoro-[1,1′-biphenyl]-4-yl)difluoromethoxy)-2,6-difluorobenzonitrile (AUUQU-2-N) and its higher homologues, the molecular structures of which include fluorinated building blocks, an oxane ring, and a terminal cyano group, all contributing to a large molecular dipole moment of about 12.5 D. We observed that AUUQU-2-N has three distinct liquid crystal phases, two of which were found to be polar phases with a spontaneous electric polarization P s of up to 6 µC cm –2 . The highest temperature phase is a common enantiotropic nematic (N) exhibiting only field-induced polarization. The lowest-temperature, monotropic phase proved to be a new example of the ferroelectric nematic phase (N F ), evidenced by a single-peak polarization reversal current response, a giant imaginary dielectric permittivity on the order of 10 3 , and the absence of any smectic layer X-ray diffraction peaks. The ordinary nematic phase N and the ferroelectric nematic phase N F are separated by an antiferroelectric liquid crystal phase which has low permittivity and a polarization reversal current exhibiting a characteristic double-peak response. In the polarizing light microscope, this antiferroelectric phase shows characteristic zig-zag defects, evidence of a layered structure. These observations suggest that this is another example of the recently discovered smectic Z A (SmZ A ) phase, having smectic layers with the molecular director parallel to the layer planes. The diffraction peaks from the smectic layering have not been observed to date but detailed 2D X-ray studies indicate the presence of additional short-range structures including smectic C-type correlations in all three phases—N, SmZ A and N F —which may shed new light on the understanding of polar and antipolar order in these phases.

36 MATERIALS SCIENCE↗

Photocarrier-induced persistent structural polarization in soft-lattice lead halide perovskites

The success of the lead halide perovskites in diverse optoelectronics has motivated considerable interest in their fundamental photocarrier dynamics. Here, in this work, we report the discovery of photocarrier-induced persistent structural polarization and local ferroelectricity in lead halide perovskites. Photoconductance studies of thin-film single-crystal CsPbBr 3 at 10 K reveal long-lasting persistent photoconductance with an ultralong photocarrier lifetime beyond 10 6 s. X-ray diffraction studies reveal that photocarrier-induced structural polarization is present up to a critical freezing temperature. Photocapacitance studies at cryogenic temperatures further demonstrate a systematic local phase transition from linear dielectric to paraelectric and relaxor ferroelectric under increasing illumination. Our theoretical investigations highlight the critical role of photocarrier–phonon coupling and large polaron formation in driving the local relaxor ferroelectric phase transition. Our findings show that this photocarrier-induced persistent structural polarization enables the formation of ferroelectric nanodomains at low temperature, which suppress carrier recombination and offer the possibility of exploring intriguing carrier–phonon interplay and the rich polaron photophysics.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Anion-tethered Single Lithium-ion Conducting Polyelectrolytes through UV-induced Free Radical Polymerization for Improved Morphological Stability of Lithium Metal Anodes

Single Li + ion conducting polyelectrolytes (SICs), which feature covalently tethered counter-anions along their backbone, have the potential to mitigate dendrite formation by reducing concentration polarization and preventing salt depletion. However, due to their low ionic conductivity and complicated synthetic procedure, the successful validation of these claimed advantages in lithium metal (Li 0 ) anode batteries remains limited. In this study, we fabricated a SIC electrolyte using a single-step UV polymerization approach. The resulting electrolyte exhibited a high Li + transference number (t + ) of 0.85 and demonstrated good Li + conductivity (6.3×10 -5 S/cm at room temperature), which is comparable to that of a benchmark dual ion conductor (DIC, 9.1×10 -5 S/cm). Benefitting from the high transference number of SIC, it displayed a three-fold higher critical current density (2.4 mA/cm 2 ) compared to DIC (0.8 mA/cm 2 ) by successfully suppressing concentration polarization-induced short-circuiting. Additionally, the t + significantly influenced the deposition behavior of Li0, with SIC yielding a uniform, compact, and mosaic-like morphology, while the low t + DIC resulted in a porous morphology with Li 0 whiskers. Using the SIC electrolyte, Li 0 ||LiFePO 4 cells exhibited stable operation for 4500 cycles with 70.5 % capacity retention at 22 °C.

25 ENERGY STORAGE↗

Anion-tethered Single Lithium-ion Conducting Polyelectrolytes through UV-induced Free Radical Polymerization for Improved Morphological Stability of Lithium Metal Anodes

Single Li + ion conducting polyelectrolytes (SICs), which feature covalently tethered counter-anions along their backbone, have the potential to mitigate dendrite formation by reducing concentration polarization and preventing salt depletion. However, due to their low ionic conductivity and complicated synthetic procedure, the successful validation of these claimed advantages in lithium metal (Li 0 ) anode batteries remains limited. In this study, we fabricated a SIC electrolyte using a single-step UV polymerization approach. The resulting electrolyte exhibited a high Li + transference number (t + ) of 0.85 and demonstrated good Li + conductivity (6.3×10 -5 S/cm at room temperature), which is comparable to that of a benchmark dual ion conductor (DIC, 9.1×10 -5 S/cm). Benefitting from the high transference number of SIC, it displayed a three-fold higher critical current density (2.4 mA/cm 2 ) compared to DIC (0.8 mA/cm 2 ) by successfully suppressing concentration polarization-induced short-circuiting. Additionally, the t + significantly influenced the deposition behavior of Li 0 , with SIC yielding a uniform, compact, and mosaic-like morphology, while the low t + DIC resulted in a porous morphology with Li 0 whiskers. In conclusion, using the SIC electrolyte, Li 0 ||LiFePO 4 cells exhibited stable operation for 4500 cycles with 70.5 % capacity retention at 22 °C.

25 ENERGY STORAGE↗

Engineering exchange bias at the interface of self-polarized ultrathin ferroelectric Ba⁢Ti⁢O 3 and ferromagnetic La 0.67⁢ Sr 0.33 ⁢Mn⁢O 3

We investigate the emergence and optimization of conventional exchange bias (EB) in ultrathin (<10 nm) ferroelectric (FE) Ba⁢Ti⁢O 3 (BTO)/ferromagnetic (FM) La 0.67 ⁢Sr 0.33⁢ Mn⁢O 3 (LSMO) epitaxial bilayers without an antiferromagnetic (AFM) material. The EB originates from the electronic orbital reconstruction at the FE-FM interface due to the ferroelectric polarization. We achieve maximum EB of approximately 42 Oe with single-domain polarization in nine-unit-cell-thick BTO, setting the BTO thickness above the critical threshold for ferroelectricity yet below the thickness of strain relaxation and multidomain breakdown. Furthermore, the LSMO layer needs to be thick enough to sustain both the FM layer and polarization-induced AFM spin configuration at the LSMO/BTO interface, yet as thin as possible to enable the EB loop shift. The temperature, training, field, and thickness dependence of the EB confirm that the LSMO/BTO interface exhibits conventional EB despite its unconventional origin. Using x-ray magnetic circular dichroism, scanning transmission electron microscopy, and density-functional-theory calculations, we confirm that the macroscopic EB effect originates from the interfacial AFM spin configuration in LSMO driven by FE-induced d-orbital modifications in interfacial Mn ions. Thus, we engineer strong interfacial EB coupling in artificial multiferroics without a conventional AFM material by controlling FE polarization, highlighting the potential for advanced spintronic applications.

exchange bias↗

Microwave emission from polar firn

The microwave emission from a half-space medium, characterized by coordinate dependent scattering and absorbing centers, was calculated by numerically solving the radiative transfer equation by the method of invariant imbedding. Rayleigh scattering phase functions and scattering induced polarization of the radiation were included in the calculation. Using the scattering and extinction data of polar firn the brightness temperature was calculated for the 1.55 cm wavelength. This study was the first quantitative comparison of the results of numerical calculation using the actual measured information of crystal size with the observed data.

Chang, A. T. C.↗

Demonstration of a third-order hierarchy of topological states in a three-dimensional acoustic metamaterial

Classical wave systems have constituted an excellent platform for emulating complex quantum phenomena, such as demonstrating topological phenomena in photonics and acoustics. Recently, a new class of topological states localized in more than one dimension of a D -dimensional system, referred to as higher-order topological (HOT) states, has been reported, offering an even more versatile platform to confine and control classical radiation and mechanical motion. Here, we design and experimentally study a 3D topological acoustic metamaterial supporting third-order (0D) topological corner states along with second-order (1D) edge states and first-order (2D) surface states within the same topological bandgap, thus establishing a full hierarchy of nontrivial bulk polarization–induced states in three dimensions. The assembled 3D topological metamaterial represents the acoustic analog of a pyrochlore lattice made of interconnected molecules, and is shown to exhibit topological bulk polarization, leading to the emergence of boundary states.

Science & Technology - Other Topics↗

Chirality-induced spin selectivity as a mechanism to control product selectivity during electrochemical CO 2 reduction

Electrocatalytic CO 2 reduction often suffers from competition with the hydrogen evolution reaction (HER), which lowers efficiency and limits product selectivity. Recent studies suggest that electron spin, when controlled at an electrode surface, can influence reaction pathways, but direct evidence linking spin effects to suppressed HER has been limited. Here, in this work, we show that helical chiral copper (Cu) electrodes reduce competing HER during CO 2 reduction, consistent with spin polarization induced via the chiral-induced spin selectivity effect. The helically structured Cu electrodes are fabricated by electrodeposition with a chiral templating reagent. Time-resolved Kerr ellipticity measurements, which track spin-polarized carriers generated by an ultrafast Seebeck current, confirm spin accumulation at the chiral Cu surface. This spin polarization disfavours H—H bond formation, thereby suppressing HER and enabling formate production alongside CO. These findings demonstrate that chirality-based spin control offers a strategy for steering selectivity in CO 2 reduction and other reactions where HER is an undesired competitor.

14 SOLAR ENERGY↗

Self‐Assembled LuFeO 3 /LuFe 2 O 4 Heterostructure with Emergent Ferroic Orderings

Abstract Achieving self‐assembling structures that exhibit emergent properties and functionalities is one of the holy grails in nanotechnology and holds great promise for a wide range of potential applications. Herein, a self‐assembled LuFeO 3 –(1/3)LuFe 2 O 4 –LuFeO 3 heterostructure that consists of two model multiferroics, i.e., hexagonal LuFeO 3 and rhombohedral LuFe 2 O 4 , is reported in single‐layer epitaxial LuFeO 3 thin films. Atomic‐scale electron microscopy investigations reveal the spontaneous organization of ferroelectric polarization in each building block, which forms a series of polar configurations. Specifically, the charge and lattice of neighboring LuFeO 3 and LuFe 2 O 4 blocks are closely coupled with competing degrees of freedom. A combination of the quantitative analysis of atomically resolved images and spectroscopy with theoretical calculations determines how charge‐ordering‐induced polarization accommodates charge naturality across the interfaces to reduce the system energy and unravels the formation mechanism of this heterostructure. The results point to the possibilities of generation and control of multiferroic self‐assembled systems, which may provide a basis for engineering novel materials with emergent properties.

Deng, Shiqing↗

Atomistic insight into the effects of electrostatic fields on hydrocarbon reaction kinetics

Reactive Molecular Dynamics (MD) and Density Functional Theory (DFT) computations are performed to provide insight into the effects of external electrostatic fields on hydrocarbon reaction kinetics. By comparing the results from MD and DFT, the suitability of the MD method in modeling electrodynamics is first assessed. Results show that the electric field-induced polarization predicted by the MD charge equilibration method is in good agreement with various DFT charge partitioning schemes. Then, the effects of oriented external electric fields on the transition pathways of non-redox reactions are investigated. Results on the minimum energy path suggest that electric fields can cause catalysis or inhibition of oxidation reactions, whereas pyrolysis reactions are not affected due to the weaker electronegativity of the hydrogen and carbon atoms. MD simulations of isolated reactions show that the reaction kinetics is also affected by applied external Lorentz forces and interatomic Coulomb forces since they can increase or decrease the energy of collision depending on the molecular conformation. In addition, electric fields can affect the kinetics of polar species and force them to align in the direction of field lines. These effects are attributed to energy transfer via intermolecular collisions and stabilization under the external Lorentz force. The kinetics of apolar species is not significantly affected mainly due to the weak induced dipole moment even under strong electric fields. The dynamics and reaction rates of species are studied by means of large-scale combustion simulations of n-dodecane and oxygen mixtures. Results show that under strong electric fields, the fuel, oxidizer, and most product molecules experience translational and rotational acceleration mainly due to close charge transfer along with a reduction in their vibrational energy due to stabilization. This study will serve as a basis to improve the current methods used in MD and to develop novel methodologies for the modeling of macroscale reacting flows under external electrostatic fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polar transport of auxin across gravistimulated roots of maize and its enhancement by calcium

The effect of Ca on the polar movement of [3H]indoleacetic acid ([3H]IAA) in gravistimulated roots was examined using 3-day-old seedlings of maize (Zea mays L.). Transport of label was measured by placing an agar donor block containing [3H]IAA on one side of the elongation zone and measuring movement of label across the root into an agar receiver block on the opposite side. In vertically oriented roots, movement of label across the elongation zone into the receiver was slight and was not enhanced by incorporating 10 millimolar CaCl2 into the receiver block. In horizontally oriented roots, movement of label across the root was readily detectable and movement to a receiver on the bottom was about 3-fold greater than movement in the opposite direction. This polarity was abolished in roots from which the caps were removed prior to gravistimulation. When CaCl2 was incorporated into the receivers, movement of label across horizontally oriented intact roots was increased about 3-fold in both the downward and upward direction. The ability of Ca to enhance the movement of label from [3H]IAA increased with increasing Ca concentration in the receiver up to 5 to 10 millimolar CaCl2. With the inclusion of CaCl2 in the receiver blocks, gravity-induced polar movement of label into receiver blocks from applied [3H]IAA was detectable within 30 minutes, and asymmetric distribution of label within the tissue was detectable within 20 minutes. The results indicate that gravistimulation induces a physiological asymmetry in the auxin transport system of maize roots and that Ca increases the total transport of auxin across the root.

NASA Program Space Biology↗

Ferroelectricity of wurtzite Al 1−x Hf x N heterovalent alloys

Thin films of aluminum hafnium nitride (Al1−xHfxN) were synthesized via reactive magnetron sputtering for Hf contents up to x = 0.13. X-ray diffraction showed a single c-axis oriented wurtzite phase for all films. Hard x-ray photoelectron spectroscopy demonstrated homogeneous Al:Hf distribution through the thin films and confirmed their insulating character. A collection of complementary tests showed unambiguous polarization inversion, and thus ferroelectricity in multiple samples. Current density vs electric field hysteresis measurements showed distinct ferroelectric switching current peaks, the piezoelectric coefficient d 33,f,meas measured using a double beam laser interferometer (DBLI) showed a reversal in sign with similar magnitude, and anisotropic wet etching confirmed field-induced polarization inversion. This demonstrates the possibility of using tetravalent–and not just trivalent–alloying elements to enable ferroelectricity in AlN-based thin films, highlighting the compositional flexibility of ferroelectricity in wurtzites and greatly expanding the chemistries that can be considered for future devices.

36 MATERIALS SCIENCE↗

Size Effect of Negative Capacitance State and Subthreshold Swing in Van der Waals Ferrielectric Field–Effect Transistors

Analytical calculations corroborated by the finite element modeling show that thin films of Van der Waals ferrielectrics covered by a 2D-semiconductor are promising candidates for the controllable reduction of the dielectric layer capacitance due to the negative capacitance (NC) effect emerging in the thin films. The NC state is conditioned by energy-degenerated poly-domain states of the ferrielectric polarization induced in the films under incomplete screening conditions in the presence of a dielectric layer. Calculations performed for the FET-type heterostructure “ferrielectric CuInP 2 S 6 film—2D-MoS 2 single-layer—SiO 2 dielectric layer” reveal the pronounced size effect of the multilayer capacitance. Derived analytical expressions for the electric polarization and multilayer capacitance allow to predict the thickness range of the dielectric layer and ferrielectric film for which the NC effect is the most pronounced in various Van der Waals ferrielectrics, and the corresponding subthreshold swing becomes much less than the Boltzmann's limit. Obtained results can be useful for the size and temperature control of the NC effect in the steep-slope ferrielectric FETs.

36 MATERIALS SCIENCE↗

Hydrostatic factors affect the gravity responses of algae and roots

The hypothesis of Wayne et al. (1990) that plant cells perceive gravity by sensing a pressure differential between the top and the bottom of the cell was tested by subjecting rice roots and cells of Caracean algae to external solutions of various densities. It was found that increasing the density of the external medium had a profound effect on the polar ratio (PR, the ratio between velocities of the downwardly and upwardly streaming cytoplasm) of the Caracean algae cells. When these cells were placed in solutions of denser compound, the PR decreased to less than 1, as the density of the external medium became higher than that of the cell; thus, the normal gravity-induced polarity was reversed, indicating that the osmotic pressure of the medium affects the cell's ability to respond to gravity. In rice roots, an increase of the density of the solution inhibited the rate of gravitropism. These results agree with predictions of a hydrostatic model for graviperception.

Staves, Mark P.↗

Low-Energy Electron Elastic Collisions with Actinide Atoms Am, Cm, Bk, Es, No and Lr: Negative-Ion Formation

The rigorous Regge-pole method is used to investigate negative-ion formation in actinide atoms through electron elastic total cross sections (TCSs) calculation. The TCSs are found to be characterized generally by negative-ion formations, shape resonances and Ramsauer-Townsend(R-T) minima, and they exhibit both atomic and fullerene molecular behavior near the threshold. Additionally, a polarization-induced metastable cross section with a deep R-T minimum is identified near the threshold in the Am, Cm and Bk TCSs, which flips over to a shape resonance appearing very close to the threshold in the TCSs for Es, No and Lr. We attribute these new manifestations to size effects and orbital collapse significantly impacting the polarization interaction. From the TCSs unambiguous and reliable ground, metastable and excited states negative-ion binding energies (BEs) for Am−, Cm−, Bk−, Es−, No− and Lr− anions formed during the collisions are extracted and compared with existing electron affinities (EAs) of the atoms. The novelty of the Regge-pole approach is in the extraction of the negative-ion BEs from the TCSs. We conclude that the existing theoretical EAs of the actinide atoms and the recently measured EA of Th correspond to excited anionic BEs.

Msezane, Alfred Z. (ORCID:0000000212485661)↗

Spectroscopic evidence of intra-unit-cell charge redistribution in a charge-neutral magnetic topological insulator

The magnetic topological insulator MnBi 6 Te 10 has emerged as a promising candidate for realizing the quantum anomalous Hall effect (QAHE), owing to its ability to retain ferromagnetism through precise control of anti-site defects. The next important task for realizing the QAHE is to tune the chemical potential into the energy gap formed by the broken time-reversal symmetry. Here we reveal an intra-unit-cell charge redistribution even when the overall doping suggests a near-charge-neutral condition. By performing time- and angle-resolved photoemission spectroscopy (trARPES) on the optimally 18% Sb-doped MnBi 6 Te 10 , we observe transient surface photovoltage (SPV) effects on both the MnBi 2 Te 4 and single-Bi 2 Te 3 terminations. Furthermore, we observe a time-dependent splitting of the band structure indicating multiple SPV shifts with different magnitudes. This observation suggests that adjacent plateaus with nominally the same terminating layer exhibit a strong intra-unit-cell charge redistribution, resulting in spontaneous electrical polarization. This is consistent with static micro-ARPES measurements revealing significant doping deviations from the charge-neutral configuration. Our findings underscore the challenges of engineering the family of Mn-Bi-Te materials to realize QAHE purely through chemical doping. Achieving the desired topological quantum phase requires both a uniform carrier doping and a ferromagnetic ground state. Furthermore, the light-induced polarization within each unit cell of ferromagnetic Mn(Bi 0.82 Sb 0.18 ) 6 Te 10 may open new possibilities for optoelectronic and spintronics.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

High-Performance Piezo-Electrocatalytic Sensing of Ascorbic Acid with Nanostructured Wurtzite Zinc Oxide

We report nanostructured piezoelectric semiconductors offer unprecedented opportunities for high-performance sensing in numerous catalytic processes of biomedical, pharmaceutical, and agricultural interests, leveraging piezocatalysis that enhances the catalytic efficiency with the strain-induced piezoelectric field. Here, we design and demonstrate for the first time a cost-efficient, high-performance piezo-electrocatalytic sensor for detecting L-ascorbic acid (AA), a critical chemical for many organisms, metabolic processes, and medical treatments. We prepared ZnO nanorods and nanosheets to characterize and compare their efficacy for the piezo-electrocatalysis of AA. The electrocatalytic efficacy of AA was significantly boosted by the piezoelectric polarization induced in the nanostructured semiconducting ZnO catalysts. We elucidated the charge transfer between the strained ZnO nanostructures and AA to reveal the mechanism for the related piezo-electrocatalytic process. The low-temperature synthesis of high-quality ZnO nanostructures allows the low-cost, scalable production and integration directly into wearable electrocatalytic sensors whose performance could be boosted by otherwise wasted mechanical energy from the working environment, e.g., the human-generated mechanical signals.

30 DIRECT ENERGY CONVERSION↗

The Moderate Resolution Imaging Spectrometer-tilt (MODIS-T)

There will be several state-of-the-art spectrometers in operation on the NASA Polar Oribting Platform (NPOP-1) as part of the Earth Observing System. The Moderate Resolution Imaging Spectrometer (MODIS) will consist of two imaging spectroradiometric instruments, one nadir-viewing (MODIS-N) and the other tiltable (MODIS-T) for ocean observation and land bidirectional reflectance studies. The MODIS-T instrument is required to cover the wavelength range of 400 to 880 nm in approximately 15 steps, have less than 2.3 percent instrument-induced polarization, be calibrated to an absolute radiometric accuracy of at least 5 percent over the full dynamic range of the instrument, have a 1.1 kilometer square instantaneous field of view at nadir, and be capable of + or - 50-deg along-track tilt.

Magner, Thomas J.↗