Polar Materials Research Articles

Factors influencing quantum evaporation of helium from polar semiconductors from first principles

While there is much indirect evidence for the existence of dark matter (DM), to date it has evaded detection. Current efforts focus on DM masses over ∼GeV—to push the sensitivity of DM searches to lower masses, new DM targets and detection schemes are needed. In this work, we focus on the latter—a novel detection scheme recently proposed to detect 10–100 meV phonons in polar target materials. Previous work showed that well-motivated models of DM can interact with polar semiconductors to produce an athermal population of phonons. This new sensing scheme proposes that these phonons then facilitate quantum evaporation of He3 from a van der Waals film deposited on the target material. However, a fundamental understanding of the underlying process is still unclear, with several uncertainties related to the precise rate of evaporation and how it can be controlled. In this work, we use density functional theory calculations to compare the adsorption energies of helium atoms on a polar target material, sodium iodide, to understand the underlying evaporation physics. We explore the role of surface termination, monolayer coverage, and elemental species on the rate of He evaporation from the target material. Using this, we discuss the optimal target features for He-evaporation experiments and their range of tunability through chemical and physical modifications such as applied field and surface termination. Published by the American Physical Society 2024

Thermal Bistability of Magnetic Susceptibility, Light Absorption, Second Harmonic Generation, and Dielectric Properties in a Polar Spin-Crossover Iron-Rhenium Chain Material.

The bistability of multiple physical properties driven by external stimuli in a solid is a desired prerequisite for its application in memory devices with convenient data readout. We present a pathway for thermal bistability detectable in four physical properties: magnetic, light absorption, second-harmonic generation (SHG), and dielectric. We report a novel heterometallic (TBA){[FeII(phIN)4][ReV(CN)8]}·(phIN) (1) (TBA = tetrabutylammonium cation, phIN = phenyl isonicotinate) cyanido-bridged chain material. Owing to an appropriate {N6} coordination sphere of Fe(II) centers, 1 reveals a thermal spin crossover (SCO) effect which is complete and cooperative providing a distinct thermal hysteresis loop in magnetic measurements. Moreover, it exhibits simultaneous thermal bistability in (a) visible-light absorption due to the presence of efficient d-d electronic transitions in the low-spin (LS) state, (b) SHG activity as it crystallizes in a polar Cc space group due to the bulky substituent on phIN ligands, and (c) dielectric parameters, including dielectric constant, which can be correlated with subtle changes in polarity between LS and HS (high spin) phases. Thus, we present a remarkable thermally controlled hysteretic behavior in four physical functionalities realized by properly functionalizing an SCO-active coordination compound.

Active learning-based automated construction of Hamiltonian for structural phase transitions: a case study on BaTiO3

The effective Hamiltonians have been widely applied to simulate the phase transitions in polarizable materials, with coefficients obtained by fitting to accurate first-principles calculations. However, it is tedious to generate distorted structures with symmetry constraints, in particular when high-ordered terms are considered. In this work, we implement and apply a Bayesian optimization-based approach to sample potential energy surfaces, automating the effective Hamiltonian construction by selecting distorted structures via active learning. Taking BaTiO3(BTO) as an example, we demonstrate that the effective Hamiltonian can be obtained using fewer than 30 distorted structures. Follow-up Monte Carlo simulations can reproduce the structural phase transition temperatures of BTO, comparable to experimental values with an error<10%. Our approach can be straightforwardly applied on other polarizable materials and paves the way for quantitative atomistic modelling of diffusionless phase transitions.

Highly Responsive Polar Vortices in All-Ferroelectric Heterostructures.

The discovery of polar vortices and skyrmions in ferroelectric-dielectric superlattices [such as (PbTiO3)n/(SrTiO3)n] has ushered in an era of novel dipolar topologies and corresponding emergent phenomena. The key to creating such emergent features has generally been considered to be related to counterpoising strongly polar and non-polar materials thus creating the appropriate boundary conditions. This limits the utility these materials can have, however, by rendering (effectively) half of the structure unresponsive to applied stimuli. Here, using advanced thin-film deposition and an array of characterization and simulation approaches, polar vortices are realized in all-ferroelectric trilayers, multilayers, and superlattices built from the fundamental building block of (PbTiO3)n/(PbxSr1- xTiO3)n wherein in-plane ferroelectric polarization in the PbxSr1- xTiO3 provides the appropriate boundary conditions. These superlattices exhibit substantially enhanced electromechanical and ferroelectric responses in the out-of-plane direction that arise from the ability of the polarization in both layers to rotate to the out-of-plane direction under field. In the in-plane direction, the layers are found to be strongly coupled during switching and when heterostructured with ferroelectric-dielectric building blocks, it is possible to produce multistate switching. This approach expands the realm of systems supporting emergent dipolar texture formation and does so with entirely ferroelectric materials thus greatly improving their responses.

Spin-deformation coupling in two-dimensional polar materials

Spin-deformation coupling in two-dimensional polar materials

Real-space investigation of polarons in hematite Fe2O3.

In polarizable materials, electronic charge carriers interact with the surrounding ions, leading to quasiparticle behavior. The resulting polarons play a central role in many materials properties including electrical transport, interaction with light, surface reactivity, and magnetoresistance, and polarons are typically investigated indirectly through these macroscopic characteristics. Here, noncontact atomic force microscopy (nc-AFM) is used to directly image polarons in Fe2O3 at the single quasiparticle limit. A combination of Kelvin probe force microscopy (KPFM) and kinetic Monte Carlo (KMC) simulations shows that the mobility of electron polarons can be markedly increased by Ti doping. Density functional theory (DFT) calculations indicate that a transition from polaronic to metastable free-carrier states can play a key role in migration of electron polarons. In contrast, hole polarons are significantly less mobile, and their hopping is hampered further by trapping centers.

Rational Design of Novel Polar Nonlinear Optical Materials in Alkali Metal Rare Earth Iodates.

Four new potassium rare earth iodates, namely, acentric K2Lu(IO3)5 and KM(IO3)4(HIO3)0.33 (M = Ce/Pr) and centric KLa(IO3)4, were successfully grown by mild hydrothermal reactions. Three of them exhibit polar structures; K2Lu(IO3)5, KCe(IO3)4(HIO3)0.33, and KPr(IO3)4(HIO3)0.33 show second-harmonic generation (SHG) responses of 3.0, 1.0, and 0.8 × KDP, respectively. These three iodates are phase-matchable for second-harmonic generation. The influence of changes in the radius and coordination mode of rare earth ions on the crystal structure and SHG response has been discussed in detail. Our findings suggest that in the alkali metal rare earth iodate, modulating the arrangement of iodate groups by changing the coordination geometry of rare earth ions is an effective strategy for designing polar NLO materials.

Thermally tunable phonon–plasmon polariton modes at hexagonal boron nitride (hBN) and indium antimonide (InSb) interfaces

Abstract This work examines the propagation of thermally tunable phonon–plasmon modes at the interfaces of hexagonal boron nitride (hBN) and isotropic indium antimonide (InSb). Both theoretical modeling and numerical simulations are carried out to analyze the effect of temperature on surface wave behavior. hBN is realized as a polar material via the Lorentzian model, while InSb ismodeled as a temperature-sensitive material (TSM) in the framework of Drude’s model. The possible plasmon–phonon polaritonic interactionsarestudied for the TSM–elliptic type interface and TSM– hyperbolic type interface. It is reported that by varying the temperature, the surface modes can be tuned for the lower and upper Reststrahlen (RS) bands of hBN. The dispersion curve, effective mode index, propagation length, and phase speed are computed for each case under different temperatures. It is concluded that the hBN–InSb-based phonon–plasmon polariton modes are actively tuned by changing the external temperature in the lower and upper RS bands. Surface waves propagating across the interface can be modulated from the terahertz (THz) region to the infrared (IR)region by changing the temperature of InSb. This study will help researchers to design innovative thermo-optical sensors, plasmonic platforms, detectors, and surface waveguides in the THz and IR regions.&amp;#xD;

On-chip phonon-enhanced IR near-field detection of molecular vibrations

Phonon polaritons – quasiparticles formed by strong coupling of infrared (IR) light with lattice vibrations in polar materials – can be utilized for surface-enhanced infrared absorption (SEIRA) spectroscopy and even for vibrational strong coupling with nanoscale amounts of molecules. Here, we introduce and demonstrate a compact on-chip phononic SEIRA spectroscopy platform, which is based on an h-BN/graphene/h-BN heterostructure on top of a metal split-gate creating a p-n junction in graphene. The metal split-gate concentrates the incident light and launches hyperbolic phonon polaritons (HPhPs) in the heterostructure, which serves simultaneously as SEIRA substrate and room-temperature infrared detector. When thin organic layers are deposited directly on top of the heterostructure, we observe a photocurrent encoding the layer’s molecular vibrational fingerprint, which is strongly enhanced compared to that observed in standard far-field absorption spectroscopy. A detailed theoretical analysis supports our results, further predicting an additional sensitivity enhancement as the molecular layers approach deep subwavelength scales. Future on-chip integration of infrared light sources such as quantum cascade lasers or even electrical generation of the HPhPs could lead to fully on-chip phononic SEIRA sensors for molecular and gas sensing.

Application of PLA/GO/ZnO and PLA/GO/Cu2O as sensor

Polylactic acid modified with graphene oxide (PLA/GO) is proposed to interact with ZnO through 6 different schemes. Density functional theory at B3LYP/LANL2DZ level was utilized to calculate total dipole moment (TDM), HOMO/LUMO energy gap (ΔE) and to map the molecular electrostatic potential (MESP). Results indicated that PLA/GO interacted with ZnO through O-atom forming PLA/GO/OZn composite. This composite interacts with methane, hydrogen sulfide, humidity (H2O), carbon dioxide and ethanol. The same gases were supposed to interact further with PLA/GO/Cu2O. Adsorption energy for the interaction between each composite and the proposed gases were calculated. Both PLA/GO/OZn and PLA/GO/Cu2O composites interacted favorably with H2O. Adsorption energy for interaction of other gases with studied structures are generally low compared to H2O. PLA/GO/OZn have adsorption energy slightly higher than that of PLA/GO/Cu2O. PLA/GO/OZn has higher TDM values than those of PLA/GO/Cu2O, indicating a more polar material. Conversely, PLA/GO/Cu2O exhibited larger ΔE values than those of PLA/GO/OZn. TDM and energy gap results for both studied structures indicated good sensing capabilities. Further insights come from analyzing the calculated density of states (DOS) and partial density of states (PDOS). PLA/GO/Cu2O exhibited high peak for copper in its DOS and PDOS spectra compared to zinc and oxygen in case of PLA/GO/OZn. This means a higher density of available electronic states associated with Cu.

Production of rGO based hybrid composite buckypaper cathodes by using copper oxide polysulfide adsorbent for Li-S batteries

Lithium-sulfur batteries are particularly noteworthy for applications requiring large capacity and long battery life. Transition metal oxides have emerged as polar host materials for lithium polysulfides to further modulate the bonding energy with polysulfides and increase the coupling density of the electrodes. Polar metal oxides naturally adsorb polysulfides on their hydrophilic surfaces. In this study, the polysulfide adsorbing ability of CuO against the shuttle effect is utilized. For this purpose, copper(II) oxide (CuO) is used as polysulfide adsorbent and CuO - reduced Graphene Oxide / Sulphur (CuO-rGO/S) hybrid composite buckypaper electrodes are produced as cathodes in Li-S batteries without using binders. In this work, optical, morphological and structural analyzes of composite films were carried out by Fourier transformed infrared spectroscopy (FT-IR), Raman spectroscopy, field emission gun scanning electron microscopy (FEG-SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Brunauer-Emmett-Teller (BET) analysis, respectively. After the CR2032 button cell was assembled using the produced cathode materials, cyclic voltammetry (CV), charge-discharge performance tests, rate capability and electrochemical impedance spectroscopy (EIS) analyzes were performed to investigate the Li-S battery capacities. With the CuO-rGO/S hybrid composite cathode containing 2 % CuO, a discharge capacity of 1205 mAh g−1 was obtained in the first cycle. At the end of the 1000 cycles, the discharge capacity of the cathode was achieved as high as 696 mAh g−1. As a result, the battery capacity of rGO/S-based composite electrodes has been improved by taking advantage of CuO added to the cathode structure to adsorb polysulfides.

Oleogel-based frying medium: influence of rice bran wax-canola oil oleogel on volatile profile in fried fish fillets

Oleogelation has proven to be a successful strategy for structuring oils. In recent years, the use of oleogels as a deep frying medium has gained popularity as an effective approach to minimise oil uptake and reduce the energy content of fried foods. This study was designed to evaluate an oleogel matrix consisting of rice bran wax and canola oil, prepared by oleogelation technique, as a deep frying medium. Two types of the oleogels (CRBO-3 with 3 g wax/100 g oil; CRBO-6 with 6 g wax/100 g oil) were formulated and these oleogels were tested as a frying medium for fish fillets. The prepared oleogels were compared with refined canola oil (CO, control) and evaluated for both the frying stability of the oils and the volatile profile of the fried fish fillets. In particular, differences were observed in the crystallization and melting profiles of oleogels before and after frying. Lower levels of total polar material, peroxide value and trans fatty acids contents were noticed in fish fillets fried in the oleogels. An increase in wax concentration had an impact on the volatile profile of fish fillets and lead significant increases in p-xylene, pentene-3-ol and nonanoic acid. In general, oleogel-based frying medium contributed to the formation of characteristic fish fillet including aroma notes of pineapple, balsamic and honey when compared to fish fried in refined canola oil. The findings suggest oleogels as an alternative frying medium for fish with reduced calorie value and improved aromatic quality.Graphical

Evaluation of micro-dispersion on oil recovery during low-salinity water-alternating-CO2 processes in sandstone cores: An integrated experimental approach

Low-salinity water (LSW) and CO2 could be combined to perform better in a hydrocarbon reservoir due to their synergistic advantages for enhanced oil recovery (EOR); however, its microscopic recovery mechanisms have not been well understood due to the nature of these two fluids and their physical reactions in the presence of reservoir fluids and porous media. In this work, well-designed and integrated experiments have been performed for the first time to characterize the in-situ formation of micro-dispersions and identify their EOR roles during a LSW-alternating-CO2 (CO2-LSWAG) process under various conditions. Firstly, by measuring water concentration and performing the Fourier transform infrared spectroscopy (FT-IR) analysis, the in-situ formation of micro-dispersions induced by polar and acidic materials was identified. Then, displacement experiments combining with nuclear magnetic resonance (NMR) analysis were performed with two crude oil samples, during which wettability, interfacial tension (IFT), CO2 dissolution, and CO2 diffusion were quantified. During a CO2-LSWAG process, the in-situ formed micro-dispersions dictate the oil recovery, while the presence of clay minerals, electrical double-layer (EDL) expansion and multiple ion exchange (MIE) are found to contribute less. Such formed micro-dispersions are induced by CO2 via diffusion to mobilize the CO2-diluated oil, alter the rock wettability towards more water-wet, and minimize the density contrast between crude oil and water.

Unveiling the Mechanism of Phonon-Polariton Damping in α-MoO3.

Phonon polaritons (PhPs), light coupled to lattice vibrations, in the highly anisotropic polar layered material molybdenum trioxide (α-MoO3) are currently the focus of intense research efforts due to their extreme subwavelength field confinement, directional propagation, and unprecedented low losses. Nevertheless, prior research has primarily concentrated on exploiting the squeezing and steering capabilities of α-MoO3 PhPs, without inquiring much into the dominant microscopic mechanism that determines their long lifetimes, which is key for their implementation in nanophotonic applications. This study delves into the fundamental processes that govern PhP damping in α-MoO3 by combining ab initio calculations with scattering-type scanning near-field optical microscopy (s-SNOM) and Fourier transform infrared (FTIR) spectroscopy measurements across a broad temperature range (8-300 K). The remarkable agreement between our theoretical predictions and experimental observations allows us to identify third-order anharmonic phonon-phonon scattering as the main damping mechanism of α-MoO3 PhPs. These findings shed light on the fundamental limits of low-loss PhPs, which is a crucial factor for assessing their implementation into nanophotonic devices.

Triggering Overall Crystal Polarization by Octahedron Elongation Distortion for Highly Boosted and Selective Aerobic Photo‐Oxidation

AbstractHigh carrier recombination causes a huge waste of photogenic charge, which severely restrains the photocatalytic efficiency. Creating polarization electric field by polar photocatalytic materials proves effective to promote charge separation, while developing efficient polarization strategy is challenging and the related micromechanism remains obscure. Here, overall polarization is achieved in Bi2MoO6 single crystal photocatalyst by lateral growth of the nanoplate along {010} facets. Gradual elongation of equatorial Mo─O bonds along the MoO6 octahedral layer occurs, while the length of apical Mo─O bonds basically remains unchanged, thus allowing the large asymmetric distortion of MoO6 octahedron for producing the microscopic polarization. Meanwhile, the lateral growth of Bi2MoO6 nanoplates enables the accumulation of distorted polar units, further increasing the polarization intensities. The inside‐out crystal polarization significantly promotes the separation and migration of photogenerated charge carriers. The finely polarized Bi2MoO6 nanoplates exhibit an exceptional photocatalytic selective oxidation rate of benzyl alcohol (BA) to benzaldehyde (BAD) under visible light irradiation (Conversion (Con.) ≈100% within 30 min, Selectivity (Sel.) ≥95%), over 70.7 times that of original Bi2MoO6 nanosheets, on the condition of comparable O2 adsorption capability. This study advances atomic‐level mechanistic insight into polarized materials toward precise design of high‐performance photocatalysts.

Low Dielectric Medium for Hyperbolic Phonon Polariton Waveguide in van der Waals Heterostructures.

Polar van der Waals (vdW) crystals, composed of atomic layers held together by vdW forces, can host phonon polaritons-quasiparticles arising from the interaction between photons in free-space light and lattice vibrations in polar materials. These crystals offer advantages such as easy fabrication, low Ohmic loss, and optical confinement. Recently, hexagonal boron nitride (hBN), known for having hyperbolicity in the mid-infrared range, has been used to explore multiple modes with high optical confinement. This opens possibilities for practical polaritonic nanodevices with subdiffractional resolution. However, polariton waves still face exposure to the surrounding environment, leading to significant energy losses. In this work, we propose a simple approach to inducing a hyperbolic phonon polariton (HPhP) waveguide in hBN by incorporating a low dielectric medium, ZrS2. The low dielectric medium serves a dual purpose-it acts as a pathway for polariton propagation, while inducing high optical confinement. We establish the criteria for the HPhP waveguide in vdW heterostructures with various thicknesses of ZrS2 through scattering-type scanning near-field optical microscopy (s-SNOM) and by conducting numerical electromagnetic simulations. Our work presents a feasible and straightforward method for developing practical nanophotonic devices with low optical loss and high confinement, with potential applications such as energy transfer, nano-optical integrated circuits, light trapping, etc.

Asymmetric Rh Diene Catalysis under Confinement: Isoxazole Ring‐Contraction in Mesoporous Solids

AbstractCovalent immobilization of chiral dienes in mesoporous solids for asymmetric heterogeneous catalysis is highly attractive. In order to study confinement effects in bimolecular vs monomolecular reactions, a series of pseudo‐C2‐symmetrical tetrahydropentalenes was synthesized and immobilized via click reaction on different mesoporous solids (silica, carbon, covalent organic frameworks) and compared with homogeneous conditions. Two types of Rh‐catalyzed reactions were studied: (a) bimolecular nucleophilic 1,2‐additions of phenylboroxine to N‐tosylimine and (b) monomolecular isomerization of isoxazole to 2H‐azirne. Polar support materials performed better than non‐polar ones. Under confinement, bimolecular reactions showed decreased yields, whereas yields in monomolecular reactions were only little affected. Regarding enantioselectivity the opposite trend was observed, i. e. effective enantiocontrol for bimolecular reactions but only little control for monomolecular reactions was found.

First measurement of Gallium Arsenide as a low-temperature calorimeter

In the quest for direct dark matter detection, innovative approaches to lower the detection threshold and explore the sub-GeV mass range, have gained high relevance in the last decade. This study presents the pioneering use of Gallium Arsenide (GaAs) as a low-temperature calorimeter for probing dark matter-electron interactions within the DAREDEVIL (DARk-mattEr DEVIces for Low energy detection) project. Our experimental setup features a GaAs crystal at an ultralow temperature of 15 mK, coupled with a Neutron Transmutation Doped Germanium (NTD-Ge) thermal sensor for precise energy estimation. This configuration is the first step towards detecting single electrons scattered by dark matter particles within the GaAs crystal, to improve the sensitivity to low-mass dark matter candidates significantly. Taking advantage of the production of optical phonons in polar materials such as GaAs gives the possibility to study the scattering of sub-MeV dark matter. This paper presents a detailed analysis of the detector’s response, using a calibration spectrum using α\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\alpha $$\\end{document} particles and X-ray events. While the results do not meet the ambitious eV scale threshold yet, they establish a solid benchmark for assessing the detector’s current performance and sensitivity. This work not only highlights the detector’s potential but also sets the stage for future enhancements aimed at achieving the eV threshold, underscoring the promising direction of this detector technology. These findings demonstrate the feasibility of using GaAs as a cryogenic calorimeter and hence open new avenues for investigating the elusive nature of dark matter through innovative direct detection techniques.

First-Principles Computational Screening of Two-Dimensional Polar Materials for Photocatalytic Water Splitting.

The band gap constraint of the photocatalyst for overall water splitting limits the utilization of solar energy. A strategy to broaden the range of light absorption is employing a two-dimensional (2D) polar material as photocatalyst, benefiting from the deflection of the energy level due to their intrinsic internal electric field. Here, by using first-principles computational screening, we search for 2D polar semiconductors for photocatalytic water splitting from both ground- and excited-state perspectives. Applying a unique electronic structure model of polar materials, there are 13 photocatalyst candidates for the hydrogen evolution reaction (HER) and 8 candidates for the oxygen evolution reaction (OER) without barrier energies from the perspective of the ground-state free energy variation calculation. In particular, Cu2As4Cl2S3 and Cu2As4Br2S3 can catalyze HER and OER simultaneously, becoming promising photocatalysts for overall water splitting. Furthermore, by combining ground-state band structure calculations with excited-state charge distribution and transfer calculated by linear-response time-dependent density functional theory (LR-TDDFT) and time-dependent ab initio nonadiabatic molecular dynamics (NAMD), respectively, the rationality of the 2D polar material model has been manifested. The intrinsic built-in electric field promotes the separation of charge carriers while suppressing their recombination. Therefore, our computational work provides a high-throughput method to design high-performance photocatalysts for water splitting.

Optimization of malic anhydrate concentration in manufacturing PP-g-MA compatibilizer on test percent of grafting degree

The difference in polarity means that two or more materials cannot react, a connecting material such as a compatibilizer is needed to react between polar and non-polar materials. This research aims to determine the effect of maleic anhydride (MA) concentration on the process of grafting MA onto polypropylene (PP) chains with the help of benzoyl peroxide (BPO) as an initiator. The method used to mix these two materials uses the blending method using an internal mixer instrument and testing the percent degree of grafting using the titration method with three repetitions of the test.The research results showed that the highest percent grafting degree occurred at a concentration of 86% PP, 11% MA, and 3% BPO, with a value of 10.28%. The Spectroscopy Fourier Transform Infrared (FTIR) analysis of Polypropylene grafted maleic anhydride (PP-g-MA) showed the presence of new peaks at wavenumbers 1707cm-1 and 1162 cm-1.Increasing the concentration of maleic anhydride had no effect on increasing the percent degree of grafting.