Electric Polarization Research Articles

Synthesis of in situ grown CNTs on MOF-derived Ni@CNT with tailorable microstructures toward regulation of electromagnetic wave absorption performance

Metal-Organic framework (MOF) derivatives have been applied as electromagnetic wave absorption (EMA) materials in recent years. Carbon nanotubes (CNTs) can achieve in situ growth on the surface of MOF derivatives. However, there is limited research on the EMA performance by regulating the morphology of the in situ grown CNTs. In this work, we prepared MOF-derived Ni@carbon nanotubes (Ni@CNT) with controllable length of CNTs by solvothermal and simple one-step pyrolysis method and revealed the CNT growth mechanism. We further investigated the effect of in situ grown CNT morphology on electromagnetic parameters and EMA performance. In situ grown CNTs of similar length on the surface of MOF derivatives lead to similar electromagnetic parameters. When the length of CNTs is short, the relaxation strength (Δε=εs−ε∞) is high, leading to excellent microwave absorption performance. For Ni@CNT-600, the reflection loss of −44.4 dB can be achieved at merely 1.72 mm. Finite element (FE) simulation was used to evaluate the EMA mechanism of different samples by calculating electric field and polarization strength. This work has explored the electromagnetic wave absorption performance from the perspective of microstructural tailoring, helpful for understanding the unique role of the in situ grown CNTs on the surface of MOF derivatives and investigating the ultra-thin electromagnetic wave absorption materials.

Integration of Electrical Properties and Polarization Loss Modulation on Atomic Fe–N-RGO for Boosting Electromagnetic Wave Absorption

HighlightsSingle-atom Fe–N4 sites embedded into graphene were successfully synthesized to exert the dielectric properties of graphene.The absorption mechanisms of metal-nitrogen doping reduced graphene oxide mainly include enhanced dipole polarization, interface polarization, conduction loss and defect-induced polarization.Excellent reflection loss of − 74.05 dB (2.0 mm) and broad effective absorption bandwidth of 7.05 GHz (1.89 mm, with filler loading only 1 wt%) were obtained.

Deconvolution of X-ray natural and magnetic circular dichroism in chiral Dy-ferroborate.

Structural chirality and magnetism, when intertwined, can have profound implications on materials properties. Using X-ray imaging and spectroscopic measurements that leverage the natural and magnetic circular dichroic effects present in magnetized chiral crystal structures, we probe the interplay between chirality and magnetism across the field-induced spin-flop transition of Dy ferroborate, ( ) . Deconvolution of natural and magnetic circular dichroic signals at the Fe K and Dy L absorption edges of the non-centrosymmetric structure was enabled by use of tunable temperature and magnetic field, providing access to element-specific magnetic information across the spin-flop transition. The magnetic response of Fe and Dy sublattices was found to be independent of domain chirality. The chiral domains were robust against both the (chirality preserving) R32 to P3 21/P3 21 structural phase transition at 280 K, and application of magnetic field up to 4 Tesla. A third flavor of X-ray dichroism, magneto-chiral dichroism, was not detected within the accuracy of our measurements. The absence of significant Fe magnetization along the screw, c-axis for the magnetic field strength used in this study, together with non-linear coupling of magnetic field to electric polarization across the spin-flop transition, may hinder observation of magneto-chiral dichroic effects in this system.

Effect of build orientation on all additively manufactured polyvinylidene fluoride with electrical poling for strain sensing and energy-harvesting application

Effect of build orientation on all additively manufactured polyvinylidene fluoride with electrical poling for strain sensing and energy-harvesting application

FMO-LC-TDDFTB method for excited states of large molecular assemblies in the strong light-matter coupling regime.

We present a new methodology to calculate the strong light-matter coupling between photonic modes in microcavities and large molecular aggregates that consist of hundreds of molecular fragments. To this end, we combine our fragment molecular orbital long-range corrected time-dependent density functional tight-binding methodology with a generalized Tavis-Cummings Hamiltonian. We employ an excitonic Hamiltonian, which is built from a quasi-diabatic basis that is constructed from locally excited and charge-transfer states of all molecular fragments. To calculate polaritonic states, we extend our quasi-diabatic basis to include photonic states of a microcavity and derive and implement the couplings between the locally excited states and the cavity states and built a Tavis-Cummings Hamiltonian that incorporates the intermolecular excitonic couplings. Subsequently, we demonstrate the capability of our methodology by simulating the influence of the electric field polarization on the polaritonic spectra for a tetracene aggregate of 125 monomers. Furthermore, we investigate the dependence of the splitting of the upper and lower polaritonic branches on the system size by comparing the spectra of five different tetracene clusters. In addition, we investigate the polariton dispersion of a large tetracene aggregate for electric field polarizations in the x, y, and z directions. Our new methodology can facilitate the future study of exciton dynamics in complex molecular systems, which consist of up to hundreds of molecules that are influenced by strong light-matter coupling to microcavities.

Individual domain characteristics determined by second-harmonic generation diffractometer for multi-domain multiferroics

We investigated the multi-domain states of a multiferroic La-doped BiFeO3 (BLFO) thin film by examining diffraction patterns in optical second-harmonic generation (SHG) measurement. By directing a laser onto the domain wall within the domain-patterned sample, we observed clear diffraction signatures of SHG waves generated from two ferroelectric domains. We explained the experimental results of the diffraction patterns, including the intensity distribution and the polarization characteristics, using Fresnel propagation of SHG waves. From this, we could determine the amplitude and phase of the SHG waves generated from each domain, and figure out not only the polarization direction of each ferroelectric domain but also the phase related to the complex-valued second-order susceptibility tensor. Consequently, we could present SHG diffractometry as an effective measurement method to reveal the phase details of electric polarization of the multi-domain states of ferroic materials.

Zipper‐Like Dynamic Switching of Coordination Bonds Gives a Polar Bimetallic Halide toward Self‐Driven X‐ray Detection

Polar molecular crystals hold a promise for controlling bulk physical properties originated in their unique switchable polarity via structural transformation. However, the mechanisms for switching polarization are mainly limited to displacive and disorder‐order phase transitions, which rarely involve the reconstruction of chemical bonds. Here, we have switched and tuned electric polarization in a bimetallic halide, (Neopentylammonium)4AgBiBr8 (1), as verified by light‐excited pyroelectric effect. Most notably, its Ag‐Br coordination bonds show a zipper‐like dynamic switching behavior from the ‘locked’ to ‘unlocked’ state, namely, reconstruction of chemical bonds. Coupling with the dynamic ordering of organic cations, this bond‐switching transition makes a contribution to switchable polarization of 1. As expected, its polarity creates pyroelectric effect for self‐driven X‐ray detection with high sensitivity (3.8×103 μC Gy‐1 cm‐2) and low limit of detection (4.8 nGy s‐1). This work on the bond‐switching mechanism provides an avenue to design polar molecular candidate for smart optoelectronic devices.

Behavior of recycled aggregates treated with cement paste with respect to capillary absorption and flexion

Recycling waste from destroyed structure as a new resource of aggregates has several technical, economic and environmental advantages although it should be noted that these aggregates have disadvantages which can reduce the mechanical concrete properties, one of the most important is the water absorption problem. The waste valorisation industry stands as an alternative solution, effectively managing waste while also preserving natural resources. In this context, the present study consists to recover waste resulting from demolition of old Sonalgaz (Electrical poles) columns built in 1947 in the wilaya of Mostaganem. The obtained aggregates are enveloped by the old cement paste, which is known for its porous nature, resulting in a significant water absorption capacity. For that purpose, it was advisable to determine the required absorbed water quantity to saturate a specific recycled aggregates (RA) volume. In this work, we have opted for the method of cement paste treatment of the aggregates 3/8 mm and 8/16 mm. This method involves covering them by a film of cement paste and letting them dry for 28 days. Additionally, this study includes an analysis of the physical properties of natural and recycled aggregates, both before and after treatment, along with their impact on the mechanical properties of concrete mixes containing fully pre-saturated aggregates (100% RA) and a blend of half recycled and half natural aggregates (50% RA + 50% NA). These results are compared to reference concrete made solely with 100% natural aggregates (NA).

Versatile Metamaterial: Exploring the Resonances of Symmetry‐Protected Modes for Multitasking Functionality

AbstractIn this work, an experimental study supported by numerical modeling that demonstrates the possibility of exciting Symmetry Protected‐Bound states In the Continuum (SP‐BICs) in a 1D silicon grating fabricated on a lithium niobate substrate is presented. bBoth transverse electric and magnetic polarization states are investigated, leading to the excitation of four quasi‐ Bound states In the Continuum (quasi‐BIC) resonances, exhibiting distinct behaviors. Under standard illumination conditions (plane of incidence perpendicular to the 1D grating lines), two of these resonances are highly sensitive to illumination conditions, while the other two resonances involving unconventional illumination directions (plane of incidence parallel to the grating lines) are more robust to the angle of incidence, but just as sensitive to external stresses in terms of resonance wavelength and quality factor. Additionally, temperature detection is experimentally demonstrated with a Sensitivity of ST = 0.81∼nm °C−1, a state‐of‐the‐art value achieved due to significant electromagnetic field enhancement inside the lithium niobate substrate at the quasi‐BIC resonance. These findings pave the way for their use in various sensing applications (such as biology, electromagnetic, and temperature sensing), as well as nonlinear applications like second harmonic generation, and electro‐ and acousto‐optic modulation.

Theoretical Investigation of Electric Polarizability in Porphyrin-Zinc and Porphyrin-Zinc-Thiazole Complexes Using Small Property-Oriented Basis Sets.

Porphyrin complexes are of great importance due to their possible applications as sensors, solar cells and photocatalysts, as well as their ability to bind additional ligands. A valuable source of knowledge on their nature is their electric properties, which can be evaluated employing density functional theory (DFT) methods, supporting the experimental research. The present work aims at the application of small property-oriented basis sets in calculation of electric properties in transition metals, their oxides and test coordination complexes. Firstly, the existing polarized ZPol basis set for the first-row transition metals is modified in order to improve atomic polarizability results. For this purpose, optimization of the f-type polarization function exponent is carried out with respect to the value of average atomic polarizability of investigated metals. Next, both the original and the modified basis sets are employed in finite field CCSD(T) calculation of transition metal oxides' dipole moments, as well as DFT calculation of polarizabilities in porphyrin-zinc and porphyrin-zinc-thiazole complexes. The obtained results show that the ZPol and ZPol-A basis sets can be successfully employed in the calculation of linear electric properties in large systems. The optimization procedure used in the present work can be employed for other source basis sets and elements, leading to new efficient polarized basis sets.

Remote Activation of Antimicrobial Properties via Magnetoeletric Stimulation of Biopolymer‐Based Nanocomposites

AbstractAntimicrobial materials are crucial for high‐touch surfaces to prevent the adhesion and proliferation of microorganisms, playing a key role in infection control measures. In this work, a magnetoelectric nanocomposite able to exert antimicrobial activity when magnetically stimulated, is obtained by solvent casting. The nanocomposites, composed of poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) and cobalt ferrite magnetostrictive nanoparticles (CFO NPs), respond to a variable magnetic field by mechanically stimulating the piezoelectric component of the material, thereby inducing an electrical polarization. The antimicrobial properties of the material are determined by exposing it to different frequencies (0.3 and 1 Hz) using a custom‐designed magnetic bioreactor, where the resulting electrical microenvironments are the contributing factor. The growth of Escherichia coli and Staphylococcus aureus over the nanocomposite is highly inhibited when magnetically stimulated (dynamic conditions) mainly at 0.3 Hz, in contrast to static conditions. The electric microenvironment is further measured upon magnetic stimulation, with PHBV films with 20% CFO inducing a voltage variation of ≈20 µV at the surface while the films with 10% CFO induced a voltage variation of ≈12 µV. This work demonstrated that magnetic stimulation, combined with magnetoelectric materials, can be used for remote antimicrobial control, thus preventing the spread of infections.

Self-healable and stretchable perovskite-elastomer gas-solid triboelectric nanogenerator for gesture recognition and gripper sensing

Gas-solid triboelectric nanogenerators (GS-TENGs) based on porous elastomers provide a promising avenue for the design of self-powered sensors. However, the intrinsic limitation of low electric output in GS-TENGs could affect the accuracy and sensitivity of sensing systems. Here, we develop a porous composite by integrating an adhesive poly(siloxane-diphenylglyoxime-urethane) (PSDU) elastomer with ferroelectric (3,3-difluorocyclobutylammonium) 2 CuCl 4 [(DF-CBA) 2 CuCl 4 ] fillers. PSDU, an intrinsically triboelectric negative material with alternating hard-soft segments and supramolecular bonds, imparts excellent compressibility, adhesion, and self-healing properties to the composite. Simultaneously, the incorporation of (DF-CBA) 2 CuCl 4 as functional fillers leverages the formation of a hydrogen bonding network to enhance charge transfer processes. These fillers facilitate charge accumulation through an electric poling process, resulting in a power output improvement that surpasses 1400 times higher than that of a dense PSDU-based GS-TENG. Tapping onto the versatile properties of porous poly(siloxane-diphenylglyoxime-urethane)-perovskite (PSDU-PK) GS-TENGs, applications such as hand gesture/food recognition and dual-mode sensing system have been demonstrated, suggesting their promising potential in wearable electronics and smart agriculture.

Design and performance of a dual-band plasmonic perfect absorber for infrared refractive index sensing

In this study, we introduce what we believe is an innovative design for a plasmonic perfect absorber (PPA) that is based on half-cut disk resonator metamaterials. This design exhibits remarkable stability and versatility, demonstrating effective functionality across a wide range of incident angles for both transverse electric (TE) and transverse magnetic (TM) polarization. The distinct operational characteristics of the PPA are highlighted by the presence of two corresponding absorption peaks at wavelengths of 870 and 1599 nm, where it achieves outstanding maximum absorption rates of 98.99% and 97.5%, respectively. The design’s ultra-narrow resonance peaks are indicative of its high-quality factors, which are vital for enhancing sensitivity in plasmonic sensory applications. This characteristic renders our PPA an exceptional candidate for refractive index (RI) sensing, where precision is critical. The dual-band perfect absorber (PA)-based sensor demonstrates significant RI sensitivity, with values approximately equal to 365 nm/RIU at the first absorption peak and 733 nm/RIU at the second. Our findings elucidate the exceptional potential inherent in this novel dual-band perfect absorber design. The versatility and efficiency across varied applications not only contribute to the existing body of knowledge but also pave the way for future advancements in plasmonic sensor technologies and metamaterial research.

Fracture behaviors and crack propagation anisotropy in multi-ions modified bismuth titanate ferroelectrics

Bismuth titanate (BIT) is widely considered a promising lead-free piezoelectric material for advanced high-temperature applications. Despite significant advances in high-performance BIT ferroelectrics, there remains little understanding of mechanical properties including fracture failure and crack propagation behaviors, hindering the optimization of stability and reliability for next-generation high-temperature ferroelectrics. In this work, we investigated mechanical fracture and crack propagation behaviors of a type of high-performance bismuth titanate-based ceramic (Bi3.96Ce0.04Ti3–2xWxNbxO12, BCTWN) with different doping contents and electric poling states. High-resolution transmission electron microscopy (HRTEM) and electron backscatter diffraction (EBSD) results reveal that the BCTWN ceramics possess a single ferroelectric phase and exhibit layered crystal structures characterized by periodic fringe features. In addition, the striped domain structures are observed on the surface of plate-like grains. Mechanical measurements indicate that fracture behaviors of BCTWN ceramics are significantly affected by doping contents. The ceramics with the largest grain size present inferior microstructure with more defects, endowing the lowest bending strength and fracture toughness. For the samples with different poling states, strong anisotropy in crack propagation and fracture toughness is observed, attributed to the different domain switching mechanisms driven by local incompatible stress fields, which is experimentally validated by the intriguing evolutions of striped domain structures around crack tips. This work advances our understanding of the fracture and crack propagation mechanisms of BIT-based ceramics and provides insight into tailoring the mechanical behaviors through doping and poling strategies.

Ultrahigh Capacitive Energy Storage in a Heterogeneous Nanolayered Composite

AbstractFerroelectric polymers with robust electrical polarization have been extensively investigated for capacitive energy storage. However, their inherent ferroelectric hysteresis loss limits the discharged energy density and compromises energy efficiency. Here, a heterogeneous nanolayered composite of ferroelectric polymer poly(vinylidene fluoride‐trifluoroethylene) (P(VDF‐TrFE)) and Al2O3 is presented, which effectively mitigates ferroelectric hysteresis loss while maintaining high polarization and enhanced breakdown strength. Phase‐field simulations indicate that the polarization behaviors of the heterogeneous layered structure are jointly influenced by the thickness and dielectric constant of each component, which balances the electrical energy and Landau energy within the heterogeneous system. Guided by the theoretical simulations, optimized polarization behaviors are achieved with a significant reduction in remnant polarization and ferroelectric loss in the P(VDF‐TrFE)/Al2O3 composites through careful control of P(VDF‐TrFE) thickness at nanometer scale. Moreover, the presence of multiple interfaces in the layered composites leads to a remarkable enhancement in polarization and breakdown strength. Consequently, an ultrahigh energy density of about 108 J cm−3 is achieved with a high charge–discharge efficiency of exceeding 80%. This work not only presents a straightforward approach to modify the polarization behaviors of ferroelectric polymers but also demonstrates a promising strategy for developing high‐energy‐density polymer nanocomposites.

Prediction of multiferroicity in the layered hydrogen-bonded system α-CrOOH: Proton transfer ferroelectricity and strain-tunable magnetic transition

Ferroelectric materials with vertical polarization could provide ground-breaking device applications, compatible with electric-field switching even in the presence of a surface-depolarizing field. Herein, we present theoretical evidence that rhombohedral chromium oxide hydroxide α-CrOOH, which has been synthesized experimentally, is a type-Ⅰ multiferroic. First-principles calculations plus Monte Carlo simulations indicate that α-CrOOH is a room temperature proton transfer ferroelectricity semiconductor with robust electric polarization as large as 24.6 μC/cm2. Moreover, the system exhibits an anti-ferromagnetism ground state with a Neel temperature of 340 K, where strain can modulate the transition from antiferromagnetic to ferromagnetic. Finally, a two-dimensional (2D) heterostructure model was designed, composed of monolayer α-CrOOH and functional MXene, for various applications such as non-volatile memory (NVM). The remarkable properties may enable the system to hold great potential for the development of future multifunctional devices.

Spontaneous parametric downconversion in a laser-poled lithium niobate nonlinear photonic crystal with nanoscale resolution.

Based on quasi-phase-matching (QPM) theory, nonlinear photonic crystals (NPCs) are capable of realizing efficient spontaneous parametric downconversion (SPDC) for the generation of photonic entangled states. However, the traditional electric field poling techniques employed in NPC fabrication often result in non-negligible processing errors of a few hundred nanometers, thus impeding the production of quantum photon pairs as intended. In this work, we investigate the SPDC photon pairs generated in a laser-poled lithium niobate (LN) NPC. By using the recently developed laser poling technique, the processing error of the NPC is substantially reduced to approximately 15 nm. Consequently, the coincidence counts of the generated photon pairs in the experiment reach 83.6% of the designed value. Our result paves the way for on-demand production of high-quality quantum sources, which has potential applications in quantum communications and quantum computations.

Surface-near domain engineering in multi-domain x-cut lithium niobate tantalate mixed crystals

Lithium niobate and lithium tantalate are among the most widespread materials for nonlinear, integrated photonics. Mixed crystals with arbitrary Nb–Ta ratios provide an additional degree of freedom to not only tune materials properties, such as the birefringence but also leverage the advantages of the singular compounds, for example, by combining the thermal stability of lithium tantalate with the larger nonlinear or piezoelectric constants of lithium niobate. Periodic poling allows to achieve phase-matching independent of waveguide geometry and is, therefore, one of the commonly used methods in integrated nonlinear optics. For mixed crystals, periodic poling has been challenging so far due to the lack of homogeneous, mono-domain crystals, which severely inhibit domain growth and nucleation. In this work, we investigate surface-near (<1μm depth) domain inversion on x-cut lithium niobate tantalate mixed crystals via electric field poling and lithographically structured electrodes. We find that naturally occurring head-to-head or tail-to-tail domain walls in the as-grown crystal inhibit domain inversion at a larger scale. However, periodic poling is possible if the gap size between the poling electrodes is of the same order of magnitude or smaller than the average size of naturally occurring domains. This work provides the basis for the nonlinear optical application of lithium niobate tantalate mixed crystals.

Unveiling the NLO Potential of New Zn (II) Complex of 6‐Methylpyridine‐2‐Carboxaldehyde: Experimental/DFT Study on Spectral, Static, and Frequency‐Dependent Linear/Nonlinear Optical Parameters

ABSTRACTOngoing exploration focuses on synthesizing and characterizing coordination compounds to improve the design of nonlinear optical (NLO)‐based materials. In this regard, to examine spectral and static/frequency–dependent linear/NLO parameters, the new Zn (II) complex {[Zn(6‐MePyAld)2(Cl)]; 6‐MePyAld: 6‐methylpyridine‐2‐carboxaldehyde} was synthesized and characterized by using 1H and 13C NMR, mass (LC‐HRMS), powder XRD, and FTIR spectra. The electronic features of synthesized complex were investigated by considering the TD‐CAM‐B3LYP/ and TD‐M06L/6‐311G(d,p)//LanL2DZ levels of time‐dependent density functional theory (TD‐DFT). Moreover, the theoretical linear optical (LO), second‐, and third‐order NLO susceptibility tensors/polarization (χ(1)/P(1), χ(2)/P(2), χ(3)/P(3)) parameters for the Zn (II) complex were computed using the DFT/M06L and DFT/CAM‐B3LYP levels. The external electric field (E), polarization (P), and electric displacement (D) values of the Zn (II) complex were also calculated using the same DFT levels. To investigate microscopic LO (isotropic polarizability <α(0;0)>/<α(−ω;ω)>, and anisotropic polarizability (∆α (0;0)/∆α (−ω;ω)) and second‐/third‐order NLO (<β(0;0,0)>/<β(−ω;ω,0), <β(−2ω;ω,ω)>/<γ(0;0,0,0)>/<γ(−ω;ω,0,0)> and <γ(−2ω;ω,ω,0)>) parameters for the Zn (II) complex, the DFT/M06L and DFT/CAM‐B3LYP levels in the gas phase were used. The ∆α (0;0), ∆α (−ω;ω), <β(0;0,0)>, <β(−ω;ω,0)>, and <β(−2ω;ω,ω)> for Zn (II) complex were computed at 17.288 × 10−24, 21.782 × 10−24, 14.692 × 10−30, 466.80 × 10−30, and 210.79 × 10−30 esu, respectively, by using the DFT/CAM‐B3LYP level. Moreover, the <γ(0;0,0,0)>/<γ(−ω;ω,0,0)> and <γ(−2ω;ω,ω,0)> in the gas phase computed at the DFT/CAM‐B3LYP level for Zn (II) complex were obtained at 129.74 × 10−36, 3997.6 × 10−36, and −886.60 × 10−36 esu, in turn. According to the CAM‐B3LYP level, the <γ(0;0,0,0)> value is 8.65 and 18.53 times higher than the values of para‐nitroaniline (pNA) and urea, respectively. The obtained static/dynamic β and γ values of Zn (II) complex are greater than those of urea and pNA. Zn (II) complex exhibited remarkably microscopic second‐order and particularly third‐order NLO features. It is predicted that our study will shed light on NLO materials that might be used in telecommunication and optoelectronics.

Pressure-induced multiple structural phase transitions on multiferroic CaMn7O12

CaMn7O12 (CMO) is an outstanding multiferroic material known for its significant magnetically-induced electric polarization. Its strong magnetoelectric (ME) effect, i.e., electric polarization controlled via magnetic fields or vice versa, makes this material suitable for a variety of technological applications. In this study, we employed synchrotron X-ray powder diffraction to explore polycrystalline CMO's pressure-induced structural phase transitions (SPTs). Our results indicate that CMO undergoes two distinct pressure-induced SPTs: the first transition occurs at pressures above 7.0 GPa, changing from a rhombohedral to an orthorhombic structure, and the second occurs around 13.0 GPa, transforming into a monoclinic structure. These findings differ from the pressure-induced behavior of CMO single crystals and highlight CMO as one of the rare quadruple perovskites exhibiting multiple pressure-induced non-isostructural phase transitions. This study expands the understanding of phase stability behavior in multiferroic materials under high-pressure conditions.