Inversion Symmetry Research Articles

Achieving strong optical nonlinearity and wide bandgap of pnictides via ionic motif-driven directed assembly of covalent groups.

Noncentrosymmetric (NCS) pnictides are indispensable for nonlinear optics, ferroelectrics, magnetic Weyl electronics, etc., areas, yet their structure design remains a substantial challenge. By using asymmetric ionic unit-driven covalent groups orienting and rigidity-flexibility coupling dual strategy, we successfully design and synthesize four NCS pnictides: [Sr4Br]2[MII3Si25P40] (MII = Mg, Cd) and [Ba3Br][MIIISi10P16] (MIII = Ga, In), which exhibit strong second harmonic generation effects (5.2 to 7.5 × AgGaS2), wide bandgaps (1.81 to 1.90 electron volts), and moderate birefringence (0.030 to 0.051). An unprecedented NCS structure-inducing mechanism analysis revealed that the (Sr4Br) and (Ba4Br) ionic units featuring the diamond-like electrostatic force field effectively break inversion symmetry and trigger uniform arrangement of the covalent tetrahedron groups. Furthermore, the nonlinear optical (NLO) properties and birefringence can be remarkably tuned by the secondary covalent building blocks (MII/IIIP4 tetrahedra) with distinct bond flexibility providing a broader space for regulating the key parameters. This work might expand chemical space for exploiting high-performance pnictide NLO materials.

Near GHz Lithium Niobate Higher-Order Topological Nanomechanical Metamaterials.

Precise control over the localization of acoustic waves at microwave frequencies reveals new opportunities in emerging fields like quantum acoustics and spin mechanics. Conventional microwave acoustic resonators, engineered via phonon band structures, are prone to disturbances from fabrication defects, constraining their further development. Acoustic high-order topological insulators, known for their defect robustness and precise localization, have emerged as the preferred approach for developing high-performance resonators. However, the operating frequencies of existing acoustic high-order topological insulators have been limited to relatively low frequencies. Here, we present on-chip acoustic higher-order topological insulators (700-750 MHz) operating in the ultrahigh-frequency band, using lithium niobate nanomechanical metamaterials with smooth surfaces and sharp corners. By breaking the inversion symmetry of honeycomb lattices, higher-order valley Hall topological insulators featuring both odd-type and even-type corner states are constructed. Together, these advances promote the practical application of topological acoustics.

Electric‐Field‐ and Stacking‐Tuned Antiferromagnetic FeClF Bilayer: The Coexistence of Bipolar Magnetic Semiconductor and Anomalous Valley Hall Effect

AbstractValley polarization from broken inversion symmetry provides a new degree of freedom for carriers, bipolar magnetic semiconductor (BMS) generates a purely spin‐polarized current under a gate voltage, but few systems possess the coexistence of valley polarization and BMS. Based on the recent experimental FeCl2 flakes, reversible electric‐field effect on the valley‐ and spin‐polarized Janus FeClF bilayer with different stackings are investigated herein. Janus FeClF bilayers in all three stacks possess interlayer antiferromagnetic (AFM) and intralayer ferromagnetic (FM) couplings. The most stable A (Cl‐Fe‐F‐Cl‐Fe‐F) stack possesses concurrent and spontaneous BMS nature and valley polarization with perpendicular magnetic anisotropy (PMA), while B (Cl‐Fe‐F‐F‐Fe‐Cl) and C (F‐Fe‐Cl‐Cl‐Fe‐F) stacks exhibit AFM semiconductor characters without valley polarization. Electric‐field achieves a transition of BMS and AFM semiconductor. Large ferrovalley (≈108 meV) exists and is mainly contributed by Fe‐dxy and orbitals. With the out‐of‐plane to in‐plane to out‐of‐plane transition of the easy axis, anomalous valley Hall effect (AVHE) can be manipulated to presence and disappearance by perpendicular electric‐field, indicating the valley switch effect (VSE). The coexisting BMS feature, PMA, AVHE and VSE make Janus FeClF bilayer a promising candidate for multifunctional valleytronic and spintronic applications, favoring broad explorations for the low‐dimensional Janus family.

Bound states in the continuum in whispering gallery resonators with pointlike impurities.

Whispering gallery resonators offer a versatile platform for manipulating the photonic transmission. Here, we study such a system, including periodically distributed pointlike impurities along the resonator with ring geometry. Based on an exact expression for the transmission probability we obtain here, we demonstrate that the bound states in the continuum (BICs) form from the whispering gallery modes at the high-symmetry momenta in the ring's Brillouin zone. Furthermore, the presence of the inversion symmetry allows for a selective decoupling of resonant states, favoring the BIC generation and, therefore, allowing extra tunability in the optical transmission of the system.

Ferrospintronic Order in Noncentrosymmetric Antiferromagnets: An Avenue toward Spintronic‐Based Computing, Data Storage, and Energy Harvesting

A ferroic order, ferrospintronic (FSp) order, arising in some magnetic materials lacking inversion symmetry is reported on. Emerging from a macroscopic spontaneous symmetry breaking of both the time reversal T and the spatial inversion, while maintaining the symmetry, the order parameter is given by the dipolar moment of the spin density . Herein a model is advanced that fulfills the symmetry requirements mentioned earlier and its properties are investigated. With the aid of a mean‐field theory, its stability against thermal fluctuations is studied and evidence of truly ferroic states that result from breaking its symmetry is provided. Three predictions that can be checked experimentally to distinguish this class of materials from other compounds are provided. In the first place, it is illustrated that FSp systems host the potential for multiferroic behavior. Second, it is shown that the generic FSp system responds under strain by generating spin currents that can be used in spintronic devices, therefore showing a piezospintronic effect. Finally, it is proven that domain walls in the FSp order parameter lead to magnetoresistive effects. All of the findings mentioned earlier are a significant breakthrough in spintronics and multiferroic phenomena and they have wide‐ranging implications for advancing materials and technologies, particularly in computing and energy harvesting.

Origin of Oxidation Variations in Ambient-Stable β-InSe.

Understanding and controlling the oxidation of layered materials remain critical issues in the final stages of their practical application in devices. Layered materials achieve a band gap by removing inversion symmetry. However, the oxidation process becomes complex, and the oxidation of these materials is not yet fully understood. As a representative example, InSe has attracted considerable attention due to its high charge mobility and Si-like band gap. However, conflicting observations such as oxidation by Se and In have been reported, including contrasting assessments of the oxidation susceptibility. In this study, we report in situ spectroscopy results detailing the origins of various oxidation pathways. We observed that at low defect densities the reduced reaction barrier of InSe due to Se vacancies leads to oxygen adsorption, while as defects increase, the lower electronegativity of In rises as a new pathway for oxidation. At low defect density, the bulk layer was more energetically favored for oxygen adsorption, allowing oxygen to diffuse to a depth sufficient to form pseudoheterojunctions and making the surface layer seemingly resistant to oxidation. Our results provide an answer to why the resulting diversity of optical responses is expected to increase as well as strategies to achieve gas stability.

Enhancing Resonant Second-Harmonic Generation in Bilayer WSe2 by Layer-Dependent Exciton-Polaron Effect.

Two-dimensional (2D) materials serve as exceptional platforms for controlled second-harmonic generation (SHG). Current approaches to SHG control often depend on nonresonant conditions or symmetry breaking via single-gate control. Here, we employ dual-gate bilayer WSe2 to demonstrate an SHG enhancement concept that leverages strong exciton resonance and a layer-dependent exciton-polaron effect. By selectively localizing injected holes within one layer, we induce exciton-polaron states in the hole-filled layer while maintaining normal exciton states in the charge-neutral layer. The distinct resonant conditions of these layers effectively break interlayer inversion symmetry, thereby promoting resonant SHG. This method achieves a remarkable 40-fold enhancement of SHG at minimal electric field, equivalent to conditions near the dielectric-breakdown threshold but using only ∼3% of the critical breakdown field. Our results highlight SHG sensitivity to carrier density and type, offering a new tool for manipulating SHG and probing quantum states in 2D excitonic systems.

Giant Bulk Photovoltaic Power Generation in 2D AgBiP2Se6 Crystals

AbstractWith the theoretical high power conversion efficiency (PCE) exceeding the thermodynamic Schockley–Queisser (S–Q) limit, the bulk photovoltaic (BPV) effect, which is manifested in acentric crystals across the entire visual spectrum, holds great potential for next‐generation light‐harvesting devices. Here the abnormally giant second harmonic generation (SHG) activity and BPV response in 2D AgBiP2Se6 crystals with broken inversion symmetry is demonstrated, which can be remarkably enhanced with the thickness downscaling. Based on the vertical device sandwiched with graphene electrodes, the wideband light absorption of 2D AgBiP2Se6 crystals with Eg of 1.49 eV enables giant BPV response in the entire visible spectrum, and efficient utilization of solar energy contributes to large short‐current (≈330 mA cm−2), high PCE (≈0.13%) and EQE (≈12.5%) under 532 nm light illumination. Furthermore, benefitting from the local ion redistribution driven by an in‐plane electric field, the BPV photocurrent generation is effectively enhanced 3 times, yielding an extremely high PCE of 0.18%, according high among the reported 2D acentric crystals. The study reintroduces AgBiP2Se6 to the 2D acentric crystal family and lays the groundwork to develop BPV devices for light‐harvesting applications.

Discovery of superconductivity and electron-phonon drag in the non-centrosymmetric Weyl semimetal LaRhGe3

We present an exploration of the effect of electron-phonon coupling and broken inversion symmetry on the electronic and thermal properties of the semimetal LaRhGe3. Our transport measurements reveal evidence for electron-hole compensation at low temperatures, resulting in a large magnetoresistance of 3000% at 1.8 K and 14 T. The carrier concentration is on the order of 1021/cm3 with high carrier mobilities of 2000 cm2/Vs. When coupled to our theoretical demonstration of symmetry-protected almost movable Weyl nodal lines, we conclude that LaRhGe3 supports a Weyl semimetallic state. We discover superconductivity in this compound with a Tc of 0.39(1) K and Bc(0) of 2.2(1) mT, with evidence from specific heat and transverse-field muon spin relaxation. We find an exponential dependence in the normal state electrical resistivity below ~50 K, while Seebeck coefficient and thermal conductivity measurements each reveal a prominent peak at low temperatures, indicative of strong electron-phonon interactions. To this end, we examine the temperature-dependent Raman spectra of LaRhGe3 and find that the lifetime of the lowest energy A1 phonon is dominated by phonon-electron scattering instead of anharmonic decay. We conclude that LaRhGe3 has strong electron-phonon coupling in the normal state, while the superconductivity emerges from weak electron-phonon coupling. These results open up the investigation of electron-phonon interactions in the normal state of superconducting non-centrosymmetric Weyl semimetals.

Observation of Highly Spin-Polarized Dangling Bond Surface States in Rare-Earth Pnictide Tellurides.

To generate and manipulate spin-polarized electronic states in solids are crucial for modern spintronics. The textbook routes employ quantum well states or Shockley/topological type surface states whose spin degeneracy is lifted by strong spin-orbit coupling and inversion symmetry breaking at the surface/interface. The resultant spin polarization is usually truncated because of the intertwining between multiple orbitals. Here a unique type of surface states is realized, namely, dangling bond surface states in a family of ternary rare-earth pnictide tellurides RePnTe (Re = La, Gd, Ce; Pn = Sb, Bi), with robust band structure and sizeable spin splitting. Spin and angle-resolved photoemission spectroscopy measurements reveal high spin polarization and distinct spin-momentum locking texture, which, according to the theoretical analysis, arise from local site asymmetry and surface-purified spin-orbital texture. The work extends the so-called "hidden spin polarization" from the bulk to the surface, presenting an intriguing spin-orbital-momentum-layer locking phenomenon, which may shed lights on potential spintronic applications.

Ferromagnetic ferroelectricity due to the Kugel-Khomskii mechanism of orbital ordering assisted by atomic Hund's second rule effects

The exchange interactions in insulators depend on the orbital state of magnetic ions, obeying certain phenomenological principles, known as Goodenough-Kanamori-Anderson rules. Particularly, the ferro order of alike orbitals tends to stabilize antiferromagnetic interactions, while the antiferro order of unlike orbitals favors ferromagnetic interactions. The Kugel-Khomskii theory provides a universal view on such coupling between spin and orbital degrees of freedom, based on the superexchange processes: namely, for a given magnetic order, the occupied orbitals tend to arrange in a way to further minimize the exchange energy. Then, if two magnetic sites are connected by the spatial inversion, the antiferro orbital order should lead to the ferromagnetic coupling break the inversion symmetry. This constitutes the basic idea of our work, which provides a pathway for designing ferromagnetic ferroelectrics: the rare but fundamentally and practically important multiferroic materials. After illustrating the basic idea on toy-model examples, we propose that such behavior can be indeed realized in the van der Waals ferromagnet VI3, employing for this analysis the realistic model derived from first-principles calculations for magnetic 3d bands. We argue that the intra-atomic interactions responsible for Hund's second rule, acting against the crystal field, tend to restore the orbital degeneracy of the ionic d2 state in VI3 and, thus, provide a necessary flexibility for activating the Kugel-Khomskii mechanism of the orbital ordering. In the honeycomb lattice, this orbital ordering breaks the inversion symmetry, stabilizing the ferromagnetic-ferroelectric ground state. The symmetry breaking leads to the canting of magnetization, which can be further controlled by the magnetic field, producing a huge change of electric polarization. Published by the American Physical Society 2024

Self-Trapped Excitons in 3R ZnIn2S4 with Broken Inversion Symmetry for High-Performance Photodetection.

Exploring novel materials with intrinsic self-trapped excitons (STEs) is crucial for advancing optoelectronic technologies. In this study, 2D 3R-phase ZnIn2S4, featuring broken inversion symmetry, is introduced to investigate intrinsic STEs. This material exhibits a broadband photoluminescence (PL) emission with a full width at half maximum of 164nm and a large Stokes shift of ≈0.6eV, which arises from the distortion of [ZnS4]6- tetrahedral unit induced by the symmetry breaking and strong electron-phonon coupling. The photophysical properties of the STEs exhibit a high Huang-Rhys factor (15.0), rapid STEs formation time (166fs), and extended STEs lifetime (1039ps), as demonstrated by experimental evidence from temperature-dependent PL, Raman spectroscopy, and ultrafast absorption spectroscopy. Additionally, STE-induced photoconductiveeffect is elucidated, indicating that intrinsic STEs in 3R-ZnIn2S4 can provide a synergistic effect that enhances absorption capacity, localization, and lifetime by capturing the self-trapped hole state. Consequently, the 2D 3R-ZnIn2S4 photodetector exhibits remarkable broad-spectrum photosensitivity, including a photo-switching ratio of 11286, response times of less than 0.6ms, responsivity of 15.2AW-1, detectivity of 1.02×10¹¹ Jones, and external quantum efficiency of 5032% under 375nm light. These findings provide new ideas for exploring materials with intrinsic STEs to achieve novel high-performance photodetector applications.

Photodetector Based on Elemental Ferroelectric Black Phosphorus-like Bismuth.

Two-dimensional ferroelectric materials have emerged as a promising candidate for the development of next-generation photodetectors owing to their inherent photogalvanic effect (PGE) and strong light-matter interactions. Recently, the first-ever elemental-based ferroelectric material, black-phosphorus-like Bi (BP-Bi), has been successfully synthesized. In this work, we investigate the PGE of the monolayer (ML) BP-Bi by using ab initio quantum transport simulation. We find that the photocurrent of the ML BP-Bi in the ferroelectric direction (armchair) is significantly larger than that in the vertical ferroelectric direction [zigzag (ZZ)]. For example, despite the comparable optical absorption rates of BP-Bi in the armchair (ARM) and ZZ directions, the maximum photocurrent (133 mA/W) in the ARM direction is 2 orders of magnitude greater than that (4.70 mA/W) in the ZZ direction. The asymmetry is attributed to the breaking and existence of the mirror inversion symmetries along the ARM and ZZ directions, respectively. Our work paves the way for the research of the low-dimensional ferroelectric photodetector.

Chiral phonons of honeycomb-type bilayer Wigner crystals

Abstract We theoretically investigated the chiral phonons of honeycomb-type bilayer Wigner crystals recently discovered in van der Waals structures of layered transition metal dichalcogenides. These chiral phonons can emerge under the inversion symmetry breaking introduced by an effective mass imbalance between the two layers or a moiré potential in one layer, as well as under the time-reversal symmetry breaking realized by applying a magnetic field. Considering the wide tunability of layered materials, the frequencies and chirality values of phonons can both be tuned by varying the system parameters. These findings suggest that bilayer honeycomb-type Wigner crystals can serve as an exciting new platform for studying chiral phonons.

Elucidating the Interplay between Symmetry Distortions in Passivated MAPbI3 and the Rashba Splitting Effect.

Hybrid organic-inorganic perovskites play a critical role in modern optoelectronic applications, particularly as single photon sources due to their unusual bright ground state. However, the presence of trap states resulting from surface dangling bonds hinders their widespread commercial application. This work uses density functional theory (DFT) to study the effects of various passivating ligands and their binding sites on Rashba splitting, a phenomenon directly linked to the bright ground state. Our results predict that X2- and X4-type ligands that adsorb at acidic oxygen binding sites and zwitterionic binding sites efficiently eliminate trap states introduced by surface iodine vacancies. Furthermore, our results show that distortions from the nominally symmetric cubic structure of the perovskite predominantly determine the presence and magnitude of the Rashba splitting. Specifically, the loss of more symmetry elements consistently leads to Rashba splitting in both the valence band (VB) and the conduction band (CB) with small Rashba splitting coefficients. Conversely, although inversion symmetry breaking alone fails to guarantee the presence of pure Rashba splitting in both the VB and the CB, it significantly increases the degree of splitting. The adsorption of ligands not only mitigates trap states but also plays a critical role in altering the local symmetry, thus influencing Rashba splitting. DFT predicts a distinct Rashba-Dresselhaus splitting in the CB with X2 ligands, causing the largest splitting. The presence of local electric fields causes consistent Rashba splitting of the VB across all studied systems except for the X4 zwitterionic passivated systems (sulfobetaine and lecithin). Electric fields are predicted to cause significant splitting of the CB, particularly for MAPbI3 and SH passivated MAPbI3 surfaces that possess freely rotating ligand binding sites. This study reveals that the wavelength, tunability of Rashba splitting through an applied electric field, and nature of Rashba-Dresselhaus splitting are influenced by the characteristics of the ligand binding site. On the other hand, pure Rashba splitting is predicted to exhibit a greater susceptibility to symmetry distortion than to specific ligand binding sites. These findings elucidate how surface passivating ligands and symmetry distortions influence Rashba splitting, shaping the optoelectronic properties of perovskite nanocrystals.

Skew scattering and ratchet effect in photonic graphene

This paper is devoted to a comprehensive theoretical study of asymmetric (skew) scattering in photonic graphene, with the main focus on its realization with semiconductor microcavity exciton-polaritons. As an important consequence of the skew scattering, we prove the appearance of the ratchet effect in this system. Triangular defects in the form of missing micropillars in a regular honeycomb lattice are considered to be ones that break the spatial inversion symmetry, thus providing the possibility of the ratchet effect. By means of the numerical solution of the effective Schrödinger equation, we provide microscopical insight into the process of skew scattering and determine indicatrices, cross sections, and asymmetry parameters. In a system with multiple coherently oriented triangular defects, a macroscopic ratchet effect occurs as a unidirectional flux upon noiselike initial conditions. Our study broadens the concept of ratchet phenomena in the field of photonics and optics of exciton-polaritons. Published by the American Physical Society 2024

Spin-valley locked topological phase transitions in reversible strain-tailoring honeycomb motifs

Using an effective low-energy k·p model on the frontier px,y orbitals, we establish a general phase diagram of spin-valley locked band inversion by introducing a mechanical strain field into nonmagnetic honeycomb motifs with robust spin–orbit coupling and intrinsically broken inversion symmetry. Using first-principles calculations, we realize such multiple topological phase transitions in a strained InTe monolayer within experimental reach with the Weyl semimetal as the nontrivial boundary state at two critical strains. The massless Weyl fermions endow the spin and valley Hall effects with ultrafast and dissipationless transport over a broad low-energy window. The valley selective circular dichroism can be regulated by strain-induced band inversion. A crossover between the topologically trivial and nontrivial regimes with sizable bandgaps makes InTe suitable for room-temperature (RT) topological strain-effect transistors. Our work not only demonstrates a fundamental mechanism for exploring tunable topological states and valley physics but also provides a potential platform for realizing many exotic phenomena and RT quantum devices.

3D 3,44T19 Type Carbon Allotrope (3,44T19‐CA): An Ideal Candidate with Phononic Stiefel–Whitney Topology and Multi–Dimensional Boundary Vibrational Modes

The Stiefel–Whitney (SW) insulator, which lacks spin‐orbit coupling and has space–time inversion () symmetry, has attracted significant interest due to its fragile topological state and unconventional bulk‐boundary correspondence. Previously, the identification of SW insulators has been widely proposed for 2D phononic systems, but it has received little attention for 3D phononic systems. Herein, it is recognized that the 3D 3,44T19 type carbon allotrope (3,44T19‐CA) possesses the possibility to attain the nontrivial phononic SW topology characterized by a nontrivial second SW number, specifically w2 = 1. In addition, the 3D 3,44T19‐CA has 2D surface vibrational modes and 1D hinge vibrational modes, providing an excellent platform for multi–dimensional topological phononic boundaries research.

Topological elastic wave transport and manipulation in three-dimensional metamaterials stacked with sandwich plates

Topological metamaterials demonstrate unprecedented wave manipulation abilities with topologically protected robustness, which have been extensively investigated in one-dimensional (1D) and two-dimensional (2D) mechanical systems, but less explored in three-dimensional (3D) systems. In this study, a 3D topological mechanical metamaterial with periodically stacked sandwich metamaterial plates is proposed to achieve 2D topological surface wave transport in a relatively low-frequency range. An innovative chiral compression-torsion coupling core is employed on the sandwich metamaterial plate to lower the band frequency. Analogous to the quantum valley Hall effect, the two-fold topological nodal line is lifted by breaking the spatial inversion symmetry, opening a topological band gap. By supercell analysis, the topological interface state is demonstrated to appear at the interface of two topologically different domains, and the topological boundary state can also be excited under appropriate free or fixed boundary conditions. Taking advantage of the 3D periodicity, the wave propagation based on both topological interface states and boundary states is examined in both 2D flat plates and 3D structures, realizing 1D topological waveguide and 2D topological surface wave transport respectively. It is found that mode symmetry matching is crucial for constructing the topological wave transport with both interface and boundary states. Leveraging the dependence of boundary states on boundary conditions, this work innovatively presents route-switchable and layer-selective wave manipulation by controlling boundary conditions without complicated structure design, enriching the strategies for tunable elastic wave manipulation. Besides, the topologically protected surface wave transport is demonstrated by introducing defects and disorders. These findings provide new insights into the topological transport of elastic waves in 3D mechanical metamaterials and contribute to the development of intelligent and robust devices for various purposes, such as vibration mitigation, energy harvesting, and signal sensing.

Strong emission and plant-growth effects of inversion symmetry lowered Mn4+ on Ca2+, Ga3+ and P5+ substituted SrAl12O19: Mn4+

The high-temperature solid-phase method was used to synthesize the co-solid phosphor (Sr, Ca) (Al, P)12O19: Mn4+, Mg2+, Ga3+. Previous studies have already observed that the doping of Ca2+ for Sr2+ site and Ga3+ for Al3+ site enhances the luminescence intensity of SrAl12O19: Mn4+. Here, we observed that the unique doping of P5+ for Al3+ significantly enhances the luminescence intensity. However, it is never known why these cations can enhance the luminescence. We analyzed Mn K-edge pre-edge peak of XANES and EXAFS and conducted Rietveld analyses of XRD. Then, we reached a comprehensive trend that in all cases, the substitution of cation having significantly larger covalency elongates nearby Mn4+/Al3+–O2- bond and shrink Mn4+/Al3+–O2- bond in opposite side in (Mn4+, Al3+)O6 octahedron, significantly lowering inversion symmetry and lowering parity forbidden transition of 1 s → 3d (pre-edge peak) and 3d → 3d (deep red emission) common as a transition of even parity → even parity. Such a deep red phosphor receiving multiple doping had high external quantum efficiency, 53 %, which much increased the yield of lettuce (+40 %) and mini-tomato (+49 %), which is world-top increase for the important growth of tomato series, compared with the growth (+20 %) under the conventional greenhouse-type sunlight converter.