Symmetry-breaking Distortions Research Articles

Si metasurface supporting multiple quasi-BICs for degenerate four-wave mixing

Abstract Dielectric metasurfaces supporting quasi-bound states in the continuum (qBICs) enable high field enhancement with narrow-linewidth resonances in the visible and near-infrared ranges. The resonance emerges when distorting the meta-atom’s geometry away from a symmetry-protected BIC condition and, usually, a given design can sustain one or two of these states. In this work, we introduce a silicon-on-silica metasurface that simultaneously supports up to four qBIC resonances in the near-infrared region. This is achieved by combining multiple symmetry-breaking distortions on an elliptical cylinder array. By pumping two of these resonances, the nonlinear process of degenerate four-wave mixing is experimentally realized. By comparing the nonlinear response with that of an unpatterned silicon film, the near-field enhancement inside the nanostructured dielectric is revealed. The presented results demonstrate independent geometric control of multiple qBICs and their interaction through wave mixing processes, opening new research pathways in nanophotonics, with potential applications in information multiplexing, multi-wavelength sensing and nonlinear imaging.

Noncollinear Electric Dipoles in a Polar Chiral Phase of CsSnBr3 Perovskite.

Polar and chiral crystal symmetries confer a variety of potentially useful functionalities upon solids by coupling otherwise noninteracting mechanical, electronic, optical, and magnetic degrees of freedom. We describe two phases of the 3D perovskite, CsSnBr3, which emerge below 85 K due to the formation of Sn(II) lone pairs and their interaction with extant octahedral tilts. Phase II (77 K < T < 85 K, space group P21/m) exhibits ferroaxial order driven by a noncollinear pattern of lone pair-driven distortions within the plane normal to the unique octahedral tilt axis, preserving the inversion symmetry observed at higher temperatures. Phase I (T < 77 K, space group P21) additionally exhibits ferroelectric order due to distortions along the unique tilt axis, breaking both inversion and mirror symmetries. This polar and chiral phase exhibits second harmonic generation from the bulk and pronounced electrostriction and negative thermal expansion along the polar axis (Q22 ≈ 1.1 m4 C-2; αb = -7.8 × 10-5 K-1) through the onset of polarization. The structures of phases I and II were predicted by recursively following harmonic phonon instabilities to generate a tree of candidate structures and subsequently corroborated by synchrotron X-ray powder diffraction and polarized Raman and 81Br nuclear quadrupole resonance spectroscopies. Preliminary attempts to suppress unintentional hole doping to allow for ferroelectric switching are described. Together, the polar symmetry, small band gap, large spin-orbit splitting of Sn 5p orbitals, and predicted strain sensitivity of the symmetry-breaking distortions suggest bulk samples and epitaxial films of CsSnBr3 or its neighboring solid solutions as candidates for bulk Rashba effects.

Ligand-Induced Chirality in ClMBA2 SnI4 2D Perovskite.

Chiral perovskites possess a huge applicative potential in several areas of optoelectronics and spintronics. The development of novel lead-free perovskites with tunable properties is a key topic of current research. Herein, we report a novel lead-free chiral perovskite, namely (R/S-)ClMBA2 SnI4 (ClMBA=1-(4-chlorophenyl)ethanamine) and the corresponding racemic system. ClMBA2 SnI4 samples exhibit a low band gap (2.12 eV) together with broad emission extending in the red region of the spectrum (∼1.7 eV). Chirality transfer from the organic ligand induces chiroptical activity in the 465-530 nm range. Density functional theory calculations show a Rashba type band splitting for the chiral samples and no band splitting for the racemic isomer. Self-trapped exciton formation is at the origin of the large Stokes shift in the emission. Careful correlation with analogous lead and lead-free 2D chiral perovskites confirms the role of the symmetry-breaking distortions in the inorganic layers associated with the ligands as the source of the observed chiroptical properties providing also preliminary structure-property correlation in 2D chiral perovskites.

Identifying native point defect configurations in α-alumina

Intimately intertwined atomic and electronic structures of point defects govern diffusion-limited corrosion and underpin the operation of optoelectronic devices. For some materials, complex energy landscapes containing metastable defect configurations challenge first-principles modeling efforts. Here, we thoroughly reevaluate native point defect geometries for the illustrative case of α-Al2O3 by comparing three methods for sampling candidate geometries in density functional theory calculations: displacing atoms near a naively placed defect, initializing interstitials at high-symmetry points of a Voronoi decomposition, and Bayesian optimization. We find symmetry-breaking distortions for oxygen vacancies in some charge states, and we identify several distinct oxygen split-interstitial geometries that help explain literature discrepancies involving this defect. We also report a surprising and, to our knowledge, previously unknown trigonal geometry favored by aluminum interstitials in some charge states. These new configurations may have transformative impacts on our understanding of defect migration pathways in aluminum-oxide scales protecting metal alloys from corrosion. Overall, the Voronoi scheme appears most effective for sampling candidate interstitial sites because it always succeeded in finding the lowest-energy geometry identified in this study, although no approach found every metastable configuration. Finally, we show that the position of defect levels within the band gap can depend strongly on the defect geometry, underscoring the need to conduct careful searches for ground-state geometries in defect calculations.

Enhanced Anharmonicity by Forming Low-Symmetry Off-Center Phase: The Case of Two-Dimensional Group-IB Chalcogenides.

Enhanced anharmonicity is required to achieve many interesting phenomena in thermoelectricity, superconductivity, ferroelectricity, etc. Here, we propose a novel mechanism for enhancing anharmonicity by forming the low-symmetry off-center ground state, such as the s(II) phase, in two-dimensional AIB2X chalcogenides (AIB = Cu, Ag and Au; X = S, Se, and Te). In this system, the in-plane rotational phonon mode introduces a much stronger anharmonicity in the distorted s(II) phase than in the nondistorted s(I) phase. We show that the stabilities of the s(I) and s(II) phases arise from the ionicity and the ionic size; for example, the low ionicity and the small ionic size favor the s(II) phase. We further demonstrate that the anharmonicity can be tuned by controlling the strain-induced s(II)-to-s(I) phase transition, which explains the anomalous lattice thermal conductivity. Our work relates anharmonicity to symmetry-breaking structural distortion and widens the ways to design excellent thermoelectric materials.

Focused-ion-beam assisted technique for achieving high pressure by uniaxial-pressure devices

Uniaxial pressure or strain can introduce a symmetry-breaking distortion on the lattice and may alter the ground states of a material. Compared to hydrostatic pressure, a unique feature of the uniaxial-pressure measurements is that a tensile force can be applied and thus a “negative” pressure can be achieved. In doing so, both ends of the sample are usually glued on the frame of the uniaxial-pressure device. The maximum force that can be applied onto the sample is sometimes limited by the shear strength of the glue, the quality of the interface between the sample and the glue, etc. Here we use focused ion beam to reduce the width of the middle part of the sample, which can significantly increase the effective pressure applied on the sample. By applying this technique to a home-made piezobender-based uniaxial-pressure device, we can easily increase the effective pressure by one or two orders of magnitude as shown by the change of the superconducting transition temperature of an iron-based superconductor. Our method thus provides a possible way to increase the upper limit of the pressure for the uniaxial-pressure devices.

Hydrogen adsorption and diffusion on doped Zr(0001) surfaces: A first-principles study

The hydrogen adsorption and diffusion behaviors on the clean and a series of element doped Zr(0001) surfaces are studied through first-principles calculations. Among the studied doping elements, Cu, Co, Y, and Mg prefer to substitute Zr on the topmost surface layer, Al, Pd, Ir, and Si are favored from topmost layer to several surface layers down, while Mo is not favored. Independent of the substitution energies, Mo, Co, and Ir induce a symmetry-breaking local distortion surface structure. Based on the obtained geometries, it is found that most dopants promote the hydrogen adsorption on their next nearest neighbor sites but hinder it on the nearest neighbor sites. Most of the dopants also promote both the hydrogen diffusion on the surface plane and the hydrogen penetration into the subsurface layers. The results indicate that element doping may facilitate the hydride nucleation in Zr alloys.

Angular Momentum Transfer via Relativistic Spin-Lattice Coupling from First Principles.

The transfer and control of angular momentum is a key aspect for spintronic applications. Only recently, it was shown that it is possible to transfer angular momentum from the spin system to the lattice on ultrashort timescales. To contribute to the understanding of angular momentum transfer between spin and lattice degrees of freedom we present a scheme to calculate fully relativistic spin-lattice coupling parameters from first principles. In addition to the dipole-dipole interactions often discussed in the literature, these parameters give, in particular, access to the spin-lattice effects controlled by spin-orbit coupling. By treating changes in the spin configuration and atomic positions at the same level, closed expressions for the atomic spin-lattice coupling parameters can be derived in a coherent manner up to any order. Analyzing the properties of these parameters, in particular their dependence on spin-orbit coupling, we find that even in bcc Fe the leading term for the angular momentum exchange between the spin system and the lattice is a Dzyaloshiskii-Moriya-type interaction, which is due to the symmetry breaking distortion of the lattice.

Emergent nematicity and intrinsic versus extrinsic electronic scattering processes in the kagome metal CsV3Sb5

Fermi surface fluctuations and lattice instabilities in the 2D metallic kagome superconductor CsV$_3$Sb$_5$ are elucidated via polarization-resolved Raman spectroscopy. The presence of a weak electronic continuum in high-quality samples marks the cross-over into the charge-density-wave (CDW) ordered phase, while impurity-rich samples promote strong defect-induced electronic scattering processes that affect the coherence of the CDW phase. CDW-induced phonon anomalies appear below $T_{\mathrm{CDW}}$, with emergent $C2$ symmetry for one of the CDW amplitude modes, alluding to nematicity. In conjunction with symmetry-breaking lattice distortions, a kink-like hardening of the A$_{1g}$ phonon energy at $T_{\mathrm{CDW}}$ signifies a concerted interplay of electronic correlations and electron-phonon coupling in the exotic CDW order.

Nonlinear deformation and elasticity of BCC refractory metals and alloys

Application of isotropic pressure or uniaxial strain alters the elastic properties of materials; sufficiently large strains can drive structural transformations. Linear elasticity describes stability against infinitesimal strains, while nonlinear elasticity describes the response to finite deformations. It was previously shown that uniaxial strain along [100] drives refractory metals and alloys towards mechanical instabilities. These include an extensional instability, and a symmetry-breaking orthorhombic distortion caused by a Jahn-Teller-Peierls instability that splays the cubic lattice vectors. Here we analyze these transitions in depth. Eigenvalues and eigenvectors of the Wallace tensor identify and classify linear instabilities in the presence of strain. We show that both instabilities are discontinuous, leading to discrete jumps in the lattice parameters. We provide physical intuition for the instabilities by analyzing the changes in first-principles energy, stress, bond lengths, and angles upon application of strain. Electronic band structure calculations show differential occupation of bonding and antibonding orbitals, driven by the changing bond lengths and leading to the structural transformations. Strain thresholds for these instabilities depend on the valence electron count.

Automated Experiment in 4D-STEM: Exploring Emergent Physics and Structural Behaviors.

Automated experiments in 4D scanning transmission electron microscopy (STEM) are implemented for rapid discovery of local structures, symmetry-breaking distortions, and internal electric and magnetic fields in complex materials. Deep kernel learning enables active learning of the relationship between local structure and 4D-STEM-based descriptors. With this, efficient and "intelligent" probing of dissimilar structural elements to discover desired physical functionality is made possible. This approach allows effective navigation of the sample in an automated fashion guided by either a predetermined physical phenomenon, such as strongest electric field magnitude, or in an exploratory fashion. We verify the approach first on preacquired 4D-STEM data and further implement it experimentally on an operational STEM. The experimental discovery workflow is demonstrated using graphene and subsequently extended toward a lesser-known layered 2D van der Waals material, MnPS3. This approach establishes a pathway for physics-driven automated 4D-STEM experiments that enable probing the physics of strongly correlated systems and quantum materials and devices, as well as exploration of beam-sensitive materials.

Neutron powder-diffraction study of phase transitions in strontium-doped bismuth ferrite: 1. Variation with chemical composition

We report results from a study of the crystal and magnetic structures of strontium-doped BiFeO3 using neutron powder diffraction and the Rietveld method. Measurements were obtained over a wide range of temperatures from 300–800 K for compositions between 10%–16% replacement of bismuth by strontium. The results show a clear variation of the two main structural deformations—symmetry-breaking rotations of the FeO6 octahedra and polar ionic displacements that give ferroelectricity—with chemical composition, but relatively little variation with temperature. On the other hand, the antiferromagnetic order shows a variation with temperature and a second-order phase transition consistent with the classical Heisenberg model. There is, however, very little variation in the behaviour of the antiferromagnetism with chemical composition, and hence with the degree of the structural symmetry-breaking distortions. We therefore conclude that there is no significant coupling between antiferromagnetism and ferroelectricity in Sr-doped BiFeO3 and, by extension, in pure BiFeO3.

Neutron powder diffraction study of the phase transitions in deuterated methylammonium lead iodide

We report the results of a neutron powder diffraction study of the phase transitions in deuterated methylammonium lead iodide, with a focus on the system of orientational distortions of the framework of PbI6 octahedra. The results are analysed in terms of symmetry-adapted lattice strains and normal mode distortions. The higher-temperature cubic–tetragonal phase transition at 327 K is weakly discontinuous and nearly tricritical. The variations of rotation angles and spontaneous strains with temperature are consistent with a standard Landau theory treatment. The lower-temperature transition to the orthorhombic phase at 165 K is discontinuous, with two systems of octahedral rotations and internal distortions that together can be described by 5 order parameters of different symmetry. In this paper we quantify the various symmetry-breaking distortions and their variation with temperature, together with their relationship to the spontaneous strains, within the formalism of Landau theory. A number of curious results in the low-temperature phase are identified, particularly regarding distortion amplitudes that decrease rather than increase with lowering temperature.

Ab initio study of CsBiO[formula omitted] oxide-perovskite, dynamical stability and bonding analysis

The quest for a new stable oxide perovskite is a crucial challenge for use in many fields of applications. However, the Jahn-Teller effect in conjunction with symmetry-breaking distortion in some compounds acts as a key ingredient for several intriguing quantum phenomena causing instability in the ideal cubic structure. Using density functional theory (DFT) calculations, we find that the CsBiO3 compound is rather stable in a distorted tetragonal structure than in an ideal cubic one. To analyze this stability, we investigated deeply the thermodynamic and dynamical properties of the title compound. The results suggest that the octahedral distortion is due to the anti-symmetric breathing modes moving the BiO6 octahedra. Both electronic and topological analyses of electron density showed that these distortions found their origin in the sp lone pair bonds in the Bi units.

Electron Polarons in Lithium Niobate: Charge Localization, Lattice Deformation, and Optical Response

Lithium niobate (LiNbO3), a material frequently used in optical applications, hosts different kinds of polarons that significantly affect many of its physical properties. In this study, a variety of electron polarons, namely free, bound, and bipolarons, are analyzed using first-principles calculations. We perform a full structural optimization based on density-functional theory for selected intrinsic defects with special attention to the role of symmetry-breaking distortions that lower the total energy. The cations hosting the various polarons relax to a different degree, with a larger relaxation corresponding to a larger gap between the defect level and the conduction-band edge. The projected density of states reveals that the polaron states are formerly empty Nb 4d states lowered into the band gap. Optical absorption spectra are derived within the independent-particle approximation, corrected by the GW approximation that yields a wider band gap and by including excitonic effects within the Bethe–Salpeter equation. Comparing the calculated spectra with the density of states, we find that the defect peak observed in the optical absorption stems from transitions between the defect level and a continuum of empty Nb 4d states. Signatures of polarons are further analyzed in the reflectivity and other experimentally measurable optical coefficients.

Probing atomic-scale symmetry breaking by rotationally invariant machine learning of multidimensional electron scattering

The 4D scanning transmission electron microscopy (STEM) method maps the structure and functionality of solids on the atomic scale, yielding information-rich data sets describing the interatomic electric and magnetic fields, structural and electronic order parameters, and other symmetry breaking distortions. A critical bottleneck is the dearth of analytical tools that can reduce complex 4D-STEM data to physically relevant descriptors. We propose an approach for the systematic exploration of 4D-STEM data using rotationally invariant variational autoencoders (rrVAE), which disentangle the general rotation of the object from other latent representations. The implementation of purely rotational rrVAE is discussed as are applications to simulated data for graphene and zincblende structures. The rrVAE analysis of experimental 4D-STEM data of defects in graphene is illustrated and compared to the classical center-of-mass analysis. This approach is universal for probing symmetry-breaking phenomena in complex systems and can be implemented for a broad range of diffraction methods.

Mass enhancement in 3d and s−p perovskites from symmetry breaking

In some d-electron oxides the measured effective mass m(exptl) has long been known to be significantly larger than the model effective mass m(model) deduced from mean-field band theory, i.e., m(exptl) = beta * m(model), where beta > 1 is the "mass enhancement", or "mass renormalization" factor. Previous applications of density functional theory (DFT), based on the smallest number of possible magnetic, orbital, and structural degrees of freedom, missed such mass enhancement, a fact that was taken as evidence of strong electronic correlation being the exclusive enabling physics. The current paper reports that known modalities of energy-lowering symmetry-broken spin and structural effects included in mean-field DFT show mass enhancement for both electrons and holes in a range of d-electron perovskites SrVO3, SrTiO3, BaTiO3, and LaMnO3 as well as p-electron perovskites CsPbI3 and SrBiO3, including metals (SrVO3) and insulators (the rest). This is revealed only when enlarged unit cells of the same parent global symmetry, which are large enough to allow for symmetry breaking distortions and concomitant variations in spin order, are explored for their ability to lower the total energy. The paper analyzes the contributions of different symmetry-broken modalities to mass enhancement, finds common effects in the range of d- as well as p-electron perovskites. Thus, symmetry breaking in mean-field theory could describe effects that were previously attributed exclusively to complex correlated treatments. Indeed, broken symmetries are often experimentally observed, e.g., octahedral tilting, Jahn-Teller distortions, or bond disproportionation, and often provide intuitive explanations in terms of degeneracy removal due to lowering of structural symmetry, or as shifting of band energies in explainable directions.

Investigating phase transitions from local crystallographic analysis based on statistical learning of atomic environments in 2D MoS2-ReS2

The mechanisms of phase transitions have been previously explored at various theoretical and experimental levels. For a wide variety of compounds, the majority of studies are limited by observations at fixed temperature and composition, in which case, relevant information can be determined only from the behaviors at topological and structural defects. All analyses to date utilize macroscopic descriptors derived from structural information such as polarization or octahedral tilts extracted from the atomic positions, ignoring the multiple degrees of freedom observable from atomically resolved images. In this article, we provide a solution, by exploring the mechanisms of a phase transition between the trigonal prismatic and distorted octahedral phases of layered chalcogenides in the 2D MoS2–ReS2 system from the observations of local degrees of freedom, namely atomic positions by scanning transmission electron microscopy. We employ local crystallographic analysis based on statistical learning of atomic environments to build a picture of the transition from the atomic level up and determine local and global variables controlling the local symmetry breaking. We highlight how the dependence of the average symmetry-breaking distortion amplitude on global and local concentration can be used to separate local chemical as well as global electronic effects on the transition. This approach allows for the exploring of atomic mechanisms beyond the traditional macroscopic descriptions, utilizing the imaging of compositional fluctuations in solids to explore phase transitions over a range of observed local stoichiometries and atomic configurations.

Novel Strongly Correlated Europium Superhydrides.

We conducted a joint experimental-theoretical investigation of the high-pressure chemistry of europium polyhydrides at pressures of 86-130 GPa. We discovered several novel magnetic Eu superhydrides stabilized by anharmonic effects: cubic EuH9, hexagonal EuH9, and an unexpected cubic (Pm3n) clathrate phase, Eu8H46. Monte Carlo simulations indicate that cubic EuH9 has antiferromagnetic ordering with TN of up to 24 K, whereas hexagonal EuH9 and Pm3n-Eu8H46 possess ferromagnetic ordering with TC = 137 and 336 K, respectively. The electron-phonon interaction is weak in all studied europium hydrides, and their magnetic ordering excludes s-wave superconductivity, except, perhaps, for distorted pseudohexagonal EuH9. The equations of state predicted within the DFT+U approach (U - J were found within linear response theory) are in close agreement with the experimental data. This work shows the great influence of the atomic radius on symmetry-breaking distortions of the crystal structures of superhydrides and on their thermodynamic stability.

Group-III quantum defects in diamond are stable spin-1 color centers

Color centers in diamond have emerged as leading solid-state artificial atoms for a range of quantum technologies, from quantum sensing to quantum networks. Concerted research activities are now underway to identify new color centers that combine stable spin and optical properties of the nitrogen vacancy (NV$^-$) with the spectral stability of the silicon vacancy (SiV$^-$) centers in diamond, with recent research identifying other group IV color centers with superior properties. In this Letter, we investigate a new class of diamond quantum emitters from first principles, the group III color centers, which we show to be thermodynamically stable in a spin-1, electric-field insensitive structure. From ab initio electronic structure methods, we characterize the product Jahn-Teller (pJT) effect present in the excited state manifold of these group III color centers, where we capture symmetry-breaking distortions associated with strong electron-phonon coupling. These predictions can guide experimental identification of group III vacancy centers and their use in applications in quantum information science and technology.