Ravi Kashikar

Ferroelectrics remain in the focus of scientific attention for decades owing to their fundamental and practical appeal. Recently, ferroelectricity has been demonstrated in semiconducting halide perovskites (Zhang et al 2022 Sci. Adv. 8 eabj5881), offering both a rare combination of ferroelectricity and semiconductivity in the same material and a possible alternative to the prevailing perovskite oxide ferroelectrics. We propose a route to simulating such materials at finite temperatures capable of reproducing key experimental and first-principle data, such as Curie temperature, phase transition sequence, spontaneous polarization, and soft mode frequencies. The key methodological finding is the superior performance of hybrid exchange correlation functionals in parametrization of effective Hamiltonians for ferroelectrics with lone pair. The parametrization for effective Hamiltonians for CsGeX ₃ (X = Cl, Br, I) is reported. The application of methodology to study polarization reversal in CsGeX ₃ allows for the development of a ‘minimalistic’ model for polarization reversal in ferroelectrics that provides an insight into the mechanisms of polarization reversal and its key features, such as the relationship between the coercive field, temperature, and AC field frequency. Importantly, the model reveals the origin of the well-known and ever-puzzling overestimation of coercive fields in computations. Furthermore, we report a variety of finite-temperature properties of CsGeX ₃ ferroelectrics, such as dielectric susceptibility, pyroelectric coefficients, and energy storage density, which reveal that these halide perovskites possess properties comparable to their oxide counterparts. We believe that our work provides significant methodological advancements, deepens fundamental understanding of ferroelectrics, and reveals the potential of halide perovskite ferroelectrics.

Ferroelectrics remain in the focus of scientific attention for decades owing to their fundamental and practical appeal. Recently, ferroelectricity has been demonstrated in semiconducting halide perovskites, offering both a rare combination of ferroelectricity and semiconductivity in the same material and a possible alternative to the prevailing perovskite oxide ferroelectrics. We propose a route to simulating such materials at finite temperatures capable of reproducing key experimental and first-principle data, such as Curie temperature, phase transition sequence, spontaneous polarization, and soft mode frequencies. The key methodological finding is the superior performance of hybrid exchange correlation functionals in parametrization of effective Hamiltonians for ferroelectrics with lone pair. The parametrization for effective Hamiltonians for CsGeX$_3$, (X=Cl, Br, I) is reported. The application of methodology to study polarization reversal in CsGeX$_3$, allows for the development of a ``minimalistic" model for polarization reversal in ferroelectrics that provides an insight into the mechanisms of polarization reversal and its key features, such as the relationship between the coercive field, temperature, and AC field frequency. Importantly, the model reveals the origin of the well-known and ever-puzzling overestimation of coercive fields in computations. Furthermore, we report a variety of finite-temperature properties of CsGeX$_3$, ferroelectrics, such as dielectric susceptibility, pyroelectric coefficients, and energy storage density, which reveal that these halide perovskites possess properties comparable to their oxide counterparts. We believe that our work provides significant methodological advancements, deepens fundamental understanding of ferroelectrics, and reveals the potential of halide perovskite ferroelectrics.

Ferroelectricity has recently been demonstrated in germanium-based halide perovskites. We use first-principles-based simulations to study 4-18 nm CsGeBr3 films and develop a theory for ferroelectric ultrathin films. The theory introduces (i) a local order parameter, which identifies phase transitions into both monodomain and polydomain phases, and (ii) a dipole pattern classifier, which allows efficient and reliable identification of dipole patterns. Application of the theory to both halides CsGeBr3 and CsGeI3 and oxide BiFeO3 ultrathin ferroelectrics reveals two distinct scenarios. First, the films transition into a monodomain phase below the critical value of the residual depolarizing field. Above this critical value, the second scenario occurs, and the film undergoes a transition into a nanodomain phase. The two scenarios exhibit opposite responses of Curie temperature to thickness reduction. Application of a dipole pattern classifier reveals rich nanodomain phases in halide films: nanostripes, labyrinths, zig-zags, pillars, and lego domains.

Hybrid organic-inorganic perovskites are famous for the diversity of their chemical compositions, phases, phase transitions, and associated physical properties. We use a combination of experimental and computational techniques to reveal a strong coupling between structure, magnetism, and spin splitting in a representative of the largest family of hybrid organic-inorganic perovskites: the formates. With the help of first-principles simulations, we find spin splitting in both conduction and valence bands of [NH2NH3]Co(HCOO)(3) induced by spin-orbit interactions, which can reach up to 14 meV. Our magnetic measurements reveal that this material exhibits canted antiferromagnetism below 15.5 K. The direction of the associated antiferromagnetic order parameter is strongly coupled with spin splitting in the centrosymmetric phase, allowing for the creation and annihilation of spin splitting through the application of a magnetic field. Furthermore, the structural phase transition to the experimentally observed polar Pna2(1) phase completely changes the aforementioned spin splitting and its coupling to magnetic degrees of freedom. This reveals that in [NH2NH3]Co(HCOO)(3), the structure and magnetism are strongly coupled to spin splitting and can be manipulated through electric and magnetic fields. We believe that our findings offer an important step toward a fundamental understanding and practical applications of materials with coupled properties.

Ferroelectricity has recently been demonstrated in germanium-based inorganic halide perovskites. We use atomistic first-principles-based simulations to study ultra-thin CsGeBr$_3$ films with thicknesses of 4-18 nm and develop a theory for ferroelectric ultrathin films. The theory introduces (i) a local order parameter, the local polarization, which allows the identification of phase transitions into both monodomain and polydomain phases, and (ii) a dipole pattern classifier, which allows efficient and reliable identification of unique dipole patterns. Application of the theory to both halides CsGeBr$_3$ and CsGeI$_3$, as well as oxide BiFeO$_3$ ultrathin ferroelectrics, which undergo paraelectric cubic to ferroelectric rhombohedral phase transition in bulk, reveal two distinct scenarios for ultrathin films. In the first one, the films transition into a monodomain phase, which is allowed below a critical value of the residual depolarizing field. Above this critical value, the second scenario occurs, and the film undergoes a phase transition into a nanodomain phase. The two scenarios are associated with the opposite response of Curie temperature to thickness reduction. As the film's thickness decreases, the transition temperature into the monodomain phase increases while the transition temperature into the nanodomain phase decreases. The surface effects are responsible for the Curie temperature enhancement, while the stripe domain pattern is the origin of the transition temperature suppression. Application of dipole pattern classifier reveals a rich variety of nanodomain phases in halide films: nano-stripes, labyrinths, zig-zags, pillars, and lego-domains. Our work could lead to both a deeper understanding of nanoscale ferroelectrics and discoveries of unusual nanoscale dipole patterns.

The piezoelectric response is a measure of the sensitivity of a material’s polarization to stress or its strain to an applied field. Using in operando X-ray Bragg coherent diffraction imaging, we observe that topological vortices are the source of a 5-fold enhancement of the piezoelectric response near the vortex core. The vortices form where several low-symmetry ferroelectric phases and phase boundaries coalesce. Unlike bulk ferroelectric solid solutions in which a large piezoelectric response is associated with coexisting phases in the proximity of the triple point, the largest responses for pure BaTiO3 at the nanoscale are in spatial regions of extremely small spontaneous polarization at vortex cores. The response decays inversely with polarization away from the vortex, analogous to the behavior in bulk ceramics as the cation compositions are varied away from the triple point. We use first-principles-based molecular dynamics to augment our observations, and our results suggest that nanoscale piezoelectric materials with a large piezoelectric response can be designed within a parameter space governed by vortex cores. Our findings have implications for the development of next-generation nanoscale piezoelectric materials.

Hybrid organic-inorganic perovskites are famous for the diversity of their chemical compositions, phases and phase transitions, and associated physical properties. We use a combination of experimental and computational techniques to reveal strong coupling between structure, magnetism, and spin splitting in a representative of the largest family of hybrid organic-inorganic perovskites: the formates. With the help of first-principles simulations, we find spin splitting in both conduction and valence bands of [NH$_2$NH$_3$]Co(HCOO)$_3$, induced by spin-orbit interactions, which can reach up to 14~meV. Our magnetic measurements reveal that this material exhibits canted antiferromagnetism below 15.5 K. The direction of the associated antiferromagnetic order parameter is strongly coupled with the spin splitting already in the centrosymmetric phase, allowing for the creation and annihilation of spin splitting through the application of a magnetic field. Furthermore, the structural phase transition into experimentally observed polar Pna2$_1$ phase completely changes the aforementioned spin splitting and its coupling to magnetic degrees of freedom. This reveals that in [NH$_2$NH$_3$]Co(HCOO)$_3$, the structure and magnetism are strongly coupled to spin splitting in a way that allows for its manipulation through both magnetic and electric fields. As an example, for a given point inside the Brillouin zone of centrosymmetric Pnma phase of [NH$_2$NH$_3$]Co(HCOO)$_3$, spin splitting can be turned on/off by aligning the antiferromagnetic vector along certain crystallographic directions or through inducing a polar phase by the application of an electric field. We believe that our findings offer an important step toward fundamental understanding and practical applications of materials with coupled properties.

Persistent spin textures are highly desirable for applications in spintronics, as they allow for long carrier spin lifetimes. However, they are also rare, as they require a delicate balance between spin-momentum coupling parameters. We used density functional theory simulations to predict the possibility of achieving these desirable spin textures through the application of uniaxial stress. Hybrid organic-inorganic perovskite MPSnBr₃ (MP = CH₃PH₃) is a ferroelectric semiconductor which exhibits persistent spin textures near its conduction band minimum and mostly Rashba type spin textures in the vicinity of its valence band maximum. Application of uniaxial stress leads to the gradual evolution of the valence band spin textures from mostly Rashba type to quasipersistent ones under a tensile load and to pure Rashba or quasipersistent ones under a compressive load. The material exhibits flexibility, a rubber-like response, and both positive and negative piezoelectric constants. A combination of such properties may create opportunities for flexible and rubbery spintronic devices.