Through model Hamiltonian studies and first-principle electronic structure calculations, we have examined the effect of inversion symmetry breaking (ISB) field and hydrostatic pressure on the band topology of halide perovskites by taking MAPbI$_3$ as a prototype. Our study shows that while hydrostatic pressure induces normal to topological insulator continuous phase transition, the ISB field makes it first order. The pressure smoothly reduces the normal bandgap, and without ISB, the system achieves a gapless state before it produces a non-trivial bandgap with inverted characters. The ISB field does not stabilize the gapless state, and therefore, the discontinuity in the bandgap with pressure gives rise to the first-order transition. Furthermore, in the non-trivial phase, the ISB field forms an invariant surface Dirac circle in the neighbourhood of TRIM, which is first of its kind. The circle is formed due to interpenetration of Dirac cones resembling the band topology of AA-stacked bilayer graphene.
Dabconium hybrid perovskites include a number of recently-discovered ferroelectric phases with large spontaneous polarisations. The origin of ferroelectric response has been rationalised in general terms in the context of hydrogen bonding, covalency, and strain coupling. Here we use a combination of simple theory, Monte Carlo simulations, and density functional theory calculations to assess the ability of these microscopic ingredients---together with the always-present through-space dipolar coupling---to account for the emergence of polarisation in these particular systems whilst not in other …
We study the circular photogalvanic effect in the organometal halide perovskite solar cell absorber CH$_3$NH$_3$PbI$_3$. For crystal structures which lack inversion symmetry, the calculated photocurrent density is about $10^{-9}$ A/W, comparable to the previously studied quantum well and bulk Rashba systems. Because of the dependence of the circular photogalvanic effect on inversion symmetry breaking, the degree of inversion asymmetry at different depths from the surface can be probed by tuning the photon energy and associated penetration depth. We propose that measurements of this effect may …
Ternary cubic perovskite compounds of the form A_(1/3)A'_(1/3)A''_(1/3)BO_3 and AB_(1/3)B'_(1/3)B''_(1/3)O_3, in which the differentiated cations form an alternating series of monolayers, are studied using first-principles methods. Such compounds are representative of a possible new class of materials in which ferroelectricity is perturbed by compositional breaking of inversion symmetry. For isovalent substitution on either sublattice, the ferroelectric double-well potential is found to persist, but becomes sufficiently asymmetric that minority domains may no longer survive. The strength of th…
Near-room-temperature magnetoelectric coupling engineered through inversion-breaking tilts in a bulk perovskite polytype
University of Warwick（华威大学）；Luxembourg Institute of Science and Technology（卢森堡科学技术研究所）；Rutherford Appleton Laboratory（鲁瑟福阿普尔顿实验室）；Durham University（杜伦大学）
Perovskite oxides ABO$_3$ containing heavy B-site elements are a class of candidate materials to host topological metals with a large spin-orbit interaction. In contrast to the band insulator BaSnO$_3$, the semimetal BaPbO$_3$ is proposed to be a typical example with an inverted band structure, the conduction band of which is composed of mainly the O-2p orbital. In this study, we exemplify a band-gap modification by systematic structural, optical, and transport measurements in BaSn$_{1-x}$Pb$_x$O$_3$ films. A sudden suppression of the conductivity and an enhancement of the weak antilocalizatio…
Stable oxide topological insulators (TIs) that could bring together the traditional oxide functionalities with the dissipationless surface states of TIs have been sought for years but none was found. Yet, heavier chalcogenides (selenides, tellurides) were readily found to be TIs. We clarify here the basic contradiction between TI-ness and stability which is maximal for oxides, and trace the basic design principles necessary to identify the window of opportunity of stable TIs. We first identify the electronic motif that can achieve topological band inversion ("topological gene") in ABO3 as bein…
Bulk and surface electronic structures, calculated using density functional theory and a tight-binding model Hamiltonian, reveal the existence of two topologically invariant (TI) surface states in the family of cubic Bi perovskites (ABiO$_3$; A = Na, K, Rb, Cs, Mg, Ca, Sr and Ba). The two TI states, one lying in the valence band (TI-V) and other lying in the conduction band (TI-C) are formed out of bonding and antibonding states of the Bi-$\{$s,p$\}$ - O-$\{$p$\}$ coordinated covalent interaction. Below a certain critical thickness of the film, which varies with A, TI states of top and bottom …
Using density-functional theory calculations, we analyze the optical absorption properties of lead (Pb)-free metal halide perovskites (AB$^{2+}$X$_3$) and double perovskites (AB$^+$B$^{3+}$X$_6$) (A = Cs or monovalent organic ion, B$^{2+}$ = non-Pb divalent metal, B$^+$ = monovalent metal, B$^{3+}$ = trivalent metal, X = halogen). We show that, if B$^{2+}$ is not Sn or Ge, Pb-free metal halide perovskites exhibit poor optical absorptions because of their indirect bandgap nature. Among the nine possible types of Pb-free metal halide double perovskites, six have direct bandgaps. Of these six typ…
We report a theoretical study of the non-linear magnetoelectric response of GdFeO$_3$ through an analytical approach combined with a Heisenberg model which is fitted against first-principles calculations. Our theory reproduces the non-linear change of polarization under applied magnetic field reported experimentally such that it allows to analyze the origin of the large responses in the different directions. We show that the non-linear character of the response in these materials originates from the fact that the antiferromagnetic order of Gd atoms changes non-linearly with respect to the appl…
We predict a new class of topological crystalline insulators (TCI) in the anti-perovskite material family with the chemical formula A$_3$BX. Here the nontrivial topology arises from band inversion between two $J=3/2$ quartets, which is described by a generalized Dirac equation for a "Dirac octet". Our work suggests that anti-perovskites are a promising new venue for exploring the cooperative interplay between band topology, crystal symmetry and electron correlation.
The oxide heterostructure [(YFeO$_3$)$_5$(LaFeO$_3$)$_5$]$_{40}$, which is magnetically ordered and piezoelectric at room temperature, has been constructed from two weak ferromagnetic AFeO$_3$ perovskites with different A cations using RHEED-monitored pulsed laser deposition. The polarisation arises through the removal of inversion centres present within the individual AFeO$_3$ components. This symmetry reduction is a result of combining ordering on the A site, imposed by the periodicity of the grown structure, with appropriate orientations of the octahedral tilting characteristic of the perov…
The centrosymmetric halide perovskites undergo a continuous phase transition from a normal insulator to a topological insulator at the critical value of strain. Contrarily, in noncentrosymmetric halide perovskites, this phase transition is discontinuous. The noncentrosymmetry does not stabilize the gapless state, causing a discontinuity in the bandgap. We have employed the density functional theory and Slater-Koster formalism-based tight-binding Hamiltonian studies to understand the evolution of band topology under the compressive strain in the halide perovskites. Our study shows that both cub…
For the intrinsic carriers of MAPbBr$_{3}$, the temperature $T$ dependent mobility $μ(T)$ of behaves like $μ\propto T^{-1/2}$ in piezoelectric tetragonal phase, $μ\propto T^{-1.4}$ in non-piezoelectric cubic phase. But for the photo-generated carriers in other halide perovskites ABX$_{3}$, $μ\propto T^{-3/2}$ behavior is typical. Due to the strong interaction of carrier with longitudinal optical phonon, in ABX$_{3}$ the carriers mainly exist as optical polarons. The softness of ABX$_{3}$ renders it without inversion center in tetragonal phase, which allows piezoelectric effect at low carrier c…
We put forward double perovskites of the R$_2$NiMnO$_6$ family (with $R$ a rare-earth atom) as a new class of multiferroics on the basis of {\it ab initio} density functional calculations. We show that changing $R$ from La to Y drives the ground-state from ferromagnetic to antiferromagnetic with $\uparrow\uparrow\downarrow\downarrow$ spin patterns. This E$^*$-type ordering breaks inversion symmetry and generates a ferroelectric polarization of few $μC/cm^2$. By analyzing a model Hamiltonian we understand the microscopic origin of this transition and show that an external electric field can be …
The monoclinic double-perovskite Sr2YRuO6 has recently gained a renewed interest in order to get a deeper insight into the exotic magnetic ground states associated with geometric frustration. Striking discrepancies between the spin order derived from the neutron diffraction refinements and the macroscopic magnetic and thermal responses is a major challenge that must be addressed. In this work, detailed neutron diffraction measurements as a function of temperature yield a completely different interpretation of the patterns. We show that at low temperatures a spin structure of the K2NiF4-type is…
The lead halide perovskites demonstrate huge potential for optoelectronic applications, high energy radiation detectors, light emitting devices and solar energy harvesting. Those materials exhibit strong spin-orbit coupling enabling efficient optical orientation of carrier spins in perovskite-based devices with performance controlled by a magnetic field. Perovskites are promising for spintronics due to substantial bulk and structure inversion asymmetry, however, their spin properties are not studied in detail. Here we show that elaborated time-resolved spectroscopy involving strong magnetic fi…
We have fabricated PbTiO$_{3}$/SrRuO$_{3}$ superlattices with ultra-thin SrRuO$_{3}$ layers. Due to the superlattice geometry, the samples show a large anisotropy in their electrical resistivity, which can be controlled by changing the thickness of the PbTiO$_{3}$ layers. Therefore, along the ferroelectric direction, SrRuO$_{3}$ layers can act as dielectric, rather than metallic, elements. We show that, by reducing the concentration of PbTiO$_{3}$, an increasingly important effect of polarization asymmetry due to compositional inversion symmetry breaking occurs. The results are significant as …
The hybrid organic inorganic perovskites (HOIPs) have attracted much attention for their potential applications as novel optoelectronic devices. Remarkably, the Rashba band splitting, together with specific spin orientations in k space (i.e., spin texture), has been found to be relevant for the optoelectronic performances. In this work, by using first principles calculations and symmetry analyses, we study the electric polarization, magnetism, and spin texture properties of the antiferromagnetic (AFM) HOIP ferroelectric TMCM_MnCl3 (TMCM = (CH3)3NCH2Cl, trimethylchloromethyl ammonium). This rec…
ThTaN$_3$, a rare cubic perovskite nitride semiconductor, has been studied using {\it ab initio} methods. Spin-orbit coupling (SOC) results in band inversion and a band gap of 150 meV at the zone center. In spite of the trivial $Z_2$ indices, two pairs of spin-polarized surface bands cross the gap near the zone center, indicating that this system is a topological crystalline insulator with the mirror Chern number of $|{\cal C}_m|=2$ protected by the mirror and $C_4$ rotational symmetries. Additionally, SOC doubles the Seebeck coefficient, leading to a maximum of $\sim$400 $μ$V/K at 150 K for c…
Perovskite photovoltaic ABX$_3$ systems are being studied due to their high energy-conversion efficiencies with current emphasis placed on pure inorganic systems. In this work, synchrotron single-crystal diffraction measurements combined with second harmonic generation measurements reveal the absence of inversion symmetry below room temperature in CsPbBr$_3$. Local structural analysis by pair distribution function and X-ray absorption fine structure methods are performed to ascertain the local ordering, atomic pair correlations, and phase evolution in a broad range of temperatures. The current…
For static crystals it is well known that electronic states are doubly degenerate in their spin degree of freedom in the presence of time reversal and inversion symmetries. This degeneracy can only be lifted by either (i) breaking time reversal symmetry, for example in a ferromagnet, or (ii) breaking inversion symmetry and having spin orbit coupling, for example in the Rashba effect. We propose that spin degeneracy can be lifted in time reversal and inversion symmetric crystals with a combination of lattice vibrations and spin-orbit coupling. We demonstrate this effect in the cubic perovskite …
In this work we report the synthesis and structural, electronic and magnetic properties of La1.5Ca0.5CoMnO6 double-perovskite. This is a re-entrant spin cluster material which exhibits a non-negligible negative exchange bias effect when it is cooled in zero magnetic field from an unmagnetized state down to low temperature. X-ray powder diffraction, X-ray photoelectron spectroscopy and magnetometry results indicate mixed valence state at Co site, leading to competing magnetic phases and uncompensated spins at the magnetic interfaces. We compare the results for this Ca-doped material with those …
We use a group theoretical approach to enumerate the possible couplings between magnetism and ferroelectric polarisation in the parent $Pm\bar{3}m$ perovskite structure. We show that third order magnetoelectric coupling terms must always involve magnetic ordering at the A and B-site which either transforms both as R-point or both as X-point time odd irreducible representations (irreps). For fourth order couplings we demonstrate that this criterion may be relaxed allowing couplings involving irreps at X, M and R-points which collectively conserve crystal momentum, producing a magnetoelectric ef…
Doubling the perovskite cell (double perovskite) has been found to open new possibilities for engineering functional materials, magnetic materials in particular. This route should be applicable to the antiperovskite (aPV) class. In the pnictide based double aPV (2aPV) class introduced here magnetism is very rare, and we address them as new topological materials, possibly with thermoelectric interest. We have found that the 2aPV supercell provides a systematically larger band gap that can serve to inhibit bulk conductivity, and also large spin-orbit coupling (SOC) for band inversion. We present…
In insulating materials with ordered magnetic spiral phases, ferroelectricity can emerge due to the breaking of inversion symmetry. This property is of both fundamental and practical interest, in particular with a view to exploiting it in low-power electronic devices. Advances towards technological applications have been hindered, however, by the relatively low ordering temperatures $T_\mathrm{spiral}$ of most magnetic spiral phases, which rarely exceed 100 K. We have recently established that the ordering temperature of a magnetic spiral can be increased up to 310 K by the introduction of che…
Bulk Photovoltaic Effect in Two-Dimensional Perovskite Oxides
Northwest University（西北大学）；Shaanxi Key Laboratory for Theoretical Physics Frontiers（陕西省理论物理前沿重点实验室）；Fundamental Discipline Research Center for Quantum Science and Technology of Shaanxi Province（陕西省量子科学与技术基础学科研究中心）；Center for Alloy Innovation and Design, State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University（西安交通大学材料力学行为国家重点实验室合金创新与设计中心）
Lead and tin-based chalcogenide semiconductors like PbTe or SnSe have long been known to exhibit an unusually low thermal conductivity that makes them very attractive thermoelectric materials. An apparently unrelated fact is that the excitonic bandgap in these materials increases with temperature, whereas for most semiconductors one observes the opposite trend. These two anomalous features are also seen in a very different class of photovoltaic materials, namely the halide-perovskites such as CsPbBr3. It has been previously proposed that emphanisis, a local symmetry-breaking phenomenon, is the…
We predict a new class of three-dimensional topological insulators (TIs) in which the spin-orbit coupling (SOC) can more effectively generate a large band gap at $Γ$ point. The band gap of conventional TI such as Bi$_2$Se$_3$ is mainly limited by two factors, the strength of SOC and, from electronic structure perspective, the band gap when SOC is absent. While the former is an atomic property, we find that the latter can be minimized in a generic rock-salt lattice model in which a stable crossing of bands {\it at} the Fermi level along with band character inversion occurs for a range of parame…
We have performed a systematic study of the electronic structures of BiMeO3 (Me = Sc, Cr, Mn, Fe, Co, Ni) series by soft X-ray emission (XES) and absorption (XAS) spectroscopy. The band gap values were estimated for all compounds in the series. For BiFeO3 a band gap of ~0.9 eV was obtained from the alignment of the O Ka XES and O 1s XAS. The O 1s XAS spectrum of BiNiO3 indicates that the formation of holes is due to a Ni2+ valency rather than a Ni3+ valency. We have found that the O Ka XES and O 1s XAS of BiMeO3 probing partially occupied and vacant O 2p states, respectively, are in agreement …
Disentangling octahedral distortion and symmetry breaking in the ordered double perovskite SrLaCoNbO$_6$
Ames National Laboratory, U.S. Department of Energy, Iowa State University（艾姆斯国家实验室，美国能源部，爱荷华州立大学）；Indian Institute of Technology Delhi（德里印度理工学院）；The University of New South Wales (UNSW)（新南威尔士大学）
Tuning the spin-orbit coupling strength via foreign element doping and/or modifying bonding strength via strain engineering are the major routes to convert normal insulators to topological insulators. We here propose an alternative strategy to realize topological phase transition by tuning the orbital level. Following this strategy, our first-principles calculations demonstrate that a topological phase transition in some cubic perovskite-type compounds CsGeBr$_3$ and CsSnBr$_3$ could be facilitated by carbon substitutional doping. Such unique topological phase transition predominantly results …
Oxides with perovskite-based structures have been known as essential materials for fascinating phenomena such as high-temperature and unconventional superconductivity. Discoveries of these oxide superconductors have driven the science community to vastly extend the concepts of strongly correlated electron systems. The base of these materials, the cubic perovskite oxides, $AB$O$_3$, also exhibit superconductivity with $T_{\mathrm{c}}$ of up to 30 K, as reported for Ba$_{0.6}$K$_{0.4}$BiO$_3$. Perovskite oxides have their counterparts, antiperovskite oxides $A_3B$O (or "$B$O$A_3$"), in which the…
In this work, we studied time-reversal-breaking topological phases as a result of the interplay between antiferromagnetism and inverted band structures in thin films of antiferromagnetic double perovskite transition-metal Sr$_2$FeOsO$_6$. By combining the first-principles calculations and analytical models, we demonstrate that the quantum anomalous Hall phase and chiral topological superconducting phase can be realized in this system. We find that to achieve time-reversal-breaking topological phases in antiferromagnetic materials, it is essential to break the combined symmetry of time reversal…
The spin-degeneracy of Bloch bands in a crystal can be lifted when spin-orbit (SO) coupling is present and inversion symmetry is absent. In two-dimensional electron systems (2DES) spin-degeneracy is lifted by Rashba interaction terms - symmetry invariants that are scalar products of spin and orbital axial vectors. Rashba interactions are symmetry allowed whenever a 2DES is not invariant under reflections through the plane it occupies. In this paper, we use a tight-binding model informed by ab initio electronic structure calculations to develop a theory of Rashba splitting in the t2g bands of t…
