We elucidate light-induced orbital and spin current through nonlinear response theory, which generalizes the well-known bulk photovoltaic effect in centrosymmetric broken materials from charge to the spin and orbital degrees of freedom. We use two-dimensional nonmagnetic ferroelectric materials (such as GeS and its analogues) to illustrate this bulk orbital/spin photovoltaic effect, through first-principles calculations. These materials possess a vertical mirror symmetry and time-reversal symmetry but lack of inversion symmetry. We reveal that in addition to the conventional photocurrent that propagates parallel to the mirror plane (under linearly polarized light), the symmetric forbidden current perpendicular to the mirror actually contains electron flows, which carry angular momentum information and move oppositely. One could observe a pure orbital moment current with zero electric charge current. This hidden photo-induced orbital current leads to a pure spin current via spin-orbit coupling interactions. Therefore, a four-terminal device can be designed to detect and measure photo-induced charge, orbital, and spin currents simultaneously. All these currents couple with electric polarization $P$, hence their amplitude and direction can be manipulated through ferroelectric phase transition. Our work provides a route to generalizing nanoscale devices from their photo-induced electronics to orbitronics and spintronics.
We investigate the effect of local electron-phonon coupling on nonlinear optical conductivity in an interacting ferroelectric system. Using real-time simulations, we show an enhancement in nonlinear conductivity under linearly-polarized light due to generation of the phonon-assisted ballistic-current in addition to the injection-current generated by electron-hole pairs. The optically excited phonon modes generate an asymmetric carrier distribution that causes a strong directional ballistic-current. The ballistic-current enhances the photocurrent several times at above band-gap excitation frequ…
The ferroelectric polarization and short-circuit photocurrent in BaTiO3 thin films have been studied for different contact configurations that allow to measure the photoresponse and polarization under the presence of large or negligible imprint field. It is found that in all cases, the direction of the photocurrent is dictated by the depolarizing field and ultimately by the film polarization, with a negligible contribution of the imprint electric field. However, dramatic differences are found in their time-dependent photoresponse. Whereas in presence of imprint, steady photocurrents are observ…
In symmetry-broken crystalline solids, pole structures of Berry curvature (BC) can emerge, and they have been utilized as a versatile tool for controlling transport properties. For example, the monopole component of the BC is induced by the time-reversal symmetry breaking, and the BC dipole arises from a lack of inversion symmetry, leading to the anomalous Hall and nonlinear Hall effects, respectively. Based on first-principles calculations, we show that the ferroelectricity in a tin telluride monolayer produces a unique BC distribution, which offers charge- and spin-controllable photocurrents…
Noncentrosymmetric bulk crystals generate photocurrent without any bias voltage. One of the dominant mechanisms, shift current, comes from a quantum interference of electron wave functions being distinct from classical current caused by electrons' drift or diffusion. The dissipation-less nature of shift current, however, has not been fully verified presumably due to the premature understanding on the role of electrodes. Here we show that the photocurrent dramatically enhances by choosing electrodes with large work function for a $p$-type ferroelectric semiconductor SbSI. An optimized device sh…
Generating and controlling spin current (SC) are of central interest in spin physics and applications. To date, the spin-orbit interaction (SOI) is an established pathway to generate SC through the spin-charge current conversion. We predict an efficient spin-light conversion via the Rashba and higher-order cubic Dresselhaus SOIs in ferroelectrics. Different from the known Edelstein effect, where SC is created by the nonequilibrium spin density, our predicted spin-polarized current is from direct interactions between light and unique spin textures generated by SOI in ferroelectrics. Using first…
Using an experimental setup designed to scan a submicron sized light spot and collect the photogenerated current through larger electrodes, we map the photovoltaic response in ferroelectric BiFeO3 single crystals. We study the effect produced by a unique 180{\textdegree} ferroelectric domain wall (DW) and show that the photocurrent maps are significantly affected by its presence and shape. The effect is large in its vicinity and in the Schottky barriers at the interface with the Au electrodes, but no extra photocurrent is observed when the illuminating spot touches the DW, indicating that this…
We calculate the bulk photovoltaic response of the ferroelectrics BaTiO$_3$ and PbTiO$_3$ from first principles by applying "shift current" theory to the electronic structure from density functional theory. The first principles results for BaTiO$_3$ reproduce eperimental photocurrent direction and magnitude as a function of light frequency, as well as the dependence of current on light polarization, demonstrating that shift current is the dominant mechanism of the bulk photovoltaic effect in BaTiO$_3$. Additionally, we analyze the relationship between response and material properties in detail…
Photoexcitation in solids brings about transitions of electrons/holes between different electronic bands. If the solid lacks an inversion symmetry, these electronic transitions support spontaneous photocurrent due to the topological character of the constituting electronic bands; the Berry connection. This photocurrent, termed shift current, is expected to emerge on the time-scale of primary photoexcitation process. We observed ultrafast time evolution of the shift current in a prototypical ferroelectric semiconductor by detecting emitted terahertz electromagnetic waves. By sweeping the excita…
The bulk photovoltaic effect (BPE) leads to the generation of a photocurrent from an asymmetric material. Despite drawing much attention due to its ability to generate photovoltages above the band gap ($E_g$), it is considered a weak effect due to the low generated photocurrents. Here, we show that a remarkably high photoresponse can be achieved by exploiting the BPE in simple planar BaTiO$_3$ (BTO) films, solely by tuning their fundamental ferroelectric properties via strain and growth orientation induced by epitaxial growth on different substrates. We find a non-monotonic dependence of the r…
The spin photocurrents, direct currents induced by light, hold great promise for introducing new elements to spintronics. However, a general theory for spin photocurrents in real materials which is applicable to systems with spin-orbit coupling or noncollinear magnetism is absent. Here, we develop such a general theory of second-order spin photocurrents. We find that the secondorder spin photocurrents can be classified into Drude, Berry curvature dipole, shift, injection, and rectification currents, which have different physical origins and symmetry properties. Surprisingly, our theory predict…
Despite their potential to exceed the theoretical Shockley-Queisser limit, ferroelectric photovoltaics (FPVs) have performed inefficiently due to their extremely low photocurrents. Incorporating Bi2FeCrO6 (BFCO) as the light absorber in FPVs has recently led to impressively high and record photocurrents [Nechache et al. Nature Photon. 2015, 9, 61], reviving the FPV field. However, our understanding of this remarkable phenomenon is far from satisfactory. Here, we use first-principles calculations to determine that such excellent performance mainly lies in the efficient separation of electron-ho…
The interplay between crystal symmetry and its optical responses is at the heart of tremendous recent advances in light-matter interactions and applications. Nonlinear optical processes that produce electric currents, for example bulk photovoltaic (BPV) effect, require inversion symmetry broken materials, such as ferroelectrics. In the current work, we demonstrate that such BPV current could be generated in centrosymmetric materials with excitation of out-of-equilibrium coherent phonons. This is much different from the generally studied static or thermally excited states. We show that dependin…
The correlation between the shift current mechanism for the bulk photovoltaic effect (BPVE) and the structural and electronic properties of ferroelectric perovskite oxides is not well understood. Here, we study and engineer the shift current photovoltaic effect using a visible-light-absorbing ferroelectric Pb(Ni$_{x}$Ti$_{1-x}$)O$_{3-x}$ solid solution from first principles. We show that the covalent orbital character dicates the direction, magnitude, and onset energy of shift current in a predictable fashion. In particular, we find that the shift current response can be enhanced via electrost…
As is well known the absorption of circularly polarized light in semiconductors results in optical orientation of electron spins and helicity-dependent electric photocurrent, and the absorption of linearly polarized light is accompanied by optical alignment of electron momenta. Here we show that the absorption of unpolarized light leads to generation of a pure spin current, although both the average electron spin and electric current vanish. We demonstrate this for direct interband and intersubband as well as indirect intraband (Drude-like) optical transitions in semiconductor quantum wells (Q…
Spontaneous polarization and bulk photovoltaic effect (BPVE) are two concomitant physical properties in ferroelectric materials. The flipping of ferroelectric order usually accompanies with the switching of BPVE as both of them are reversed under the inversion symmetry. In this study, we report the distinctive BPVE characters in two-dimensional (2D) interlayer sliding ferroelectric materials featuring unswitchable in-plane BPVE (light-induced photocurrent in the xy plane) and switchable out-of-plane BPVE (light-induced polarization along the z-direction). Symmetry analysis within abstract bila…
The pure spin currents, i.e., the counterflow of particles with opposite spin orientations, can be optically injected in semiconductors. Here, we develop a phenomenological theory, which describes the polarization dependencies of spin currents excited by linearly polarized light in bulk semiconductors and quantum well structures of various symmetries. We present microscopic descriptions of the pure spin photocurrents for interband optical transitions in undoped quantum wells as well as for direct intersubband and indirect intrasubband (Drude-like) transitions in n-doped quantum well structures…
The bulk photovoltaic effect (BPVE) refers to the phenomenon of generating photocurrent or photovoltage in homogeneous noncentrosymmetric materials under illumination, and the intrinsic contribution to the BPVE is known as the shift current effect. We calculate the shift current conductivities of the ferroelectric SnTe monolayer using first-principles methods. We find that the monolayer SnTe has giant shift-current conductivity near the valley points. More remarkably, the linear optical absorption coefficient at this energy is very small, and therefore leads to an enormous Glass coefficient th…
Bulk photovoltaic (BPVE) effect in crystals lacking inversion symmetry offers great potential for optoelectronic applications due to its unique properties such as above bandgap photovoltage and switchable photocurrent. Because of their large spontaneous polarizations, ferroelectric materials are ideal platforms for studying BPVE. However, identifying the origin of experimentally observed photovoltaic response is often challenging due to the entanglement between bulk and interface effects, leading to much debate in the field. This issue is particularly pronounced in vertical heterostructures, w…
Crystal Symmetry Selected Pure Spin Photocurrent in Altermagnetic Insulators
School of Physics, Beijing Institute of Technology（北京理工大学物理学院）；Key Lab of Advanced Optoelectronic Quantum Architecture and Measurement (Ministry of Education), Beijing Institute of Technology（北京理工大学先进光电子量子架构与测量教育部重点实验室）；Shenzhen Institute for Quantum Science and Engineering and Department of Physics, Southern University of Science and Technology（南方科技大学量子科学工程研究院及物理系）
Enhanced Photocurrent Response in Epitaxial 0.5PZT-0.5PFN Multiferroic Thin Films
FZU - Institute of Physics of the Czech Academy of Sciences（捷克科学院物理研究所）；Catalan Institute of Nanoscience and Nanotechnology, ICN 2, CSIC and The Barcelona Institute of Science and Technology (BIST)（加泰罗尼亚纳米科学与技术研究所，西班牙国家研究委员会与巴塞罗那科学与技术学院）
The intertwined ferroelectricity and photovoltaics in two-dimensional (2D) materials will enable the favorable improvement and control of photovoltaic preformances. In this paper, we take 2D 3R bilayer BX (X=P, As, Sb) as model systems to study the photovoltaic characteristics of intrinsic 2D out-of-plane (OOP) ferroelectric material, and try to explore a strategy to regulate the photoelectric properties by changing the strength of ferroelectric polarization. Due to the spatial inversion symmetry broken caused by special 3R stacking, spontaneous OOP ferroelectric polarization will appear in th…
Spin current generators are critical components for spintronics-based information processing. In this work, we theoretically and computationally investigate the bulk spin photovoltaic (BSPV) effect for creating DC spin current under light illumination. The only requirement for BPSV is inversion symmetry breaking, thus it applies to a broad range of materials and can be readily integrated with existing semiconductor technologies. The BSPV effect is a cousin of the bulk photovoltaic (BPV) effect, whereby a DC charge current is generated under light. Thanks to the different selection rules on spi…
The noncollinear cycloidal magnetic order breaks the inversion symmetry in CaMn$_{7}$O$_{12}$, generating one of the largest spin-orbit driven ferroelectric polarizations measured to date. In this Letter, the microscopic origin of the polarization, including its direction, charge density redistribution, magnetic exchange interactions, and its coupling to the spin helicity, is explored via first principles calculations. The Berry phase computed polarization exhibits almost pure electronic behavior, as the Mn displacements are negligible, $\approx$~0.7~m\textrmÅ. The polarization magnitude and d…
Bent band structures have been empirically described in ferroelectric materials to explain the functioning of recently developed ferroelectric tunneling junction and photovoltaic devices. This report presents experimental evidence for ferroelectric band bending, which was observed in the depth profiles of atomic orbitals of angle-resolved hard x-ray photoemission spectra of ferroelectric BaTiO3 thin films. The ferroelectric bent band structure is separated into three depth regions; the shallowest and deepest regions are slightly modulated by the screening effect at surface and interface, respe…
We present experimental evidence for hexagonal domain faceting in the ferroelectric polymer PVDF-TrFE films having the lower orthorhombic crystallographic symmetry. This effect can arise from purely electrostatic depolarizing forces. We show that in contrast to magnetic bubble shape domains where such type of deformation instability has a predominantly elliptical character, the emergence of more symmetrical circular harmonics is favored in ferroelectrics with high dielectric constant.
The bulk photovoltaic effect generates intrinsic photocurrents in materials without inversion symmetry. Shift current is one of the bulk photovoltaic phenomena related to the Berry phase of the constituting electronic bands: photo-excited carriers coherently shift in real space due to the difference in the Berry connection between the valence and conduction bands. Ferroelectric semiconductors and Weyl semimetals are known to exhibit such nonlinear optical phenomena. Here we consider chalcopyrite semiconductor ZnSnP$_2$ which lacks inversion symmetry and calculate the shift current conductivity…
2D Ferroelectric Ruddlesden-Popper Perovskites: an Emerging Fully Electronically Controllable Shift Current and Persistent Spin Helix
North University of China（中北大学）；Institute of Materials Science, Technology University of Darmstadt（达姆施塔特工业大学材料科学研究所）；School of Microelectronics, Xidian University（西安电子科技大学微电子学院）
Using a joint approach of density functional theory and model calculations, we demonstrate that a prototypical charge ordered half-doped manganite, La$_{1/2}$Ca$_{1/2}$MnO$_3$ is multiferroic. The combination of a peculiar charge-orbital ordering and a tendency to form spin dimers breaks inversion symmetry, leads to a ferroelectric ground-state with a polarization up to several $μC/cm^2$. The presence of improper ferroelectricity does not depend on hotly debated structural details of this material: in the Zener-polaron structure we find a similar dramatic ferroelectric response with a large po…
Materials with formula of A2B2O7 is a famous family with more than 300 compounds, and have abundant properties, like ferroelectric, multiferroic, and photocatalyst properties, etc. Generally, two structures dominate this family, which are pyrochlore and perovskite-like layered (PL) structure. Previously, the structure and properties design of these materials are usually complex, and solid solutions, which complicates the manufacture, as well as introducing complexity in the study of the microscopic origins of the properties. Here, we report that the pyrochlore-PL structure change happened in p…
We theoretically study the stability conditions of the ferroelectric ice of the Cmc21 structure, which has been considered, for decades, one of the most promising candidates of the low temperature proton-ordered phase of pure ice Ih. It turned out that the Cmc21 structure is stable only with a certain amount of dopant and the true proton-ordered phase of pure ice Ih remains to be found at lower temperature. Implication for spin ice is mentioned.
We investigate the variation of the spontaneous ferroelectric polarization with epitaxial strain for BaTiO$_3$, PbTiO$_3$, LiNbO$_3$, and BiFeO$_3$ using first principles calculations. We find that while the strain dependence of the polarization is very strong in the simple perovskite systems BaTiO$_3$ and PbTiO$_3$ it is only weak in LiNbO$_3$ and BiFeO$_3$. We show that this different behavior can be understood purely in terms of the piezoelectric and elastic constants of the unstrained bulk material, and we discuss several factors that determine the strain behavior of a certain material.
High performance lead-free multiferroic composites are desired to replace the lead-based ceramics in multifunctional devices applications. Laminated compounds were prepared from ferroelectric and ferromagnetic materials. In this work, we present laminated ceramics compound by considering the ferromagnetic La0.5Ca0.5MnO3 (LCMO) and the ferroelectric BaTi0.8Sn0.2O3 (BTSO) in two different proportions. Compounds (1-x) LCMO-(x) BTSO with x=1 and 0 (pure materials) were synthesized by the sol gel method and x=0.7 and 0.5 (laminated) compounds were elaborated by welding appropriate mass ratios of ea…
The site-doping strategy of barium titanate (BaTiO3) is a promising way to develop new lead-free materials for energy with enhanced dielectric and piezoelectric properties. A novel strategy to elaborated pure and crystalline Ba0.85Ca0.15Zr0.1Ti0.9O3(BCZT) ferroelectric powders at low temperature is proposed. It is based on sol-gel method followed by a hydrothermal reaction. The effects of preparation temperature on structure, crystallinity, purity, morphology and particles size distribution of BCZT powders were studied. It was clearly shown that pure and crystalline BCZT could be obtained over…
Metal-organic frameworks (MOFs) possess a hybrid nature, combining the inorganic properties from the metal ions and the organic properties from the molecular linkers. Stroppa, \textit{et al.}, showed that the perovskite-type MOF [C(NH$_2$)$_3$]M[(HCOO)$_3$] (M = Cr, Cu) exhibits the magneto-electric coupled multiferroicity [Angew. Chem. Int. Ed. 50, 5847 (2011) and Adv. Mater. 25, 2284 (2013)]. Moreover, their ferroelectricity arises from the hybrid improper mechanism, which also explains the magneto-electric coupling. In this work, we further examine the electric and magnetic properties of [C…
We study the polarization induced via spin-orbit interaction by a magnetic cycloidal order in orthorhombic TbMnO3 using first-principle methods. The case of magnetic spiral lying in the b-c plane is analyzed, in which the pure electronic contribution to the polarization is shown to be small. We focus our attention on the lattice-mediated contribution, and study it's dependence on the Coulomb interaction parameter U in the LDA+U method and on the wave-vector of the spin spiral. The role of the spin-orbit interaction on different sites is also analyzed.
Charge and spin photogalvanic effects in the p-wave magnet NiI2
University of Milan-Bicocca（米兰比可卡大学）；Consiglio Nazionale delle Ricerche CNR-SPIN（意大利国家研究委员会 SPIN 研究所）；Vinča Institute of Nuclear Sciences - National Institute of the Republic of Serbia, University of Belgrade（贝尔格莱德大学 Vinča 核科学研究所）；Centro de Física de Materiales (CSIC-UPV/EHU)（材料物理中心 (西班牙科学理事会-巴斯克自治区大学)）；IKERBASQUE, Basque Foundation for Science（伊克尔巴斯科奎，巴斯克科学基金会）；Donostia International Physics Center (DIPC)（圣塞巴斯蒂安国际物理中心）；Ca’ Foscari University of Venice（威尼斯大学）
Magnetic Compton scattering is an established tool for probing magnetism in ferromagnetic or ferrimagnetic materials with a net spin polarization. Here we show that, counterintuitively, {\it non-magnetic} systems can also have a non-zero magnetic Compton profile, provided that space-inversion symmetry is broken. The magnetic Compton profile is antisymmetric in momentum and, if the inversion symmetry is broken by an electric-field switchable ferroelectric distortion, can be reversed using an electric field. We show that the underlying physics of the magnetic Compton profile and its electrical c…
Bulk photovoltaic (BPV) effect, a second order nonlinear process that generates static current under light irradiation, requires centrosymmetric broken systems as its application platform. In order to realize measurable BPV photocurrent in spatially centrosymmetric materials, various schemes such as chemical doping, structural deformation, or electric bias have been developed. In the current work, we suggest that magnetic proximity effect via van der Waals interfacial interaction, a contact-free strategy, also breaks the centrosymmetry and generate large BPV photocurrents. Using the Bi2Te3 qui…
As is well known the absorption of circularly polarized light in semiconductors results in optical orientation of electron spins and helicity-dependent electric photocurrent, and the absorption of linearly polarized light is accompanied by optical alignment of electron momenta. Here we show that the absorption of unpolarized light in a quantum well (QW) leads to generation of a pure spin current, although both the average electron spin and electric current are vanishing.
Machine-learning-identified two-dimensional van der Waals multiferroics for four-state nonvolatile memory
College of Physics and Optoelectronic Engineering, Shenzhen University（深圳大学物理与光电工程学院）；International School of Microelectronics, Dongguan University of Technology（东莞理工学院微电子学院）
It is shown that the free-carrier (Drude) absorption of circularly polarized radiation in quantum well structures leads to an electric current flow. The photocurrent reverses its direction upon switching the light helicity. A pure orbital mechanism of such a circular photogalvanic effect is proposed that is based on interference of different pathways contributing to the light absorption. Calculation shows that the magnitude of the helicity dependent photocurrent in $n$-doped quantum well structures corresponds to recent experimental observations.
Guidelines for the optimization of hafnia-based ferroelectrics through superlattice engineering
University of Groningen（格罗宁根大学）；Luxembourg Institute for Science and Technology (LIST)（卢森堡科学与技术研究所）；University of Twente（特温特大学）；University of Luxembourg（卢森堡大学）
Machine learning has emerged as a powerful tool for the analysis of mesoscopic and atomically resolved images and spectroscopy in electron and scanning probe microscopy, with the applications ranging from feature extraction to information compression and elucidation of relevant order parameters to inversion of imaging data to reconstruct structural models. However, the fundamental limitation of machine learning methods is their correlative nature, leading to extreme susceptibility to confounding factors. Here, we implement the workflow for causal analysis of structural scanning transmission el…
We have studied the magnetic structure of the ferroelectric frustrated spin-1/2 chain material LiCuVO4 in applied electric and magnetic fields using polarized neutrons. A symmetry and mean-field analysis of the data rules out the presence of static Dzyaloshinskii-Moriya interaction, while exchange striction is shown to be negligible by our specific-heat measurements. The experimentally observed magnetoelectric coupling is in excellent agreement with the predictions of a purely electronic mechanism based on spin supercurrents.
We argue that the homogeneous distribution of spins in the spin-spiral state of orthorhombic manganites is deformed by the relativistic spin-orbit interaction. The thus induced spin-spiral inhomogeneity gives rise to the ferroelectric response of the purely electronic origin in even-periodic magnetic structures. The mechanism is generic and explains the appearance of ferroelectricity in the twofold periodic structure of HoMnO3 as well as the fourfold periodic structure of TbMnO3. Nevertheless, odd-periodic magnetic structures preserve the inversion symmetry and thus are not ferroelectric. Our …
Anomalous Transverse Response and Multi-Field Ferrialtermagnetic-Ferroelectric Valve with CrSb Flakes
Huazhong University of Science and Technology（华中科技大学）；Beijing Institute of Technology（北京理工大学）；Chongqing University of Posts and Telecommunications（重庆邮电大学）
研究提出铁磁反铁磁体概念，以 CrSb 薄片实现，集成铁电体和 Cu 间隔层设计出铁磁反铁磁-铁电阀，该阀有高自旋过滤率等特性，确立了铁磁反铁磁体在多场控制等自旋电子学和电子学方面的丰富平台地位。
