We report optical enhancement in polarization and dielectric constant near room temperature in Pb0.6Li0.2Bi0.2Zr0.2Ti0.8O3 (PLBZT) electro-ceramics; these are doubly substituted members of the most important commercial ferroelectric PbZr0.2Ti0.8O3 (PZT:20/80). Partial (40%) substitution of equal amounts of Li+1 and Bi+3 in PZT: 20/80 retains the PZT tetragonal structure with space group P4mm. Under illumination of white light and weak 405-nm near-ultraviolet laser light (30 mW), an unexpectedly large (200-300%) change in polarization and displacement current was observed. Light also changes the dc conduction current density by one to two orders of magnitude with a large switchable open circuit voltage (Voc ~ 2 V) and short circuit current (Jsc ~ 5x10-8 A). The samples show a photo-current ON/OFF ratio of order 6:1 under illumination of weak light.
Giant electrocaloric (EC) effect is observed in BaTiO3 multilayer thick film structure. The temperature change is as high as 4.0 oC under an applied electric field of 352 kV/cm. Most importantly, the EC effect is found to depend on the varying rate of the applied field. Based on the giant net cooling (~0.37 J/g) resulting from the difference in the varying rates of rising and falling fields, the kinetic EC effect provides an effective solution for the design of refrigeration cycle in ferroelectric micro-refrigerator.
Ferroelectrics subject to suitable electric boundary conditions present a steady negative capacitance response. When the ferroelectric is in a heterostructure, this behavior yields a voltage amplification in the other elements, which experience a potential difference larger than the one applied, holding promise for low-power electronics. So far research has focused on verifying this effect and little is known about how to optimize it. Here we describe an electrostatic theory of ferroelectric/dielectric superlattices, convenient model systems, and show the relationship between the negative perm…
We have recently observed a giant electrocaloric effect (12 K in 25 V) in 350 nm sol-gel Pb Zr_0.95 Ti_0.05 O_3 films near the ferroelectric Curie temperature of 242oC. Here we demonstrate a giant electrocaloric effect (5 K in 25 V) in 260 nm sol-gel films of the relaxor ferroelectric 0.9 PbMg_(1/3)Nb_(2/3)O_3 - 0.1 PbTiO_3 near the Curie temperature of 60oC. This reduction in operating temperature widens the potential for applications in novel cooling systems.
Molecular dynamics simulations predict a giant electrocaloric effect at the ferroelectric-antiferroelectric phase boundary in PZT (PbTiO$_3$-PbZrO$_3$). These large-scale simulations also give insights into the atomistic mechanisms of the electrocaloric effect in PZT materials. Studying a range of ferroelectric (FE) and antiferroelectric (AFE) PZT materials we found positive electrocaloric effect in FE composites, but AFE ones exhibit a positive-to-negative crossover. At the AFE-FE phase boundary we find complex domain patterns. We demonstrate that the origin of giant electrocaloric change of …
The out-of-plane and in-plane polarization of (Pb0.6Li0.2Bi0.2)(Zr0.2Ti0.8)O3(PLBZT) thin film has studied in the dark and under illumination of a weak light source of a comparable bandgap. A highly oriented PLBZT thin film was grown on LaNiO3 (LNO)/LaAlO3(LAO) substrate by pulsed laser deposition system which illustrates well-saturated polarization and its significant enhancement under illumination of light. We have employed two configurations for polarization characterization; first deals with out of plane polarization with single capacitor under investigation, whereas second demonstrates th…
The synthesis of layered ferrite-lead titanate zirconate (PZT) and lanthanum nanganite-PZT and the observation of giant magneto-electric interactions are discussed. The ferrites used in our studies included pure and Zn substituted cobalt-, nickel- and lithium ferrites. Ferromagnetic manganites used included both calcium and strontium substituted systems. The samples were prepared from 10-40 mm thick films obtained by tape-casting. Our studies showed strong ME coupling in manganite-PZT and cobalt zinc ferrite-PZT, and a giant ME effect in nickel zinc ferrite-PZT. We found evidence for Zn assist…
Recently large Rashba-like spin splitting has been observed in certain bulk ferroelectrics. In contrast with the relativistic Rashba effect, the chiral spin texture and large spin-splitting of the electronic bands depend strongly on the character of the band and atomic spin-orbit coupling. We establish that this can be traced back to the so-called orbital Rashba effect, also in the bulk. This leads to an additional dependence on the orbital composition of the bands, which is crucial for a complete picture of the effect. Results from first-principles calculations on ferroelectic GeTe verify the…
Giant photostriction in lead-free ferroelectric stemming from photo-excited thermalized carriers
Université Paris-Saclay, CentraleSupélec（巴黎萨克雷大学、中央理工-高等电力学院）；CNRS, Laboratoire SPMS（法国国家科学研究中心，SPMS实验室）；ENS Paris-Saclay（巴黎萨克雷高等师范学院）；LuMIn；Centre de Nanosciences et de Nanotechnologies (C2N)（纳米科学与工程中心）；Le Mans Université（勒芒大学）；Institut des Molécules et Matériaux du Mans（勒芒分子与材料研究所）；FZU- Institute of Physics, Czech Academy of Sciences（捷克科学院物理研究所）
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…
We have studied ferroelectricity and photovoltaic effects in atomic layer deposited (ALD) 40-nm thick SnTiO$_{x}$ films deposited directly onto p-type (001)Si substrate. These films showed well-saturated, square and repeatable hysteresis loops with remnant polarization of 1.5 $μ$C/cm$^{2}$ at room temperature, as detected by out-of-plane polarization versus electric field (P-E) and field cycling measurements. A photo-induced enhancement in ferroelectricity was also observed as the spontaneous polarization increased under white-light illumination. The ferroelectricity exhibits relaxor character…
BiFeO$_3$ is the most famous multiferroic material, but it has no strong spontaneous magnetization due to its antiferromagnetism. Here we show that giant ferroelectric polarization and strong spontaneous magnetization can be both realized in double perovskite Bi$_2$FeMoO$_6$ with R3 (\#146) space group based on BiFeO$_3$. Our first-principles phonon spectra establishes that this multiferroic R3 phase is stable. Our systematic calculations show that it is a spin-polarized semiconductor with gap reaching to 0.54 eV and has a strong ferroelectric polarization of 85$μ$C/cm$^2$. This ferroelctricit…
We present a unique example of giant magnetoelectric effect in a conventional multiferroic HoMnO3, where polarization is very large (~56 mC/m2) and the ferroelectric transition temperature is higher than the magnetic ordering temperature by an order. We attribute the uniqueness of the giant magnetoelectric effect to the ferroelectricity induced entirely by the off-center displacement of rare earth ions with large magnetic moments. This finding suggests a new avenue to design multiferroics with large polarization and higher ferroelectric transition temperature as well as large magnetoelectric e…
High-mobility layered semiconductors have the potential to enable the next-generation electronics and computing. This paper demonstrates that the ultrahigh electron mobility observed in the layered semiconductor Bi$_2$O$_2$Se originates from an incipient ferroelectric transition that endows the material with a robust protection against mobility degradation by Coulomb scattering. Based on first-principles calculations of electron-phonon interaction and ionized impurity scattering, it is shown that the electron mobility of Bi$_2$O$_2$Se can reach 10$^4$ to 10$^6$ cm$^2$V$^{-1}$s$^{-1}$ over a wi…
A giant tunneling electroresistance effect may be achieved in a ferroelectric tunnel junction by exploiting the magnetoelectric effect at the interface between a ferroelectric barrier and magnetic La1-xSrxMnO3 electrode. Using first-principles density functional theory we demonstrate that a few magnetic monolayers of La1-xSrxMnO3 near the interface act, in response to ferroelectric polarization reversal, as an atomic scale spin-valve by filtering spin-dependent current. This effect produces more than an order of magnitude change in conductance, and thus constitutes a giant resistive switching …
The interest in ferroelectric van der Waals crystals arises from the potential to realize ultrathin ferroic systems owing to the reduced surface energy of these materials and the layered structure that allows for exfoliation. Here, we quantitatively unravel giant negative electrostriction of van der Waals layered copper indium thiophosphate (CIPS), which exhibits an electrostrictive coefficient Q33 as high as -3.2 m4/C2 and a resulting bulk piezoelectric coefficient d33 up to -85 pm/V. As a result, the electromechanical response of CIPS is comparable in magnitude to established perovskite ferr…
We use molecular dynamics with a first-principles-based shell model potential to study the electrocaloric effect (ECE) in lithium niobate, LiNbO$_3$, and find a giant electrocaloric effect along a line passing through the ferroelectric transition. With applied electric field, a line of maximum ECE passes through the zero field ferroelectric transition, continuing along a Widom line at high temperatures with increasing field, and along the instability that leads to homogeneous ferroelectric switching below $T_c$ with an applied field antiparallel to the spontaneous polarization. This line is de…
We investigate the electrostrictive response across a ferroelectric phase transition from first-principles calculations and refute the prevailing view of constant electrostriction across the ferroelectric phase boundary. We take as a case study the epitaxial strain-induced transition from para- to feroelectricity of \ce{KTaO3}. We show that the magnitude of the electrostriction diverges with the permitivity at the transition, hence exhibiting giant responses through a calculation of both the M and Q electrostrictive tensors. We explain the origin of this giant electrostrictive response in \ce{…
Light-matter interaction is one of the key routes to understanding and manipulating geometric and electronic behaviors of materials, especially two-dimensional materials which are optically accessible owing to their high surface to volume ratio. In the current work we focus on the recently discovered two-dimensional sliding ferroelectric materials, in which the out-of-plane electric polarization can be switched with a small horizontal translation in one layer. Combining symmetry analysis and first-principles calculations, we predict that light illumination could inject non-equilibrium magnetic…
$α$-GeTe(111) is a non-centrosymmetric ferroelectric material, for which a strong spin-orbit interaction gives rise to giant Rashba split states in the bulk and at the surface. The detailed dispersions of the surface states inside the bulk band gap remains an open question because they are located in the unoccupied part of the electronic structure, making them inaccessible to static angle-resolved photoemission spectroscopy. We show that this difficulty can be overcome via in-situ potassium doping of the surface, leading to a rigid shift of 80 meV of the surface states into the occupied states…
GeTe wins the renewed research interest due to its giant bulk Rashba spin orbit coupling (SOC), and becomes the father of a new multifunctional material, i.e., ferroelectric Rashba semiconductor. In the present work, we investigate Rashba SOC at the interface of the ferroelectric semiconductor superlattice GeTe(111)/InP(111) by using the first principles calculation. Contribution of the interface electric field and the ferroelectric field to Rashba SOC is revealed. A large modulation to Rashba SOC and a reversal of the spin polarization is obtained by switching the ferroelectric polarization. …
The coupling between strain gradients and polarization, known as flexoelectricity, offers a new mechanism to control the functionality of dielectric materials. However, for the effect to be practically attractive, dynamic control of the strain gradient with magnitudes far exceeding those achievable via mechanical deformation (~10 $m^{-1}$) is needed. Strain-engineered thin films exhibit extraordinary strain gradients of $10^5-10^6 m{-1}$ arising from structural relaxation within a short space range that greatly enhances the steady-state flexoelectric effect. Here we report a giant, optically i…
We report on nanoscale strain gradients in ferroelectric HoMnO3 epitaxial thin films, resulting in a giant flexoelectric effect. Using grazing-incidence in-plane X-ray diffraction, we measured strain gradients in the films, which were 6 or 7 orders of magnitude larger than typical values reported for bulk oxides. The combination of transmission electron microscopy, electrical measurements, and electrostatic calculations showed that flexoelectricity provides a means of tuning the physical properties of ferroelectric epitaxial thin films, such as domain configurations and hysteresis curves.
Lead free, silicon compatible materials showing large electromechanical responses comparable to, or better than conventional relaxor ferroelectrics, are desirable for various nanoelectromechanical devices and applications. Defect-engineered electrostriction has recently been gaining popularity to obtain enhanced electromechanical responses at sub 100 Hz frequencies. Here, we report record values of electrostrictive strain coefficients (M31) at frequencies as large as 5 kHz (1.04 x 10-14 m2 per V2 at 1 kHz, and 3.87 x 10-15 m2 per V2 at 5 kHz) using A-site and oxygen-deficient barium titanate t…
By extending our general spin-current model to non-centrosymmetric spin dimers and performing density functional calculations, we investigate the causes for the helical magnetic order and the origin of the giant ferroelectric polarization of CaMn7O12. The giant ferroelectric polarization is proposed to be caused by the symmetric exchange striction due to the canting of the Mn4+ spin arising from its strong Dzyaloshinskii-Moriya (DM) interaction. Our study suggests that CaMn7O12 may exhibit a novel magnetoelectric coupling mechanism in which the magnitude of the polarization is governed by the …
An atomistic effective Hamiltonian is used to investigate electrocaloric (EC) effects of Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_{3}$ (PMN) relaxor ferroelectrics in its ergodic regime, and subject to electric fields applied along the pseudocubic [111] direction. Such Hamiltonian qualitatively reproduces (i) the electric field-versus-temperature phase diagram, including the existence of a critical point where first-order and second-order transitions meet each other; and (ii) a giant EC response near such critical point. It also reveals that such giant response around this critical point is microscopically …
We study electron transport in granular film placed above the ferroelectric substrate. We show that the conductivity of granular film strongly depends on the ferroelectric state due to screening effects which modify the Coulomb blockade in granular film. In particular, the electric current in granular film is controlled by the direction of ferroelectric polarization. We show that the ferroelectric/granular film system has a large electro-resistance effect. This effect can be utilized in memory and electric field sensor applications.
In order to establish the correlation between the magnetoelectric coupling and magnetic instability, we have studied the structural, magnetic, and ferroelectric properties of \textit{x}BaTiO${_3}$-(1-\textit{x})BiCoO${_3}$ as a function of BaTiO$_3$ concentration ($x$) and volume.The $G-$type antiferromagnetic ordering is found to be energetically favorable for $x<$ 0.45 and higher concentrations stabilize with nonmagnetic states. We observe metamagnetic spin state transitions associated with paraelectric to ferrolectric transitions as a function of volume and $x$ using synchrotron diffraction…
There is a surge of interest in developing environmentally friendly cooling technology based on the solid--state electrocaloric effect (ECE). Here, we point out that negative ECE with a fast cooling rate ($\approx$10$^{11}$ K/s) can be achieved by driving solid crystals to a high--temperature phase with a properly designed electric field pulse. Specifically, we predict that an ultrafast electric field pulse can cause a negative ECE up to 35 K in PbTiO$_3$ occurring on few picosecond time scales. We acquire and analyze these results by clarifying the mechanism of ECE during an adiabatic irrever…
Mechanical displacement in commonly used piezoelectric materials is typically restricted to linear or biaxial in nature and to a few percent of the material dimensions. Here, we show that free-standing BaTiO$_3$ membranes exhibit non-conventional electromechanical coupling. Under an external electric field, these superelastic membranes undergo controllable and reversible 'sushi-rolling-like' 180$^\circ$ folding-unfolding cycles. This crease-free folding is mediated by charged ferroelectric domains, leading to a giant > 3.8 and 4.6 $μ$m displacements for a 30-nm thick membrane at room temperatu…
Proximity to phase transitions (PTs) is frequently responsible for the largest dielectric susceptibilities in ferroelectrics. The impracticality of using temperature as a control parameter to reach those large responses has motivated the design of solid solutions with phase boundaries between different polar phases at temperatures (typically room temperature) significantly lower than the paraelectric-ferroelectric critical temperature. The flat energy landscapes close to these PTs give rise to polarization rotation under external stimuli, being responsible for the best piezoelectrics so far an…
Magnetoelastic and magnetoelectric coupling in the artificial multiferroic heterostructures facilitate valuable features for device applications such as magnetic field sensors and electric write magnetic-read memory devices. In a ferromagnetic/ferroelectric heterostructures, the strain mediated coupling exploits piezoelectricity/electrostriction in ferroelectric phase and magnetostriction/piezomagnetism in ferromagnetic phase. Such verity of these combined effect can be manipulated by an external perturbation, such as electric field, temperature or magnetic field. Here, we demonstrate the remo…
The direct magnetoelectric (ME) effect mediated by lattice strains induced in a ferroelectric film by a ferromagnetic substrate is evaluated using first-principles-based calculations. To that end, the strain sensitivity of ferroelectric polarization and the film permittivity are calculated as a function of the in-plane biaxial strain for Pb(Zr0.52Ti0.48)O3 films under various depolarizing fields. It is found that the ME voltage coefficient varies nonmonotonically with this strain and may reach giant values exceeding 100 Vcm-1 Oe-1 over a strain range that can be controlled through the electric…
We report $α$-Cu$_2$V$_2$O$_7$ to be an improper multiferroic with the simultaneous development of electric polarization and magnetization below $T_C$ = 35 K. The observed spontaneous polarization of magnitude 0.55 $μ$Ccm$^{-2}$ is highest among the copper based improper multiferroic materials. Our study demonstrates sizable amount of magneto-electric coupling below $T_C$ even with a low magnetic field. The theoretical calculations based on density functional theory (DFT) indicate magnetism in $α$-Cu$_2$V$_2$O$_7$ is a consequence of {\em ferro-orbital} ordering driven by polar lattice distort…
In systems with broken inversion symmetry spin-orbit coupling (SOC) yields a Rashba-type spin splitting of electronic states, manifested in a k-dependent splitting of the bands. While most research had previously focused on 2D electron systems, recently a three-dimensional (3D) form of such Rashba-effect was found in a series of bismuth tellurohalides. Whereas these materials exhibit a very large spin-splitting, they lack an important property concerning functionalization, namely the possibility to switch or tune the spin texture. This limitation can be overcome in a new class of functional ma…
Ferroelectric domain walls are nm-sized interfaces between sections of different allowed values of the spontaneous polarization, the so-called domains. These walls - neutral or charged - can be created, displaced, deleted, and recreated again in ferroelectric materials. [1-3] Owing to the recent progress in the studies of ferroelectrics, they are expected to be functional active elements of the future nano-electronics.[1,4,5] Metallic-like conductivity of charged domain walls (CDWs) in insulating ferroelectrics, predicted in 1970s6 and detected recently,[7-10] is especially attractive for appl…
Multiferroics with coupling between ferroelectricity and magnetism have been pursued for decades. However, their magnetoelectric performances remain limited due to the common trade-off between ferroelectricity and magnetism. Here, a family of nitride perovskites is proposed as multiferroics with prominent physical properties and nontrivial mechanisms. Taking GdWN$_3$ as a prototype, our first-principles calculations found that its perovskite phases own large polarizations (e.g. $111.3$ $μ$C/cm$^2$ for the $R3c$ phase) and a magnetic moment $7$ $μ_{\rm B}$/Gd$^{3+}$. More interestingly, its fer…
Relaxor ferroelectric perovskites are highly polarizable and can exhibit giant coupling between elastic strain and an applied electric field. Here, we report an in situ extended X-ray absorption fine structure (EXAFS) study of a PbZn1/3Nb2/3O3 (PZN) single crystal as a function of the electric field. We show that the strong dipoles in the NbO6 octahedra bonds are aligned along the four \textless{} 011 \textgreater{} directions close to the orientation of the electric field, while a small reversible polar shift occurs for Zn in the direction of the electric field, i.e., positive or negative. Th…
Multilayers based on quantum materials (complex oxides, topological insulators, transition-metal dichalcogenides, etc) have enabled the design of devices that could revolutionize microelectronics and optoelectronics. However, heterostructures incorporating quantum materials from different families remain scarce, while they would immensely broaden the range of possible applications. Here we demonstrate the large-scale integration of compounds from two highly-multifunctional families: perovskite oxides and transition-metal dichalcogenides (TMDs). We couple BiFeO$_3$, a room-temperature multiferr…
Ferroelectrics have shown potential as a promising alternative material for future photovoltaic applications. Observance of high open circuit voltages in ferroelectric thin films, have generated considerable interest in the field of ferroelectric photovoltaic in recent years. The field of ferroelectric photovoltaic is evolving and not yet completely understood compared to the semiconductor based photovoltaic technology. This dissertation investigates photovoltaic characteristics of ferroelectric films in an attempt to further the understanding of ferroelectric photovoltaic. This dissertation p…
Tunneling electroresistance (TER) effect is the change in the electrical resistance of a ferroelectric tunnel junction (FTJ) associated with polarization reversal in the ferroelectric barrier layer. Here we predict that a FTJ with a composite barrier that combines a functional ferroelectric film and a thin layer of a non-polar dielectric can exhibit a significantly enhanced TER. Due to the change in the electrostatic potential with polarization reversal the non-polar dielectric barrier acts as a switch that changes its barrier height from a low to high value. The predicted values of TER are gi…
We have measured the bending-induced polarization of Pb(Mg1/3Nb2/3)O3-PbTiO3 single crystals with compositions at the relaxor-ferroelectric phase boundary. The crystals display very large flexoelectricity, with flexocoupling coefficients an order of magnitude bigger than the theoretical upper limit set by the theories of Kogan and Tagantsev. This enhancement persists in the paraphrase up to a temperature T* that coincides with the start of elastic softening in the crystals. Analysis of the temperature dependence and cross-correlation between flexoelectric, dielectric and elastic properties ind…
Electrocaloric (EC) materials show promise in eco-friendly solid-state refrigeration and integrable on-chip thermal management. While direct measurement of EC thin-films still remains challenging, a generic theoretical framework for quantifying the cooling properties of rich EC materials including normal-, relaxor-, organic- and anti-ferroelectrics is imperative for exploiting new flexible and room-temperature cooling alternatives. Here, we present a versatile theory that combines Master equation with Maxwell relations and analytically relates the macroscopic cooling responses in EC materials …
We investigate the impact of uniaxial strain on atomic shifts, dipolar interactions, polarization and electric permittivity in TiO$_2$ (rutile) by using two different implementations of density functional theory. It is shown that calculations using the Vienna ab inito simulation package (VASP) and the plane-wave self-consistent field method (PWscf) yield qualitatively the same atomic relaxations and ferroelectric trends under strain. The phonon dispersion curves of unstrained and strained TiO$_2$ (rutile) obtained by employing the linear response method confirm previous calculations of the gia…
During the last fifteen years, multiferroic (MF) research communities have been searching for an alternative room temperature MF material with large magnetoelectric (ME) coupling for possible applications in high density electronic components, low heat dissipation memory and logic devices. We have studied Pb(Zr0.20Ti0.80)0.70Pd0.30O3-δ (PZTP30) system with an unusually large (30%) palladium occupancy in B site of PZT. This material exhibited a giant ME coupling coefficient ~0.36 mV/cm.Oe. Interestingly, this is the first time any room temperature single phase compound that showed ME trends, an…
