Electrochemical phenomena in ferroelectrics are of particular interest for catalysis and sensing applications, with recent studies highlighting the combined role of the ferroelectric polarisation, applied surface voltage and overall switching history. Here, we present a systematic Kelvin probe microscopy study of the effect of relative humidity and polarisation switching history on the surface charge dissipation in ferroelectric Pb(Zr$_{0.2}$Ti$_{0.8}$)O$_3$ thin films. We analyze the interaction of surface charges with ferroelectric domains through the framework of physically constrained unsupervised machine learning matrix factorization, Dictionary Learning, and reveal a complex interplay of voltage-mediated physical processes underlying the observed signal decays. Additional insight into the observed behaviours is given by a Fitzhugh-Nagumo reaction-diffusion model, highlighting the lateral spread and charge passivation process contributors within the Dictionary Learning analysis.
Ferroelectric domain switching in c-axis-oriented epitaxial Pb(Zr$_{0.2}$Ti$_{0.8}$)O$_3$ thin films was studied using biased scanning probe microscopy tips. While linear and logarithmic dependence of domain size on tip bias and writing time, respectively, are well known, we report an additional linear dependence on relative humidity in the 28-65% range. We map out the switched domain size as a function of both the tip bias and the applied pulse time and describe a growth-limited regime for very short pulses and a nucleation-limited regime for very low tip bias. Using "interrupted-switching" m…
The electrophysical reaction of rubidium polytungstate Rb4W11O35 ceramics (RPTC) on fast humidity impact has been investigated by studying the influence of wet air pulse of 1-3 s of duration on the peculiarities of dynamic current-voltage (I-V-) and charge-voltage (Q-V-) loops and transient current-time (I-t-) curves. The revealed peculiarities of I-V- and Q-V-loops and I-t-curves for RPTC subjected to humidity impact were compared with similar ones observed for water damaged hydrogen-bounded ferroelectric triglicyne sulphate (TGS) crystals. The obtained data indicate at least two possible sce…
Interest to ferroelectric materials has been increased significantly in last decades due to development of new generation of nonlinear optical and data storage devices. Scanning probe microscopy (SPM) can be used both for study of domain structures with nanoscale spatial resolution and for writing the isolated nanodomains by local application of the electric field. Tip-induced switching in the ambient still needs experimental investigations and theoretical explorations. Here we studied influence of the value of relative humidity in the SPM chamber on the process of tip-induced polarization swi…
Recent experimental reports on in-plane proton conduction in reduced graphene oxide (rGO) films open a new way for the design of proton exchange membrane essential in fuel cells and chemical filters. At high humidity condition, water molecules attached on the rGO sheet are expected to play a critical role, but theoretical works for such phenomena have been scarcely found in the literature. In this study, we investigate the proton migration on water-adsorbed monolayer and bilayer rGO sheets using first-principles calculations in order to reveal the mechanism. We devise a series of models for th…
Electromechanical activity, remanent polarization states, and hysteresis loops in paraelectric TiO2 and SrTiO3 are observed. The coupling between the ionic dynamics and incipient ferroelectricity in these materials is analyzed using extended Ginsburg Landau Devonshire (GLD) theory. The possible origins of electromechanical coupling including ionic dynamics, surface-charge induced electrostriction, and ionically-induced ferroelectricity are identified. For the latter, the ionic contribution can change the sign of first order GLD expansion coefficient, rendering material effectively ferroelectri…
Trirutile-type LiFe$_2$F$_6$ is a charge-ordered material with Fe$^{2+}$/Fe$^{3+}$ configuration. Here its physical properties, including magnetism, electronic structure, phase transition, and charge ordering, are studied theoretically. On one hand, the charge ordering leads to improper ferroelectricity with a large polarization. On the other hand, its magnetic ground state can be tuned from the antiferromagnetic to ferrimagnetic by moderate compressive strain. Thus, LiFe$_2$F$_6$ can be a rare multiferroic with both large magnetization and polarization. Most importantly, since the charge orde…
We demonstrate that the magnetization of a ferromagnet in contact with an antiferromagnetic multiferroic (LuMnO3) can be speedily reversed by electric field pulsing, and the sign of the magnetic exchange bias can switch and recover isothermally. As LuMnO3 is not ferroelastic, our data conclusively show that this switching is not mediated by strain effects but is a unique electric-field driven decoupling of the ferroelectric and ferromagnetic domains walls. Their distinct dynamics are essential for the observed magnetic switching.
Ferroelectric BiFeO3 thin films and artificial superlattices of (BiFeO3)m(SrTiO3)m (m~ 1 to 10 unit cells) were fabricated on (001)-oriented SrTiO3 substrates by pulsed laser ablation. The variation of leakage current and macroscopic polarization with periodicity was studied. Piezo force microscopy studies revealed the presence of large ferroelectric domains in the case of BiFeO3 thin films while a size reduction in ferroelectric domains was observed in the case of superlattice structures. The results show that the modification of ferroelectric domains through superlattice, could provide an ad…
The interfacial screening charge that arises to compensate electric fields of dielectric or ferroelectric thin films is now recognized as the most important factor in determining the capacitance or polarization of ultrathin ferroelectrics. Here we investigate using aberration-corrected electron microscopy and density functional theory how interfaces cope with the need to terminate ferroelectric polarization. In one case, we show evidence for ionic screening, which has been predicted by theory but never observed. For a ferroelectric film on an insulating substrate, we found that compensation ca…
We present a phenomenological scheme to study the size-dependent electric voltage-controlled magnetic anisotropy in ferromagnetic (FM)/ferroelectric (FE) heterostructures. The FM layers are either metallic Fe(001), Ni(001), Co(0001), or half-metallic (La, Sr)MnO3 films. Two magnetoelectric mechanisms, i.e., interface-charge and strain-mediated couplings, are considered. We show that the interface-charge mediated coupling is the main mechanism for the magnetoelectic coupling when the FM film thickness is below a certain transition thickness dtr while the strain-mediated coupling dominates above…
Using Landau-Ginzburg-Devonshire approach we calculated the equilibrium distributions of electric field, polarization and space charge in the ferroelectric-semiconductor heterostructures containing proper or incipient ferroelectric thin films. The role of the polarization gradient and intrinsic surface energy, interface dipoles and free charges on polarization dynamics are specifically explored. The intrinsic field effects, which originated at the ferroelectric-semiconductor interface, lead to the surface band bending and result into the formation of depletion space-charge layer near the semic…
Although several multiferroic materials/heterostructures have been extensively studied, finding strong magnetoelectric couplings for the electric field control of the magnetization remains challenging. Here, a novel interfacial magnetoelectric coupling based on three components (ferroelectric dipole, magnetic moment, and antiferromagnetic order) is analytically formulated. As an extension of carrier-mediated magnetoelectricity, the new coupling is shown to induce an electric-magnetic hysteresis loop. Realizations employing BiFeO$_3$ bilayers grown along the [$111$] axis are proposed. Without i…
Electric-field modulation of magnetism in strain-mediated multiferroic heterostructures is considered a promising scheme for enabling memory and magnetic microwave devices with ultralow power consumption. However, it is not well understood how electric-field-induced strain influences magnetic relaxation, an important physical process for device applications. Here we investigate resonant magnetization dynamics in ferromagnet/ferrolectric multiferroic heterostructures, FeGaB/PMN-PT and NiFe/PMN-PT, in two distinct strain states provided by electric-field-induced ferroelectric phase transition. T…
The ability to switch between distinct states of polarization comprises the defining property of ferroelectrics. However, the microscopic mechanism responsible for switching is not well understood and theoretical estimates based on coherent monodomain switching typically overestimate experimentally determined coercive fields by orders of magnitude. In this work we present a detailed first principles characterization of domain walls (DWs) in two-dimensional ferroelectric GeS, GeSe, SnS and SnSe. In particular, we calculate the formation energies and migration barriers for 180 and 90 DWs, and th…
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 show that the presence of free carriers in a substance can generate the multiferroic behavior. Namely, if the substance has mixed-valence ions, which can supply free carriers and have electric dipole and spin moments, all three types of long-range order (ferromagnetic, ferroelectric and magnetoelectric (ME)) can occur at low temperature. The physical origin of the effect is that charge carriers can mediate the multiferroic behavior via spin - spin (RKKY), dipole-dipole and dipole - spin interactions. Our estimate of the interaction magnitude shows that there exist an optimal carrier concent…
The strain dependent functional properties of epitaxial transition metal oxide films can be significantly modified via substrate selection. However, large lattice mismatches preclude dislocation-free epitaxial growth on ferroelectric substrates, whose strain states are modified by applied electric fields. Here we overcome this mismatch problem by depositing an epitaxial film of ferromagnetic La0.7Sr0.3MnO3 on a single crystal substrate of well lattice matched SrTiO3 via a film of SrRuO3 that we subsequently dissolved, permitting the transfer of unstrained La0.7Sr0.3MnO3 to a ferroelectric subs…
Interfacial spin to charge conversion arises due to an electric potential perpendicular to the interface. The electric potential can be artificially induced, for example, using ferroelectric and piezoelectric thin films at the interface. An alternate way to induce the electric potential could be flexoelectric field. The flexoelectricity can be observed in all the material that either have or lack inversion symmetry, additionally no large gate bias is needed. In this experimental study, we report large spin to charge conversion (spin-Hall angle- 0.578) at Ni80Fe20/amorphous-Si interfaces attrib…
Hybrid heterostructure based phototransistors are attractive owing to their high gain induced by photogating effect. However, the absence of an in-plane built-in electric field in the single channel layer transistor results in a relatively higher dark current and require a large operating gate voltage of the device. Here, we report novel air-stable cesium lead iodide/tungsten di-sulfide (CsPbI$_3$/WS$_2$) mixed dimensional heterostructure based photo-field-effect-transistors (photo-FETs) with asymmetric metal electrodes (Cr/WS$_2$/Au), exhibiting extremely low dark current (~10-12 A) with a re…
We investigate theoretically the magnetic dynamics in a ferroelectric/ferromagnetic heterostructure coupled via strain-mediated magnetoelectric interaction. We predict an electric field-induced magnetic switching in the plane perpendicular to the magneto-crystalline easy axis, and trace this effect back to the piezoelectric control of the magnetoelastic coupling. We also investigate the magnetic remanence and the electric coercivity.
Strain-mediated magnetoelectric (ME) coupling in ferroelectric (FE) / ferromagnetic (FM) heterostructures offers a unique opportunity for both fundamental scientific research and low power multifunctional devices. Relaxor-ferroelectrics, like (1-x)Pb(Mg1/3Nb2/3)O3-(x)PbTiO3 (PMN-xPT), are ideal FE layer candidates due to their giant piezoelectricity. But thin films of PMN-PT suffer from substrate clamping which substantially reduces piezoelectric in-plane strains. Here we present the first demonstration of low voltage ME coupling in an all-thin-film heterostructure which utilizes the anisotrop…
We study the coexistence of strain- and charge-mediated magnetoelectric coupling in a cobalt (0-7 nm) wedge on ferroelectric [Pb(Mg$_{1/3}$/Nb$_{2/3}$)O$_{3}$]$_{0.68}$-[PbTiO$_{3}$]$_{0.32}$ (011) using surface-sensitive x-ray magnetic circular dichroism spectroscopy at the Co L$_{3,2}$ edges. Three distinct electric field driven remanent magnetization states can be set in the Co film at room temperature. Ab-initio density functional theory calculations unravel the relative contributions of both strain and charge to the observed magnetic anisotropy changes illustrating magnetoelectro-elastic …
Large magnetoelectric response in thin films is highly desired for high-throughput and high-density microelectronic applications. However, the d0 rule in single-phase compounds usually results in a weak interaction between ferroelectric and magnetic orders; the magnetoelectric coupling via elastic resonance in composites restricts their thin-film integration in broadband. Here, we effectuate a concurrence of ferroelectric-like and antiferromagnetic phase transitions in Sr2IrO4/SrTiO3 superlattices by artificial design periodically non-equivalent interfaces, where a maximum magnetoelectric coef…
Ferroelectric switching in BiFeO$_3$ multiferroic thin films with intrinsic ``stripe-like'' and ``bubble-like'' polydomain configurations was studied by piezoresponse force microscopy. Using the local electric field applied by a scanning probe microscope tip, we observe reversal of both out-of-plane and in-plane components of the polarization, with the final domain state depending on the tip sweeping direction. In ``bubble-like'' samples, complete control of the polarization is achieved, with in-plane polarization change mediated and stabilized by out-of-plane polarization reversal. In ``strip…
The quantitative understanding of converse magnetoelectric effects, i.e., the variation of the magnetization as a function of an applied electric field, in extrinsic multiferroic hybrids is a key prerequisite for the development of future spintronic devices. We present a detailed study of the strain-mediated converse magnetoelectric effect in ferrimagnetic Fe3O4 thin films on ferroelectric BaTiO3 substrates at room temperature. The experimental results are in excellent agreement with numerical simulation based on a two-region model. This demonstrates that the electric field induced changes of …
We present a study of the control of electric field induced strain on the magnetic and electrical transport properties in a magneto-elastically coupled artificial multiferroic Fe3O4/BaTiO3 heterostructure. In this Fe3O4/BaTiO3 heterostructure, the Fe3O4 thin film is epitaxially grown in the form of bilateral domains, analogous to a-c stripe domains of the underlying BaTiO3(001) substrate. By in-situ electric field dependent magnetization measurements, we demonstrate the extrinsic control of the magnetic anisotropy and the characteristic Verwey metal-insulator transition of the epitaxial Fe3O4 …
