Epitaxial thin films of the multiferroic double perovskite Bi2FeCrO6 grown on (100)-oriented SrTiO3 substrates: Growth, characterization, and optimization
Riad Nechache, Catalin Harnagea, Louis-Philippe Carignan, Olivier Gautreau, Lucian Pintilie, Mangala P. Singh, David Menard, Patrick Fournier, Marin Alexe, Alain Pignolet
备注：
Manuscript accepted for publication in J. Appl. Phys (ISIF conference- multiferroics special issue)
The influence of the deposition pressure PO2 and substrate temperature TS during the growth of Bi2FeCrO6 thin films grown by pulsed laser deposition has been investigated. It is found that the high volatility of Bi makes the deposition very difficult and that the growth of pure Bi2FeCrO6 thin films on SrTiO3 substrates is possible only in a narrow deposition parameter window. We find that the pure Bi2FeCrO6 phase is formed within a narrow window around an oxygen pressure PO2 =1.210-2 mbar and around a substrate temperature TS=680 degC. At lower temperature or higher pressure, Bi7.38Cr0.62O12+x_also called (b*Bi2O3)and Bi2Fe4O9 /Bi2(Fe,Cr)4O9+x phases are detected, while at lower pressure or higher temperature a (Fe,Cr)3O4 phase forms. Some of these secondary phases are not well known and have not been previously studied. We previously reported Fe/Cr cation ordering as the probable origin of the tenfold improvement in magnetization at saturation of our Bi2FeCrO6 film, compared to BiFeO3. Here, we address the effect of the degree of cationic ordering on the magnetic properties of the Bi2FeCrO6 single phase. Polarization measurements at room temperature reveal that our Bi2FeCrO6 films have excellent ferroelectric properties with ferroelectric hysteresis loops exhibiting a remanent polarization as high as 55-60 miroC/cm2 along the pseudocubic (001) direction.
This review devoted to multiferroic properties of Bismuth-based perovskites falls into two parts. The first part focuses on BiFeO3 and summarizes the recent progress made in the studies of its pressure-temperature phase diagram and magnetoelectric coupling phenomena. The second part discusses in a more general way the issue of polar - and multiferroic - phases in BiBO3 perovskites and the competition between ferroelectricity and other structural instabilities, from an inventory of recently synthetized compounds.
A current challenge in the field of magnetoelectric multiferroics is to identify systems that allow a controlled tuning of states displaying distinct magnetoelectric responses. Here we show that the multiferroic ground state of the archetypal multiferroic TbMnO3 is dramatically modified by epitaxial strain. Neutron diffraction reveals that in highly strained films the magnetic order changes from the bulk-like incommensurate bc-cycloidal structure to commensurate magnetic order. Concomitant with the modification of the magnetic ground state, optical second-harmonic generation (SHG) and electric…
Epitaxial growth of multiferroic Pb(Zr0.57Ti0.43)O3-Pb(Fe2/3W1/3)O3 solid-solution thin films and their magnetoelectric effects
本文报道了用脉冲激光沉积法外延生长单相[Pb（Zr 0.57 Ti 0.43）O3]0.8[Pb（Fe 2/3 W 1/3）O3]0.2（PZT-PFW）固溶体薄膜。X射线衍射测试表明薄膜具有四方晶系结构。该薄膜在室温下表现出铁电性和弱铁磁响应。磁电效应进行了研究，非线性磁电系数进行了测量，发现是可比的多铁性六方锰氧化物，但至少两个数量级小于多晶PZT-PFW薄膜。
Epitaxial strain has been shown to drive structural phase transitions along with novel functionalities in perovskite-based thin-films. Aliovalent doping at the A-site can drive an insulator-to-metal and magnetic transitions in perovskites along with a variety of interesting structural and electronic phenomena. Using first-principles calculations, we demonstrate here, how coupling epitaxial strain with A-site hole doping in a multiferroic double perovskite, Bi2FeCrO6, could lead to mitigation of issues related to anti-site defects and lowered magnetisation in thin-films of the material. We also…
CoFe${}_{2}$O${}_{4}$ (CFO)-BiFeO${}_{3}$ (BFO) nanocomposites are an intriguing option for future memory and logic technologies due to the magnetoelctric properties of the system. However, these nanocomposites form with CFO pillars randomly located within a BFO matrix, making implementation in devices difficult. To overcome this, we present a technique to produce patterned nanocomposites through self-assembly. CFO islands are patterned on Nb-doped SrTiO${}_{3}$ to direct the self-assembly of epitaxial CFO-BFO nanocomposites, producing square arrays of CFO pillars.
We propose experimental verification and theoretical explanation of magnetic anomalies in the complex Fe-contained double perovskite multiferroics like PbFe$_{1/2}$Nb$_{1/2}$O$_3$. The theoretical part is based on our model of coexistence of long-range magnetic order and spin glass in the above substances. In our model, the exchange interaction is anisotropic, coupling antiferromagnetically $z$ spin components of Fe$^{3+}$ ions. At the same time, the $xy$ components are coupled by much weaker exchange interaction of ferromagnetic sign. In the system with spatial disorder (half of corresponding…
We have investigated the effect of epitaxial strain on the magnetic properties and $B$-site cation ordering in multiferroic Bi$_2$FeCrO$_6$ (001) thin films using a density-functional theory approach. We find that in thin films with rock-salt ordering of Fe and Cr the ground state is characterised by C-type anti-ferromagnetic (AFM) order. This is in contrast to the bulk form of the material which was predicted to be a ferrimagnet with G-type AFM order. Furthermore, the cation ordered thin-films undergo a transition with epitaxial strain from C to A-type AFM order. Other magnetic orders appear …
In this paper we investigated the influence of the rare-earth ionic radii on the spin-phonon coupling in RE2NiMnO6 double perovskites by Raman spectroscopy. Spin-phonon in dense Nd2NiMnO6 and Gd2NiMnO6 ceramics were investigated by Raman spectroscopy at low temperatures. The magnitude of the coupling observed in comparison with other isostructural compounds shows that it is not influenced by the rare-earth ionic radius, as well as the deviation of the position of the stretching phonon in the ferromagnetic phase with relation to the anharmonic contributions follows a power law.
We investigate a magnetic hysteresis loop with a remanent moment that couples to electric polarization to create coupled hysteretic multiferroic behavior in Lu2MnCoO6. Measurements of elastic neutron diffraction, muon spin relaxation, and micro-Hall magnetometry demonstrate an unusual mechanism for the magnetic hysteresis, namely the hysteretic evolution of a microscopic magnetic order, and not classic ferromagnetic domain effects. We show how the frustrated spin system evolves from antiferromagnetism with an incommensurate long-wavelength modulation and strong fluctuations towards a net magne…
In this article, we perform the symmetry analysis of perovskite-based multiferroics: bismuth ferrite (BiFeO3)-like, orthochromites (RCrO3), and Ruddlesden-Popper perovskites (Ca3Mn2O7-like), being the typical representatives of multiferroics of the trigonal, rhombic, and tetragonal crystal families and explore the effect of crystallographic distortions on magnetoelectric properties. We determine the principal order parameters for each of the considered structures and obtain their invariant combinations consistent with the particular symmetry. This approach allowed us to analyze the features of…
We report on domain pattern transfer from a ferroelectric BaTiO$_{\mathrm{3}}$ substrate with a $(111)$-orientation of the surface to an epitaxial Co film grown on a Pd buffer layer. Spatially modulated interfacial strain transfer from ferroelectric/ferroelastic domains and inverse magnetostriction in the ferromagnetic film induce stripe regions with a modulation of the in-plane uniaxial magnetic anisotropy direction. Using spin-polarized low energy electron microscopy, we observe the formation of two distinct anisotropy configurations between stripe regions. Moreover, through application of a…
We investigate the crystal structure in multiferroic tetragonal perovskite Sr$_{1/2}$Ba$_{1/2}$MnO$_3$ with high accuracy of the order of 10$^{-3}$ Angstrom for an atomic displacement. The large atomic displacement for Mn ion from the centerosymmetric position, comparable with the off-centering distortion in the tetragonal ferroelectric BaTiO$_3$, is observed in the ferroelectric phase ($T_\mathrm{N}$ $\leq$ $T$ $\leq$ $T_\mathrm{C}$). In stark contrast, in the multiferroic phase ($T$ $\leq$ $T_\mathrm{N}$), the atomic displacement for Mn ion is suppressed, but those for O ions are enlarged. T…
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…
In this article the mechanism of the linear magnetoelectric (ME) effect in the rhombohedral multiferroic BiFeO$_3$ is considered. The study is based on the symmetry approach of the GinzburgLandau type, in which polarization, antiferrodistortion, and antiferromagnetic momentum vectors are viewed as ordering parameters. We demonstrate that the linear ME effect in BFO is caused by reorientation of the antiferrodistortion vector in either electric or magnetic field. The numerical estimations, which show quantitative agreement with the results of the recent measurements in film samples, have been p…
The perovskite (1-x)YMnO$_3$-xBiFeO$_3$ binary system is very promising because of its multiferroic end members. Nanocrystalline phases have been recently obtained by mechanosynthesis across the system, and the perovskite structural evolution has been described. Two continuous solid solutions with orthorhombic Pnma and rhombohedral R3c symmetries were found, which coexist within a broad compositional interval of 0.5 < x < 0.9. This might be a polar-nonpolar morphotropic phase boundary region, at which strong phase-change magnetoelectric responses can be expected. A major issue is phase decompo…
The magnetic order, spin dynamics, and crystal structure of the multiferroic Sr0.56Ba0.44MnO3 have been investigated using neutron and x-ray scattering. Ferroelectricity develops at TC=305 K with a polarization of 4.2 microC/cm2 associated with the displacements of the Mn ions, while the Mn4+ spins order below TN = 200 K into a simple G-type commensurate magnetic structure. Below TN the ferroelectric order decreases dramatically demonstrating that the two order parameters are strongly coupled. The ground state spin dynamics are characterized by a spin gap of 4.6(5) meV and the magnon density o…
We use resonant and non-resonant X-ray diffraction measurements in combination with first-principles electronic structure calculations and Monte Carlo simulations to study the relationship between crystal structure and multiferroic orders in the orthorhombic perovskite manganites, o-$R$MnO$_3$ ($R$ is a rare-earth cation or Y). In particular, we focus on how the internal lattice parameters (Mn-O bond lengths and Mn-O-Mn bond angles) evolve under chemical pressure and epitaxial strain, and the effect of these structural variations on the microscopic exchange interactions and long-range magnetic…
Optimal materials to induce bulk photovoltaic effects should lack inversion symmetry and have an optical gap matching the energies of visible radiation. Ferroelectric perovskite oxides such as BaTiO$_3$ and PbTiO$_3$ exhibit substantial polarization and stability, but have the disadvantage of excessively large band gaps. We use both density functional theory and dynamical mean field theory calculations to design a new class of Mott multiferroics--double perovskite oxides $A_2$VFeO$_6$ ($A$=Ba, Pb, etc). While neither perovskite $A$VO$_3$ nor $A$FeO$_3$ is ferroelectric, in the double perovskit…
Multiferroic materials open up the possibility to design novel functionality in electronic devices, with low energy consumption. However, there are very few materials that show multiferroicity at room temperature, which is essential to be practically useful. AlxFe2-xO3 (x-AFO) thin films, belonging to the k-Al2O3 family are interesting because they show room temperature ferrimagnetism and have a polar crystal structure. However, it is difficult to realise its ferroelectric properties at room temperature, due to low resistivity of the films. In this work, we have deposited x-AFO (0.5 <= x <= 1)…
Chalcogenide perovskites have emerged as a new class of electronic materials, but fundamental properties and applications of chalcogenide perovskites remain limited by the lack of high quality epitaxial thin films. We report epitaxial thin film growth of BaZrS3, a prototypical chalcogenide, by pulsed laser deposition. X-ray diffraction studies show that the films are strongly textured out of plane and have a clear in-plane epitaxial relationship with the substrate. Electron microscopy studies confirm the presence of epitaxy for the first few layers of the film at the interface, even though awa…
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…
Ferromagnetic insulators (FMIs) are one of the most important components in developing dissipationless electronic and spintronic devices. However, since ferromagnetism generally accompanies metallicity, FMIs are innately rare to find in nature. Here, novel room-temperature FMI films are epitaxially synthesized by deliberate control of the ratio of two B-site cations in the double perovskite Sr2FeReO6. In contrast to the known ferromagnetic metallic phase in stoichiometric Sr2FeReO6, a FMI state with a high Curie temperature (Tc~400 K) and a large saturation magnetization (MS~1.8 μB/f.u.) is fo…
Symmetry-Driven Unconventional Magnetoelectric Coupling in Perovskite Altermagnets: From Bulk to the Two-Dimensional Limit
Eastern Institute of Technology（宁波东方理工大学）；Ningbo Institute of Digital Twin, Eastern Institute of Technology（宁波东方理工大学数字孪生研究院）；Eastern Institute for Advanced Study, Eastern Institute of Technology（宁波东方理工大学高等研究院）；School of Physics and Astronomy, Shanghai Jiao Tong University（上海交通大学物理与天文学院）；School of Physical Science and Technology, Suzhou University of Science and Technology（苏州科技大学物理科学与技术学院）
Recently, the perovskite BiCoO$_3$ has been shown experimentally to be isostructural with PbTiO$_3$, while simultaneously the $d^6$ Co$^{3+}$ ion has a high spin ground state with $C$-type antiferromagnetic ordering. Using hybrid density functional calculations, we investigate the atomic, electronic and magnetic structure of BiCoO$_3$ to elucidate the origin of the multiferroic state. To begin with, we perform a qualitative trend sudy of the role of $d$ electrons in affecting the tendency for perovskite materials to exhibit a ferroelectric distortion; this work initially explores a qualitative…
Epitaxial III-V semiconductor heterostructures are key components in modern microelectronics, electro-optics and optoelectronics. With superior semiconducting properties, halide perovskite materials are rising as promising candidates for coherent heterostructure devices. In this report, spinodal decomposition is proposed and experimentally implemented to produce epitaxial double heterostructures in halide perovskite system. Pristine epitaxial mixed halide perovskites rods and films were synthesized via Van der Waals epitaxy by chemical vapor deposition method. At room temperature, photon was a…
