Temperature dependent impedance spectroscopy enables the many contributions to the dielectric and resistive properties of condensed matter to be deconvoluted and characterized separately. We have achieved this for multiferroic epitaxial thin films of BiFeO3 (BFO) and BiMnO3 (BMO), key examples of materials with strong magneto-electric coupling. We demonstrate that the true film capacitance of the epitaxial layers is similar to that of the electrode interface, making analysis of capacitance as a function of film thickness necessary to achieve deconvolution. We modeled non-Debye impedance response using Gaussian distributions of relaxation times and reveal that conventional resistivity measurements on multiferroic layers may be dominated by interface effects. Thermally activated charge transport models yielded activation energies of 0.60 eV +- 0.05 eV (BFO) and 0.25 eV +- 0.03 eV (BMO), which is consistent with conduction dominated by oxygen vacancies (BFO) and electron hopping (BMO). The intrinsic film dielectric constants were determined to be 320 +- 75 (BFO) and 450 +- 100 (BMO).
Multiferroics with the coexistence of ferroelectric and ferromagnetic orders are ideal candidates for magnetoelectric applications. Unfortunately, only very few ferroelectric-ferromagnetic multiferroics (with low magnetic critical temperature) were discovered. Here we perform first principles calculations to investigate the effects of the epitaxial strain on the properties of BiMnO3 films grown along the pseudocubic [001] direction. Unlike the ground state with the centrosymmetric C2/c space group in bulk, we reveal that the tensile epitaxial strain stabilizes the ferromagnetic and ferroelectr…
Multiferroic BiFeO3 epitaxial films with thickness ranging from 40 nm to 960 nm were grown by pulsed laser deposition on SrTiO3 (001) substrates with SrRuO3 bottom electrodes. X-ray characterization shows that the structure evolves from angularly-distorted tetragonal with c/a ~ 1.04 to more bulk-like distorted rhombohedral (c/a ~ 1.01) as the strain relaxes with increasing thickness. Despite this significant structural evolution, the ferroelectric polarization along the body diagonal of the distorted pseudo-cubic unit cells, as calculated from measurements along the normal direction, barely ch…
We have combined neutron scattering and piezoresponse force microscopy to study the relation between the exchange bias observed in CoFeB/BiFeO3 heterostructures and the multiferroic domain structure of the BiFeO3 films. We show that the exchange field scales with the inverse of the ferroelectric and antiferromagnetic domain size, as expected from Malozemoff's model of exchange bias extended to multiferroics. Accordingly, polarized neutron reflectometry reveals the presence of uncompensated spins in the BiFeO3 film at the interface with the CoFeB. In view of these results we discuss possible st…
We report on the functionalization of multiferroic BiFeO3 epitaxial films for spintronics. A first example is provided by the use of ultrathin layers of BiFeO3 as tunnel barriers in magnetic tunnel junctions with La2/3Sr1/3MnO3 and Co electrodes. In such structures, a positive tunnel magnetoresistance up to 30% is obtained at low temperature. A second example is the exploitation of the antiferromagnetic spin structure of a BiFeO3 film to induce a sizeable (~60 Oe) exchange bias on a ferromagnetic film of CoFeB, at room temperature. Remarkably, the exchange bias effect is robust upon magnetic f…
We report on the growth of epitaxial bilayers of the La2/3Sr1/3MnO3 (LSMO) half-metallic ferromagnet and the BiFeO3 (BFO) multiferroic, on SrTiO3(001) by pulsed laser deposition. The growth mode of both layers is two-dimensional, which results in unit-cell smooth surfaces. We show that both materials keep their properties inside the heterostructures, i.e. the LSMO layer (11 nm thick) is ferromagnetic with a Curie temperature of ~330K, while the BFO films shows ferroelectricity down to very low thicknesses (5 nm). Conductive-tip atomic force microscope mappings of BFO/LSMO bilayers for differen…
The magnetic exchange bias between epitaxial thin films of the multiferroic (antiferromagnetic and ferroelectric) hexagonal YMnO3 oxide and a soft ferromagnetic (FM) layer is used to couple the magnetic response of the ferromagnetic layer to the magnetic state of the antiferromagnetic one. We will show that biasing the ferroelectric YMnO3 layer by an appropriate electric field allows modifying and controlling the magnetic exchange bias and subsequently the magnetotransport properties of the FM layer. This finding may contribute to pave the way towards a new generation of electric-field control…
We have grown epitaxial thin films of multiferroic BiMnO$_3$ using pulsed laser deposition. The films were grown on SrTiO$_3$ (001) substrates by ablating a Bi-rich target. Using x-ray diffraction we confirmed that the films were epitaxial and the stoichiometry of the films was confirmed using Auger electron spectroscopy. The films have a ferromagnetic Curie temperature ($T_C$) of 85$\pm$5 K and a saturation magnetization of 1 $μ_B$/Mn. The electric polarization as a function of electric field ($P-E$) was measured using an interdigital capacitance geometry. The $P-E$ plot shows a clear hystere…
Ultrafast optical pump-probe spectroscopy is used to reveal the coexistence of coupled antiferromagnetic/ferroelectric and ferromagnetic orders in multiferroic TbMnO3 films through their time domain signatures. Our observations are explained by a theoretical model describing the coupling between reservoirs with different magnetic properties. These results can guide researchers in creating new kinds of multiferroic materials that combine coupled ferromagnetic, antiferromagnetic and ferroelectric properties in one compound.
The physical properties of epitaxial films can fundamentally differ from those of bulk single crystals even above the critical thickness. By a combination of non-resonant x-ray magnetic scattering, neutron diffraction and vector-mapped x-ray magnetic linear dichroism photoemission electron microscopy, we show that epitaxial (111)-BiFeO3 films support sub-micron antiferromagnetic domains, which are magneto-elastically coupled to a coherent crystallographic monoclinic twin structure. This unique texture, which is absent in bulk single crystals, should enable control of magnetism in BiFeO3 film d…
Magnetic phase transitions in multiferroic bismuth ferrite (BiFeO3) induced by magnetic field, epitaxial strain, and composition modification are considered. These transitions from a spatially modulated spin spiral state to a homogenous antiferromagnetic one are accompanied by the release of latent magnetization and a linear magnetoelectric effect that makes BiFeO3-based materials efficient room-temperature single phase multiferroics.
In this work multiferroic thin films of Bi containing perovskite oxides are discussed, where the driving force for ferroelectricity are the Bi3+ lone-pair electrons. First, a brief introduction of Bi containing multiferroic perovskite oxides will be presented to describe the mechanisms for establishing magnetic and ferroelectric order in these compounds and some recent developments in this field of research are reported. The second section addresses experimental aspects of epitaxial thin film growth of BiMnO3, (Bi0.9La0.1)2NiMnO6 (BLNMO) and BiFeO3 thin films by pulsed laser deposition. The th…
Multiferroic properties of orthorhombic HoMnO3 (Pbnm space group) are significantly modified by epitaxial compressive strain along the a-axis. We are able to focus on the effect of strain solely along the a-axis by using an YAlO3 (010) substrate, which has only a small lattice mismatch with HoMnO3 along the other in-plane direction (the c-axis). Multiferroic properties of strained and relaxed HoMnO3 thin films are compared with those reported for bulk, and are found to differ widely. A relaxed film exhibits bulk-like properties such as a ferroelectric transition temperature of 25 K and an inco…
We report the structural and magnetoelectrical properties of La$_{0.7}$Ca$_{0.3}$MnO$_3$/BaTiO$_3$ perovskite superlattices grown on (001)-oriented SrTiO$_3$ by the pulsed laser deposition technique. Magnetic hysteresis loops together with temperature dependent magnetic properties exhibit well-defined coercivity and magnetic transition temperature (T$_C$) \symbol{126}140 K. $DC$ electrical studies of films show that the magnetoresistance (MR) is dependent on the BaTiO$_3$ thickness and negative $MR$ as high as 30% at 100K are observed. The $AC$ electrical studies reveal that the impedance and …
A series of superlattices composed of ferromagnetic La$_{0.7}$Ca$_{0.3}$MnO$_3$ (LCMO) and ferroelectric/paraelectric Ba$_{1-x}$Sr$_x$TiO$_3$ (0$\leq $x$\leq $1) were deposited on SrTiO$_3$ substrates using the pulsed laser deposition. Films of epitaxial nature comprised of spherical mounds having uniform size are obtained. Magnetotransport properties of the films reveal a ferromagnetic Curie temperature in the range of 145-158 K and negative magnetoresistance as high as 30%, depending on the type of ferroelectric layers employed for their growth (\QTR{it}{i.e.} '\QTR{it}{x'} value). Ferroelec…
Strain is a leading candidate for controlling magnetoelectric coupling in multiferroics. Here, we use x-ray diffraction to study the coupling between magnetic order and structural distortion in epitaxial films of the orthorhombic (o-) perovskite LuMnO$_3$. An antiferromagnetic spin canting in the E-type magnetic structure is shown to be related to the ferroelectrically induced structural distortion and to a change in the magnetic propagation vector. By comparing films of different orientations and thicknesses, these quantities are found to be controlled by b-axis strain. It is shown that compr…
The recent study of oxides led to the discovery of several new fascinating physical phenomena. High-temperature superconductivity, colossal magnetoresistance, dilute magnetic doping, or multiferroicity were discovered and investigated in transition-metal oxides, representing a prototype class of strongly correlated electronic systems. This development was accompanied by an enormous progress regarding thin film fabrication. Within the past two decades, epitaxial thin films with crystalline quality approaching semiconductor standards became available using laser molecular beam epitaxy. This evol…
Epitaxial thin films of hexagonal ErMnO3 fabricated on Pt(111)/Al2O3(0001) and YSZ(111) substrates exhibited both ferroelectric character and magnetic ordering at low temperatures. As the temperature was reduced, the ErMnO3 films first showed antiferromagnetism. At lower temperatures, the films deposited at lower oxygen partial pressures exhibited spin glass behavior. This re-entrant spin glass behavior was attributed to competition between an antiferromagnetic interaction in the hexagonal geometry and a ferromagnetic interaction caused by a change in Mn valence induced by excess electrons fro…
We report on the growth and functional characterization of epitaxial thin films of the multiferroic YMnO3. We show that using Pt as a seed layer on SrTiO3(111) substrates, epitaxial YMnO3 films (0001) textured are obtained. An atomic force microscope has been used to polarize electric domains revealing the ferroelectric nature of the film. When a Permalloy layer is grown on top of the YMnO3(0001) film, clear indications of exchange bias and enhanced coercivity are observed at low temperature. The observation of coexisting antiferromagnetism and electrical polarization suggests that the biferro…
GeCu$_2$O$_4$ is a high-pressure recoverable cuprate with a strongly tetragonally elongated spinel structure and magnetic lattice formed by $S=1/2$ CuO$_2$ linear chains with frustrated exchange interactions and exotic magnetic behavior. Here we report on the first stabilization of epitaxial thin films of GeCu$_2$O$_4$ on (001)-oriented MgAl$_2$O$_4$ substrate. Developed growth mode, surface morphology, crystal structure and copper valence state were characterized by \emph{in-situ} reflection high-energy electron diffraction, atomic force microscopy, X-ray reflectivity, X-ray diffraction and X…
We report a study on the thermodynamic stability and structure analysis of the epitaxial BiFeO3 (BFO) thin films grown on YAlO3 (YAO) substrate. First we observe a phase transition of MC-MA-T occurs in thin sample (<60 nm) with an utter tetragonal-like phase (denoted as MII here) with a large c/a ratio (~1.23). Specifically, MII phase transition process refers to the structural evolution from a monoclinic MC structure at room temperature to a monoclinic MA at higher temperature (150oC) and eventually to a presence of nearly tetragonal structure above 275oC. This phase transition is further con…
Using resonant soft X-ray techniques we follow the magnetic behavior of a strained epitaxial film of CoCr2O4, a type-II multiferroic. The film is [110]-oriented, such that both the ferroelectric and ferromagnetic moments can coexist in plane. X-ray magnetic circular dichroism (XMCD) is used in scattering and in transmission modes to probe the magnetization of Co and Cr separately. The transmission measurements utilized X-ray excited optical luminescence from the substrate. Resonant soft X-ray diffraction (RSXD) was used to study the magnetic order of the low temperature phase. The XMCD signals…
The effects of strain on a film of mulitferroic GdMnO3 are investigated using both magnetometry and magneto-optic spectroscopy. Optical spectra, in the energy range 1.5eV - 3.5eV, were taken in Faraday geometry in an applied magnetic field and also at remanence. This yielded rich information on the effects of strain on the spin ordering in these films. Epitaxial films of GdMnO3 were grown on SrTiO3 and LaAlO3 substrates. The LaAlO3 was twinned and so produced a highly strained film whereas the strain was less for the film grown on SrTiO3. The Neél temperatures and coercive fields were measured…
Thin films and heterostructures of hexagonal manganites as promising multiferroic materials have attracted a considerable interest recently. We report structural transformations of high quality epitaxial h-TMO/YSZ(111) films, analyzed by means of various characterization techniques. A phase transition from P63mc to P63mcm structure at TC~800 K was observed by temperature dependent Raman spectroscopy and optical ellipsometry. The latter probing directly electronic system, indicates its modification at the structural phase transition likely due to charge transfer from oxygen to Mn. In situ trans…
