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Helium implantation in epitaxial thin films is a way to control the out-of-plane deformation independently from the in-plane strain controlled by epitaxy. In particular, implantation by means of a helium microscope allows for local implantation and patterning down to the nanometer resolution, which is of interest for device applications. We present here a study of bismuth ferrite (BiFeO3) films where strain was patterned locally by helium implantation. Our combined Raman, XRD and TEM study shows that the implantation causes an elongation of the BiFeO3 unit cell and ultimately a transition towards the so-called super-tetragonal polymorph via states with mixed phases. In addition, TEM reveals the onset of amorphization at a threshold dose that does not seem to impede the overall increase in tetragonality. The phase transition from the R-like to T-like BiFeO3 appears as first-order in character, with regions of phase coexistence and abrupt changes in lattice parameters.

While ferromagnets are at the heart of daily life applications, their large magnetization and resulting energy cost for switching bring into question their suitability for reliable low-power spintronic devices. Non-collinear antiferromagnetic systems do not suffer from this problem and often possess remarkable extra functionalities: non-collinear spin order may break space-inversion symmetry and thus allow electric-field control of magnetism, or produce emergent spin-orbit effects, which enable efficient spin-charge interconversion. To harness these unique traits for next-generation spintronics, the nanoscale control and imaging capabilities that are now routine for ferromagnets must be developed for antiferromagnetic systems. Here, using a non-invasive scanning nanomagnetometer based on a single nitrogen-vacancy (NV) defect in diamond, we demonstrate the first real-space visualization of non-collinear antiferromagnetic order in a magnetic thin film, at room temperature. We image the spin cycloid of a multiferroic BiFeO$_3$ thin film and extract a period of $\sim70$ nm, consistent with values determined by macroscopic diffraction. In addition, we take advantage of the magnetoelectric coupling present in BiFeO$_3$ to manipulate the cycloid propagation direction by an electric field. Besides highlighting the unique potential of NV magnetometry for imaging complex antiferromagnetic orders at the nanoscale, these results demonstrate how BiFeO$_3$ can be used as a versatile platform for the design of reconfigurable nanoscale spin textures.

Antiferromagnetic thin films are currently generating considerable excitement for low dissipation magnonics and spintronics. However, while tuneable antiferromagnetic textures form the backbone of functional devices, they are virtually unknown at the submicron scale. Here we image a wide variety of antiferromagnetic spin textures in multiferroic BiFeO3 thin films that can be tuned by strain and manipulated by electric fields through room temperature magnetoelectric coupling. Using piezoresponse force microscopy and scanning NV magnetometry in self-organized ferroelectric patterns of BiFeO3, we reveal how strain stabilizes different types of non-collinear antiferromagnetic states (bulk-like and exotic spin cycloids) as well as collinear antiferromagnetic textures. Beyond these local-scale observations, resonant elastic X-ray scattering confirms the existence of both types of spin cycloids. Finally, we show that electric-field control of the ferroelectric landscape induces transitions either between collinear and non-collinear states or between different cycloids, offering perspectives for the design of reconfigurable antiferromagnetic spin textures on demand.

The application of PhotoEmission Electron Microscopy (PEEM) and Low Energy Electron Microscopy (LEEM) techniques to the study of the electronic and chemical structure of ferroelectric materials is reviewed. Electron optics in both techniques gives spatial resolution of a few tens of nanometres. PEEM images photoelectrons whereas LEEM images reflected and elastically backscattered electrons. Both PEEM and LEEM can be used in direct and reciprocal space imaging. Together, they provide access to surface charge, work function, topography, chemical mapping, surface crystallinity and band structure. Examples of applications for the study of ferroelectric thin films and single crystals are presented., Comment: 15 pages, 9 figures

The electric field control of functional properties is a crucial goal in oxide-based electronics. Non-volatile switching between different resistivity or magnetic states in an oxide channel can be achieved through charge accumulation or depletion from an adjacent ferroelectric. However, the way in which charge distributes near the interface between the ferroelectric and the oxide remains poorly known, which limits our understanding of such switching effects. Here we use a first-of-a-kind combination of scanning transmission electron microscopy with electron energy loss spectroscopy, near-total-reflection hard X-ray photoemission spectroscopy, and ab-initio theory to address this issue. We achieve a direct, quantitative, atomic-scale characterization of the polarization-induced charge density changes at the interface between the ferroelectric BiFeO3 and the doped Mott insulator Ca1-xCexMnO3, thus providing insight on how interface-engineering can enhance these switching effects., Comment: Work supported by ERC Consolidator grant MINT (Contract No. 615759)

The control of optical fields is usually achieved through the electro-optic or acousto-optic effect in single-crystal ferroelectric or polar compounds such as LiNbO3 or quartz. In recent years, tremendous progress has been made in ferroelectric oxide thin film technology - a field which is now a strong driving force in areas such as electronics, spintronics and photovoltaics. Here, we apply epitaxial strain engineering to tune the optical response of BiFeO3 thin films, and find a very large variation of the optical index with strain, corresponding to an effective elasto-optic coefficient larger than that of quartz. We observe a concomitant strain-driven variation in light absorption - reminiscent of piezochromism - which we show can be manipulated by an electric field. This constitutes an electrochromic effect that is reversible, remanent and not driven by defects. These findings broaden the potential of multiferroics towards photonics and thin film acousto-optic devices, and suggest exciting device opportunities arising from the coupling of ferroic, piezoelectric and optical responses., Comment: Work supported by ERC Consolidator grant MINT (Contract No. 615759)

In all-oxide ferroelectric (FE) - superconductor (S) bilayers, due to the low carrier concentration of oxides compared to transition metals, the FE interfacial polarization charges induce an accumulation (or depletion) of charge carriers in the S. This leads either to an enhancement or a depression of its critical temperature depending on FE polarization direction.Here we exploit this effect at a local scale to define planar weak-links in high-temperature superconducting wires. This is realized in BiFeO3(FE)/YBa2Cu3O7(S)bilayers in which the remnant FE domain structure is written at will by locally applying voltage pulses with a conductive-tip atomic force microscope. In this fashion, the FE domain pattern defines a spatial modulation of superconductivity. This allows us to write a device whose electrical transport shows different temperature regimes and magnetic field matching effects that are characteristic of Josephson coupled weak-links. This illustrates the potential of the ferroelectric approach for the realization of high-temperature superconducting devices.

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 particular entity is not the heart of specific photo-electric properties. Using 3D modelling, we argue that the measured effect is due to the spatial distribution of internal fields which are significantly affected by the charge of the DW due to its distortion.

In tunnel junctions with ferroelectric barriers, switching the polarization direction modifies the electrostatic potential profile and the associated average tunnel barrier height. This results in strong changes of the tunnel transmission and associated resistance. The information readout in ferroelectric tunnel junctions (FTJs) is thus resistive and non-destructive, which is an advantage compared to the case of conventional ferroelectric memories (FeRAMs). Initially, endurance limitation (i.e. fatigue) was the main factor hampering the industrialization of FeRAMs. Systematic investigations of switching dynamics for various ferroelectric and electrode materials have resolved this issue, with endurance now reaching $10^{14}$ cycles. Here we investigate data retention and endurance in fully patterned submicron Co/BiFeO$_3$/Ca$_{0.96}$Ce$_{0.04}$MnO$_3$ FTJs. We report good reproducibility with high resistance contrasts and extend the maximum reported endurance of FTJs by three orders of magnitude ($4\times10^6$ cycles). Our results indicate that here fatigue is not limited by a decrease of the polarization or an increase of the leakage but rather by domain wall pinning. We propose directions to access extreme and intermediate resistance states more reliably and further strengthen the potential of FTJs for non-volatile memory applications.

We measure the remnant polarization of ferroelectric domains in BiFeO3 films down to 3.6 nm using low energy electron and photoelectron emission microscopy. The measured polarization decays strongly below a critical thickness of 5-7 nm predicted by continuous medium theory whereas the tetragonal distortion does not change. We resolve this apparent contradiction using first-principles-based effective Hamiltonian calculations. In ultra thin films the energetics of near open circuit electrical boundary conditions, i.e. unscreened depolarizing field, drive the system through a phase transition from single out-of-plane polarization to a nanoscale stripe domains, giving rise to an average remnant polarization close to zero as measured by the electron microscopy whilst maintaining the relatively large tetragonal distortion imposed by the non-zero polarization state of each individual domain., Comment: main article: 5 pages, 6 figures; supplementary materials: 6 pages, 6 figures. Published in Phys. Rev. Lett

We investigate the magneto-transport characteristics of nanospintronics single-electron devices. The devices consist of single non-magnetic nano-objects (nanometer size nanoparticles of Al or Cu) connected to Co ferromagnetic leads. The comparison with simulations allows us attribute the observed magnetoresistance to either spin accumulation or anisotropic magneto-Coulomb effect (AMC), two effects with very different origins. The fact that the two effects are observed in similar samples demonstrates that a careful analysis of Coulomb blockade and magnetoresistance behaviors is necessary in order to discriminate them in magnetic single-electron devices. As a tool for further studies, we propose a simple way to determine if spin transport or AMC effect dominates from the Coulomb blockade I-V curves of the spintronics device.

In multiferroic BiFeO3 thin films grown on highly mismatched LaAlO3 substrates, we reveal the coexistence of two differently distorted polymorphs that leads to striking features in the temperature dependence of the structural and multiferroic properties. Notably, the highly distorted phase quasi-concomitantly presents an abrupt structural change, transforms from a hard to a soft ferroelectric and transitions from antiferromagnetic to paramagnetic at 360+/-20 K. These coupled ferroic transitions just above room temperature hold promises of giant piezoelectric, magnetoelectric and piezomagnetic responses, with potential in many applications fields.

In studies using piezoresponse force microscopy, we observe a non-zero lateral piezoresponse at 180$^\circ$ domain walls in out-of-plane polarized, c-axis-oriented tetragonal ferroelectric Pb(Zr$_{0.2}$Ti$_{0.8}$)O$_3$ epitaxial thin films. We attribute these observations to a shear strain effect linked to the sign change of the $d_{33}$ piezoelectric coefficient through the domain wall, in agreement with theoretical predictions. We show that in monoclinically distorted tetragonal BiFeO$_3$ films, this effect is superimposed on the lateral piezoresponse due to actual in-plane polarization, and has to be taken into account in order to correctly interpret the ferroelectric domain configuration., Comment: 4 pages, 3 figures

Using a low-temperature conductive-tip atomic force microscope in cross-section geometry we have characterized the local transport properties of the metallic electron gas that forms at the interface between LaAlO3 and SrTiO3. At low temperature, we find that the carriers do not spread away from the interface but are confined within ~10 nm, just like at room temperature. Simulations taking into account both the large temperature and electric-field dependence of the permittivity of SrTiO3 predict a confinement over a few nm for sheet carrier densities larger than ~6 10^13 cm-2. We discuss the experimental and simulations results in terms of a multi-band carrier system. Remarkably, the Fermi wavelength estimated from Hall measurements is ~16 nm, indicating that the electron gas in on the verge of two-dimensionality., Comment: Accepted for publication in Physical Review Letters

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 strategies to switch the magnetization of a ferromagnet by an electric field using BiFeO3., Comment: submitted to Phys. Rev. Lett

At the interface between complex insulating oxides, novel phases with interesting properties may occur, such as the metallic state reported in the LaAlO3/SrTiO3 system. While this state has been predicted and reported to be confined at the interface, some works indicate a much broader spatial extension, thereby questioning its origin. Here we provide for the first time a direct determination of the carrier density profile of this system through resistance profile mappings collected in cross-section LaAlO3/SrTiO3 samples with a conducting-tip atomic force microscope (CT-AFM). We find that, depending upon specific growth protocols, the spatial extension of the high-mobility electron gas can be varied from hundreds of microns into SrTiO3 to a few nanometers next to the LaAlO3/SrTiO3 interface. Our results emphasize the potential of CT-AFM as a novel tool to characterize complex oxide interfaces and provide us with a definitive and conclusive way to reconcile the body of experimental data in this system., Comment: This updated version contains new experimental data

We have analyzed the morphology of ferroelectric domains in very thin films of multiferroic BiFeO3. Unlike the more common stripe domains observed in thicker films BiFeO3 or in other ferroics, the domains tend not to be straight, but irregular in shape, with significant domain wall roughening leading to a fractal dimensionality. Also contrary to what is usually observed in other ferroics, the domain size appears not to scale as the square root of the film thickness. A model is proposed in which the observed domain size as a function of film thickness can be directly linked to the fractal dimension of the domains., Comment: 4 pages, 3 figures

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 field cycling, with no indications of training., Comment: 15 pages, 4 figures

We have fabricated nanometer sized magnetic tunnel junctions using a new nanoindentation technique in order to study the transport properties of a single metallic nanoparticle. Coulomb blockade effects show clear evidence for single electron tunneling through a single 2.5 nm Au cluster. The observed magnetoresistance is the signature of spin conservation during the transport process through a non magnetic cluster., Comment: 3 pages

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 different BFO thicknesses reveal a high and homogeneous resistive state for the BFO film that can thus be used as a ferroelectric tunnel barrier in tunnel junctions based on a half-metal.

We report on experiments of spin filtering through ultra-thin single-crystal layers of the insulating and ferromagnetic oxide BiMnO3 (BMO). The spin polarization of the electrons tunneling from a gold electrode through BMO is analyzed with a counter-electrode of the half-metallic oxide La2/3Sr1/3MnO3 (LSMO). At 3 K we find a 50% change of the tunnel resistances according to whether the magnetizations of BMO and LSMO are parallel or opposite. This effect corresponds to a spin filtering effciency of up to 22%. Our results thus show the potential of complex ferromagnetic insulating oxides for spin filtering and injection.

We have explored the influence of deposition pressure and temperature on the growth of BiFeO3 thin films by pulsed laser deposition onto (001)-oriented SrTiO3 substrates. Single-phase BiFeO3 films are obtained in a region close to 10-2 mbar and 580C. In non-optimal conditions, X-ray diffraction reveals the presence of Fe oxides or of Bi2O3. We address the influence of these parasitic phases on the magnetic and electrical properties of the films and show that films with Fe2O3 systematically exhibit a ferromagnetic behaviour, while single-phase films have a low bulk-like magnetic moment. Conductive-tip atomic force microscopy mappings also indicate that Bi2O3 conductive outgrowths create shortcuts through the BiFeO3 films, thus preventing their practical use as ferroelectric elements in functional heterostructures., Comment: sumbitted to Appl. Phys. Lett

We report on the fabrication of nanocontacts by indentation of an ultrathin insulating photoresist layer deposited on various types of conductive structures. A modified atomic force microscope (AFM) designed for local resistance measurements is used as a nanoindenter. The nanoindentation is performed while measuring continuously the resistance between the conductive tip of the AFM and the conductive layer, which is used as the trigger parameter to stop the indentation. This allows an extremely accurate control of the indentation process. The indented hole is subsequently filled by a metal to create a contact on the underlying layer. We show that nanocontacts in the range of 1 to 10 nm2 can be created with this technique.