Single-phase magnetoelectric multiferroics are ferroelectric materials that display some form of magnetism. In addition, magnetic and ferroelectric order parameters are not independent of one another. Thus, the application of either an electric or magnetic field simultaneously alters both the electrical dipole configuration and the magnetic state of the material. The technological possibilities that could arise from magnetoelectric multiferroics are considerable and a range of functional devices has already been envisioned. Realising these devices, however, requires coupling effects to be significant and to occur at room temperature. Although such characteristics can be created in piezoelectric-magnetostrictive composites, to date they have only been weakly evident in single-phase multiferroics. Here in a newly discovered room temperature multiferroic, we demonstrate significant room temperature coupling by monitoring changes in ferroelectric domain patterns induced by magnetic fields. An order of magnitude estimate of the effective coupling coefficient suggests a value of ~1 × 10−7 sm−1.

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Almost free-standing single crystal mesoscale and nanoscale dots of ferroelectric BaTiO(3) have been made by direct focused ion beam patterning of bulk single crystal material. The domain structures which appear in these single crystal dots, after cooling through the Curie temperature, were observed to form into quadrants, with each quadrant consisting of fine 90 degrees stripe domains. The reason that these rather complex domain configurations form is uncertain, but we consider and discuss three possibilities for their genesis: first, that the quadrant features initially form to facilitate field-closure, but then develop 90 degrees shape compensating stripe domains in order to accommodate disclination stresses; second, that they are the result of the impingement of domain packets which nucleate at the sidewalls of the dots forming "Forsbergh" patterns (essentially the result of phase transition kinetics); and third, that 90 degrees domains form to conserve the shape of the nanodot as it is cooled through the Curie temperature but arrange into quadrant packets in order to minimize the energy associated with uncompensated surface charges (thus representing an equilibrium state). While the third model is the preferred one, we note that the second and third models are not mutually exclusive.

Naturally occurring boundaries between bundles of 90° stripe domains, which form in BaTiO(3) lamellae on cooling through the Curie Temperature, have been characterized using both piezoresponse force microscopy (PFM) and scanning transmission electron microscopy (STEM). Detailed interpretation of the dipole configurations present at these boundaries (using data taken from PFM) shows that in the vast majority of cases they are composed of simple zigzag 180° domain walls. Topological information from STEM shows that occasionally domain bundle boundaries can support chains of dipole flux closure and quadrupole nanostructures, but these kinds of boundaries are comparatively rare; when such chains do exist, it is notable that singularities at the cores of the dipole structures are avoided. The symmetry of the boundary shows that diads and centers of inversion exist at positions where core singularities should have been expected.

In an attempt to explore and understand domain configurations that occur in idealized ferroelectric nanowires, a focused ion beam microscope has been used to directly cut columns in a variety of sizes from single-crystal barium titanate. The scanning transmission electron microscope has then been used to image the ferroelectric domain patterns evident after cooling through the Curie temperature in the vacuum environment of the electron microscope. As the overall length of the wires is physically constrained, the observed length-conserving packets of 90°d omains with {110} pseudocubic domain-wall orientations can easily be rationalized. Such domain structures necessarily dictate that although half of the domains can be such that their polarization direction lies parallel to the axis of the wire, the other half of the domains will have polarization directions approximately perpendicular to the wire axis (nonaxial). This situation introduces a depolarizing field and associated energy, which is minimized when the nonaxial polarization is oriented perpendicular to the smallest dimension of the column. Locally changing the aspect ratio of the column dimensions therefore allows local variations in the direction of polarization to be introduced. This was demonstrated by fabricating wire structures in which dimensions were varied along their length. Such wires did indeed show morphologically controlled polar reorientation. The study suggests that shape engineering alone could be used to create complex heterogeneous dipole configurations in ferroelectrics at the nanoscale without the need for externally applied poling electric fields. Possibilities for the further development of this observation might include introducing chiral variations in wire thickness, for example, to create dipole helices.

The periodicity of 180 • stripe domains as a function of crystal thickness scales with the width of the domain walls, both for ferroelectric and for ferromagnetic materials. Here we derive an analytical expression for the generalized ferroic scaling factor and use this to calculate the domain wall thickness and gradient coefficients (exchange constants) in some ferroelectric and ferromagnetic materials. We then use these to discuss some of the wider implications for the physics of ferroelectric nanodevices and periodically poled photonic crystals.

Freestanding BaTiO3 nanodots exhibit domain structures characterized by distinct quadrants of ferroelastic 90° domains in transmission electron microscopy (TEM) observations. These differ significantly from flux-closure domain patterns in the same systems imaged by piezoresponse force microscopy. Based upon a series of phase field simulations of BaTiO3 nanodots, we suggest that the TEM patterns result from a radial electric field arising from electron beam charging of the nanodot. For sufficiently large charging, this converts flux-closure domain patterns to quadrant patterns with radial net polarizations. Not only does this explain the puzzling patterns that have been observed in TEM studies of ferroelectric nanodots, but also suggests how to manipulate ferroelectric domain patterns via electron beams.

We describe extensive studies on a family of perovskite oxides that are ferroelectric and ferromagnetic at ambient temperatures. The data include x-ray diffraction, Raman spectroscopy, measurements of ferroelectric and magnetic hysteresis, dielectric constants, Curie temperatures, electron microscopy (both scanning electron microscope and transmission electron microscopy (TEM)) studies, and both longitudinal and transverse magnetoelectric constants α33 and α31. The study extends earlier work to lower Fe, Ta, and Nb concentrations at the B-site (from 15%–20% down to 5%). The magnetoelectric constants increase supralinearly with Fe concentrations, supporting the earlier conclusions of a key role for Fe spin clustering. The room-temperature orthorhombic C2v point group symmetry inferred from earlier x-ray diffraction studies is confirmed via TEM, and the primitive unit cell size is found to be the basic perovskite Z = 1 structure of BaTiO3, also the sequence of phase transitions with increasing temperature from rhombohedral to orthorhombic to tetragonal to cubic mimics barium titanate.