Multiferroic materials displaying coupled ferroelectric and ferromagnetic order parameters could provide a means for data storage whereby bits could be written electrically and read magnetically, or vice versa. Thin films of Aurivillius phase Bi6Ti2.8Fe1.52Mn0.68O18, previously prepared by a chemical solution deposition (CSD) technique, are multiferroics demonstrating magnetoelectric coupling at room temperature. Here we demonstrate the growth of a similar composition, Bi6Ti2.99Fe1.46Mn0.55O18, via the liquid injection chemical vapor deposition technique. High resolution magnetic measurements reveal a considerably higher in-plane ferromagnetic signature than CSD grown films (MS = 24.25 emu/g (215 emu/cm 3 ), MR = 9.916 emu/g (81.5 emu/cm 3 ), HC = 170 Oe). A statistical analysis of the results from a thorough microstructural examination of the samples, allows us to conclude that the ferromagnetic signature can be attributed to the Aurivillius phase, with a confidence level of 99.95 %. In addition, we report the direct piezoresponse force i E-mail: lynette.keeney@tyndall.ieJournal of the American Ceramic Society DOI: 10.1111DOI: 10. /jace.14597 (2016 2 microscopy (PFM) visualization of ferroelectric switching while going through a full in-plane magnetic field cycle, where increased volumes (8.6 to 14 % compared with 4 to 7 % for the CSDgrown films) of the film engage in magnetoelectric coupling and demonstrate both irreversible and reversible magnetoelectric domain switching. IntroductionMultiferroic materials which exhibit more than one mutually-coupled ferroic (e.g. ferroelectric (FE) / ferromagnetic (FM) / ferroelastic) order parameter (OP) in a single phase, provide additional degrees of OP freedom that can be exploited in novel multistate memory and sensing devices.Magnetoelectricity (the generation of a change in magnetization by an applied electric field or vice versa), on the other hand, is a related phenomenon that will arise in any material that is both electrically and magnetically polarizable and possesses an appropriate magnetic symmetry, regardless of whether it is multiferroic or not. For example, the magnetoelectric Cr2O3 is an antiferromagnetic dielectric and is neither FE nor FM 1 . The unique advantage of single phase magnetoelectric multiferroics is that not only could they find application in high storage density, lowpower memory devices that can be electrically written and magnetically read, but also memory technologies with 4-state logic might be achieved by constructing devices that exploit the presence of both ferroelectric and ferromagnetic states 2 -representing a clear improvement over current 2-state logic devices. However, there are relatively few 3-8 materials demonstrating ferroelectric and ferromagnetic properties in a single-phase at room temperature. Due to conflicting electronic structure requirements for ferroelectricity (empty d orbitals) and ferromagnetism (partially filled d orbitals), the two properties tend to be mutually exclusive 9 . Examples of multiferroic material...

Here, we report the effect of A-site substitution of Tb at the expense of Bi on the ferroelectric and magnetic properties in m = 5 layered 2-D Aurivillius Bi6Ti3Fe2O18 thin films. The nominal stoichiometry of the prepared compound is Tb0.40Bi5.6Fe2Ti3O18, Tb0.90Bi5.1Fe2Ti3O18, and Bi6Ti3Fe2O18. Phase examination reveals that only 0.40 mol. % is successfully substituted forming Tb0.40Bi5.6Fe2Ti3O18 thin films. Lateral and vertical piezoresponse switching loops up to 200 °C reveal responses for Bi6Ti3Fe2O18, Tb substituted Tb0.40Bi5.6Fe2Ti3O18, and Tb0.90Bi5.1Fe2Ti3O18 thin films along the in-plane (±42.31 pm/V, 88 pm/V and ±134 pm/V, respectively) compared with the out-of-plane (±6.15 pm/V, 19.83 pm/V and ±37.52 pm/V, respectively). The macroscopic in-plane polarization loops reveal in-plane saturation (Ps) and remanence polarization (Pr) for Bi6Ti3Fe2O18 of ±26.16 μC/cm2 and ±22 μC/cm2, whereas, ±32.75 μC/cm2 and ±22.11 μC/cm2, ±40.30 μC/cm2 and ±28.5 μC/cm2 for Tb0.40Bi5.6Fe2Ti3O18 and Tb0.90Bi5.1Fe2Ti3O18 thin films, respectively. No ferromagnetic signatures were observed for Bi6Ti3Fe2O18 and Tb0.40Bi5.6Fe2Ti3O18. However, a weak response was observed for the Tb0.90Bi5.1Fe2Ti3O18 at 2 K. Microstructural analysis of Tb0.90Bi5.1Fe2Ti3O18 revealed that it contains 4 vol. % Fe:Tb rich areas forming FexTbyOz, which accounts for the observed magnetic moment. This study demonstrates the importance of thorough microstructural analysis when determining whether magnetic signatures can be reliably assigned to the single-phase system. We conclude that Tb0.40Bi5.6Fe2Ti3O18 and Tb0.90Bi5.1Fe2Ti3O18 samples are not multiferroic but demonstrate the potential for Fe-RAM applications.

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The ability to control the growth, texture and orientation of self-nanostructured lead-free Aurivillius phase thin films can in principle, greatly improve their ferroelectric properties, since in these materials the polarization direction is dependent on crystallite orientation. Here, we report the growth of c-plane oriented Bi6Ti3Fe2O18 (B6TFO) functional oxide Aurivillius phase thin films on c-plane sapphire substrates by liquid injection chemical vapour deposition (LI-CVD). Microstructural analysis reveals that B6TFO thin films annealed at 850°C are highly crystalline, well textured (Lotgering factor of 0.962) and single phase. Typical Aurivillius plate-like morphology with an average film thickness of 110nm and roughness 24nm was observed. The potential of B6TFO for use as a material in lead-free piezoelectric and ferroelectric data storage applications was explored by investigating local electromechanical (piezoelectric) and ferroelectric properties at the nano-scale. Vertical and lateral piezoresponse force microscopy (PFM) reveals stronger in-plane polarization due to the controlled growth of the a-axis oriented grains lying in the plane of the B6TFO films. Switching spectroscopy PFM (SS-PFM) hysteresis loops obtained at higher temperatures (up to 200°C) and at room temperature reveal a clear ferroelectric signature with only minor changes in piezoresponse observed with increasing temperature. Ferroelectric domain patterns were written at 200°C using PFM lithography. Hysteresis loops generated inside the poled regions at room and higher temperatures show a significant increase in piezoresponse due to alignment of the c-axis polarization components under the external electric field. No observable change in written domain patterns was observed after 20hrs of PFM scanning at 200°C, confirming that B6TFO retains polarization over this finite period of time. These studies demonstrate the potential of B6TFO thin films for use in piezoelectric applications at elevated temperatures and for use in non-volatile ferroelectric memory applications.

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