Materials that couple strong ferroelectric and ferromagnetic order hold tremendous promise for next-generation memory devices. Meticulous engineering has produced novel ferroelectric and multiferroic materials, although known single-phase multiferroics remain limited by antiferromagnetic or weak ferromagnetic alignments, by a lack of coupling between the order parameters, or by having properties that emerge only well below room temperature. Here we construct single-phase multiferroic materials in which ferroelectricity and strong magnetic ordering are coupled near room temperature. Starting with hexagonal LuFeO₃—a geometric ferroelectric with planar rumpling—we introduce individual monolayers of ferrimagnetic LuFe₂O₄ within the LuFeO₃ matrix, that is, (LuFeO₃)_m/(LuFe₂O₄)₁ superlattices. The rumpling of the LuFeO₃ drives the ferrimagnetic LuFe₂O₄ into a ferroelectric state, reducing the LuFe₂O₄ spin frustration. This increases the magnetic transition temperature to 281K for m=9. Moreover, the ferroelectric order couples to the ferrimagnetism, enabling direct electric-field control of magnetism at 200 kelvin. Further, charged ferroelectric domain walls align at LuFe₂O₄ layers, resulting in charge transfer which increases the magnetic moment. We are currently pursuing higher temperature multiferroics by incorporating cubic spinels with high magnetic ordering temperatures, such as CoFe₂O₄, into the LuFeO₃ matrix. Our results demonstrate a design methodology for creating higher-temperature magnetoelectric multiferroics through epitaxial engineering.

The ability to reduce the size of antennae would enable a revolution in wearable and implantable electronic devices. Multiferroic antennae, composed of individual ferromagnetic and piezoelectric phases, could reduce antenna size by up to five orders of magnitude through the efficient coupling of magnetization and electric polarization via strain. This strategy requires a material with strong magnetoelastic coupling and acceptable magnetic losses at high frequency.

Galfenol (Fe₈₄Ga₁₆ or FeGa) is a promising candidate material due to its large magnetostriction (200 µε), large piezomagnetic coefficient (5 ppm/Oe), and high stiffness (60 GPa), but it is highly lossy in the GHz regime. On the other hand, Permalloy (Ni₈₁Fe₁₉ or NiFe) is a soft magnetic material that has very low loss in the GHz regime, with a ferromagnetic resonance (FMR) linewidth of 10 Oe, but almost no magnetostriction. In this work, nanoscale laminates containing alternating layers of FeGa and NiFe were fabricated via DC magnetron sputtering to combine the complementary properties of the two magnetic phases, resulting in a composite material with a small coercive field, narrow FMR linewidth, and high permeability (Rementer et al., 2017). Optical magnetostriction measurements confirmed that these laminates retain the large saturation magnetostriction of FeGa (200 µε) while enhancing the piezomagnetic coefficient (7 ppm/Oe), allowing for optimal piezomagnetic actuation at substantially reduced magnetic bias fields. Furthermore, multiferroic composites incorporating these magnetic laminates were studied via polarized neutron reflectometry, demonstrating uniform rotation of the individual layers’ magnetization with an applied electric field across distances much larger than the exchange length of either material.

Due to the metallic nature of these FeGa/NiFe multilayer composites, however, resulting devices would be inefficient due to the generation of eddy currents at high frequency. To mitigate these losses, ultrathin layers of Al₂O₃ were incorporated into the multilayer materials to reduce the conductivity and mitigate the generation of eddy currents. The effect of Al₂O₃ thickness, FeGa:NiFe volume ratio, and multilayer architecture on the soft magnetic properties was also studied, resulting in a 50% reduction in the FMR linewidth. Optimized magnetic laminates were shown to exhibit a small coercive field (<20 Oe), narrow ferromagnetic resonance linewidth (<50 Oe), and high relative permeability (>500) while maintaining excellent magnetoelastic coupling, showing great promise for the use of FeGa/NiFe/Al₂O₃ laminates in strain-mediated micro-scale communications systems.

Modern ferroelectric technologies utilize perovskite structured materials, which have limited Si compatibility and modest bandgaps requiring thick films to reduce leakage current, hindering their implementation in realizable thin film devices. HfO₂ has been extensively researched as a gate dielectric thin film with excellent Si processing compatibility and has recently been found to exhibit ferroelectricity induced by a combination of impurity substitution, mechanical confinement by capping, intergranular surface area, and film thickness effects. This work investigates the microstructural characteristics, the ferroelectric response, and the potential for concomitant magnetic properties in sputtered Gd:HfO₂ thin films.

Gd-substituted HfO₂ thin films are a promising candidate as a multiferroic material, due to the presence of the magnetically active Gd³⁺ ion. Though substituting with Gd is known to induce ferroelectricity in HfO₂, the magnetic properties of Gd:HfO₂ have yet to be studied in depth. In this study, Gd:HfO₂ films are fabricated on TaN substrates by radio frequency sputtering of a composite Gd metal and HfO₂ oxide target in a mixed Ar and O₂ atmosphere. Grazing incidence x-ray diffraction is used to evaluate the suppression of the paraelectric monoclinic phase and stabilization of the ferroelectric orthorhombic phase. Electrical polarization measurements are used to study the room temperature spontaneous polarization in TaN/Gd:HfO₂/TaN metal-insulator-metal capacitors. Surface morphology of the films is characterized using atomic force microscopy, while magnetic properties are measured by variable temperature magnetometry. Initial magnetometry shows that Gd-substituted HfO₂ exhibits remnant magnetization at room temperature.

The scalability and simplicity of Gd:HfO₂, if it exhibits magnetoelectric coupling, make it an attractive model system for future developments in thin film multiferroics, having potential impacts for spintronics and other magnetoelectronic devices.

High-quality epitaxial growth of antiferromagnetic thin films is essential for future spintronic devices, as it allows small antiferromagnetic domain sizes and efficient electrical manipulation of domain walls via reading and writing currents. Antiferromagnetic materials are candidates for ultrafast operation due to THz antiferromagnetic spin dynamics, high packing densities due to the absence of stray magnetic fields, and stability due to insensitivity to external magnetic fields [1,2]. Meanwhile, the long spin diffusion lengths [3] and theoretically predicted superfluid transport of spin currents [4] in antiferromagnetic insulators are crucial for low-power device operation. The electrical control of magnetic spin textures has been thus far realized in epitaxially grown NiO on MgO substrates [5] and ferrimagnetic maghemite (γ−Fe2O3) and magnetite (Fe3O4) thin films [6].

We report the preparation of antiferromagnetic NiO thin films with (111) orientation on c-plane sapphire (1000) substrates by off-axis RF magnetron sputtering from a NiO target. The off-axis angle was 45°, and the sputtering pressure was 5 mTorr. Samples were grown with thicknesses ranging from 5 – 50 nm, and with growth temperatures from room temperature to 600°C, to determine optimum conditions. Structural characterization by x-ray diffraction demonstrates a high degree of epitaxy across a range of deposition temperatures and thicknesses. The deposition temperature and thickness dependence of epitaxial quality is investigated, with a characterization of the strain state, mosaicity, and crystallographic relationship between substrate and film. Evidence for antiferromagnetic order forming domains in NiO is provided via magnetic characterization of the films. Our results are essential for the optimization of the fabrication of high quality epitaxial antiferromagnetic films for practical spintronics devices.

[1] J. Železný, P. Wadley, K. Olejník, A. Hoffmann, and H. Ohno, Nat. Phys. 14, 220 (2018)

[2] V. Baltz, A. Manchon, M. Tsoi, T. Moriyama, T. Ono, and Y. Tserkovnyak, Rev. Mod. Phys. 90, 015005 (2018).

[3] R. Lebrun, A. Ross, S. A. Bender, A. Qaiumzadeh, L. Baldrati, J. Cramer, A. Brataas, R. A. Duine, and M. Kläui, Nature 561, 222 (2018).

[4] S. Takei, B. I. Halperin, A. Yacoby, and Y. Tserkovnyak, Phys. Rev. B 90, 094408 (2014).

[5] T. Moriyama, K. Oda, T. Ono, Sci. Rep. 8, 14167 (2018).

[6] L. Baldrati, A. Ross, T. Niizeki, C. Schneider, R. Ramos, J. Cramer, O. Gomonay, M. Filianina, T. Savchenko, D. Heinze, A. Kleibert, E. Saitoh, J. Sinova, and M. Kläui, Phys. Rev. B 98, 024422 (2018).

Silicon-integrated ferroelectric thin films have been leveraged over the last two decades for fabrication of high performance piezoelectric microelectromechanical systems (MEMS) devices. Ceramic Pb(Zr_xTi_{1- x})O₃(PZT) thin films have been often the material of choice, due to their large electromechanical response, especially at morphotropic phase boundary compositions (MPB at x ~0.52), where co-existence of multiple crystallographic distortions can enhance extrinsic electromechanical contributions. However, ferroelectric thin films suffer from extrinsic size effects that lead to deteriorated piezoelectric properties in thin and ultra-thin films. Here we report on different strategies for processing of thin films with enhanced piezoelectric response with respect to traditionally processed PZT thin films.

Specifically, we will discuss preparation of superlattice-like polycrystalline PZT thin films through chemical solution depositions, polycrystalline relaxor-ferroelectric thin films (PMN-PT), and finally alternative non-ferroelectric compositions, where the electric field-induced phase transitions can result in substantial enhancement in thinner films, even where traditional

1Susner et al, Adv. Mater. 29,1602852 (2018)

2Neumayer et al, Phys. Rev. Materials 3, 024401 (2019)

3Balke et al, ACS Appl. Mater. Interfaces 10, 27188 (2018)

⁴Brehm et al, in review

A major challenge for ferroelectric devices is the depolarizing field, which competes with and often destroys long-range polar order in the limit of ultrathin films. Recent theoretical predictions suggest a new class of materials, termed hyperferroelectics [1], should be immune to the depolarizing field and enable ferroelectric devices down to the monolayer limit. Here we demonstrate the epitaxial growth of hexagonal LiZnSb, one of the hyperferroelectric candidate materials, on GaSb (111) substrates. Due to the high volatility of all three atomic species, we find that stoichiometric films can be grown in a thermodynamically adsorption-controlled window, using an excess zinc flux. Outstanding challenges remain in controlling the point defects of LiZnSb and in controlling polytypism. While the films primarily grow in a hexagonal “stuffed wurtzite” phase (space group P6₃mc), which is has the desired polar structure, there exists a competing cubic “stuffed zincblende” polymorph that is nonopolar (F-43m). We will discuss our strategy towards controlling defects and polytypism in LiZnSb, which is based in large part on the wurtzite – zincblende polytypism observed in InAs. We will also present preliminary electrical measurements on phase pure ferroelectric capacitor structures.

This work was supported by the Army Research office (W911NF-17-1-0254) and the National Science Foundation (DMR-1752797).

[1] K. F. Garrity, K. M. Rabe, and D. Vanderbilt, Phys. Rev. Lett. 112, 127601(2014).