Clamping enables enhanced electromechanical responses in antiferroelectric thin films.

Thin-film materials with large electromechanical responses are fundamental enablers of next-generation micro-/nano-electromechanical applications. Conventional electromechanical materials (for example, ferroelectrics and relaxors), however, exhibit severely degraded responses when scaled down to submicrometre-thick films due to substrate constraints (clamping). This limitation is overcome, and substantial electromechanical responses in antiferroelectric thin films are achieved through an unconventional coupling of the field-induced antiferroelectric-to-ferroelectric phase transition and the substrate constraints. A detilting of the oxygen octahedra and lattice-volume expansion in all dimensions are observed commensurate with the phase transition using operando electron microscopy, such that the in-plane clamping further enhances the out-of-plane expansion, as rationalized using first-principles calculations. In turn, a non-traditional thickness scaling is realized wherein an electromechanical strain (1.7%) is produced from a model antiferroelectric PbZrO3 film that is just 100 nm thick. The high performance and understanding of the mechanism provide a promising pathway to develop high-performance micro-/nano-electromechanical systems.

Tunable Artificial Relaxor Behavior in [BaTiO_{3}]_{m}/[BaZrO_{3}]_{n} Superlattices.

[BaTiO_{3}]_{m}/[BaZrO_{3}]_{n} (m, n=4-12) superlattices are used to demonstrate the fabrication and deterministic control of an artificial relaxor. X-ray diffraction and atomic-resolution imaging studies confirm the production of high-quality heterostructures. With decreasing BaTiO_{3} layer thickness, dielectric measurements reveal systematically lower dielectric-maximum temperatures, while hysteresis loops and third-harmonic nonlinearity studies suggest a transition from ferroelectriclike to relaxorlike behavior driven by tuning the random-field strength. This system provides a novel platform for studying the size effect and interaction length scale of the nanoscale-polar structures in relaxors.

Defect-Induced, Ferroelectric-Like Switching and Adjustable Dielectric Tunability in Antiferroelectrics.

Antiferroelectrics, which undergo a field-induced phase transition to ferroelectric order that manifests as double-hysteresis polarization switching, exhibit great potential for dielectric, electromechanical, and electrothermal applications. Compared to their ferroelectric cousins, however, considerably fewer efforts have been made to understand and control antiferroelectrics. Here, it is demonstrated that the polarization switching behavior of an antiferroelectric can be strongly influenced and effectively regulated by point defects. In films of the canonical antiferroelectric PbZrO3 , decreasing oxygen pressure during deposition (and thus increasing adatom kinetic energy) causes unexpected "ferroelectric-like" polarization switching although the films remain in the expected antiferroelectric orthorhombic phase. This "ferroelectric-like" switching is correlated with the creation of bombardment-induced point-defect complexes which pin the antiferroelectric-ferroelectric phase boundaries, and thus effectively delay the phase transition under changing field. The effective pinning energy is extracted via temperature-dependent switching-kinetics studies. In turn, by controlling the concentration of defect complexes, the dielectric tunability of the PbZrO3 can be adjusted, including being able to convert between "positive" and "negative" tunability near zero field. This work reveals the important role and strong capability of defects to engineer antiferroelectrics for new performance and functionalities.

Emergent Ferroelectric Switching Behavior from Polar Vortex Lattice.

Topologically protected polar textures have provided a rich playground for the exploration of novel, emergent phenomena. Recent discoveries indicate that ferroelectric vortices and skyrmions not only host properties markedly different from traditional ferroelectrics, but also that these properties can be harnessed for unique memory devices. Using a combination of capacitor-based capacitance measurements and computational models, it is demonstrated that polar vortices in dielectric-ferroelectric-dielectric trilayers exhibit classical ferroelectric bi-stability together with the existence of low-field metastable polarization states. This behavior is directly tied to the in-plane vortex ordering, and it is shown that it can be used as a new method of non-destructive readout-out of the poled state.

Thin-Film Ferroelectrics.

Over the last 30 years, the study of ferroelectric oxides has been revolutionized by the implementation of epitaxial-thin-film-based studies, which have driven many advances in the understanding of ferroelectric physics and the realization of novel polar structures and functionalities. New questions have motivated the development of advanced synthesis, characterization, and simulations of epitaxial thin films and, in turn, have provided new insights and applications across the micro-, meso-, and macroscopic length scales. This review traces the evolution of ferroelectric thin-film research through the early days developing understanding of the roles of size and strain on ferroelectrics to the present day, where such understanding is used to create complex hierarchical domain structures, novel polar topologies, and controlled chemical and defect profiles. The extension of epitaxial techniques, coupled with advances in high-throughput simulations, now stands to accelerate the discovery and study of new ferroelectric materials. Coming hand-in-hand with these new materials is new understanding and control of ferroelectric functionalities. Today, researchers are actively working to apply these lessons in a number of applications, including novel memory and logic architectures, as well as a host of energy conversion devices.

Growth mode and strain effect on relaxor ferroelectric domains in epitaxial 0.67Pb(Mg1/3Nb2/3)O3-0.33PbTiO3/SrRuO3 heterostructures.

Controlling the growth of complex relaxor ferroelectric thin films and understanding the relationship between biaxial strain-structural domain characteristics are desirable for designing materials with a high electromechanical response. For this purpose, epitaxial thin films free of extended defects and secondary phases are urgently needed. Here, we used optimized growth parameters and target compositions to obtain epitaxial (40-45 nm) 0.67Pb(Mg1/3Nb2/3)O3-0.33PbTiO3/(20 nm) SrRuO3 (PMN-33PT/SRO) heterostructures using pulsed-laser deposition (PLD) on singly terminated SrTiO3 (STO) and ReScO3 (RSO) substrates with Re = Dy, Tb, Gd, Sm, and Nd. In situ reflection high-energy electron diffraction (RHEED) and high-resolution X-ray diffraction (HR-XRD) analysis confirmed high-quality and single-phase thin films with smooth 2D surfaces. High-resolution scanning transmission electron microscopy (HR-STEM) revealed sharp interfaces and homogeneous strain further confirming the epitaxial cube-on-cube growth mode of the PMN-33PT/SRO heterostructures. The combined XRD reciprocal space maps (RSMs) and piezoresponse force microscopy (PFM) analysis revealed that the domain structure of the PMN-33PT heterostructures is sensitive to the applied compressive strain. From the RSM patterns, an evolution from a butterfly-shaped diffraction pattern for mildly strained PMN-33PT layers, which is evidence of stabilization of relaxor domains, to disc-shaped diffraction patterns for high compressive strains with a highly distorted tetragonal structure, is observed. The PFM amplitude and phase of the PMN-33PT thin films confirmed the relaxor-like for a strain state below ∼1.13%, while for higher compressive strain (∼1.9%) the irregularly shaped and poled ferroelectric domains were observed. Interestingly, the PFM phase hysteresis loops of the PMN-33PT heterostructures grown on the SSO substrates (strain state of ∼0.8%) exhibited an enhanced coercive field which is about two times larger than that of the thin films grown on GSO and NSO substrates. The obtained results show that epitaxial strain engineering could serve as an effective approach for tailoring and enhancing the functional properties in relaxor ferroelectrics.

Maskless Patterning of Biodegradable Conductors by Selective Laser Sintering of Microparticle Inks and Its Application in Flexible Transient Electronics.

Biodegradable electronic devices are able to break down into benign residues after their service life, which may effectively alleviate the environmental impacts as a consequence of the proliferation of consumer electronic technology. The widespread adaptation to biodegradable systems is currently impeded by the lack of economic fabrication techniques for functional devices. Here, a facile approach to generate a biodegradable conductor is developed based on selective laser sintering of zinc and iron microparticle ink. The sintering process is effective to convert naturally oxidized microparticles into interconnected conductors. Arbitrary conductive features are readily created over flexible biodegradable substrates under ambient conditions, which exhibits excellent conductivity (∼2 × 106 S m-1), low sheet resistance (∼0.64 Ω â–¡ - 1), fine feature resolution (∼45 µm), and mechanical flexibility. The practical suitability is demonstrated by fabricating a miniaturized near-field communication tag with the dimension to mount on the fingernail. The methodology is further extended to create a metallic grid as a biodegradable transparent electrode with low sheet resistance (2.5 Ω â–¡-1) and high optical transmittance (96%), which is employed as an epidermal transparent heater for thermotherapy. Maskless patterning of biodegradable conductors may find a broad range of applications in environment friendly gadgets and implantable medical devices.