Size-Induced Ferroelectricity in Antiferroelectric Oxide Membranes.

Despite extensive studies on size effects in ferroelectrics, how structures and properties evolve in antiferroelectrics with reduced dimensions still remains elusive. Given the enormous potential of utilizing antiferroelectrics for high-energy-density storage applications, understanding their size effects will provide key information for optimizing device performances at small scales. Here, the fundamental intrinsic size dependence of antiferroelectricity in lead-free NaNbO3 membranes is investigated. Via a wide range of experimental and theoretical approaches, an intriguing antiferroelectric-to-ferroelectric transition upon reducing membrane thickness is probed. This size effect leads to a ferroelectric single-phase below 40 nm, as well as a mixed-phase state with ferroelectric and antiferroelectric orders coexisting above this critical thickness. Furthermore, it is shown that the antiferroelectric and ferroelectric orders are electrically switchable. First-principle calculations further reveal that the observed transition is driven by the structural distortion arising from the membrane surface. This work provides direct experimental evidence for intrinsic size-driven scaling in antiferroelectrics and demonstrates enormous potential of utilizing size effects to drive emergent properties in environmentally benign lead-free oxides with the membrane platform.

Mechanical nanolattices printed using nanocluster-based photoresists.

Natural materials exhibit emergent mechanical properties as a result of their nanoarchitected, nanocomposite structures with optimized hierarchy, anisotropy, and nanoporosity. Fabrication of such complex systems is currently challenging because high-quality three-dimensional (3D) nanoprinting is mostly limited to simple, homogeneous materials. We report a strategy for the rapid nanoprinting of complex structural nanocomposites using metal nanoclusters. These ultrasmall, quantum-confined nanoclusters function as highly sensitive two-photon activators and simultaneously serve as precursors for mechanical reinforcements and nanoscale porogens. Nanocomposites with complex 3D architectures are printed, as well as structures with tunable, hierarchical, and anisotropic nanoporosity. Nanocluster-polymer nanolattices exhibit high specific strength, energy absorption, deformability, and recoverability. This framework provides a generalizable, versatile approach for the use of photoactive nanomaterials in additive manufacturing of complex systems with emergent mechanical properties.