Out-of-plane ferroelectricity with a high transition temperature in ultrathin films is important for the exploration of new domain physics and scaling down of memory devices. However, depolarizing electrostatic fields and interfacial chemical bonds can destroy this long-range polar order at two-dimensional (2D) limit. Here we report the experimental discovery of the locking between out-of-plane dipoles and in-plane lattice asymmetry in atomically thin In_{2}Se_{3} crystals, a new stabilization mechanism leading to our observation of intrinsic 2D out-of-plane ferroelectricity. Through second harmonic generation spectroscopy and piezoresponse force microscopy, we found switching of out-of-plane electric polarization requires a flip of nonlinear optical polarization that corresponds to the inversion of in-plane lattice orientation. The polar order shows a very high transition temperature (∼700  K) without the assistance of extrinsic screening. This finding of intrinsic 2D ferroelectricity resulting from dipole locking opens up possibilities to explore 2D multiferroic physics and develop ultrahigh density memory devices.

The need for efficient energy utilization is driving research into ways to harvest ubiquitous waste heat. Here, we explore pyroelectric energy conversion from low-grade thermal sources that exploits strong field- and temperature-induced polarization susceptibilities in the relaxor ferroelectric 0.68Pb(MgNb)O-0.32PbTiO. Electric-field-driven enhancement of the pyroelectric response (as large as -550 μC m K) and suppression of the dielectric response (by 72%) yield substantial figures of merit for pyroelectric energy conversion. Field- and temperature-dependent pyroelectric measurements highlight the role of polarization rotation and field-induced polarization in mediating these effects. Solid-state, thin-film devices that convert low-grade heat into electrical energy are demonstrated using pyroelectric Ericsson cycles, and optimized to yield maximum energy density, power density and efficiency of 1.06 J cm, 526 W cm and 19% of Carnot, respectively; the highest values reported to date and equivalent to the performance of a thermoelectric with an effective ZT ≈ 1.16 for a temperature change of 10 K. Our findings suggest that pyroelectric devices may be competitive with thermoelectric devices for low-grade thermal harvesting.

Ordering of ferroelectric polarization and its trajectory in response to an electric field are essential for the operation of non-volatile memories, transducers and electro-optic devices. However, for voltage control of capacitance and frequency agility in telecommunication devices, domain walls have long been thought to be a hindrance because they lead to high dielectric loss and hysteresis in the device response to an applied electric field. To avoid these effects, tunable dielectrics are often operated under piezoelectric resonance conditions, relying on operation well above the ferroelectric Curie temperature, where tunability is compromised. Therefore, there is an unavoidable trade-off between the requirements of high tunability and low loss in tunable dielectric devices, which leads to severe limitations on their figure of merit. Here we show that domain structure can in fact be exploited to obtain ultralow loss and exceptional frequency selectivity without piezoelectric resonance. We use intrinsically tunable materials with properties that are defined not only by their chemical composition, but also by the proximity and accessibility of thermodynamically predicted strain-induced, ferroelectric domain-wall variants. The resulting gigahertz microwave tunability and dielectric loss are better than those of the best film devices by one to two orders of magnitude and comparable to those of bulk single crystals. The measured quality factors exceed the theoretically predicted zero-field intrinsic limit owing to domain-wall fluctuations, rather than field-induced piezoelectric oscillations, which are usually associated with resonance. Resonant frequency tuning across the entire L, S and C microwave bands (1-8 gigahertz) is achieved in an individual device-a range about 100 times larger than that of the best intrinsically tunable material. These results point to a rich phase space of possible nanometre-scale domain structures that can be used to surmount current limitations, and demonstrate a promising strategy for obtaining ultrahigh frequency agility and low-loss microwave devices.

A range of modern applications require large and tunable dielectric, piezoelectric or pyroelectric response of ferroelectrics. Such effects are intimately connected to the nature of polarization and how it responds to externally applied stimuli. Ferroelectric susceptibilities are, in general, strongly temperature dependent, diminishing rapidly as one transitions away from the ferroelectric phase transition (TC). In turn, researchers seek new routes to manipulate polarization to simultaneously enhance susceptibilities and broaden operational temperature ranges. Here, we demonstrate such a capability by creating composition and strain gradients in Ba1−xSrxTiO3 films which result in spatial polarization gradients as large as 35 μC cm−2 across a 150 nm thick film. These polarization gradients allow for large dielectric permittivity with low loss (ɛr≈775, tan δ<0.05), negligible temperature-dependence (13% deviation over 500 °C) and high-dielectric tunability (greater than 70% across a 300 °C range). The role of space charges in stabilizing polarization gradients is also discussed.

Understanding of polarization-heat interactions in pyroelectric and electrocaloric thin-film materials requires that the electrothermal response is reliably characterized. While most work, particularly in electrocalorics, has relied on indirect measurement protocols, here we report a direct technique for measuring both pyroelectric and electrocaloric effects in epitaxial ferroelectric thin films. We demonstrate an electrothermal test platform where localized high-frequency (∼ 1 kHz) periodic heating and highly-sensitive thin-film resistance thermometry allow direct measurement of pyrocurrents (< 10 pA) and electrocaloric temperature changes (< 2 mK) using the "2-omega" and an adapted "3-omega" technique, respectively. Frequency-domain, phase-sensitive detection permits extraction of pyrocurrent from the total current, which is often convoluted by thermally-stimulated currents. The wide frequency range measurements employed in this study further show the effect of secondary contributions to pyroelectricity due to the mechanical constraints of the substrate. Similarly, measurement of the electrocaloric effect on the same device in the frequency-domain (∼ 100 kHz) allows decoupling of Joule heating from the electrocaloric effect. Using one-dimensional, analytical heattransport models, the transient temperature profile of the heterostructure is characterized to extract pyroelectric and electrocaloric coefficients.