Antiferroelectric thin films are demonstrated as a new class of giant electrocaloric materials that exhibit a negative electrocaloric response of about -5 K near room temperature. The giant negative electrocaloric effect may open up a new paradigm for light, compact, reliable, and high-efficiency refrigeration devices.

It has been ten years since the discovery of the giant electrocaloric effect in ferroelectric materials showed that it is possible to employ this effect for substantial cooling applications. This last decade has been marked by increasing research interest, especially in characterizing and measuring the electrocaloric effect using both the so-called indirect and direct approaches. In this context, a comprehensive summary and careful reexamination of these approaches are very timely and of great importance to justify the assumptions used in different measurement techniques. This review is therefore dedicated to cover recent important and rapid advances from both the indirect and direct measurements and provides critical insights relevant for quantifying the electrocaloric effect. It involves electrocaloric materials from normal ferroelectrics, antiferroelectrics, and relaxors, and it fundamentally focuses on how the electrocaloric entropy changes in response to electric field in these typical electrocalorics. The article addresses recent developments, especially during the past three years, such as technical selection of proper polarization-electric field loops, negative electrocaloric effect in antiferroelectrics and relaxors, the controversial debate on the indirect method in relaxors, the important role of field dependence of specific heat, kinetic factors, and so on. Moreover, this review also is concerned with extracting reliable data by direct measurements. Four typical techniques and devices used recently, such as thermocouples, differential scanning calorimeters, specifically designed calorimeters, and scanning thermal microscopy, are briefly reviewed, while infrared cameras are emphasized. We hope that our review will not only provide a useful background to understand fundamentally the electrocaloric effect and what one really measures but also may act as a practical guide to exploit and develop electrocalorics towards the design of suitable devices. Published by AIP Publishing. [http://dx

Environmentally friendly ultrathin BaTiO3 capacitors can exhibit a giant stress-induced elastocaloric effect without hysteresis loss or Joule heating. By combining this novel elastocaloric effect with the intrinsic electrocaloric effect, an ideal refrigeration cycle with high performance (temperature change over 10 K with a wide working-temperature window of 60 K) at room temperature is proposed for future cooling applications.

Organic electronics is emerging for large-area applications such as photovoltaic cells, rollable displays or electronic paper. Its future development and integration will require a simple, low-power organic memory, that can be written, erased and readout electrically. Here we demonstrate a non-volatile memory in which the ferroelectric polarisation state of an organic tunnel barrier encodes the stored information and sets the readout tunnel current. We use high-sensitivity piezoresponse force microscopy to show that films as thin as one or two layers of ferroelectric poly(vinylidene fluoride) remain switchable with low voltages. Submicron junctions based on these films display tunnel electroresistance reaching 1,000% at room temperature that is driven by ferroelectric switching and explained by electrostatic effects in a direct tunnelling regime. Our findings provide a path to develop low-cost, large-scale arrays of organic ferroelectric tunnel junctions on silicon or flexible substrates.

Giant magnetocaloric materials are promising for solid-state refrigeration, as an alternative to hazardous gases used in conventional cooling devices. A giant magnetocaloric effect was discovered near room temperature in near-equiatomic FeRh alloys some years before the benchmark study in Gd5Si2Ge2 that launched the field. However, FeRh has attracted significantly less interest in cooling applications mainly due to irreversibility in magnetocaloric cycles associated with the large hysteresis of its first-order metamagnetic phase transition. Here we overcome the irreversibility via a dual-stimulus magnetic-electric refrigeration cycle in FeRh thin films via coupling to a ferroelectric BaTiO3 substrate. This experimental realization of a multicaloric cycle yields larger reversible caloric effects than either stimulus alone. While magnetic hysteretic losses appear to be reduced by 96% in dual-stimulus loops, we show that the losses are simply transferred into an elastic cycle, contrary to common belief. Nevertheless, we show that these losses do not necessarily prohibit integration of FeRh in practical refrigeration systems. Our demonstration of a multicaloric refrigeration cycle suggests numerous designs for efficient solid-state cooling applications.

Barocaloric effect in BaTiO3 single crystal is studied by a thermodynamic phenomenological model. It is demonstrated that a giant barocaloric effect can be achieved near room temperature with an adiabatic temperature change of more than 3 K and a temperature span about 50 K. As expected, the electrocaloric peak can be shifted towards room temperature by pressure. However, a slight reduction of the electrocaloric peak is found in contrast to relaxor ferroelectrics and LiNbO3. We believe that our findings could open a potential route by combining the barocaloric effect and pressure-mediated electrocaloric effect in BaTiO3 single crystal for cooling devices.

In this work we study the influence of grain and particle size on the structural and optical properties of BiFeO 3 (BFO) nanoparticles and the resulting photocatalytic activity. Unexpectedly, the photocatalytic activity is found to decrease while the expected surface reaction area increases by decreasing the particles size. We show that while the global structure, polarization, particle morphology, and band gap are only weakly altered, if at all, some optical features, namely, the Urbach energy and low-energy bands, in the absorption spectra are substantially changed. We argue that these optical modifications related to defects and local distortions are mainly affected at the skin layer that is inherent to oxides like BFO. By reducing the particle size of BFO nanoparticles, the skin layer is thus altered, which in turn changes the photocatalytic properties.

Many important breakthroughs and significant engineering developments have been achieved during the past two decades in the field of caloric materials. In this review, we address ferroelectrics emerging as ideal materials which permit both giant elastocaloric and/or electrocaloric responses near room temperature. We summarize recent strategies for improving caloric responses using geometrical optimization, maximizing the number of coexisting phases, combining positive and negative caloric responses, introducing extra degree of freedom like mechanical stress/pressure, and multicaloric effect driven by either single stimulus or multiple stimuli. This review highlights the promising perspective of ferroelectrics for developing next-generation solid-state refrigeration.