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Nanoscale thin films are widely implemented across a plethora of technological and scientific areas, and form the basis for many advancements that have driven human progress, owing to the high degree of functional tunability based on the chemical composition. Pulsed laser deposition is one of the multiple physical vapour deposition routes to fabricate thin films, employing laser energy to eject material from a target in the form of a plasma. A substrate, commonly a single-crystal oxide, is placed in the path of the plume and acts as a template for the arriving species from the target to coalesce and self-assemble into a thin film. This technique is tremendously useful to produce crystalline films, due to the wide range of atmospheric conditions and the extent of possible chemical complexity of the target. However, this flexibility results in a high degree of complexity, oftentimes requiring rigorous optimisation of the growth parameters to achieve high quality crystalline films with desired composition. In this tutorial review, we aim to reduce the complexity and the barrier to entry for the controlled growth of complex oxides by pulsed laser deposition. We present an overview of the fundamental and practical aspects of pulsed laser deposition, discuss the consequences of tailoring the growth parameters on the thin film properties, and describe in situ monitoring techniques that are useful in gaining a deeper understanding of the properties of the resultant films. Particular emphasis is placed on the general relationships between the growth parameters and the consequent structural, chemical and functional properties of the thin films. In the final section, we discuss the open questions within the field and possible directions to further expand the utility of pulsed laser deposition.
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Within the emerging field of proton-conducting fuel cells, BaZr0.9Y0.1O3-δ (BZY10) is an attractive material due to its high conductivity and stability. The fundamentals of conduction in sintered pellets and thin films heterostructures have been explored in several studies; however, the role of crystallographic orientation, grains, and grain boundaries is poorly understood for proton conduction. This article reports proton conduction in a self-assembled multi-oriented BZY10 thin film grown on top of a (110) NdGaO3 substrate. The multiple orientations are composed of different lattices, which provide a platform to study the lattice-dependent conductivity through different orientations in the vicinity of grain boundary between them and the substrate. The crystalline stacking of each orientation is confirmed by X-ray diffraction analysis and scanning transmission electron microscopy. The transport measurements are carried out under different gas atmospheres. The highest conductivity of 3.08 × 10-3 S cm-1 at 400 °C is found under a wet H2 environment together with an increased lattice parameter of 4.208 Å, while under O2 and Ar environments, the film shows lower conductivity and lattice parameter. Our findings not only demonstrate the role of crystal lattice for conduction properties but also illustrate the importance of self-assembled strategies to achieve high proton conduction in BZY10 thin films.
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Layered 2D crystals have unique properties and rich chemical and electronic diversity, with over 6000 2D crystals known and, in principle, millions of different stacked hybrid 2D crystals accessible. This diversity provides unique combinations of properties that can profoundly affect the future of energy conversion and harvesting devices. Notably, this includes catalysts, photovoltaics, superconductors, solar-fuel generators, and piezoelectric devices that will receive broad commercial uptake in the near future. However, the unique properties of layered 2D crystals are not limited to individual applications and they can achieve exceptional performance in multiple energy conversion applications synchronously. This synchronous multisource energy conversion (SMEC) has yet to be fully realized but offers a real game-changer in how devices will be produced and utilized in the future. This perspective highlights the energy interplay in materials and its impact on energy conversion, how SMEC devices can be realized, particularly through layered 2D crystals, and provides a vision of the future of effective environmental energy harvesting devices with layered 2D crystals.
RESUMO
The piezoelectric effect, mechanical-to-electrical and electrical-to-mechanical energy conversion, is highly beneficial for functional and responsive electronic devices. To fully exploit this property, miniaturization of piezoelectric materials is the subject of intense research. Indeed, select atomically thin 2D materials strongly exhibit the piezoelectric effect. The family of 2D crystals consists of over 7000 chemically distinct members that can be further manipulated in terms of strain, functionalization, elemental substitution (i.e. Janus 2D crystals), and defect engineering to induce a piezoelectric response. Additionally, most 2D crystals can stack with other similar or dissimilar 2D crystals to form a much greater number of complex 2D heterostructures whose properties are quite different to those of the individual constituents. The unprecedented flexibility in tailoring 2D crystal properties, coupled with their minimal thickness, make these emerging highly attractive for advanced piezoelectric applications that include pressure sensing, piezocatalysis, piezotronics, and energy harvesting. This review summarizes literature on piezoelectricity, particularly out-of-plane piezoelectricity, in the vast family of 2D materials as well as their heterostructures. It also describes methods to induce, enhance, and control the piezoelectric properties. The volume of data and role of machine learning in predicting piezoelectricity is discussed in detail, and a prospective outlook on the 2D piezoelectric field is provided.
Assuntos
Eletricidade , Eletrônica , Estudos ProspectivosRESUMO
Contact electrification and the triboelectric effect are complex processes for mechanical-to-electrical energy conversion, particularly for highly deformable polymers. While generating relatively low power density, contact electrification can occur at the contact-separation interface between nearly any two polymer surfaces. This ubiquitousness of surfaces enables contact electrification to be an important phenomenon to understand energy conversion and harvesting applications. The mechanism of charge generation between polymeric materials remains ambiguous, with electron transfer, material (also known as mass) transfer, and adsorbed chemical species transfer (including induced ionization of water and other molecules) all being proposed as the primary source of the measured charge. Often, all sources of charge, except electron transfer, are dismissed in the case of triboelectric energy harvesters, leading to the generation of the "triboelectric series", governed by the ability of a polymer to lose, or accept, an electron. Here, this sole focus on electron transfer is challenged through rigorous experiments, measuring charge density in polymer-polymer (196 polymer combinations), polymer-glass (14 polymers), and polymer-liquid metal (14 polymers) systems. Through the investigation of these interfaces, clear evidence of material transfer via heterolytic bond cleavage is provided. Based on these results, a generalized model considering the cohesive energy density of polymers as the critical parameter for polymer contact electrification is discussed. This discussion clearly shows that material transfer must be accounted for when discussing the source of charge generated by polymeric mechanical energy harvesters. Thus, a correlated physical property to understand the triboelectric series is provided.
RESUMO
Piezoelectric fluoropolymers convert mechanical energy to electricity and are ideal for sustainably providing power to electronic devices. To convert mechanical energy, a net polarization must be induced in the fluoropolymer, which is currently achieved via an energy-intensive electrical poling process. Eliminating this process will enable the low-energy production of efficient energy harvesters. Here, by combining molecular dynamics simulations, piezoresponse force microscopy, and electrodynamic measurements, we reveal a hitherto unseen polarization locking phenomena of poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) perpendicular to the basal plane of two-dimensional (2D) Ti3C2Tx MXene nanosheets. This polarization locking, driven by strong electrostatic interactions enabled exceptional energy harvesting performance, with a measured piezoelectric charge coefficient, d33, of -52.0 picocoulombs per newton, significantly higher than electrically poled PVDF-TrFE (approximately -38 picocoulombs per newton). This study provides a new fundamental and low-energy input mechanism of poling fluoropolymers, which enables new levels of performance in electromechanical technologies.
RESUMO
Piezoelectric polymers are emerging as exceptionally promising materials for energy harvesting. While the theoretical figures of merit for piezoelectric polymers are comparable to ceramics, the measurement techniques need to be retrofitted to account for the different mechanical properties of the softer polymeric materials. Here, how contact electrification, including friction and contact separation, is often mistaken for piezoelectric charge is examined, and a perspective for how to separate these effects is provided. The state of the literature is assessed, and recommendations are made for clear and simple guidelines in reporting, for both sample geometry and testing methods, to enable accurate determination of piezoelectric figures of merit in polymers. Such improvements will allow an understanding of what types of material manipulation are required in order to enhance the piezoelectric output from polymers and enable the next generation of polymer energy harvester design.
