A scalable nanogenerator based on self-poled piezoelectric polymer nanowires with high energy conversion efficiency

Nanogenerators based on piezoelectric materials convert ever-present mechanical vibrations into electrical power for energetically autonomous wireless and electronic devices. Nanowires of piezoelectric polymers are particularly attractive for harvesting mechanical energy in this way, as they are flexible, lightweight and sensitive to small vibrations. Previous studies have focused exclusively on nanowires grown by electrospinning, but this involves complex equipment, and high voltages of $\approx$ 10 kV that electrically pole the nanowires and thus render them piezoelectric. Here we demonstrate that nanowires of poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) grown using a simple and cost-effective template-wetting technique, can be successfully exploited in nanogenerators without poling. A typical nanogenerator comprising $\approx$ 10$^{10}$ highly crystalline, self-poled, aligned nanowires spanning $\approx$ 2 cm$^2$ is shown to produce a peak output voltage of 3 V at 5.5 nA in response to low-level vibrations. The mechanical-to-electrical conversion efficiency of 11% exhibited by our template-grown nanowires is comparable with the best previously reported values. Our work therefore offers a scalable means of achieving high-performance nanogenerators for the next generation of self-powered electronics.SKN is grateful for support from the Royal Society through a Dorothy Hodgkin Fellowship. VN acknowledges the Herchel Smith Fund, University of Cambridge for a Fellowship. This work was supported by the EPSRC Cambridge NanoDTC, EP/G037221/1.This is the final version of the article. It first appeared from Wiley via http://dx.doi.org/10.1002/aenm.20140051

Localized electromechanical interactions in ferroelectric P(VDF-TrFE) nanowires investigated by scanning probe microscopy

We investigate the electromechanical interactions in individual polyvinylidene fluoride-trifluoroethylene nanowires in response to localized electrical poling via a conducting atomic force microscope tip. Spatially resolved measurements of piezoelectric coefficients and elastic moduli before and after poling reveal a striking dependence on the polarity of the poling field, notably absent in thin films of the same composition. These observations are attributed to the unclamped nature of the nanowires and the inherent asymmetry in their chemical and electrical interactions with the tip and underlying substrate. Our findings provide insights into the mechanism of poling/switching in polymer nanowires critical to ferroelectric device performance.S.K.-N. and Y.C. are grateful for financial support from the European Research Council through an ERC Starting Grant (Grant No. ERC-2014-STG-639526, NANOGEN). R.A.W. thanks the EPSRC Cambridge NanoDTC, EP/G037221/1, for studentship funding. Q.J. is grateful for financial support through a Marie Sklodowska Curie Fellowship, H2020-MSCA-IF-2015-702868

Enhanced thermoelectric properties of flexible aerosol-jet printed carbon nanotube-based nanocomposites

Aerosol-jet printing allows functional materials to be printed from inks with a wide range of viscosities and constituent particle sizes onto various substrates, including the printing of organic thermoelectric materials on flexible substrates for low-grade thermal energy harvesting. However, these materials typically suffer from relatively poor thermoelectric performance, compared to traditional inorganic counterparts, due to their low Seebeck coefficient, S, and electrical conductivity, σ. Here, we demonstrate a modified aerosol-jet printing technique that can simultaneously incorporate well dispersed high S Sb2Te3 nanoflakes, and high-σ multi-walled carbon nanotubes (MWCNTs) providing good inter-particle connectivity, to significantly enhance the thermoelectric performance of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) structures on flexible polyimide substrates. A nominal loading fraction of 85 wt.% yielded a power factor of ~41 µW/mK2, which is among the highest for printed organic-based structures. Rigorous flexing and fatigue tests were performed to confirm the robustness and stability of these aerosol-jet printed MWCNT-based thermoelectric nanocomposites

Observation of Confinement-Induced Self-Poling Effects in Ferroelectric Polymer Nanowires Grown by Template Wetting

Ferroelectric polymer nanowires grown using a template-wetting method are shown to achieve an orientated 'self-poled' structure resulting from the confined growth process. Self-poling is highly desirable as it negates the need for high electric fields, mechanical stretching and/or high temperatures typically associated with poling treatments in ferroelectric polymers, as required for piezoelectric and/or pyroelectric applications. Here, we present differential scanning calorimetry, infrared spectroscopy and dielectric permittivity measurements on as-fabricated template-grown polyvinylidene fluoride-trifluoroethylene (P(VDF-TrFE)) nanowires, and quantitatively compare the results with spin-cast films of the same composition that have been electrically poled, both before and after subsequent de-poling temperature treatment. The measurements reveal remarkably similar trends between the physical properties of the as-grown nanowires and the electrically poled film samples, providing insight into the material structure of the 'self-poled' nanowires. In addition, piezo-response force microscopy (PFM) data is presented that allow s for unambiguous identification of self-poling in ferroelectric polymer nanostructures, and indicates the suitability of the template-wetting approach in fabricating nanowires that can be used directly for piezoelectric/pyroelectric applications, without the need for post-deposition poling/processing.The authors are grateful for financial support from the European Research Council through an ERC Starting Grant (Grant no. ERC-2014-STG-639526, NANOGEN). R.A.W. thanks the EPSRC Cambridge NanoDTC, EP/G037221/1, for studentship funding.This is the author accepted manuscript. It is currently under an indefinite embargo pending publication by Wiley

Piezoelectric Semiconducting Nanowires

© 2018 Elsevier Inc. Piezoelectric semiconducting nanowires have generated much interest due to the interplay of their mechanical, electrical, and optical properties, which paves the way for potential applications in mechanical energy harvesting as well as sensing. The nature of piezoelectricity in these nanowires is governed by the crystalline phases present, which in turn can be controlled during the nanowire growth process. This chapter provides insight into the manifestation of piezoelectricity in semiconducting nanowires, the effect of growth on their piezoelectric properties, and importantly, how piezoelectricity is characterized at the nanoscale in these materials. Energy-related applications of semiconducting piezoelectric nanowires are described in detail, including their incorporation into nanogenerators for energy harvesting, as well as in piezotronic and photo-piezotronics devices based on the electromechanical and opto-electromechanical interactions taking place in piezoelectric semiconductor-nanowire junction-based devices. Advances in nanofabrication, nanoscale characterization, and device engineering, coupled with a greater understanding and control of piezoelectricity in semiconducting nanowires, will ultimately help unlock the full potential of these fascinating nanomaterials.European Research Council (Grant no. ERC–2014–STG–639526, NANOGEN

Coaxial Nickel Poly(Vinylidene Fluoride Trifluoroethylene) Nanowires for Magnetoelectric Applications

Magnetoelectric (ME) composite materials, in which the coupling between magnetostricitve and piezoelectric effects is achieved, are potential candidates for multifunctional devices where the interplay between electrical, magnetic and mechanical properties of these structures can be fully exploited. Nanostructured composites are particularly interesting due to the enhancement of ME coupling expected at the nanoscale. However, direct studies of ME coupling in nanocomposites by scanning probe techniques are rare due to the complex interplay of forces at play, including those arising from electrostatic, magnetic and electromechanical interactions. In this work, the ME coupling of coaxial nickel - polyvinylidene fluoride trifluoroethylene [Ni-P(VDF-TrFE)] composite nanowires, fabricated by a scalable template-wetting based technique, is studied using a systematic sequence of scanning probe techniques. Individual ME nanowires were subjected to an electric field sufficient for ferroelectric poling in piezo-response force microscopy (PFM) mode, while magnetic force microscopy (MFM) was used to measure localised changes in magnetization as a result of electrical poling. Kelvin probe force microscopy (KPFM) measurements of surface potential were conducted to eliminate for the effect of contact potential differences during these measurements. An inverse, static, magnetoelectric coupling coefficient of ~1 x 10-11 s m-1 was found in our coaxial nanocomposite nanowires, comparable to other types of planar composites studied in this work, despite having an inferior piezoelectric-to-magnetostrictive volume ratio. The efficient ME coupling in our coaxial nanowires is attributed to the larger surface-to-volume interfacial contact between Ni and P(VDF-TrFE), and is promising for future integration into ME composite devices such as magnetic field sensors or energy harvesters

Piezoelectricity in non-nitride III–V nanowires: Challenges and opportunities

The increasing demand for portable and low-power electronics for applications in self-powered devices and sensors has spurred interest in the development of efficient piezoelectric materials, via which mechanical energy from ambient vibrations can be transformed into electrical energy for autonomous devices, or which can be used in strain-sensitive applications. Semiconducting piezoelectric materials are ideal candidates in the emerging field of piezotronics and piezophototronics, where the development of a piezopotential in response to stress/strain can be used to tune the band structure of the semiconductor and hence its electronic and/or optical properties. Furthermore, research into nanowires of these materials has intensified due to the enhancement of piezoelectric properties at the nanoscale. In this regard, nanowires of ZnO and the III-nitrides have been extensively studied, but the piezoelectric properties of non-nitride III–V semiconductor nanowires remain less-explored. Indeed, direct measurements of the piezoelectric properties of single III–V nanowires are tellingly rare due to the difficulties associated with measurements of piezoelectric properties of nanoscale objects using conventional scanning probe microscopy techniques. This review addresses the challenges related to the study of piezoelectricity in III–V nanowires and the opportunities that lie therein in terms of device applications.S.K-N and Y.C are grateful for financial support from the European Research Council through an ERC Starting Grant (Grant No. ERC-2014-STG-639526, NANOGEN)

Modified energy harvesting figures of merit for stress- and strain-driven piezoelectric systems

© 2019, The Author(s). Piezoelectrics are an important class of materials for mechanical energy harvesting technologies. In this paper we evaluate the piezoelectric harvesting process and define the key material properties that should be considered for effective material design and selection. Porous piezoceramics have been shown previously to display improved harvesting properties compared to their dense counterparts due to the reduction in permittivity associated with the introduction of porosity. We further this concept by considering the effect of the increased mechanical compliance of porous piezoceramics on the energy conversion efficiency and output electrical power. Finite element modelling is used to investigate the effect of porosity on relevant energy harvesting figures of merit. The increase in compliance due to porosity is shown to increase both the amount of mechanical energy transmitted into the system under stress-driven conditions, and the stress-driven figure of merit, FoM33X, despite a reduction in the electromechanical coupling coefficient. We show the importance of understanding whether a piezoelectric energy harvester is stress- or strain-driven, and demonstrate how porosity can be used to tailor the electrical and mechanical properties of piezoceramic harvesters. Finally, we derive two new figures of merit based on the consideration of each stage in the piezoelectric harvesting process and whether the system is stress- (FijX), or strain-driven (Fijx)

Caloric materials near ferroic phase transitions

A magnetically, electrically or mechanically responsive material can undergo significant thermal changes near a ferroic phase transition when its order parameter is modified by the conjugate applied field. The resulting magnetocaloric, electrocaloric and mechanocaloric (elastocaloric or barocaloric) effects are compared here in terms of history, experimental method, performance and prospective cooling applications