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The thin film configuration presents obvious practical advantages over the 1D implementation in energy harvesting systems such as easily manufacturing and processing and long lasting and stable devices. However, most of the ZnO-based piezoelectric nanogenerators (PENGs) reported so far relay in the exploitation of single-crystalline ZnO nanowires because their self-orientation in the c-axis and ability to accommodate long deformations resulting in a high piezoelectric performance. Herein, we show an innovative approach aiming to produce PENGs by combining polycrystalline ZnO layers fabricated at room temperature by plasma assisted deposition with supported small-molecule organic nanowires (ONWs) acting as 1D scaffold. The resulting hybrid nanostructure is formed by a single-crystalline organic nanowire conformally surrounded by a three dimensional (3D) ZnO shell that combines the mechanical properties of the organic core with the piezoelectric response of the ZnO layer. In a loop forward towards the integration of multiple functions within a single wire, we have also developed ONW@Au@ZnO nanowires including a gold shell acting as inner nanoscopic electrode. Thus, we have built and compare thin films and 3D core@shell ONW@ZnO and ONW@Au@ZnO PENGs showing output piezo-voltages up to 170 mV. The synergistic combination of functionalities in the ONW@Au@ZnO devices promotes an enhanced performance generating piezo-currents almost twenty times larger than the ONW@ZnO nanowires and superior to the thin film nanogenerators for equivalent and higher thicknesses.
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Harvesting all sources of available clean energy is an essential strategy to contribute to healing current dependence on non-sustainable energy sources. Recently, triboelectric nanogenerators (TENGs) have gained visibility as new mechanical energy harvester offering a valid alternative to batteries, being particularly suitable for portable devices. Here, the increased capacitance of a few-layer graphene-based electrode is obtained by incorporating nitrogen-doped graphene (N_graphene), enabling a 3_fold enhancement in TENGs power output. The dependence of TENGs performance on the electronic properties of different N_graphene types, varying in the doping concentration and in the relative content of N-pyridinic and N-graphitic sites is investigated. These sites have different electron affinities, and synergistically contribute to the variation of the capacitive and resistive properties of N-graphene and consequently, TENG performance. It is demonstrated that the power enhancement of the TENG occurs when the N_graphene, an n-semiconductor, is interfaced between the positive triboelectric material and the electrode, while a deterioration of the electrical performance is observed when it is placed at the interface with the negative triboelectric material. This behavior is explained in terms of the dependence of N_graphene quantum capacitance on the electrode chemical potential which shifts according to the opposite polarization induced at the two electrodes upon triboelectrification.
We introduce herein the advanced application of low pressure plasma procedures for the development of piezo and triboelectric mode I hybrid nanogenerators. Thus, plasma assisted deposition and functionalization methods are presented as key enabling technologies for the nanoscale design of ZnO polycrystalline shells, the formation of conducting metallic cores in core@shell nanowires, and for the solventless surface modification of polymeric coatings and matrixes. We show how the perfluorinated chains grafting of PDMS provides a reliable approach to increase the hydrophobicity and surface charges at the same time that keeping the PDMS mechanical properties. In this way, we produce efficient Ag/ZnO convoluted piezoelectric nanogenerators supported on flexible substrates and embedded in PDMS compatible with a contact separation triboelectric architecture. Factors like crystal-line texture, ZnO thickness, nanowires aspect ratio, and surface chemical modification of the PDMS are explored to optimize the power output of the nanogenerators aimed for harvesting from low-frequency vibrations. Just by manual trigger-ing, the hybrid device can charge a microcapacitor to switch on an array of color LEDs. Outstandingly, this simple three-layer architecture allows for harvesting vibration energy in a wide bandwidth, thus, we show the performance characteristics for frequencies between 1 Hz to 50 Hz and demonstrate the successful activation of the system up to ca. 800 Hz
Strain-coupled magnetoelectric (ME) phenomena in piezoelectric / ferromagnetic thin-film bilayers are a promising paradigm for sensors and information storage devices, where strain is utilized to manipulate the magnetization of the ferromagnetic film. In-plane magnetization rotation with an electric field across the film thickness has been challenging due to the virtual elimination of in-plane piezoelectric strain by substrate clamping, and to the requirement of anisotropic in-plane strain in two-terminal devices. We have overcome both of these limitations by fabricating lithographically patterned devices with a piezoelectric membrane on a soft substrate platform, in which in-plane strain is freely generated, and a patterned edge constraint that transforms the nominally isotropic piezoelectric strain into the required uniaxial strain. We fabricated 500 nm thick, (001) oriented [Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_3$]$_{0.7}$-[PbTiO$_3$]$_{0.3}$ (PMN-PT) unclamped piezoelectric membranes with ferromagnetic Ni overlayers. Guided by analytical and numerical continuum elastic calculations, we designed and fabricated two-terminal devices exhibiting Ni magnetization rotation in response to an electric field across the PMN-PT. Similar membrane heterostructures could be used to apply designed strain patterns to many other materials systems to control properties such as superconductivity, band topology, conductivity, and optical response.
We present a design for a piezoelectric-driven uniaxial stress cell suitable for use at ambient and cryogenic temperatures, and that incorporates both a displacement and a force sensor. The cell has a diameter of 46 mm and a height of 13 mm. It can apply a zero-load displacement of up to ~45 $mu$m, and a zero-displacement force of up to ~245 N. With combined knowledge of the displacement and force applied to the sample, it can quickly be determined whether the sample and its mounts remain within their elastic limits. In tests on the oxide metal Sr$_2$RuO$_4$, we found that at room temperature serious plastic deformation of the sample onset at a uniaxial stress of ~0.2 GPa, while at 5 K the sample deformation remained elastic up to almost 2 GPa. This result highlights the usefulness of in situ tuning, in which the force can be applied after cooling samples to cryogenic temperatures.
We present a piezoelectric-driven uniaxial pressure cell that is optimized for muon spin relaxation and neutron scattering experiments, and that is operable over a wide temperature range including cryogenic temperatures. To accommodate the large samples required for these measurement techniques, the cell is designed to generate forces up to 1000 N, and to minimize the background signal the space around the sample is kept as open as possible. We demonstrate here that by mounting plate-like samples with epoxy, a uniaxial stress exceeding 1 GPa can be achieved in an active volume of 5 mm3. We show that for practical operation it is important to monitor both the force and displacement applied to the sample. Also, because time is critical during facility experiments, samples are mounted in detachable holders that can be rapidly exchanged. The piezoelectric actuators are likewise contained in an exchangeable cartridge.
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