Synthesis and enhanced room-temperature thermoelectric properties of CuO-MWCNT hybrid nanostructured composites.

This work presents the synthesis of novel copper oxide-multiwalled carbon nanotube (CuO-MWCNT) hybrid nanostructured composites and a systematic study of their thermoelectric performance at near-room temperatures as a function of MWCNT wt% in the composite. The CuO-MWCNT hybrid nanostructured composites were synthesized by thermal oxidation of a thin metallic Cu layer pre-deposited on the MWCNT network. This resulted in the complete incorporation of MWCNTs in the nanostructured CuO matrix. The thermoelectric properties of the fabricated CuO-MWCNT composites were compared with the properties of CuO-MWCNT networks prepared by mechanical mixing and with the properties of previously reported thermoelectric [CuO]99.9[SWCNT]0.1 composites. CuO-MWCNT hybrid composites containing MWCNTs below 5 wt% showed an increase in the room-temperature thermoelectric power factor (PF) by ∼2 times compared with a bare CuO nanostructured reference thin film, by 5-50 times compared to mixed CuO-MWCNT networks, and by ∼10 times the PF of [CuO]99.9[SWCNT]0.1. The improvement of the PF was attributed to the changes in charge carrier concentration and mobility due to the processes occurring at the large-area CuO-MWCNT interfaces. The Seebeck coefficient and PF reached by the CuO-MWCNT hybrid nanostructured composites were 688 µV K-1 and ∼4 µW m-1 K-2, which exceeded the recently reported values for similar composites based on MWCNTs and the best near-room temperature inorganic thermoelectric materials such as bismuth and antimony chalcogenides and highlighted the potential of CuO-MWCNT hybrid nanostructured composites for applications related to low-grade waste heat harvesting and conversion to useable electricity.

Enhanced thermoelectric properties of self-assembling ZnO nanowire networks encapsulated in nonconductive polymers.

The near-room temperature thermoelectric properties of self-assembling ZnO nanowire networks before and after encapsulation in nonconductive polymers are studied. ZnO nanowire networks were synthesized via a two-step fabrication technique involving the deposition of metallic Zn networks by thermal evaporation, followed by thermal oxidation. Synthesized ZnO nanowire networks were encapsulated in polyvinyl alcohol (PVA) or commercially available epoxy adhesive. Comparison of electrical resistance and Seebeck coefficient of the ZnO nanowire networks before and after encapsulation showed a significant increase in the network's electrical conductivity accompanied by the increase of its Seebeck coefficient after the encapsulation. The thermoelectric power factor (PF) of the encapsulated ZnO nanowire networks exceeded the PF of bare ZnO networks by ~ 5 and ~ 185 times for PVA- and epoxy-encapsulated samples, respectively, reaching 0.85 µW m-1 K-2 and ZT ~ 3·10-6 at room temperature, which significantly exceeded the PF and ZT values for state-of-the-art non-conductive polymers based thermoelectric flexible films. Mechanisms underlying the improvement of the thermoelectrical properties of ZnO nanowire networks due to their encapsulation are discussed. In addition, encapsulated ZnO nanowire networks showed excellent stability during 100 repetitive bending cycles down to a 5 mm radius, which makes them perspective for the application in flexible thermoelectrics.

Positive and Negative Changes in the Electrical Conductance Related to Hybrid Filler Distribution Gradient in Composite Flexible Thermoelectric Films Subjected to Bending.

P-type multiwalled carbon nanotubes (MWCNTs), as well as heterostructures fabricated by direct deposition of inorganic thermoelectric materials as antimony and bismuth chalcogenides on MWCNT networks are known as perspective materials for application in flexible thermoelectric polymer-based composites. In this work, the electrical response of three types of Sb2Te3-MWCNT heterostructures-based flexible films-free standing on a flexible substrate, encapsulated in polydimethylsiloxane (PDMS), and mixed in polyvinyl alcohol (PVA) is studied in comparison with the flexible films prepared by the same methods using bare MWCNTs. The electrical conductance of these films when each side of it was subsequently subjected to compressive and tensile stress during the film bending down to a 3 mm radius is investigated in relation to the distribution gradient of Sb2Te3-MWCNT heterostructures or bare MWCNTs within the film. It is found that all investigated Sb2Te3-MWCNT films exhibit a reversible increase in the conductance in response to the compressive stress of the film side with the highest filler concentration and its decrease in response to the tensile stress. In contrast, free-standing and encapsulated bare MWCNT networks with uniform distribution of nanotubes showed a decrease in the conductance irrelevant to the bending direction. In turn, the samples with the gradient distribution of the MWCNTs, prepared by mixing the MWCNTs with PVA, revealed behavior that is similar to the Sb2Te3-MWCNT heterostructures-based films. The analysis of the processes impacting the changes in the conductance of the Sb2Te3-MWCNT heterostructures and bare MWCNTs is performed. The proposed in this work bending method can be applied for the control of the uniformity of distribution of components in heterostructures and fillers in polymer-based composites.

Low-Vacuum Catalyst-Free Physical Vapor Deposition and Magnetotransport Properties of Ultrathin Bi2Se3 Nanoribbons.

In this work, a simple catalyst-free physical vapor deposition method is optimized by adjusting source material pressure and evaporation time for the reliable obtaining of freestanding nanoribbons with thicknesses below 15 nm. The optimum synthesis temperature, time and pressure were determined for an increased yield of ultrathin Bi2Se3 nanoribbons with thicknesses of 8-15 nm. Physical and electrical characterization of the synthesized Bi2Se3 nanoribbons with thicknesses below 15 nm revealed no degradation of properties of the nanoribbons, as well as the absence of the contribution of trivial bulk charge carriers to the total conductance of the nanoribbons.

Epoxy-Encapsulated ZnO-MWCNT Hybrid Nanocomposites with Enhanced Thermoelectric Performance for Low-Grade Heat-to-Power Conversion.

This work is devoted to the development of epoxy-encapsulated zinc oxide-multiwalled carbon nanotubes (ZnO-MWCNT) hybrid nanostructured composites and the investigation of their thermoelectric performance in relation to the content of MWCNTs in the composite. For the preparation of nanocomposites, self-assembling Zn nanostructured networks were coated with a layer of dispersed MWCNTs and subjected to thermal oxidation. The resulting ZnO-MWCNT hybrid nanostructured networks were encapsulated in commercially available epoxy adhesive. It was found that encapsulation of ZnO-MWCNT hybrid networks in epoxy adhesive resulted in a simultaneous decrease in their electrical resistance by a factor of 20-60 and an increase in the Seebeck coefficient by a factor of 3-15, depending on the MWCNT content. As a result, the thermoelectric power factor of the epoxy-encapsulated ZnO-MWCNTs hybrid networks exceeded that of non-encapsulated networks by more than 3-4 orders of magnitude. This effect was attributed to the ZnO-epoxy interface's unique properties and to the MWCNTs' contribution. The processes underlying such a significant improvement of the properties of ZnO-MWCNT hybrid nanostructured networks after encapsulation in epoxy adhesive are discussed. In addition, a two-leg thermoelectric generator composed of epoxy-encapsulated ZnO-MWCNT hybrid nanocomposite as n-type leg and polydimethylsiloxane-encapsulated CuO-MWCNT hybrid nanocomposite as p-type leg characterized at room temperatures showed better performance at temperature difference 30 °C compared with the similar devices, thus proving the potential of the developed nanocomposites for applications in domestic waste heat conversion devices.

Humidity-dependent electrical performance of CuO nanowire networks studied by electrochemical impedance spectroscopy.

Electrochemical impedance spectroscopy was applied for studying copper oxide (CuO) nanowire networks assembled between metallic microelectrodes by dielectrophoresis. The influence of relative humidity (RH) on electrical characteristics of the CuO nanowire-based system was assessed by measurements of the impedance Z. A slight increase of Z with increasing RH at low humidity was followed by a three orders of magnitude decrease of Z at RH above 50-60%. The two opposite trends observed across the range of the examined RH of 5-97% can be caused by water chemisorption and physisorption at the nanowire interface, which suppress electronic transport inside the p-type semiconductor nanowire but enhance ionic transport in the water layers adsorbed on the nanowire surface. Possible physicochemical processes at the nanowire surface are discussed in line with equivalent circuit parameters obtained by fitting impedance spectra. The new investigation data can be useful to predict the behavior of nanostructured CuO in humid environments, which is favorable for advancing technology of nanowire-based systems suitable for sensor applications.

p-Type PVA/MWCNT-Sb2Te3 Composites for Application in Different Types of Flexible Thermoelectric Generators in Combination with n-Type PVA/MWCNT-Bi2Se3 Composites.

This work is devoted to the fabrication of p-type polyvinyl alcohol (PVA)-based flexible thermoelectric composites using multiwall carbon nanotubes-antimony telluride (MWCNT-Sb2Te3) hybrid filler, the study of the thermoelectrical and mechanical properties of these composites, and the application of these composites in two types (planar and radial) of thermoelectric generators (TEG) in combination with the previously reported PVA/MWCNT-Bi2Se3 flexible thermoelectric composites. While the power factors of PVA/MWCNT-Sb2Te3 and PVA/MWCNT-Bi2Se3 composites with 15 wt.% filler were found to be similar, the PVA/MWCNT-Sb2Te3 composite with 25 wt.% filler showed a ~2 times higher power factor in comparison with the PVA/MWCNT-Bi2Se3 composites with 30 wt.% filler, which is attributed to its reduced electrical resistivity. In addition, developed PVA/MWCNT-Sb2Te3 composites showed a superior mechanical, electrical, and thermoelectric stability during 100 consequent bending cycles down to a 3 mm radius, with insignificant fluctuations of the resistance within 0.01% of the initial resistance value of the not bent sample. Demonstrated for the first time, 2-leg TEGs composed from p-type PVA/MWCNT-Sb2Te3 and n-type PVA/MWCNT-Bi2Se3 composites showed a stable performance under different external loads and showed their potential for applications involving low temperature gradients and power requirements in the range of nW.

Nanometric Moiré Stripes on the Surface of Bi2Se3 Topological Insulator.

Mismatch between adjacent atomic layers in low-dimensional materials, generating moiré patterns, has recently emerged as a suitable method to tune electronic properties by inducing strong electron correlations and generating novel phenomena. Beyond graphene, van der Waals structures such as three-dimensional (3D) topological insulators (TIs) appear as ideal candidates for the study of these phenomena due to the weak coupling between layers. Here we discover and investigate the origin of 1D moiré stripes on the surface of Bi2Se3 TI thin films and nanobelts. Scanning tunneling microscopy and high-resolution transmission electron microscopy reveal a unidirectional strained top layer, in the range 14-25%, with respect to the relaxed bulk structure, which cannot be ascribed to the mismatch with the substrate lattice but rather to strain induced by a specific growth mechanism. The 1D stripes are characterized by a spatial modulation of the local density of states, which is strongly enhanced compared to the bulk system. Density functional theory calculations confirm the experimental findings, showing that the TI surface Dirac cone is preserved in the 1D moiré stripes, as expected from the topology, though with a heavily renormalized Fermi velocity that also changes between the top and valley of the stripes. The strongly enhanced density of surface states in the TI 1D moiré superstructure can be instrumental in promoting strong correlations in the topological surface states, which can be responsible for surface magnetism and topological superconductivity.

High-Yield Growth and Tunable Morphology of Bi2Se3 Nanoribbons Synthesized on Thermally Dewetted Au.

The yield and morphology (length, width, thickness) of stoichiometric Bi2Se3 nanoribbons grown by physical vapor deposition is studied as a function of the diameters and areal number density of the Au catalyst nanoparticles of mean diameters 8-150 nm formed by dewetting Au layers of thicknesses 1.5-16 nm. The highest yield of the Bi2Se3 nanoribbons is reached when synthesized on dewetted 3 nm thick Au layer (mean diameter of Au nanoparticles ~10 nm) and exceeds the nanoribbon yield obtained in catalyst-free synthesis by almost 50 times. The mean lengths and thicknesses of the Bi2Se3 nanoribbons are directly proportional to the mean diameters of Au catalyst nanoparticles. In contrast, the mean widths of the Bi2Se3 nanoribbons do not show a direct correlation with the Au nanoparticle size as they depend on the contribution ratio of two main growth mechanisms-catalyst-free and vapor-liquid-solid deposition. The Bi2Se3 nanoribbon growth mechanisms in relation to the Au catalyst nanoparticle size and areal number density are discussed. Determined charge transport characteristics confirm the high quality of the synthesized Bi2Se3 nanoribbons, which, together with the high yield and tunable morphology, makes these suitable for application in a variety of nanoscale devices.

Flexible N-Type Thermoelectric Composites Based on Non-Conductive Polymer with Innovative Bi2Se3-CNT Hybrid Nanostructured Filler.

This research is devoted to the fabrication of polyvinyl alcohol (PVOH) based n-type thermoelectric composites with innovative hybrid bismuth selenide-multiwalled carbon nanotube (Bi2Se3-MWCNT) fillers for application in flexible thermoelectric devices. Hybrid fillers were synthesized by direct deposition of Bi2Se3 on multiwalled carbon nanotubes using a physical vapor deposition method, thus ensuring direct electrical contact between the carbon nanotubes and Bi2Se3. The Seebeck coefficient of prepared PVOH/Bi2Se3-MWCNT composites was found to be comparable with that for the Bi2Se3 thin films, reaching -100 µV·K-1 for the composite with 30 wt.% filler, and fluctuations of the resistance of these composites did not exceed 1% during 100 repetitive bending cycles down to 10 mm radius, indicating the good mechanical durability of these composites and proving their high potential for application in flexible thermoelectrics. In addition, other properties of the fabricated composites that are important for the use of polymer-based materials such as thermal stability, storage modulus and linear coefficient of thermal expansion were found to be improved in comparison with the neat PVOH.

Two-terminal nanoelectromechanical devices based on germanium nanowires.

A two-terminal bistable device, having both ON and OFF regimes, has been demonstrated with Ge nanowires using an in situ TEM-STM technique. The function of the device is based on delicately balancing electrostatic, elastic, and adhesion forces between the nanowires and the contacts, which can be controlled by the applied voltage. The operation and failure conditions of the bistable device were investigated, i.e. the influence of nanowire diameter, the surface oxide layer on the nanowires and the current density. During ON/OFF cycles the Ge nanowires were observed to be more stable than carbon nanotubes, working at similar conditions, due to the higher mechanical stability of the nanowires. The higher resistivity of Ge nanowires, compared to carbon nanotubes, provides potential application of these 1D nanostructures in high-voltage devices.

Surface structure promoted high-yield growth and magnetotransport properties of Bi2Se3 nanoribbons.

In the present work, a catalyst-free physical vapour deposition method is used to synthesize high yield of Bi2Se3 nanoribbons. By replacing standard glass or quartz substrates with aluminium covered with ultrathin porous anodized aluminium oxide (AAO), the number of synthesized nanoribbons per unit area can be increased by 20-100 times. The mechanisms of formation and yield of the nanoribbons synthesized on AAO substrates having different arrangement and size of pores are analysed and discussed. It is shown that the yield and average length of the nanoribbons can base tuned by adjustment of the synthesis parameters. Analysis of magnetotransport measurements for the individual Bi2Se3 nanoribbons transferred on a Si/SiO2 substrate show the presence of three different populations of charge carriers, originating from the Dirac surface states, bulk carriers and carriers from a trivial 2DEG from an accumulation layer at the Bi2Se3 nanoribbon interface with the substrate.

Effect of graphene substrate type on formation of Bi2Se3 nanoplates.

Knowledge of nucleation and further growth of Bi2Se3 nanoplates on different substrates is crucial for obtaining ultrathin nanostructures and films of this material by physical vapour deposition technique. In this work, Bi2Se3 nanoplates were deposited under the same experimental conditions on different types of graphene substrates (as-transferred and post-annealed chemical vapour deposition grown monolayer graphene, monolayer graphene grown on silicon carbide substrate). Dimensions of the nanoplates deposited on graphene substrates were compared with the dimensions of the nanoplates deposited on mechanically exfoliated mica and highly ordered pyrolytic graphite flakes used as reference substrates. The influence of different graphene substrates on nucleation and further lateral and vertical growth of the Bi2Se3 nanoplates is analysed. Possibility to obtain ultrathin Bi2Se3 thin films on these substrates is evaluated. Between the substrates considered in this work, graphene grown on silicon carbide is found to be the most promising substrate for obtaining of 1-5 nm thick Bi2Se3 films.

Review: Electrostatically actuated nanobeam-based nanoelectromechanical switches - materials solutions and operational conditions.

This review summarizes relevant research in the field of electrostatically actuated nanobeam-based nanoelectromechanical (NEM) switches. The main switch architectures and structural elements are briefly described and compared. Investigation methods that allow for exploring coupled electromechanical interactions as well as studies of mechanically or electrically induced effects are covered. An examination of the complex nanocontact behaviour during various stages of the switching cycle is provided. The choice of the switching element and the electrode is addressed from the materials perspective, detailing the benefits and drawbacks for each. An overview of experimentally demonstrated NEM switching devices is provided, and together with their operational parameters, the reliability issues and impact of the operating environment are discussed. Finally, the most common NEM switch failure modes and the physical mechanisms behind them are reviewed and solutions proposed.

Bulk-free topological insulator Bi2Se3 nanoribbons with magnetotransport signatures of Dirac surface states.

Many applications of topological insulators (TIs) as well as new phenomena require devices with reduced dimensions. While much progress has been made to realize thin films of TIs with low bulk carrier densities, nanostructures have not yet been reported with similar properties, despite the fact that reduced dimensions should help diminish the contributions from bulk carriers. Here we demonstrate that Bi2Se3 nanoribbons, grown by a simple catalyst-free physical-vapour deposition, have inherently low bulk carrier densities, and can be further made bulk-free by thickness reduction, thus revealing the high mobility topological surface states. Magnetotransport and Hall conductance measurements, in single nanoribbons, show that at thicknesses below 30 nm, the bulk transport is completely suppressed which is supported by self-consistent band-bending calculations. The results highlight the importance of material growth and geometrical confinement to properly exploit the unique properties of topological surface states.

Role of Nanoelectromechanical Switching in the Operation of Nanostructured Bi2Se3 Interlayers between Conductive Electrodes.

We demonstrate a simple low-cost method of preparation of layered devices for opto- and thermoelectric applications. The devices consist of a functional Bi2Se3 layer of randomly oriented nanoplates and flexible nanobelts enclosed between two flat indium tin oxide (ITO) electrodes. The number of functional interconnections between the ITO electrodes and correspondingly the efficiency of the device can be increased by gradual nanoelectromechanical (NEM) switching of flexible individual Bi2Se3 nanobelts in the circuit. NEM switching is achieved through applying an external voltage to the device. For the first time, we investigate in situ NEM switching and breakdown parameters of Bi2Se3 nanobelts, visualize the processes occurring in the device under the influence of applied external voltage, and establish the limitations to the possible operational conditions.