Transitioning from Si to SiGe Nanowires as Thermoelectric Material in Silicon-Based Microgenerators.

The thermoelectric performance of nanostructured low dimensional silicon and silicon-germanium has been functionally compared device-wise. The arrays of nanowires of both materials, grown by a VLS-CVD (Vapor-Liquid-Solid Chemical Vapor Deposition) method, have been monolithically integrated in a silicon micromachined structure in order to exploit the improved thermoelectric properties of nanostructured silicon-based materials. The device architecture helps to translate a vertically occurring temperature gradient into a lateral temperature difference across the nanowires. Such thermocouple is completed with a thin film metal leg in a unileg configuration. The device is operative on its own and can be largely replicated (and interconnected) using standard IC (Integrated Circuits) and MEMS (Micro-ElectroMechanical Systems) technologies. Despite SiGe nanowires devices show a lower Seebeck coefficient and a higher electrical resistance, they exhibit a much better performance leading to larger open circuit voltages and a larger overall power supply. This is possible due to the lower thermal conductance of the nanostructured SiGe ensemble that enables a much larger internal temperature difference for the same external thermal gradient. Indeed, power densities in the µW/cm2 could be obtained for such devices when resting on hot surfaces in the 50-200 °C range under natural convection even without the presence of a heat exchanger.

Tin Selenide Molecular Precursor for the Solution Processing of Thermoelectric Materials and Devices.

In the present work, we report a solution-based strategy to produce crystallographically textured SnSe bulk nanomaterials and printed layers with optimized thermoelectric performance in the direction normal to the substrate. Our strategy is based on the formulation of a molecular precursor that can be continuously decomposed to produce a SnSe powder or printed into predefined patterns. The precursor formulation and decomposition conditions are optimized to produce pure phase 2D SnSe nanoplates. The printed layer and the bulk material obtained after hot press displays a clear preferential orientation of the crystallographic domains, resulting in an ultralow thermal conductivity of 0.55 W m-1 K-1 in the direction normal to the substrate. Such textured nanomaterials present highly anisotropic properties with the best thermoelectric performance in plane, i.e., in the directions parallel to the substrate, which coincide with the crystallographic bc plane of SnSe. This is an unfortunate characteristic because thermoelectric devices are designed to create/harvest temperature gradients in the direction normal to the substrate. We further demonstrate that this limitation can be overcome with the introduction of small amounts of tellurium in the precursor. The presence of tellurium allows one to reduce the band gap and increase both the charge carrier concentration and the mobility, especially the cross plane, with a minimal decrease of the Seebeck coefficient. These effects translate into record out of plane ZT values at 800 K.

Large-area and adaptable electrospun silicon-based thermoelectric nanomaterials with high energy conversion efficiencies.

Large amounts of waste heat generated in our fossil-fuel based economy can be converted into useful electric power by using thermoelectric generators. However, the low-efficiency, scarcity, high-cost and poor production scalability of conventional thermoelectric materials are hindering their mass deployment. Nanoengineering has proven to be an excellent approach for enhancing thermoelectric properties of abundant and cheap materials such as silicon. Nevertheless, the implementation of these nanostructures is still a major challenge especially for covering the large areas required for massive waste heat recovery. Here we present a family of nano-enabled materials in the form of large-area paper-like fabrics made of nanotubes as a cost-effective and scalable solution for thermoelectric generation. A case study of a fabric of p-type silicon nanotubes was developed showing a five-fold improvement of the thermoelectric figure of merit. Outstanding power densities above 100 W/m2 at 700 °C are therefore demonstrated opening a market for waste heat recovery.

Direct manufacturing of ultrathin graphite on three-dimensional nanoscale features.

There have been many successful attempts to grow high-quality large-area graphene on flat substrates. Doing so at the nanoscale has thus far been plagued by significant scalability problems, particularly because of the need for delicate transfer processes onto predefined features, which are necessarily low-yield processes and which can introduce undesirable residues. Herein we describe a highly scalable, clean and effective, in-situ method that uses thin film deposition techniques to directly grow on a continuous basis ultrathin graphite (uG) on uneven nanoscale surfaces. We then demonstrate that this is possible on a model system of atomic force probe tips of various radii. Further, we characterize the growth characteristics of this technique as well as the film's superior conduction and lower adhesion at these scales. This sets the stage for such a process to allow the use of highly functional graphite in high-aspect-ratio nanoscale components.

Substrate control for large area continuous films of monolayer MoS2 by atmospheric pressure chemical vapor deposition.

Growing monolayer MoS2 films that are continuous with large domain sizes by chemical vapor deposition is one of the major challenges in 2D materials research at the moment. Here, we explore how atmospheric pressure CVD can be used to grow centimeter scale continuous films of monolayer MoS2 films directly on Si substrates with an oxide layer whilst also obtaining large domain sizes exceeding 20 µm within the films. This is achieved by orientating the growth substrate in a vertical position to improve the uniformity of precursor feed-stock compared to horizontally orientated growth substrates. This leads to continuous films of monolayer MoS2 over a significantly larger area without the need for low-pressure vacuum systems or volatile precursors. This provides important insights into novel approaches for maximizing domain sizes within MoS2 films, with concomitant large area uniform coverage.

Electroluminescence Dynamics across Grain Boundary Regions of Monolayer Tungsten Disulfide.

We study how grain boundaries (GB) in chemical vapor deposition (CVD) grown monolayer WS2 influence the electroluminescence (EL) behavior in lateral source-drain devices under bias. Real time imaging of the WS2 EL shows arcing between the electrodes when probing across a GB, which then localizes at the GB region as it erodes under high bias conditions. In contrast, single crystal WS2 domains showed no signs of arcing or localized EL. Analysis of the eroded GB region shows the formation of micro- and nanoribbons across the monolayer WS2 domains. Comparison of the EL spectrum with the photoluminescence spectrum from the monolayer WS2 shows close agreement, indicating the EL emission comes from direct band gap excitonic recombination. These results provide important insights into EL devices that utilize CVD grown monolayer transition metal dichalcogenides when GBs are present in the active device region.

Controlled preferential oxidation of grain boundaries in monolayer tungsten disulfide for direct optical imaging.

Synthetic 2D crystal films grown by chemical vapor deposition are typically polycrystalline, and determining grain size within domains and continuous films is crucial for determining their structure. Here we show that grain boundaries in the 2D transition metal dichalcogenide WS2, grown by CVD, can be preferentially oxidized by controlled heating in air. Under our developed conditions, preferential degradation at the grain boundaries causes an increase in their physical size due to oxidation. This increase in size enables their clear and rapid identification using a standard optical microscope. We demonstrate that similar treatments in an Ar environment do no show this effect, confirming that oxidation is the main role in the structural change. Statistical analysis of grain boundary (GB) angles shows dominant mirror formation. Electrical biasing across the GB is shown to lead to changes at the GB and their observation under an optical microscope. Our approach enables high-throughput screening of as-synthesized WS2 domains and continuous films to determine their crystallinity and should enable improvements in future CVD growth of these materials.

Real time protein recognition in a liquid-gated carbon nanotube field-effect transistor modified with aptamers.

The combination of optimized and passivated Field Effect Transistors (FETs) based on carbon nanotubes (CNTs) together with the appropriate choice and immobilization strategy of aptamer receptors and buffer concentration have allowed the highly sensitive and real time biorecognition of proteins in a liquid-gated configuration. Specifically we have followed the biorecognition process of thrombin by its specific aptamer. The aptamer modified device is sensitive enough to capture a change in the electronic detection mechanism, one operating at low protein concentrations and the other in a higher target concentration range. The high sensitivity of the device is also sustained by the very low detection limits achieved (20 pM) and their high selectivity when other target proteins are used. Moreover, the experimental results have allowed us to quantify the equilibrium constant of the protein-aptamer binding and confirm its high affinity by using the Langmuir equation.

A reusable impedimetric aptasensor for detection of thrombin employing a graphite-epoxy composite electrode.

Here, we report the application of a label-free electrochemical aptasensor based on a graphite-epoxy composite electrode for the detection of thrombin; in this work, aptamers were immobilized onto the electrodes surface using wet physical adsorption. The detection principle is based on the changes of the interfacial properties of the electrode; these were probed in the presence of the reversible redox couple [Fe(CN)(6)](3-)/[Fe(CN)(6)](4-) using impedance measurements. The electrode surface was partially blocked due to formation of aptamer-thrombin complex, resulting in an increase of the interfacial electron-transfer resistance detected by Electrochemical Impedance Spectroscopy (EIS). The aptasensor showed a linear response for thrombin in the range of 7.5 pM to 75 pM and a detection limit of 4.5 pM. The aptasensor was regenerated by breaking the complex formed between the aptamer and thrombin using 2.0 M NaCl solution at 42 °C, showing its operation for different cycles. The interference response caused by main proteins in serum has been characterized.