Roadmap on thermoelectricity.

The increasing energy demand and the ever more pressing need for clean technologies of energy conversion pose one of the most urgent and complicated issues of our age. Thermoelectricity, namely the direct conversion of waste heat into electricity, is a promising technique based on a long-standing physical phenomenon, which still has not fully developed its potential, mainly due to the low efficiency of the process. In order to improve the thermoelectric performance, a huge effort is being made by physicists, materials scientists and engineers, with the primary aims of better understanding the fundamental issues ruling the improvement of the thermoelectric figure of merit, and finally building the most efficient thermoelectric devices. In this Roadmap an overview is given about the most recent experimental and computational results obtained within the Italian research community on the optimization of composition and morphology of some thermoelectric materials, as well as on the design of thermoelectric and hybrid thermoelectric/photovoltaic devices.

Water-based 2-dimensional anatase TiO2 inks for printed diodes and transistors.

2-Dimensional (2D) materials are attracting strong interest in printed electronics because of their unique properties and easy processability, enabling the fabrication of devices with low cost and mass scalable methods such as inkjet printing. For the fabrication of fully printed devices, it is of fundamental importance to develop a printable dielectric ink, providing good insulation and the ability to withstand large electric fields. Hexagonal boron nitride (h-BN) is typically used as a dielectric in printed devices. However, the h-BN film thickness is usually above 1 µm, hence limiting the use of h-BN in low-voltage applications. Furthermore, the h-BN ink is composed of nanosheets with broad lateral size and thickness distributions, due to the use of liquid-phase exfoliation (LPE). In this work, we investigate anatase TiO2 nanosheets (TiO2-NS), produced by a mass scalable bottom-up approach. We formulate the TiO2-NS into a water-based and printable solvent and demonstrate the use of the material with sub-micron thickness in printed diodes and transistors, hence validating the strong potential of TiO2-NS as a dielectric for printed electronics.

Biodegradable albumen dielectrics for high-mobility MoS2 phototransistors.

This work demonstrates the fabrication and characterization of single-layer MoS2 field-effect transistors using biodegradable albumen (chicken eggwhite) as gate dielectric. By introducing albumen as an insulator for MoS2 transistors high carrier mobilities (up to ~90 cm2 V-1 s-1) are observed, which is remarkably superior to that obtained with commonly used SiO2 dielectric which we attribute to ionic gating due to the formation of an electric double layer in the albumen MoS2 interface. In addition, the investigated devices are characterized upon illumination, observing responsivities of 4.5 AW-1 (operated in photogating regime) and rise times as low as 52 ms (operated in photoconductivity regime). The presented study reveals the combination of albumen with van der Waals materials for prospective biodegradable and biocompatible optoelectronic device applications. Furthermore, the demonstrated universal fabrication process can be easily adopted to fabricate albumen-based devices with any other van der Waals material.

Silicon Nanowires: A Breakthrough for Thermoelectric Applications.

The potentialities of silicon as a starting material for electronic devices are well known and largely exploited, driving the worldwide spreading of integrated circuits. When nanostructured, silicon is also an excellent material for thermoelectric applications, and hence it could give a significant contribution in the fundamental fields of energy micro-harvesting (scavenging) and macro-harvesting. On the basis of recently published experimental works, we show that the power factor of silicon is very high in a large temperature range (from room temperature up to 900 K). Combining the high power factor with the reduced thermal conductivity of monocrystalline silicon nanowires and nanostructures, we show that the foreseen figure of merit ZT could be very high, reaching values well above 1 at temperatures around 900 K. We report the best parameters to optimize the thermoelectric properties of silicon nanostructures, in terms of doping concentration and nanowire diameter. At the end, we report some technological processes and solutions for the fabrication of macroscopic thermoelectric devices, based on large numbers of silicon nanowire/nanostructures, showing some fabricated demonstrators.

Seebeck coefficient of silicon nanowire forests doped by thermal diffusion.

Thermoelectric generators made by large arrays of nanowires perpendicular to a silicon substrate, that is, so-called silicon nanowire forests are fabricated on large areas by an inexpensive metal-assisted etching technique. After fabrication, a thermal diffusion process is used for doping the nanowire forest with phosphorous. A suitable experimental technique has been developed for the measurement of the Seebeck coefficient under static conditions, and results are reported for different doping parameters. These results are in good agreement with numerical simulations of the doping process applied to silicon nanowires. These devices, based on doped nanowire forests, offer a possible route for the exploitation of the high power factor of silicon, which, combined with the very low thermal conductivity of nanostructures, will yield a high efficiency of the conversion of thermal to electrical energy.

On the mechanism ruling the morphology of silicon nanowires obtained by one-pot metal-assisted chemical etching.

One-pot Ag-assisted chemical etching (SACE) of silicon provides an effective, simple way to obtain Si nanowires (NWs) of potential interest for technological applications ranging from photovoltaics to thermoelectricity. The detailed mechanism ruling the process has not been yet fully elucidated, however. In this paper we report the results of an extended analysis of the interplay among doping level and type of silicon, nanowire nanomorphology and the parameters controlling the chemistry of the etching process. We provide evidence that the SACE mechanism entirely occurs at the interface between the etching solution and the Si substrate as a result of Si extrusion by sinking self-propelled Ag particles. Also, a rationale is advanced to explain the reported formation of (partially) porous NWs at high doping levels in both p- and n-type Si. A model not relying on the asserted formation of potential barriers enables to recover full consistency between SACE electrochemistry and the mechanism of formation of porous silicon in electrochemical cells.

High Power Thermoelectric Generator Based on Vertical Silicon Nanowires.

Thermoelectric generators, which convert heat directly into electrical power, have great potentialities in the energy harvesting field. The exploitation of these potentialities is limited by the materials currently used, characterized by good thermoelectric properties, but also by several drawbacks. This work presents a silicon-based thermoelectric generator, made of a large collection of heavily p-doped silicon nanostructures. This macroscopic device (area of several mm2) collects together the good thermoelectric features of silicon, in terms of high power factor, and a very reduced thermal conductivity, which resulted in being exceptionally low (1.8 W/(m K), close to the amorphous limit). The generated electrical power density is remarkably high for a Si-based thermoelectric generator, and it is suitable for scavenging applications which can exploit small temperature differences. A full characterization of the device (Seebeck coefficient, thermal conductivity, maximum power output) is reported and discussed.

Potentialities of silicon nanowire forests for thermoelectric generation.

Silicon is a material with very good thermoelectric properties, with regard to Seebeck coefficient and electrical conductivity. Low thermal conductivities, and hence high thermal to electrical conversion efficiencies, can be achieved in nanostructures, which are smaller than the phonon mean free path but large enough to preserve the electrical conductivity. We demonstrate that it is possible to fabricate a leg of a thermoelectric generator based on large collections of long nanowires, placed perpendicularly to the two faces of a silicon wafer. The process exploits the metal assisted etching technique which is simple, low cost, and can be easily applied to large surfaces. Copper can be deposited by electrodeposition on both faces, so that contacts can be provided, on top of the nanowires. Thermal conductivity of silicon nanowire forests with more than 107 nanowires mm-2 have been measured; the result is comparable with that achieved by several groups on devices based on few nanowires. On the basis of the measured parameters, numerical calculations of the efficiency of silicon-based thermoelectric generators are reported, and the potentialities of these devices for thermal to electrical energy conversion are shown. Criteria to improve the conversion efficiency are suggested and described.

Reliable Fabrication of Metal Contacts on Silicon Nanowire Forests.

We present a technique for the fabrication of an electrical (and thermal) contact on the top ends of a large number of vertical silicon nanowires, which are fabricated perpendicularly to a silicon wafer (silicon nanowire forest). The technique is based on electrochemical deposition of copper and has been developed on silicon nanowire forests, fabricated by metal assisted chemical etching. We demonstrate that copper grows selectively only on the top end of the silicon nanowires, forming a layer onto the top of the forest. The presence of a predeposited metal seed is fundamental for the selective growth, meanwhile the process is very strong with respect to other parameters, such as concentration of the electrolytic solution and current density, used during the metal deposition. Typical I-V characteristics of top-to-bottom conduction through silicon nanowire forests with different n-doping are shown and discussed.