Tellurium and its alloys are used in many applications such as photoconductors, piezoelectric devices, thermoelectric generators and coolers [1]. For thermoelectric applications, the transport properties (thermal conductivity, electrical resistivity, Seebeck coefficient) of tellurium and its compounds can be improved by nanostructuring [2]. One-dimensional nanostructures like nanowires [3] and core-shell nanowires [4] are particularly promising due to the high phonon interface scattering and the blocking of the phonon conduction along the wire axis which lead to an increase of the thermoelectric conversion efficiency. Te nanowires can represent a base to create core-shell structures, being the core that could be further capped with a shell to get arrays of Te-based thermoelectric nanostructures like BiTe [5], AgTe [6] or LaTe [7].

Template assisted electrodeposition is a low cost technique widely used in literature for the synthesis of nanowires but implies several preparation steps and the removal of the template after the growth of the nanowires. The aim of this work is to develop a template free synthesis route that would be more convenient. For this purpose, Room-Temperature Ionic Liquids (RTILs) appear as promising solvents. Indeed, it has been highlighted that they can act as stabilizing agents for nanoparticles and nanostructured films synthesis [8]. In a previous work ([9]), our laboratory showed that Te nanowires can be obtained in an ionic liquid binary mixture: 1-ethyl-1-octyl-piperidinium bis(trifluoromethylsulfonyl)imide:1-ethyl-1-octyl-piperidinium bromide (EOPipTFSI:EOPipBr).

In the present work, several morphologies were obtained by varying the synthesis parameters (applied fixed potential, Te(IV) concentration, electrolyte composition). Under charge transfer control, micrometer faceted grains are formed. Under diffusion control, the deposits are composed of nanowires, which are single crystalline as proven by SAED (Selected Area Electronic Diffraction) and TEM (Transmission Electron Microscopy) analyses. In highest tested overpotential conditions, nanowires turn progressively into crystallized hollow nanostructures (HNs) when the coulometric charge increases. This phenomenon is more accentuated at low concentration and disappears when using a soluble anode, showing that the formation of HNs is due to a limitation by species supply. The geometry of HNs, with a high surface to volume ratio, is particularly interesting to create high performances thermoelectric materials. Indeed, this geometry could further decrease the lattice part of the thermal diffusion coefficient by phonon confinement. By decreasing the bromide content of the electrolyte, hair-like single crystalline nanowires with a high aspect ratio can be obtained. HRTEM (High Resolution Transmission Electron Spectroscopy) analyses reveal a growth along the c-axis, with a smooth interface. No surface contaminants were observed by STEM (Scanning Transmission Electron Microscopy), proving that halogenide ions do not play the role of capping agents, unlike observed in other works [10].

References

[1] Q. Wang et al, Adv. Mater.2013, 25, 3915

[2] K.T. Kim et al, Adv. Powder Technol.2011, 22, 566

[3] Caballero-Calero, O.; Martín-González, M., Scripta Materialia 2015, 10.1016/j.scriptamat.2015.04.020.

[4] Poon, S. J.; Petersen, A. S.; Wu, D. Appl. Phys. Lett. 2013, 102.

[5] Kang, J.; Roh, J. W.; Shim, W.; Ham, J.; Noh, J. S.; Lee, W. Advanced Materials 2011, 23, 3414.

[6] Fang, H. Y.; Yang, H. R.; Wu, Y. Chemistry of Materials 2014, 26, 3322.

[7] May, A. F.; Fleurial, J. P.; Snyder, G. J. Phys. Rev. B 2008, 78.

[8] Z. Li et al, Current Opinion in Solid State and Materials Science2008, 12, 1

[9] J. Szymczak et al.,Electrochem. Comm.2012, 24, 57

[10] Al-Salman, R.; Sommer, H.; Brezesinski, T.; Janek, J. Chemistry of Materials 2015, 27, 3830.

Figure 1: SEM (a) and HRTEM (b) images of Te nanostructures electrodeposited in EOPipTFSI ionic liquid