In this discussion paper we discuss our recent results on the electrodeposition of materials and in situ STM/AFM measurements which demonstrate that ionic liquids should not be regarded as neutral solvents which all have similar properties. In particular, we focus on differences in interfacial structure (solvation layers) on metal electrodes as a function of ionic liquid species. Recent theoretical and experimental results show that conventional double layers do not form on metal electrodes in ionic liquid systems. Rather, a multilayer architecture is present, with the number of layers determined by the ionic liquid species and the properties of the surface; up to seven discrete interfacial solvent layers are present on electrode surfaces, consequently there is no simple electrochemical double layer. Both the electrodeposition of aluminium and of tantalum are strongly influenced by ionic liquids: in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide, [Py(1,4)]TFSA, aluminium is obtained as a nanomaterial, whereas in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide, [EMIm]TFSA, a microcrystalline material is made. Tantalum can be deposited from [Py(1,4)]TFSA, whereas from [EMIm]TFSA only non-stoichiometric tantalum fluorides TaF(x) are obtained. It is likely that solvation layers influence these reactions.

The electrodeposition of Ge, Si and, for the first time, of Si(x)Ge(1-x) from the air- and water-stable ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([Py(1,4)]Tf(2)N) containing GeCl(4) and/or SiCl(4) as precursors is investigated by cyclic voltammetry and high-resolution scanning electron microscopy. GeCl(2) in [Py(1,4)]Tf(2)N is electrochemically prepared in a two-compartment cell to be used as Ge precursor instead of GeCl(4) in order to avoid the chemical attack of Ge(iv) on deposited Ge. Silicon, germanium and Si(x)Ge(1-x) can be deposited reproducibly and easily in this ionic liquid. Interestingly, the Si(x)Ge(1-x) deposit showed a strong colour change (from red to blue) at room temperature during electrodeposition, which is likely to be due to a quantum size effect. The observed colours are indicative of band gaps between at least 1.5 and 3.2 eV. The potential of ionic liquids in Si(x)Ge(1-x) electrodeposition is demonstrated.

In this paper we report for the first time on the room temperature template synthesis of germanium and silicon nanowires by potentiostatic electrochemical deposition from the air- and water stable ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([Py(1,4)]Tf(2)N) containing GeCl(4) and SiCl(4) as a Ge and Si source, respectively. Commercially-available track-etched polycarbonate membranes (PC) with an average nominal pore diameter of 90-400 nm were used as templates. Ge and Si nanowires with an average diameter corresponding to the nanopores' diameter and lengths of a few micrometres were reproducibly obtained. Structural characterization of the nanowires was performed by EDX, TEM, HR-SEM and Raman spectroscopy. Despite the rough surface of the nanowires, governed mostly by the original shape of the nanopore's wall of the commercially-available PC membrane, preliminary structural characterizations demonstrate the promising prospective of this innovative elaboration process compared to constraining high vacuum and high temperature methods.

A promising method for the production of germanium photonic crystals consists of electrodeposition of Ge from GeCl(4)-containing ionic liquids inside templates of polystyrene colloidal crystals and subsequent removal of the template. This room-temperature method gives rise to the fabrication of a three-dimensional highly ordered macroporous germanium nanostructure (see picture; scale: 2 microm) as a prototype of a photonic crystal.

A facile low-temperature and template-free synthesis route to high aspect ratio Sn nanowires is described. The nanowires are prepared by electrochemical deposition from SnCl 4 /ionic liquid solutions containing SiCl 4 onto a variety of substrates, including glassy carbon as well as Cu, Al, and Sn foils. SiCl 4 is found to strongly promote the growth of nanowires under specific conditions, while only bulk structures are achieved in the absence of SiCl 4 . The nanowires exhibit a unique hair-like morphology with very high areal density (≥5 × 10 9 cm −2 ), and they have diameters in the sub-30 nm size range over lengths of up to 90 μm, leading to aspect ratios as high as 5 × 10 3 . Diffraction, spectroscopy, and microscopy studies establish that the nanowires are of high quality and consist of single phase, anisometric β-Sn crystallites. The morphology of the deposits is very uniform over centimeter-sized areas and can be tailored by changing key parameters such as the concentration of SiCl 4 and/or SnCl 4 and the electrode potential. Perhaps more importantly, this approach is not restricted to the synthesis of Sn nanowires and can be applied to other metals and semimetals with an anisotropic crystal structure (e.g., Zn and Te).