Thickness-Dependent Charge Transport in Three Dimensional Ru(II)- Tris(phenanthroline)-Based Molecular Assemblies.

Gupta, Ritu; Bhandari, Shapath; Kaya, Savas; Katin, Konstantin P; Mondal, Prakash Chandra · Nano Lett · 2023

basic_science · Level V

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Abstract

We describe here the fabrication of large-area molecular junctions with a configuration of ITO/[Ru(Phen)<sub>3</sub>]/Al to understand temperature- and thickness-dependent charge transport phenomena. Thanks to the electrochemical technique, thin layers of electroactive ruthenium(II)-tris(phenanthroline) [Ru(Phen)<sub>3</sub>] with thicknesses of 4-16 nm are covalently grown on sputtering-deposited patterned ITO electrodes. The bias-induced molecular junctions exhibit symmetric current-voltage (j-V) curves, demonstrating highly efficient long-range charge transport and weak attenuation with increased molecular film thickness (β = 0.70 to 0.79 nm<sup>-1</sup>). Such a lower β value is attributed to the accessibility of Ru(Phen)<sub>3</sub> molecular conduction channels to Fermi levels of both the electrodes and a strong electronic coupling at ITO-molecules interfaces. The thinner junctions (d = 3.9 nm) follow charge transport via resonant tunneling, while the thicker junctions (d = 10-16 nm) follow thermally activated (activation energy, E<sub>a</sub> ∼ 43 meV) Poole-Frenkel charge conduction, showing a clear "molecular signature" in the nanometric junctions.