Molecular electronics originally proposed that small molecules sandwiched between electrodes would accomplish electronic functions and enable ultimate scaling to be reached. However, so far, functional molecular devices have only been demonstrated at low frequency. Here, we demonstrate molecular diodes operating up to 17.8 GHz. Direct current and radio frequency (RF) properties were simultaneously measured on a large array of molecular junctions composed of gold nanocrystal electrodes, ferrocenyl undecanethiol molecules and the tip of an interferometric scanning microwave microscope. The present nanometre-scale molecular diodes offer a current density increase by several orders of magnitude compared with that of micrometre-scale molecular diodes, allowing RF operation. The measured S₁₁ parameters show a diode rectification ratio of 12 dB which is linked to the rectification behaviour of the direct current conductance. From the RF measurements, we extrapolate a cut-off frequency of 520 GHz. A comparison with the silicon RF-Schottky diodes, architecture suggests that the RF-molecular diodes are extremely attractive for scaling and high-frequency operation.

E-beam lithography has been used for reliable and versatile fabrication of sub-15 nm single-crystal gold nanoarrays and led to convincing applications in nanotechnology. However, so far this technique was either too slow for centimeter to wafer-scale writing or fast enough with the so-called dot on the fly (DOTF) technique but not optimized for sub-15 nm dots dimension. This prevents use of this technology for some applications and characterization techniques. Here, we show that the DOTF technique can be used without degradation in dots dimension. In addition, we propose two other techniques. The first one is an advanced conventional technique that goes five times faster than the conventional one. The second one relies on sequences defined before writing which enable versatility in e-beam patterns compared to the DOTF technique with same writing speed. By comparing the four different techniques, we evidence the limiting parameters for the writing speed. Wafer-scale fabrication of such arrays with 50 nm pitch allowed XPS analysis of a ferrocenylalkyl thiol self-assembled monolayer coated gold nanoarray.

Lack of reproducibility hampers molecular devices integration into large-scale circuits. Thus, incorporating operando characterization can facilitate the understanding of multiple features producing disparities in different devices. In this work, we report the realization of hybrid molecular graphene field effect transistors (m-GFETs) based on 11-(Ferrocenyl)undecanethiol (FcC₁₁SH) micro self-assembled monolayers (μSAMs) and high-quality graphene (Gr) in a back-gated configuration. On the one hand, Gr enables redox electron transfer, avoids molecular degradation and permits operando spectroscopy. On the other hand, molecular electrode decoration shifts the Gr Dirac point (V_DP) to neutrality and generates a photocurrent in the Gr electron conduction regime. Benefitting from this heterogeneous response, the m-GFETs can implement optoelectronic AND/OR logic functions. Our approach represents a step forward in the field of molecular scale electronics with implications in sensing and computing based on sustainable chemicals.