Single Molecules in Strong Optical Fields: A Variable-Temperature Molecular Junction Spectroscopy Setup.

In order to advance the development of molecular electronic devices, it is mandatory to improve the understanding of electron transport and functionalities in single molecules, integrated in a well-defined environment. However, limited information can be obtained by solely analyzing I-V characteristics, whence multiparameter studies are required to obtain more information on such systems including chemical bonds, geometry, and intramolecular strain. Therefore, we developed an analytical method incorporating an optical near-field technique, which allows us to investigate single-molecule junctions at variable temperatures in strong optical fields. An apertureless near-field emitter acts as a counter electrode and a plasmonic waveguide to focus surface plasmon polaritons into the molecular junctions, where a strongly enhanced evanescent field is confined to only a few nanometers around the apex of the tip. The proof of concept, even at low temperatures, is demonstrated by simultaneously investigating electronic and optical features of the molecule p-terphenyl-4,4″-dithiol in dependence of its charge state. This multichannel method can be employed to analyze a variety of nearly unexplored properties in single-molecule junctions such as photoconductance and photocurrent generation and allows a characterization of the molecular junctions by spectroscopic means as well.

Voltage-Driven Conformational Switching with Distinct Raman Signature in a Single-Molecule Junction.

Precisely controlling well-defined, stable single-molecule junctions represents a pillar of single-molecule electronics. Early attempts to establish computing with molecular switching arrays were partly challenged by limitations in the direct chemical characterization of metal-molecule-metal junctions. While cryogenic scanning probe studies have advanced the mechanistic understanding of current- and voltage-induced conformational switching, metal-molecule-metal conformations are still largely inferred from indirect evidence. Hence, the development of robust, chemically sensitive techniques is instrumental for advancement in the field. Here we probe the conformation of a two-state molecular switch with vibrational spectroscopy, while simultaneously operating it by means of the applied voltage. Our study emphasizes measurements of single-molecule Raman spectra in a room-temperature stable single-molecule switch presenting a signal modulation of nearly 2 orders of magnitude.