Electron transport through self-assembled monolayers of tripeptides

TL;DR

This study investigates how copper ion complexation affects electron transport and work function in GGH peptide monolayers, revealing density-dependent conformational and electronic changes with implications for molecular electronics.

Contribution

It demonstrates the density-dependent effects of Cu2+ complexation on electron transport and work function in peptide monolayers, supported by experimental and first-principles calculations.

Findings

Copper complexation increases work functions systematically.

Low-density monolayers show enhanced electron transport upon Cu2+ binding.

High-density monolayers become more insulating after copper complexation.

Abstract

We report how the electron transport through a solid-state metal/Gly-Gly-His tripeptide (GGH) monolayer/metal junction and the metal/GGH work function are modified by the GGH complexation with Cu2+ ions. Conducting AFM is used to measure the current-voltage histograms. The work function is characterized by combining macroscopic Kelvin probe and Kelvin probe force microscopy at the nanoscale. We observe that the Cu2+ ions complexation with the GGH monolayer is highly dependent on the molecular surface density and results in opposite trends. In the case of a high density monolayer the conformational changes are hindered by the proximity of the neighboring peptides, hence forming an insulating layer in response to copper-complexation. Whereas the slightly lower density monolayers allow for the conformational change to a looped peptide wrapping the Cu-ion, which results in a more conductive monolayer. Copper-ion complexation to the high- and low-density monolayers systematically induces an increase of the work functions. Copper-ion complexation to the low-density monolayer induces an increase of electron transport efficiency, while the copper-ion complexation to the high-density monolayer results in a slight decrease of electron transport. Both of the observed trends are in agreement with first-principle calculations. Complexed copper to low density GGH-monolayer induces a new gap state slightly above the Au Fermi energy that is absent in the high density monolayer.