Simultaneous Determination of Conductance and Thermopower of Single Molecule Junctions

TL;DR

This study introduces a method to simultaneously measure conductance and thermopower of single-molecule junctions, revealing their relationship and confirming theoretical predictions with high precision.

Contribution

It is the first to concurrently determine conductance and thermopower of single-molecule junctions using a scanning tunneling microscope-based technique.

Findings

Seebeck coefficient is negative for LUMO-conducting junctions and positive for HOMO-conducting junctions.

No strong temperature dependence of the Seebeck coefficient within 30 K gradients.

Power factor GS^2 increases with conductance G.

Abstract

We report the first concurrent determination of conductance (G) and thermopower (S) of single-molecule junctions via direct measurement of electrical and thermoelectric currents using a scanning tunneling microscope-based break-junction technique. We explore several amine-Au and pyridine-Au linked molecules that are predicted to conduct through either the highest occupied molecular orbital (HOMO) or the lowest unoccupied molecular orbital (LUMO), respectively. We find that the Seebeck coefficient is negative for pyridine-Au linked LUMO-conducting junctions and positive for amine-Au linked HOMO-conducting junctions. Within the accessible temperature gradients (<30 K), we do not observe a strong dependence of the junction Seebeck coefficient on temperature. From histograms of 1000's of junctions, we use the most probable Seebeck coefficient to determine a power factor, GS^2, for each junction studied, and find that GS^2 increases with G. Finally, we find that conductance and Seebeck coefficient values are in good quantitative agreement with our self-energy corrected density functional theory calculations.