Traditional Marcus theory accounts for electron transfer reactions in solutions, and the polarity of solvent molecule matters for them. How such an environment polarity affects electron transfer reactions in solid-state devices, however, remains uncertain. This paper describes how the Marcus inverted charge transport is influenced by solid-state molecular dilution in large-area tunneling junctions. A monolayer of 2,2′-bipyridyl terminated n-alkanethiolate (SC11BIPY), which rectifies currents via electron hopping within the inverted regime, is diluted with n-alkanethiolate (SCn) of different lengths (n = 8, 10, or 18) or at different surface mole fractions. The dilution introduces nonpolar environments within the monolayer, hinders stabilization of charged BIPY species upon electron hopping, and pushes the equilibrium of BIPY ⇄ BIPY•- process toward the reverse direction. Our work demonstrates that solid-state molecular dilution permits systematic control of the environment polarity of active component in nanoscale devices, much like solvent polarity control in solution, and their performances.
Bibliographical noteFunding Information:
This research was supported by the NRF of Korea (NRF-2019R1A2C2011003 and NRF-2019R1A6A1A11044070).
© 2021 American Chemical Society.
ASJC Scopus subject areas
- Materials Science(all)
- Physical and Theoretical Chemistry