Solid State Dilution Controls Marcus Inverted Transport in Rectifying Molecular Junctions

Hungu Kang, Gyu Don Kong, Hyo Jae Yoon

Research output: Contribution to journalArticlepeer-review

16 Citations (Scopus)


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.

Original languageEnglish
Pages (from-to)982-988
Number of pages7
JournalJournal of Physical Chemistry Letters
Issue number3
Publication statusPublished - 2021 Jan 28

Bibliographical note

Funding Information:
This research was supported by the NRF of Korea (NRF-2019R1A2C2011003 and NRF-2019R1A6A1A11044070).

Publisher Copyright:
© 2021 American Chemical Society.

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry


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