Large Increase in the Dielectric Constant and Partial Loss of Coherence Increases Tunneling Rates across Molecular Wires

Xiaoping Chen, Teddy Salim, Ziyu Zhang, Xiaojiang Yu, Ira Volkova, Christian A. Nijhuis*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

17 Citations (Scopus)
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Although the dielectric behavior of monolayers is important in a large range of applications, its role in charge transport studies involving molecular junctions is largely ignored. This paper describes a large increase in the relative static dielectric constant (ϵr) by simply increasing the thickness of well-organized monolayers of oligoglycine and oligo(ethylene glycol) from 7 up to 14. The resulting large capacitance of 3.5-5.1 μF/cm2 is thickness-independent, which is highly attractive for field-effect transistor applications. This increase of ϵr results in a linear increase of the thermal activation energy by a factor of 6, which suggests that the mechanism of charge transport gradually changes from coherent to (partially) incoherent tunneling. The comparisons of oligoglycine (which readily forms hydrogen bonds with neighboring molecules) and methyl terminated oligo(ethylene glycol) (which lacks hydrogen bond donors) monolayers, kinetic isotope effects, and relative humidity-dependent measurements all indicate the importance of strong hydrogen bonds involving ionic species and strongly bonded water in the unusual dielectric behavior and the incoherent tunneling mechanism. This partial loss of coherence of the charge carriers can explain the unusually small tunneling decay coefficients across long molecular wires, and the length-dependent increase of ϵr of monolayers opens up interesting new applications.

Original languageEnglish
Pages (from-to)45111-45121
Number of pages11
JournalACS applied materials & interfaces
Issue number40
Publication statusPublished - 7 Oct 2020
Externally publishedYes


  • dielectric constant
  • capacitance
  • charge transport mechanism
  • self-assembled monolayers
  • molecular junctions


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