Interstitially Mixed Self-Assembled Monolayers Enhance Electrical Stability of Molecular Junctions

Gyu Don Kong, Hyunsun Song, Seungmin Yoon, Hungu Kang, Rakwoo Chang, Hyo Jae Yoon

Research output: Contribution to journalArticlepeer-review

39 Scopus citations


Electrical breakdown is a critical problem in electronics. In molecular electronics, it becomes more problematic because ultrathin molecular monolayers have delicate and defective structures and exhibit intrinsically low breakdown voltages, which limit device performances. Here, we show that interstitially mixed self-assembled monolayers (imSAMs) remarkably enhance electrical stability of molecular-scale electronic devices without deteriorating function and reliability. The SAM of the sterically bulky matrix (SC11BIPY rectifier) molecule is diluted with a skinny reinforcement (SCn) molecule via the new approach, so-called repeated surface exchange of molecules (ReSEM). Combined experiments and simulations reveal that the ReSEM yields imSAMs wherein interstices between the matrix molecules are filled with the reinforcement molecules and leads to significantly enhanced breakdown voltage inaccessible by traditional pure or mixed SAMs. Thanks to this, bias-driven disappearance and inversion of rectification is unprecedentedly observed. Our work may help to overcome the shortcoming of SAM's instability and expand the functionalities.

Original languageEnglish
Pages (from-to)3162-3169
Number of pages8
JournalNano Letters
Issue number7
StatePublished - 14 Apr 2021


  • electrical breakdown
  • electrical stability
  • interstitially mixed self-assembled monolayers (imSAMs)
  • repeated surface exchange of molecules (ReSEM)
  • tunneling junctions


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