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Substituting fluorine for hydrogen in self-assembled monolayers (SAMs) significantly lowers charge transport rates. This finding impacts the design of molecular electronic devices by revealing how fluorination affects tunneling currents.

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Area of Science:

  • Materials Science
  • Organic Electronics
  • Surface Chemistry

Background:

  • Charge transport through molecular junctions is crucial for molecular electronics.
  • Self-assembled monolayers (SAMs) are used to control interfaces in electronic devices.
  • Fluorination of organic molecules can alter their electronic properties.

Purpose of the Study:

  • To investigate the effect of fluorine substitution on charge transport rates in molecular junctions.
  • To compare the tunneling behavior of perfluorinated and hydrocarbon-based SAMs.
  • To identify the interface responsible for changes in charge transport.

Main Methods:

  • Fabrication of Ag(TS)O2C(CH2)n(CF2)(m)T//Ga2O3/EGaIn junctions with varying SAMs.
  • Measurement of current densities and analysis using the Simmons equation.
  • Comparative study of terminal fluorine substituents in ω-tolyl- and -phenyl-alkanoates.

Main Results:

  • Perfluorinated SAMs exhibited 20-30 times lower current densities than hydrocarbon analogs.
  • Attenuation factors for methylene and difluoromethylene groups were similar but higher for difluoromethylene.
  • The C-F//Ga2O3 interface was identified as the primary site for reduced tunneling currents.

Conclusions:

  • Fluorine substitution in SAMs decreases charge transport rates, likely by increasing the tunneling barrier height or altering interfacial interactions.
  • The terminal CF3 group significantly impacts tunneling, suggesting interface-specific effects.
  • Understanding these effects is key for designing functional molecular electronic components.