Energy Level Alignment of Organic Molecules with Chemically Modified Alkanethiolate Self-Assembled Monolayers

Masahiro Shibuta, Munehisa Ogura, Toyoaki Eguchi, Atsushi Nakajima

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

We have employed two-photon photoemission spectroscopy to nondestructively resolve the unoccupied energy levels of fullerene C60 molecules deposited on alkanethiolate self-assembled monolayers (SAMs). By fluorine substitution of the hydrogen atoms in the alkyl chain, the work function (WF) increased from 4.3 eV for the alkanethiolate-SAM (H-SAM) to 5.7 eV for the fluorine-substituted SAM (F-SAM), owing to the formation of surface dipole layers. When C60 is deposited on the H-SAM and F-SAM, the energy positions of the unoccupied/occupied levels of C60 are pinned to the vacuum level (Fermi level (EF) + WF). As a result of the energy level alignment, on the F-SAM, the relative energy from EF of the highest occupied molecular orbital of C60 almost equals that of the lowest unoccupied molecular orbital, implying that the C60 film on the F-SAM exhibits both p- and n-type (ambipolar) charge transport properties, while C60 is known as a typical n-type semiconductor. The energetics are preserved even with multilayered C60 films at least up to ∼5 nm in thickness, showing that the dipole layers induced by SAMs are robust against molecular overlayers. Such a spectroscopic study on the energy levels for organic films will be of importance for further development of organic thin film devices.

Original languageEnglish
Pages (from-to)27399-27405
Number of pages7
JournalJournal of Physical Chemistry C
Volume121
Issue number49
DOIs
Publication statusPublished - 2017 Dec 14

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

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