Correlation of frontier orbital positions and conduction type of molecular semiconductors as derived from UPS in combination with electrical and photoelectrochemical experiments

D. Schlettwein, Neal R Armstrong

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84 Citations (Scopus)

Abstract

He I photoelectron spectra collected from selected phthalocyanine thin films on Au substrates have been used to determine the position of the highest occupied orbitals and threshold ionization potentials in the solid state. Relative as well as absolute positions are given. Chemical modifications of these dyes (substitution of nitrogen heteroatoms to create the pyrido- or pyrazinotetraazaporphyrin complexes, addition of electron-withdrawing substituents to the ring periphery) and changes in the crystal structure of the solid affect the size of the frontier orbital (band) gap and especially the absolute HOMO and LUMO energies. The influence of different substituents with varying electron-donating or electron-accepting properties is investigated in detail. Photoemission data are compared with redox potentials and molecular orbital (MO) calculations from the literature. The frontier orbital positions strongly correlate with the conduction type of the thin film, the nature of electrical property changes seen during interactions with gases such as O2 and NH3, and the photoelectrochemical properties in different aqueous electrolytes.

Original languageEnglish (US)
Pages (from-to)11771-11779
Number of pages9
JournalJournal of Physical Chemistry
Volume98
Issue number45
StatePublished - Jan 1 1994
Externally publishedYes

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Semiconductor materials
conduction
orbitals
Electrons
Thin films
Orbital calculations
Ionization potential
Experiments
Chemical modification
Photoemission
Molecular orbitals
Photoelectrons
Electrolytes
electrons
Electric properties
Energy gap
Substitution reactions
Coloring Agents
Nitrogen
Dyes

ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

Cite this

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title = "Correlation of frontier orbital positions and conduction type of molecular semiconductors as derived from UPS in combination with electrical and photoelectrochemical experiments",
abstract = "He I photoelectron spectra collected from selected phthalocyanine thin films on Au substrates have been used to determine the position of the highest occupied orbitals and threshold ionization potentials in the solid state. Relative as well as absolute positions are given. Chemical modifications of these dyes (substitution of nitrogen heteroatoms to create the pyrido- or pyrazinotetraazaporphyrin complexes, addition of electron-withdrawing substituents to the ring periphery) and changes in the crystal structure of the solid affect the size of the frontier orbital (band) gap and especially the absolute HOMO and LUMO energies. The influence of different substituents with varying electron-donating or electron-accepting properties is investigated in detail. Photoemission data are compared with redox potentials and molecular orbital (MO) calculations from the literature. The frontier orbital positions strongly correlate with the conduction type of the thin film, the nature of electrical property changes seen during interactions with gases such as O2 and NH3, and the photoelectrochemical properties in different aqueous electrolytes.",
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N2 - He I photoelectron spectra collected from selected phthalocyanine thin films on Au substrates have been used to determine the position of the highest occupied orbitals and threshold ionization potentials in the solid state. Relative as well as absolute positions are given. Chemical modifications of these dyes (substitution of nitrogen heteroatoms to create the pyrido- or pyrazinotetraazaporphyrin complexes, addition of electron-withdrawing substituents to the ring periphery) and changes in the crystal structure of the solid affect the size of the frontier orbital (band) gap and especially the absolute HOMO and LUMO energies. The influence of different substituents with varying electron-donating or electron-accepting properties is investigated in detail. Photoemission data are compared with redox potentials and molecular orbital (MO) calculations from the literature. The frontier orbital positions strongly correlate with the conduction type of the thin film, the nature of electrical property changes seen during interactions with gases such as O2 and NH3, and the photoelectrochemical properties in different aqueous electrolytes.

AB - He I photoelectron spectra collected from selected phthalocyanine thin films on Au substrates have been used to determine the position of the highest occupied orbitals and threshold ionization potentials in the solid state. Relative as well as absolute positions are given. Chemical modifications of these dyes (substitution of nitrogen heteroatoms to create the pyrido- or pyrazinotetraazaporphyrin complexes, addition of electron-withdrawing substituents to the ring periphery) and changes in the crystal structure of the solid affect the size of the frontier orbital (band) gap and especially the absolute HOMO and LUMO energies. The influence of different substituents with varying electron-donating or electron-accepting properties is investigated in detail. Photoemission data are compared with redox potentials and molecular orbital (MO) calculations from the literature. The frontier orbital positions strongly correlate with the conduction type of the thin film, the nature of electrical property changes seen during interactions with gases such as O2 and NH3, and the photoelectrochemical properties in different aqueous electrolytes.

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