Molecular engineering versus energy level alignment:: Interface formation between oligothiophene derivatives and a metal substrate studied with photoemission spectroscopy

Two series of thin films of oligothiophene derivatives grown on Ag substrates have been studied with photoelectron spectroscopy. The oligothiophenes were end-capped with either electron-deficient (dismesitylboryl) or electron-rich (diphenyltolylamine) moieties to create molecules with electron-accepting or -donating properties, respectively. The position of the highest occupied molecular orbital (HOMO) at the metal/organic interface is found to be strongly dependent on the effective pi-conjugation length of the oligothiophenes capped with dimesitylboryl groups, whereas in the oligothiophenes capped with diphenyltolylamine, the position of the HOMO is independent of the molecular length. The difference in the observed HOMO characteristics is attributed to the different make-up of the frontier orbitals in the two molecular series. This will particularly affect the overall energy barrier for charge injection at the conductor/organic interface in a device structure, such as an organic light-emitting diode, utilizing the investigated molecules for carrier injection and transport. (C) 2002 American Institute of Physics.