Site-specific intermolecular valence-band dispersion in α-phase crystalline films of cobalt phthalocyanine studied by angle-resolved photoemission spectroscopy.

Abstract

The valence band structure of α-phase crystalline films of cobalt phthalocyanine (CoPc) grown on Au(111) is investigated by using angle-resolved photoemission spectroscopy (ARPES) with synchrotron radiation. The photo-induced change in the ARPES peaks is noticed in shape and energy of the highest occupied molecular orbital (HOMO, C 2p) and HOMO-1 (Co 3d) of CoPc, and is misleading the interpretation of the electronic properties of CoPc films. From the damage-free normal-emission ARPES measurement, the clear valence-band dispersion has been first observed, showing that orbital-specific behaviors are attributable to the interplay of the intermolecular π-π and π-d interactions. The HOMO band dispersion of 0.1 eV gives the lower limit of the hole mobility for α-CoPc of 28.9 cm(2)V(-1)s(-1) at 15 K. The non-dispersive character of the split HOMO-1 bands indicates that the localization of the spin state is a possible origin of the antiferromagnetism.