From a free electron gas to confined states: A mixed island of PTCDA and copper phthalocyanine on Ag(111)

When perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) is deposited on the Ag(111) surface at submonolayer coverage, it forms islands under which the native Shockley state of the Ag(111) surface can no longer be found. Previous work has shown that this state shifts upwards to form a new interface state starting at 0.6 V above the Fermi level, having properties of a two-dimensional electron gas (2DEG). We investigated mixed islands of PTCDA and copper phthalocyanine (CuPc) to study the change in the electronic state with the addition of an electron donor. We no longer observe a 2DEG state and instead identify states at 0.46 and 0.79 V. While one state appears in dI/dV images as an array of one-dimensional quantum wells, our analysis shows that this state does not act as a free electron gas and that the features are instead localized above individual PTCDA molecules.