We studied LaAlO3/SrTiO3 interfaces for varying LaAlO3 thickness by
core-level photoemission spectroscopy. In Ti 2p spectra for conducting "n-type"
interfaces, Ti3+ signals appeared, which were absent for insulating "p-type"
interfaces. The Ti3+ signals increased with LaAlO3 thickness, but started well
below the critical thickness of 4 unit cells for metallic transport. Core-level
shifts with LaAlO3 thickness were much smaller than predicted by the polar
catastrophe model. We attribute these observations to surface
defects/adsorbates providing charges to the interface even below the critical
thickness