We have studied the electronic structure at the heterointerface between the band insulators LaAlO3 and SrTiO3 using in situ photoemission spectroscopy. Our experimental results clearly reveal the formation of a notched structure on the SrTiO3 side due to band bending at the metallic LaAlO3=TiO2-SrTiO3 interface. The structure, however, is absent at the insulating LaAlO3=SrO-SrTiO3 interface. The present results indicate that the metallic states originate not from the charge transfer through the interface on a short-range scale but from the accumulation of carriers on a long-range scale.
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