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The doping behavior of Cd atoms in the CuInSe2 thin films and their influences on electronic structures are investigated. The doped Cd atoms replace Cu atoms and prefer to stay at the (112) surface of the thin films. They combine with Cu vacancies to form defect pairs due to low formation energy. The Cd atom does not by itself modify significantly the electronic structure of the surface, but the defect pairs have important influences. They result in a down shift of valence band maximum and form a hole barrier at the surface, which can prevent holes from reaching the surface and reduce the recombination of carriers.

(112) Surface of CuInSe2 Thin Films with Doped Cd Atoms