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We tested the theoretical prediction that the band structures on the opposite sides of a homojunction can be artificially displaced in energy with respect to each other by means of double intralayers of atomiclike thickness, producing band discontinuities of potential interest for practical applications. Evidence of such discontinuities was found when Ga-As, Al-As, Ga-P, or Al-P intralayers were inserted between Si and Si or Ge and Ge.