The effect of dimensional confinement on the optical band gap of SrTiO3 is investigated by periodically introducing one extra SrO monolayer every n SrTiO3 layers. The result is the n = 1–5 and 10 members of the Srn+1TinO3n+1 Ruddlesden-Popper homologous series. Spectroscopic ellipsometry, optical transmission, and cathodoluminescence measurements reveal these Srn+1TinO3n+1 phases to have indirect optical band gaps at room temperature with values that decrease monotonically with increasing n. First-principles calculations suggest that as n increases and the TiO6 octahedra become connected for increasing distances along the c-axis, the band edge electronic states become less confined. This is responsible for the decrease in band gaps with increasing n (for finite n) among Srn+1TinO3n+1 phases.
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