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Energy band calculations revealed that Cu-Ch hybridized bands only spread in the (Cu2Ch2)2- layers, which suggests that hole carriers in these bands are confined by the potential barriers formed by the (Ln2O2)2+ layers. Stepwise absorption spectra of a series of LnCuOCh experimentally verified that an exciton in the (Cu2Ch2)2- layers shows a two-dimensional behavior. These theoretical and experimental results indicate that LnCuOCh has “natural multiple quantum wells” built into its layered 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