Photocurrent generation from semiconducting manganese oxide nanosheets in response to visible light.

Unilamellar nanosheet crystallites of manganese oxide generated the anodic photocurrent under visible light irradiation (lambda < 500 nm), while the nanosheets themselves were stable as revealed by in-plane XRD and UV-visible absorption spectra. The band gap energy was estimated to be 2.23 eV on the basis of the photocurrent action spectrum. The molecular thickness of approximately 0.5 nm may facilitate the charge separation of excited electrons and holes, which is generally very difficult for strongly localized d-d transitions. The monolayer film of MnO2 nanosheets exhibited the incident photon-to-electron conversion efficiency of 0.16% in response to the monochromatic light irradiation (lambda = 400 nm), which is comparable to those for sensitization of monolayer dyes adsorbed on a flat single-crystal surface. The efficiency declined with increasing the layer number of MnO2 nanosheets, although the optical absorption was enhanced. The recombination of the excited electron-hole pairs may become dominant when the carriers need to migrate a longer distance than 1 layer through multilayered nanosheets.