The Role of Connectivity on Electronic Properties of Lead Iodide Perovskite-Derived Compounds

Machteld E Kamminga, Gilles De Wijs, Remco W A Havenith, Graeme R Blake, Thomas T M Palstra

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Abstract

We use a layered solution crystal growth method to synthesize high-quality single crystals of two different benzylammonium lead iodide perovskite-like organic/inorganic hybrids. The well-known (C6H5CH2NH3)(2)PbI4 phase is obtained in the form of bright orange platelets, with a structure comprised of single <100 >-terminated sheets of corner-sharing PbI6 octahedra separated by bilayers of the organic cations. The presence of water during synthesis leads to formation of a novel minority phase that crystallizes in the form of nearly transparent, light yellow bar-shaped crystals. This phase adopts the monoclinic space group P2(1)/n and incorporates water molecules, with structural formula (C6H5CH2NH3)(4)Pb5I14 center dot 2H2O. The crystal structure consists of ribbons of edge-sharing PbI6 octahedra separated by the organic cations. Density functional theory calculations including spin orbit coupling show that these edge-sharing PbI6 octahedra cause the band gap to increase with respect to corner-sharing PbI6 octahedra in (C6H5CH2NH3)(2)PbI4. To gain systematic insight, we model the effect of the connectivity of PbI6 octahedra on the band gap in idealized lead iodide perovskite-derived compounds. We find that increasing the connectivity from corner-, via edge-, to face sharing causes a significant increase in the band gap. This provides a new mechanism to tailor the optical properties in organic/inorganic hybrid compounds.

Original languageEnglish
Pages (from-to)8408-8414
Number of pages7
JournalInorganic Chemistry
Volume56
Issue number14
DOIs
Publication statusPublished - 17-Jul-2017

Keywords

  • ORGANOMETAL HALIDE PEROVSKITE
  • SOLAR-CELL APPLICATIONS
  • AUGMENTED-WAVE METHOD
  • BROAD-BAND EMISSION
  • HYBRID PEROVSKITES
  • CRYSTAL
  • CH3NH3PBI3
  • PB
  • BR

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