Experiment‐Driven Modeling of Crystalline Phosphorus Nitride P3N5: Wide‐Ranging Implications from a Unique Structure |
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Authors: | Thomas M. Tolhurst Dr. Cordula Braun Dr. Teak D. Boyko Prof. Dr. Wolfgang Schnick Prof. Dr. Alexander Moewes |
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Affiliation: | 1. Department of Physics and Engineering Physics, University of Saskatchewan, Saskatoon, Saskatchewan, Canada;2. Karlsruher Institut für Technologie (KIT Karlsruhe), Institut für Angewandte Materialien-Energiespeichersysteme (IAM-ESS), Eggenstein-Leopoldshafen, Germany;3. Fachbereich Material- und Geowissenschaften, Fachgebiet Strukturforschung, TU Darmstadt, Darmstadt, Germany;4. Department of Chemistry, University of Munich (LMU), Munich, Germany |
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Abstract: | Nitridophosphates have emerged as advanced materials due to their structural variability and broad technical applicability. Their binary parent compound P3N5, a polymeric network of corner‐ and edge‐sharing PN4 tetrahedra with N 2 and N 3 sites, is a particularly interesting example. We present a study of the band gap and electronic structure of α‐P3N5 by using soft X‐ray spectroscopy measurements and DFT calculations. The band gap, which is crucial for all applications, is measured to be 5.87±0.20 eV. This agrees well with the calculated, indirect band gap of 5.21 eV. The density of states are found to show dramatic variation between the nonequivalent N sites and a high degree of covalency. Coupled to these results is what is, to our knowledge, the largest core hole shift reported to date for a soft X‐ray absorption spectrum. We propose an intuitive bonding scheme for α‐P3N5 that explains the observed band gap and unique density of states, while providing a framework for predicting these properties in known and yet to be discovered PN compounds. We briefly consider the implications of these results for new low‐dimensional P and PN materials, which alongside graphene, could become important materials for nanoelectronics. |
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Keywords: | band gap density functional theory electronic structure nitrides X-ray spectroscopy |
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