Experiment-Driven Modeling of Crystalline Phosphorus Nitride P3 N5 : Wide-Ranging Implications from a Unique Structure.
Nitridophosphates have emerged as advanced materials due to their structural variability and broad technical applicability. Their binary parent compound P3 N5 , a polymeric network of corner- and edge-sharing PN4 tetrahedra with N and N sites, is a particularly interesting example. We present a study of the band gap and electronic structure of α-P3 N5 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-P3 N5 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.
Department of Physics and Engineering Physics, University of Saskatchewan, 116 Science Place, Saskatoon, Saskatchewan, S7N 5E2, Canada.
Thomas M
TM
Tolhurst
Karlsruher Institut für Technologie (KIT Karlsruhe), Institut für Angewandte Materialien-Energiespeichersysteme (IAM-ESS), Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany.|Fachbereich Material- und Geowissenschaften, Fachgebiet Strukturforschung, TU Darmstadt, Alarich-Weiss-Straße 2, 64287, Darmstadt, Germany.
Cordula
C
Braun
Department of Physics and Engineering Physics, University of Saskatchewan, 116 Science Place, Saskatoon, Saskatchewan, S7N 5E2, Canada.
Teak D
TD
Boyko
Department of Chemistry, University of Munich (LMU), Butenandtstrasse 5-13, 81377, Munich, Germany.
Wolfgang
W
Schnick
Department of Physics and Engineering Physics, University of Saskatchewan, 116 Science Place, Saskatoon, Saskatchewan, S7N 5E2, Canada. alex.moewes@usask.ca.
Alexander
http://orcid.org/0000-0002-9218-2280
A
Moewes
X-ray spectroscopy; band gap; density functional theory; electronic structure; nitrides