Revealing Phosphorus Nitrides up to the Megabar Regime: Synthesis of α'-P3 N5, δ-P3 N5 and PN2

Dominique Laniel; Florian Trybel; Adrien Néri; Yuqing Yin; Andrey Aslandukov; Timofey Fedotenko; Saiana Khandarkhaeva; Ferenc Tasnádi; Stella Chariton; Carlotta Giacobbe; Eleanor Lawrence Bright; Michael Hanfland; Vitali Prakapenka; Wolfgang Schnick; Igor A Abrikosov; Leonid Dubrovinsky; Natalia Dubrovinskaia

doi:10.1002/chem.202201998

Revealing Phosphorus Nitrides up to the Megabar Regime: Synthesis of α'-P₃ N_5, δ-P₃ N₅ and PN₂

Chemistry. 2022 Nov 7;28(62):e202201998. doi: 10.1002/chem.202201998. Epub 2022 Oct 17.

Authors

Dominique Laniel^{1

2}, Florian Trybel³, Adrien Néri⁴, Yuqing Yin^{1

5}, Andrey Aslandukov^{1

4}, Timofey Fedotenko⁶, Saiana Khandarkhaeva⁴, Ferenc Tasnádi³, Stella Chariton⁷, Carlotta Giacobbe⁸, Eleanor Lawrence Bright⁸, Michael Hanfland⁸, Vitali Prakapenka⁷, Wolfgang Schnick⁹, Igor A Abrikosov³, Leonid Dubrovinsky⁴, Natalia Dubrovinskaia^{1

3}

Affiliations

¹ Material Physics and Technology at Extreme Conditions, Laboratory of Crystallography, University of Bayreuth, 95440, Bayreuth, Germany.
² Centre for Science at Extreme Conditions and School of Physics and Astronomy, University of Edinburgh, EH9 3FD, Edinburgh, UK.
³ Department of Physics, Chemistry and Biology (IFM), Linköping University, 58183, Linköping, Sweden.
⁴ Bayerisches Geoinstitut, University of Bayreuth, 95440, Bayreuth, Germany.
⁵ State Key Laboratory of Crystal Materials, Shandong University, Jinan, 250100, P. R. China.
⁶ Deutsches Elektronen-Synchrotron, Notkestr. 85, 22607, Hamburg, Germany.
⁷ Center for Advanced Radiation Sources, University of Chicago, Chicago, IL 60637, USA.
⁸ European Synchrotron Radiation Facility, B.P. 220, 38043, Grenoble Cedex, France.
⁹ Department of Chemistry, University of Munich (LMU), Butenandtstrasse 5-13, 81377, Munich, Germany.

Abstract

Non-metal nitrides are an exciting field of chemistry, featuring a significant number of compounds that can possess outstanding material properties. These properties mainly rely on maximizing the number of strong covalent bonds, with crosslinked XN₆ octahedra frameworks being particularly attractive. In this study, the phosphorus-nitrogen system was studied up to 137 GPa in laser-heated diamond anvil cells, and three previously unobserved phases were synthesized and characterized by single-crystal X-ray diffraction, Raman spectroscopy measurements and density functional theory calculations. δ-P₃ N₅ and PN₂ were found to form at 72 and 134 GPa, respectively, and both feature dense 3D networks of the so far elusive PN₆ units. The two compounds are ultra-incompressible, having a bulk modulus of K₀ =322 GPa for δ-P₃ N₅ and 339 GPa for PN₂ . Upon decompression below 7 GPa, δ-P₃ N₅ undergoes a transformation into a novel α'-P₃ N₅ solid, stable at ambient conditions, that has a unique structure type based on PN₄ tetrahedra. The formation of α'-P₃ N₅ underlines that a phase space otherwise inaccessible can be explored through materials formed under high pressure.

Keywords: PN6 octahedra; high-pressure high-temperature synthesis; non-metal nitrides; synchrotron single-crystal X-ray diffraction; ultra-incompressibility.

Abstract

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