1. Anisotropic thermal expansion of black phosphorus from nanoscale dynamics of phosphorene layers
- Author
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Gaston Garbarino, Mohamed Mezouar, Volodymyr Svitlyk, David Sifré, Frédéric Datchi, Matteo Ceppatelli, Manuel Serrano-Ruiz, Laura Henry, Maurizio Peruzzini, European Synchrotron Radiation Facility (ESRF), Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster (WWU), Istituto di Chimica dei Composti Organometallici (ICCOM), Consiglio Nazionale delle Ricerche (CNR), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), ANR-13-BS04-0015,MOFLEX,Structure et dynamique des fluides moléculaires simples sous conditions extrêmes de pression et température(2013), European Project: 670173,H2020,ERC-2014-ADG,PHOSFUN(2015), Westfälische Wilhelms-Universität Münster = University of Münster (WWU), and National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR)
- Subjects
Diffraction ,Materials science ,Condensed matter physics ,Ab initio ,Black phosphorus ,02 engineering and technology ,Crystal structure ,Atmospheric temperature range ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,phosphorene ,Thermal expansion ,0104 chemical sciences ,Phosphorene ,chemistry.chemical_compound ,chemistry ,Thermal ,[PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci] ,General Materials Science ,0210 nano-technology ,Anisotropy ,thermal expansion measurements - Abstract
International audience; Black phosphorus (bP) is a crystalline material which can be seen as an ordered stacking of two-dimensional layers, referred to as Phosphorene. The knowledge of the linear thermal expansion coefficients (LTEC) of bP is of great interest in the field of 2D materials for a better understanding of the anistropic thermal properties and exfoliation mechanism of this material. Despite several theoretical and experimental studies important uncertainties remain in the determination of the LTEC of bP. Here, we report accurate thermal expansion measurements along the three crystallographic axes using in-situ high temperature x-ray diffraction. From the progressive reduction of the diffracted intensities with temperature we monitored the loss of the crystal structure of bP across the investigated temperature range, evidencing two thermal expansion regimes at temperature below and above 706 K. Below 706 K, we observe a strong out-of-plane anisotropy, while at temperatures above 706 K a larger thermal expansion occurs along the a crystallographic direction. From our data and by taking advantage of ab-initio optimization, we propose a detailed anisotropic thermal expansion mechanism of bP, which leads to an inter- and intra-layer destabilization. An interpretation of it, based on the high T perturbation of the stabilizing sp orbital mixing effect, is provided, consistently with high pressure data.
- Published
- 2020
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