Abstract
Hexagonal boron nitride is a model lamellar compound where weak, non-local van der Waals interactions ensure the vertical stacking of two-dimensional honeycomb lattices made of strongly bound boron and nitrogen atoms. We study the isotope engineering of lamellar compounds by synthesizing hexagonal boron nitride crystals with nearly pure boron isotopes (10B and 11B) compared to those with the natural distribution of boron (20 at% 10B and 80 at% 11B). On the one hand, as with standard semiconductors, both the phonon energy and electronic bandgap varied with the boron isotope mass, the latter due to the quantum effect of zero-point renormalization. On the other hand, temperature-dependent experiments focusing on the shear and breathing motions of adjacent layers revealed the specificity of isotope engineering in a layered material, with a modification of the van der Waals interactions upon isotope purification. The electron density distribution is more diffuse between adjacent layers in 10BN than in 11BN crystals. Our results open perspectives in understanding and controlling van der Waals bonding in layered materials.
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Acknowledgements
We gratefully acknowledge C. L’Henoret for his technical support at the mechanics workshop, and A. Dréau, V. Jacques and E. Rousseau for fruitful discussions. This work and the PhD funding of T.Q.P.V. were financially supported by the network GaNeX (ANR-11-LABX-0014). GaNeX belongs to the publicly funded Investissements d’Avenir program managed by the French ANR agency. G.C. is member of ‘Institut Universitaire de France’. B.G. acknowledges the Russian Megagrant program (14.W03.31.0011) at the Ioffe Institute, Saint Petersburg, Russia. This work was also supported by the Spanish MINECO/FEDER under contract MAT2015-71305-R. The hBN crystal growth is based upon work supported by the National Science Foundation under Grant No. CMMI 1538127.
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S.L. and J.H.E. synthesized the samples. T.Q.P.V., P.V. and G.C. performed photoluminescence spectroscopy. A.V.d.L. the X-ray diffraction measurements. R.C., L.A. and T.M. the Raman scattering experiments. All authors contributed to the interpretation of the results. The project was initiated by B.G. and the manuscript was written by G.C.
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Vuong, T., Liu, S., Van der Lee, A. et al. Isotope engineering of van der Waals interactions in hexagonal boron nitride. Nat. Mater. 17, 152–158 (2018). https://doi.org/10.1038/nmat5048
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DOI: https://doi.org/10.1038/nmat5048
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