Phonon polaritons—light coupled to lattice vibrations—in polar van der Waals crystals are promising candidates for controlling the flow of energy on the nanoscale due to their strong field confinement, anisotropic propagation and ultra-long lifetime in the picosecond range1,2,3,4,5. However, the lack of tunability of their narrow and material-specific spectral range—the Reststrahlen band—severely limits their technological implementation. Here, we demonstrate that intercalation of Na atoms in the van der Waals semiconductor α-V2O5 enables a broad spectral shift of Reststrahlen bands, and that the phonon polaritons excited show ultra-low losses (lifetime of 4 ± 1 ps), similar to phonon polaritons in a non-intercalated crystal (lifetime of 6 ± 1 ps). We expect our intercalation method to be applicable to other van der Waals crystals, opening the door for the use of phonon polaritons in broad spectral bands in the mid-infrared domain.
This is a preview of subscription content, access via your institution
Open Access articles citing this article.
Nature Nanotechnology Open Access 18 August 2022
Nature Communications Open Access 03 August 2022
eLight Open Access 18 July 2022
Subscribe to Nature+
Get immediate online access to the entire Nature family of 50+ journals
Subscribe to Journal
Get full journal access for 1 year
only $9.92 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Get time limited or full article access on ReadCube.
All prices are NET prices.
The custom code employed in this work to perform all calculations is available from the corresponding authors on reasonable request.
Dai, S. et al. Tunable phonon polaritons in atomically thin van der Waals crystals of boron nitride. Science 343, 1125–1129 (2014).
Ma, W. et al. In-plane anisotropic and ultra-low-loss polaritons in a natural van der Waals crystal. Nature 562, 557–562 (2018).
Giles, A. J. et al. Ultralow-loss polaritons in isotopically pure boron nitride. Nat. Mater. 17, 134–139 (2017).
Zheng, Z. et al. Highly confined and tunable hyperbolic phonon polaritons in van der waals semiconducting transition metal oxides. Adv. Mat. 30, 1705318 (2018).
Zheng, Z. et al. A mid-infrared biaxial hyperbolic van der Waals crystal. Sci. Adv. 5, eaav8690 (2019).
Low, T. et al. Polaritons in layered two-dimensional materials. Nat. Mater. 16, 182 (2016).
Basov, D. N., Fogler, M. M. & García de Abajo, F. J. Polaritons in van der Waals materials. Science 354, aag1992 (2016).
Li, P. et al. Reversible optical switching of highly confined phonon-polaritons with an ultrathin phase-change material. Nat. Mater. 15, 870–875 (2016).
Sukimura, H. et al. Highly confined and switchable mid-infrared surface phonon polariton resonances of planar circular cavities with a phase change material. Nano Lett. 19, 2549–2554 (2019).
Caldwell, J. D. et al. Photonics with hexagonal boron nitride. Nat. Rev. Mater. 4, 552–567 (2019).
Dunkelberger, A. D. et al. Active tuning of surface phonon polariton resonances via carrier photoinjection. Nat. Photonics 12, 50–56 (2018).
Ratchford, D. C. et al. Controlling the infrared dielectric function through atomic-scale heterostructures. ACS Nano 13, 6730–6741 (2019).
Bhandari, C. & Lambrecht, W. R. L. Phonons and related spectra in bulk and monolayer V2O5. Phys. Rev. B. 89, 045109 (2014).
Sucharitakul, S. et al. V2O5: A 2D van der waals oxide with strong in-plane electrical and optical anisotropy. ACS Appl. Mater. Interfaces 9, 23949–23956 (2017).
Clauws, P. & Vennik, J. Lattice vibrations of V2O5. Determination of TO and LO frequencies from infrared reflection and transmission. Phys. Status Solidi 76, 707–713 (1976).
Gomez-Diaz, J. S. & Alù, A. Flatland optics with hyperbolic metasurfaces. ACS Photonics 3, 2211–2224 (2016).
Gomez-Diaz, J. S., Tymchenko, M. & Alù, A. Hyperbolic plasmons and topological transitions over uniaxial metasurfaces. Phys. Rev. Lett. 114, 233901 (2015).
Chen, J. et al. Optical nano-imaging of gate-tunable graphene plasmons. Nature 487, 77–81 (2012).
Fei, Z. et al. Gate-tuning of graphene plasmons revealed by infrared nano-imaging. Nature 487, 82–85 (2012).
Autore, M. et al. Boron nitride nanoresonators for phonon-enhanced molecular vibrational spectroscopy at the strong coupling limit. Light.: Sci. Appl. 14, 17172 (2018).
Huth, F., Schnell, M., Wittborn, J., Ocelic, N. & Hillenbrand, R. Infrared-spectroscopic nanoimaging with a thermal source. Nat. Mater. 10, 352–356 (2011).
Braithwaite, J. S., Catlow, C. R. A., Gale, J. D. & Harding, J. H. Lithium intercalation into vanadium pentoxide: a theoretical study. Chem. Mater. 11, 1990–1998 (1999).
Liu, J., Xia, H., Xue, D. & Lu, L. Double-shelled nanocapsules of V2O5-based composites as high-performance anode and cathode materials for Li ion batteries. J. Am. Chem. Soc. 131, 12086–12087 (2009).
Xiong, F. et al. Li intercalation in MoS2: in situ observation of its dynamics and tuning optical and electrical properties. Nano Lett. 15, 6777–6784 (2015).
Cha, JudyJ. et al. Two-dimensional chalcogenide nanoplates as tunable metamaterials via chemical intercalation. Nano Lett. 13, 5913–5918 (2013).
Zhang, R., Waters, J., Geim, A. K. & Grigorieva, I. V. Intercalant-independent transition temperature in superconducting black phosphorus. Nat. Commun. 8, 15036 (2017).
Pons-Valencia, P. et al. Launching of hyperbolic phonon-polaritons in h-BN slabs by resonant metal plasmonic antennas. Nat. Commun. 10, 3242 (2019).
Woessner, A. et al. Highly confined low-loss plasmons in graphene–boron nitride heterostructures. Nat. Mater. 14, 421–425 (2014).
Kwabena Bediako, D. Heterointerface effects in the electrointercalation of van der Waals heterostuctures. Nature 558, 425–429 (2018).
Talwar, N. T. Direct evidence of LO phonon-plasmons coupled modes in n-GaN. Appl. Phys. Lett. 97, 051902 (2010).
Haemers, J. Purification and single crystal growth of V2O5. Bull. des. Soci. Chim. Belg. 79, 473–477 (1970).
Isobe, M., Kagami, C. & Ueda, Y. Crystal growth of new spin-Peierls compound NaV2O5. J. Cryst. Growth 181, 314–317 (1997).
Álvarez-Pérez, G. et al. Infrared permittivity of the biaxial van der Waals semiconductor α-MoO3 from near- and far-field correlative studies. Preprint at https://arxiv.org/abs/1912.06267 (2019).
J.T.-G. and G.Á.-P. acknowledge support through the Severo Ochoa Program from the Government of the Principality of Asturias (nos. PA-18-PF-BP17-126 and PA-20-PF-BP19-053, respectively). J.M.-S. acknowledges finantial support from the Clarín Programme from the Government of the Principality of Asturias and a Marie Curie-COFUND grant (PA-18-ACB17-29) and the Ramón y Cajal Program from the Government of Spain (RYC2018-026196-I). K.C., X.P.A.G., H.V. and M.H.B. acknowledge the Air Force Office of Scientific Research (AFOSR) grant no. FA 9550-18-1-0030 for funding support. I.E. acknowledges financial support from the Spanish Ministry of Economy and Competitiveness (grant no. FIS2016-76617-P). A.Y.N. acknowledges the Spanish Ministry of Science, Innovation and Universities (national project no. MAT2017-88358-C3-3-R) and the Basque Government (grant no. IT1164-19). Q.B. acknowledges the support from Australian Research Council (grant nos. FT150100450, IH150100006 and CE170100039). R.H. acknowledges support from the Spanish Ministry of Economy, Industry, and Competitiveness (national project RTI2018-094830-B-100 and the Project MDM-2016-0618 of the María de Maeztu Units of Excellence Program) and the Basque Goverment (grant no. IT1164-19). P.A.-G. acknowledges support from the European Research Council under starting grant no. 715496, 2DNANOPTICA.
R.H. is cofounder of Neaspec GmbH, a company producing s-SNOM systems, such as the one used in this study. The remaining authors declare no competing interests.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Fig1c.xlsx is an excel file containing the permittivity values of α-V2O5 along the three crystallographic directions.
This contains four sheets: Fig2a, Fig2b and Fig2c with the ascii data matrix files of the third harmonic s-SNOM images, and Fig. 2g with the dispersion values.
About this article
Cite this article
Taboada-Gutiérrez, J., Álvarez-Pérez, G., Duan, J. et al. Broad spectral tuning of ultra-low-loss polaritons in a van der Waals crystal by intercalation. Nat. Mater. 19, 964–968 (2020). https://doi.org/10.1038/s41563-020-0665-0
Nature Nanotechnology (2022)
Nature Reviews Physics (2022)