Abstract
Nonlinear nanophotonics leverages engineered nanostructures to funnel light into small volumes and intensify nonlinear optical processes with spectral and spatial control. Owing to its intrinsically large and electrically tunable nonlinear optical response, graphene is an especially promising nanomaterial for nonlinear optoelectronic applications. Here we report on exceptionally strong optical nonlinearities in graphene–insulator–metal heterostructures, which demonstrate an enhancement by three orders of magnitude in the third-harmonic signal compared with that of bare graphene. Furthermore, by increasing the graphene Fermi energy through an external gate voltage, we find that graphene plasmons mediate the optical nonlinearity and modify the third-harmonic signal. Our findings show that graphene–insulator–metal is a promising heterostructure for optically controlled and electrically tunable nano-optoelectronic components.
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The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.
References
Choi, I. & Choi, Y. Plasmonic nanosensors: review and prospect. IEEE J. Sel. Top. Quantum Electron. 18, 1110–1121 (2011).
Tame, M. S. et al. Quantum plasmonics. Nat. Phys. 9, 329–340 (2013).
Kauranen, M. & Zayats, A. V. Nonlinear plasmonics. Nat. Photon. 6, 737–748 (2012).
Stockman, M. I. Nanoplasmonics: the physics behind the applications. Phys. Today 64, 39–44 (2011).
Chikkaraddy, R. et al. Single-molecule strong coupling at room temperature in plasmonic nanocavities. Nature 535, 127–130 (2016).
Abd El-Fattah, Z. M. et al. Plasmonics in atomically thin crystalline silver films. ACS Nano 13, 7771–7779 (2019).
Echarri, A. R., Cox, J. D. & de Abajo, F. J. G. Quantum effects in the acoustic plasmons of atomically thin heterostructures. Optica 6, 630–641 (2019).
Maier, S. A. Plasmonics: Fundamentals and Applications (Springer Science & Business Media, 2007).
Kravets, V. G., Kabashin, A. V., Barnes, W. L. & Grigorenko, A. N. Plasmonic surface lattice resonances: a review of properties and applications. Chem. Rev. 118, 5912–5951 (2018).
Kumar, N. et al. Third harmonic generation in graphene and few-layer graphite films. Phys. Rev. B 87, 121406 (2013).
Jiang, T. et al. Gate-tunable third-order nonlinear optical response of massless Dirac fermions in graphene. Nat. Photon. 112, 430–436 (2018).
Hong, S.-Y. et al. Optical third-harmonic generation in graphene. Phys. Rev. X 3, 021014 (2013).
Soavi, G. et al. Broadband, electrically tunable third-harmonic generation in graphene. Nat. Nanotechnol. 13, 583–588 (2018).
Hendry, E., Hale, P. J., Moger, J., Savchenko, A. K. & Mikhailov, S. A. Coherent nonlinear optical response of graphene. Phys. Rev. Lett. 105, 097401 (2010).
Dremetsika, E. et al. Measuring the nonlinear refractive index of graphene using the optical Kerr effect method. Opt. Lett. 41, 3281–3284 (2016).
Yoshikawa, N., Tamaya, T. & Tanaka, K. High-harmonic generation in graphene enhanced by elliptically polarized light excitation. Science 356, 736–738 (2017).
Baudisch, M. et al. Ultrafast nonlinear optical response of Dirac fermions in graphene. Nat. Commun. 9, 1018 (2018).
Ooi, K. J., Ang, L. K. & Tan, D. T. Waveguide engineering of graphene’s nonlinearity. Appl. Phys. Lett. 105, 111110 (2014).
Ju, L. et al. Graphene plasmonics for tunable terahertz metamaterials. Nat. Nanotechnol. 6, 630 (2011).
Koppens, F. H., Chang, D. E. & García de Abajo, F. J. Graphene plasmonics: a platform for strong light–matter interactions. Nano Lett. 11, 3370–3377 (2011).
Grigorenko, A., Polini, M. & Novoselov, K. Graphene plasmonics. Nat. Photon. 6, 749–758 (2012).
Garcia de Abajo, F. J. Graphene plasmonics: challenges and opportunities. ACS Photon. 1, 135–152 (2014).
Iranzo, D. A. et al. Probing the ultimate plasmon confinement limits with a van der Waals heterostructure. Science 360, 291–295 (2018).
Lee, I.-H., Yoo, D., Avouris, P., Low, T. & Oh, S.-H. Graphene acoustic plasmon resonator for ultrasensitive infrared spectroscopy. Nat. Nanotechnol. 14, 313 (2019).
Thongrattanasiri, S., Koppens, F. H. & García de Abajo, F. J. Complete optical absorption in periodically patterned graphene. Phys. Rev. Lett. 108, 047401 (2012).
Kim, S. et al. Electronically tunable perfect absorption in graphene. Nano Lett. 18, 971–979 (2018).
Gullans, M., Chang, D. E., Koppens, F. H. L., García de Abajo, F. J. & Lukin, M. D. Single-photon nonlinear optics with graphene plasmons. Phys. Rev. Lett. 111, 247401 (2013).
Alonso Calafell, I. et al. Quantum computing with graphene plasmons. npj Quantum Inf. 5, 37 (2019).
Mikhailov, S. A. Theory of the giant plasmon-enhanced second-harmonic generation in graphene and semiconductor two-dimensional electron systems. Phys. Rev. B 84, 045432 (2011).
Gorbach, A. V. Nonlinear graphene plasmonics: amplitude equation for surface plasmons. Phys. Rev. A 87, 013830 (2013).
Cox, J. D. & García de Abajo, F. J. Electrically tunable nonlinear plasmonics in graphene nanoislands. Nat. Commun. 6725, 5725 (2014).
Manzoni, M. T., Silveiro, I., García de Abajo, F. J. & Chang, D. E. Second-order quantum nonlinear optical processes in single graphene nanostructures and arrays. New J. Phys. 17, 083031 (2015).
Cox, J. D., Marini, A. & García de Abajo, F. J. Plasmon-assisted high-harmonic generation in graphene. Nat. Commun. 8, 14380 (2017).
Rostami, H., Katsnelson, M. I. & Polini, M. Theory of plasmonic effects in nonlinear optics: the case of graphene. Phys. Rev. B 95, 035416 (2017).
Constant, T. J., Hornett, S. M., Chang, D. E. & Hendry, E. All-optical generation of surface plasmons in graphene. Nat. Phys. 12, 124–127 (2016).
Kundys, D. et al. Nonlinear light mixing by graphene plasmons. Nano Lett. 18, 282–287 (2018).
Jadidi, M. M. et al. Nonlinear terahertz absorption of graphene plasmons. Nano Lett. 16, 2734–2738 (2016).
Mikhailov, S. A. Quantum theory of the third-order nonlinear electrodynamic effects of graphene. Phys. Rev. B 93, 085403 (2016).
Cheng, J. L., Vermeulen, N. & Sipe, J. Third-order nonlinearity of graphene: effects of phenomenological relaxation and finite temperature. Phys. Rev. B 91, 235320 (2015).
Saynatjoki, A. et al. Rapid large-area multiphoton microscopy for characterization of graphene. ACS Nano 7, 8441–8446 (2013).
Woodward, R. et al. Characterization of the second-and third-order nonlinear optical susceptibilities of monolayer MoS2 using multiphoton microscopy. 2D Mater. 4, 011006 (2016).
Mikhailov, S. A. Quantum theory of the third-order nonlinear electrodynamic effects of graphene. Phys. Rev. B 93, 085403 (2016).
Phare, C. T., Lee, Y.-H. D., Cardenas, J. & Lipson, M. Graphene electro-optic modulator with 30 GHz bandwidth. Nat. Photon. 9, 511 (2015).
Woessner, A. et al. Highly confined low-loss plasmons in graphene–boron nitride heterostructures. Nat. Mater. 14, 421–425 (2015).
Soavi, G. et al. Hot electrons modulation of third-harmonic generation in graphene. ACS Photon. 6, 2841–2849 (2019).
Mikhailov, S. A. Theory of the strongly nonlinear electrodynamic response of graphene: a hot electron model. Phys. Rev. B 100, 115416 (2019).
Shi, S.-F. et al. Controlling graphene ultrafast hot carrier response from metal-like to semiconductor-like by electrostatic gating. Nano Lett. 14, 1578–1582 (2014).
Manceau, J.-M., Zanotto, S., Sagnes, I., Beaudoin, G. & Colombelli, R. Optical critical coupling into highly confining metal–insulator–metal resonators. Appl. Phys. Lett. 103, 091110 (2013).
Yu, R., Manjavacas, A. & García de Abajo, F. J. Ultrafast radiative heat transfer. Nat. Commun. 8, 2 (2017).
Acknowledgements
We thank S. Zanotto for assistance with the Matlab code. P.W. acknowledges support from the European Commission through ErBeSta (no. 800942), the Austrian Research Promotion Agency (FFG) through the QuantERA ERA-NET Cofund project HiPhoP, the Austrian Science Fund (FWF) through CoQuS (W 1210-N25), NaMuG (P30067-N36) and BeyondC (F 7113-N38), the US Air Force Office of Scientific Research (FA2386-233 17-1-4011 and FA8655-20-1-7030) and Red Bull GmbH. F.J.G.A. acknowledges support from the ERC (Advanced Grant 789104-eNANO) and the Spanish MINECO (MAT2017-88492-R). F.H.L.K. acknowledges support from the Government of Spain (FIS2016-81044, Severo Ochoa CEX2019-000910-S), Fundació Cellex, Fundació Mir-Puig and Generalitat de Catalunya (CERCA, AGAUR, SGR 1656). Furthermore, the research leading to these results received funding from the European Union’s Horizon 2020 under grant agreements no. 785219 (Graphene flagship Core2) and no. 881603 (Graphene flagship Core3). This work was supported by the ERC TOPONANOP under grant agreement no. 726001. ICFO is financially supported by the Spanish MINECO (SEV2015-0522), the Catalan CERCA, Fundació Privada Cellex, the Spanish Ministry of Economy and Competitiveness through the ‘Severo Ochoa’ Programme for Centres of Excellence in R&D (SEV-2015-0522) and Fundacio Cellex Barcelona, Generalitat de Catalunya, through the CERCA programme. The MIT portion of this work was supported in part by the NSF Center for Integrated Quantum Materials (CIQM), the US Army Research Office (Award W911NF-17-1-0435) and the Institute for Soldier Nanotechnologies (contract no. W911NF-18-2-0048). The Center for Nano Optics is financially supported by the University of Southern Denmark (SDU 2020 funding). J.D.C. was supported by VILLUM Fonden (grant no. 16498). I.A.C. and P.K.J. acknowledge support from the University of Vienna via the Vienna Doctoral School. L.A.R. acknowledges support from the Templeton World Charity Foundation (fellowship no. TWCF0194). D.A.I. acknowledges support from the Spanish MINECO FPI Grant (BES-2014-068504). A.T. acknowledges support from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement no. 801110 and the Austrian Federal Ministry of Education, Science and Research (BMBWF). All authors acknowledge support from the European Commission via GRASP (No. 613024). This article reflects only the authors’ views—the EU Agency is not responsible for any use that may be made of the information it contains.
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I.A.C., L.A.R., F.H.L.K. and A.T. designed the experiment, performed the measurements and analysed the results. I.A.C., L.A.R., D.A.I., F.H.L.K. and J.D.C. wrote the manuscript. D.A.I., S.N., A.K. and F.H.L.K. fabricated and characterized the samples. D.A.I., J.D.C., P.K.J., H.B. and F.J.G.A. provided theoretical support and simulations. P.W., F.H.L.K. and F.J.G.A. supervised the project. All the authors read and commented on the manuscript.
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Alonso Calafell, I., Rozema, L.A., Alcaraz Iranzo, D. et al. Giant enhancement of third-harmonic generation in graphene–metal heterostructures. Nat. Nanotechnol. 16, 318–324 (2021). https://doi.org/10.1038/s41565-020-00808-w
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DOI: https://doi.org/10.1038/s41565-020-00808-w
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