Probing low-energy hyperbolic polaritons in van der Waals crystals with an electron microscope

Van der Waals materials exhibit intriguing structural, electronic, and photonic properties. Electron energy loss spectroscopy within scanning transmission electron microscopy allows for nanoscale mapping of such properties. However, its detection is typically limited to energy losses in the eV range-too large for probing low-energy excitations such as phonons or mid-infrared plasmons. Here, we adapt a conventional instrument to probe energy loss down to 100 meV, and map phononic states in hexagonal boron nitride, a representative van der Waals material. The boron nitride spectra depend on the flake thickness and on the distance of the electron beam to the flake edges. To explain these observations, we developed a classical response theory that describes the interaction of fast electrons with (anisotropic) van der Waals slabs, revealing that the electron energy loss is dominated by excitation of hyperbolic phonon polaritons, and not of bulk phonons as often reported. Thus, our work is of fundamental importance for interpreting future low-energy loss spectra of van der Waals materials.We acknowledge financial support from the European Commission under the Graphene Flagship (GrapheneCore1, grant no. 696656), the ERC starting grant SPINTROS (grant no. 257654), and the Spanish Ministry of Economy and Competitiveness (National plans MAT2014-53432-C5-4-R, MAT2015-65159-R, MAT2015-65525-R, and FIS2016-80174-P). A.K. also thanks for the Czechoslovak Microscopic Society/FEI scholarship.Peer Reviewe

Remote near-field spectroscopy of vibrational strong coupling between organic molecules and phononic nanoresonators

Vibrational strong coupling (VSC) promises ultrasensitive IR spectroscopy and modification of material properties. Here, nanoscale mapping of VSC between organic molecules and individual IR nanoresonators is achieved by remote near-field spectroscopy. Phonon polariton (PhP) nanoresonators can dramatically enhance the coupling of molecular vibrations and infrared light, enabling ultrasensitive spectroscopies and strong coupling with minute amounts of matter. So far, this coupling and the resulting localized hybrid polariton modes have been studied only by far-field spectroscopy, preventing access to modal near-field patterns and dark modes, which could further our fundamental understanding of nanoscale vibrational strong coupling (VSC). Here we use infrared near-field spectroscopy to study the coupling between the localized modes of PhP nanoresonators made of h-BN and molecular vibrations. For a most direct probing of the resonator-molecule coupling, we avoid the direct near-field interaction between tip and molecules by probing the molecule-free part of partially molecule-covered nanoresonators, which we refer to as remote near-field probing. We obtain spatially and spectrally resolved maps of the hybrid polariton modes, as well as the corresponding coupling strengths, demonstrating VSC on a single PhP nanoresonator level. Our work paves the way for near-field spectroscopy of VSC phenomena not accessible by conventional techniques.This work was supported by the MCIN/AEI/10.13039/501100011033 under the María de Maeztu Units of Excellence Program (CEX2020-001038-M) and the Projects RTI2018-094830-B-100, PID2021-123949OB-I00, PID2019-107432GB-I00 and PID2021-122511OB-I00, as well as by the Graphene Flagship (GrapheneCore3, No. 881603). J.L. and J.H.E. are grateful for support from the Office of Naval Research (Award No. N00014-20-1-2474), for the BN crystal growth. S.V. acknowledges financial support by the Comunidad de Madrid through the Atracción de Talento program (grant no. 2020-T1/IND-20041). C.M.-E., R.E., and J.A. received funding from grant no. IT 1526-22 from the Basque Government for consolidated groups of the Basque University

Active and Passive Tuning of Ultranarrow Resonances in Polaritonic Nanoantennas

[EN] Optical nanoantennas are of great importance for photonic devices and spectroscopy due to their capability of squeezing light at the nanoscale and enhancing light-matter interactions. Among them, nanoantennas made of polar crystals supporting phonon polaritons (phononic nanoantennas) exhibit the highest quality factors. This is due to the low optical losses inherent in these materials, which, however, hinder the spectral tuning of the nanoantennas due to their dielectric nature. Here, active and passive tuning of ultranarrow resonances in phononic nanoantennas is realized over a wide spectral range (approximate to 35 cm(-1), being the resonance linewidth approximate to 9 cm(-1)), monitored by near-field nanoscopy. To do that, the local environment of a single nanoantenna made of hexagonal boron nitride is modified by placing it on different polar substrates, such as quartz and 4H-silicon carbide, or covering it with layers of a high-refractive-index van der Waals crystal (WSe2). Importantly, active tuning of the nanoantenna polaritonic resonances is demonstrated by placing it on top of a gated graphene monolayer in which the Fermi energy is varied. This work presents the realization of tunable polaritonic nanoantennas with ultranarrow resonances, which can find applications in active nanooptics and (bio)sensing.J.M.-S. acknowledges financial support from the Ramon y Cajal Program of the Government of Spain and FSE (Grant No. RYC2018-026196-I) and the Spanish Ministry of Science and Innovation (State Plan for Scientific and Technical Research and Innovation Grant Number PID2019-110308GA-I00). P.A.-G. acknowledges support from the European Research Council under starting Grant No. 715496, 2DNANOPTICA, and the Spanish Ministry of Science and Innovation (State Plan for Scientific and Technical Research and Innovation Grant Number PID2019-111156GB-I00). G.a.-P. and J.T.-G. acknowledge support through the Severo Ochoa Program from the Government of the Principality of Asturias (Grant nos. PA20-PF-BP19-053 and PA-18-PF-BP17-126, respectively). A.Y.N. acknowledges the Spanish Ministry of Science and Innovation (Grant Nos. MAT201788358-C3-3-R and PID2020-115221GB-C42) and the Basque Department of Education (Grant No. PIBA-2020-1-0014) J.H.E. acknowledges support for h-BN crystal growth from the National Science Foundation, Award Number CMMI-1538127. R.H. acknowledges financial support from the Spanish Ministry of Science, Innovation and Universities (National Project Grant No. RTI2018-094830-B-100 and the Project Grant No. MDM-2016-0618 of the Marie de Maeztu Units of Excellence Program), the Basque Government (Grant No. IT1164-19), and the European Union's Horizon 2020 research and innovation programme under the Graphene Flagship (Grant Agreement Numbers 785219 and 881603, GrapheneCore2 and GrapheneCore3). I.D. acknowledges the Basque Government (Grant No. PRE_2019_2_0164). Work at MIT was partly supported through AFOSR Grant No. FA9550-16-1-0382, through the NSF QII-TAQS program (Grant No. 1936263), and the Gordon and Betty Moore Foundation EPiQS Initiative through Grant No. GBMF9643 to P.J.-H

Probing low-energy hyperbolic polaritons in van der Waals crystals with an electron microscope

Resumen del trabajo presentado a la International Conference on Nanoscience + Technology (ICN+T), celebrada en Brno (Czech Republic) del 22 al 27 de julio de 2018.Only recently, specially designed instrumentation for spatially-resolved electron energy-loss spectroscopy (EELS) has been developed to substantially improve spectral resolution and operating spectral range. This progress has dramatically broadened application potential of EELS in probing low-loss vibrational excitations. Pioneering experiments demonstrated capability of probing vibrational signal in organic samples, ionic crystals, and also van der Waals materials. In our work, we theoretically and experimentally studied the very low-loss EELS of multilayer hexagonal boron nitride (h-BN), a representative van der Waals structure. The weak coupling between individual atomic layer results in extreme optical anisotropy, which gives rise to hyperbolic phonon polaritons (h-PhPs): coupled excitations of optical phonons and light with hyperbolic dispersion in the range of 90 – 200 meV. H-PhPs might be a key to many emerging photonic technologies relying on nanoscale light confinement and manipulation. Thus, efficient design and utilization of h-BN structures require spectroscopic studies with adequate spatial resolution, which can be provided by EELS utilizing electrons as localized electromagnetic probes. To that end, we performed spatially-resolved EELS on a simple h-BN flake structure with an optimized STEM-EELS tool, which revealed the peak energy dependence on the h-BN thickness and on the proximity of the electron beam to the h-BN edge. Such behavior is a consequence of the polaritonic nature of the induced excitations. Indeed, with help of the classical dielectric response theory for EELS, applied to anisotropic slabs and edges, we demonstrate that the electron energy loss in h-BN is dominated by h-PhP excitation and not directly by bulk phonons as in preliminary interpretations. This finding describes and quantitatively matches experimental observations. We thus suggest that EELS can be a technique complementary to scanning near-field optical microscopy for characterization of low-energy phonon polaritons.Peer reviewe

Phonon-enhanced mid-infrared CO2 gas sensing using boron nitride nanoresonators

Hexagonal boron nitride (hBN) hosts long-lived phonon polaritons, yielding a strong mid-infrared (mid-IR) electric field enhancement and concentration on the nanometer scale. It is thus a promising material for highly sensitive mid-IR sensing and spectroscopy. In addition, hBN possesses high chemical and thermal stability as well as mechanical durability, making it suitable for operation in demanding environments. In this work, we demonstrate a mid-IR CO2 gas sensor exploiting phonon polariton (PhP) modes in hBN nanoresonators functionalized by a thin CO2-adsorbing polyethylenimine (PEI) layer. We find that the PhP resonance shifts to lower frequency, weakens, and broadens for increasing CO2 concentrations, which are related to the change of the permittivity of PEI upon CO2 adsorption. Moreover, the PhP resonance exhibits a high signal-to-noise ratio even for small ribbon arrays of 30 × 30 μm2. Our results show the potential of hBN nanoresonators to become a novel platform for miniaturized phonon-enhanced SEIRA gas sensors.The research leading to these results has received funding from the H2020 Programme under Grant Agreement No. 881603 (Graphene Flagship). This project has received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Sklodowska-Curie Grant Agreement No. 754510. This project has received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Sklodowska-Curie Grant Agreement No. 665884. This work was partially funded by CEX2019-000910-S [MICINN/AEI/10.13039/501100011033] and Project TUNA-SURF (PID2019-106892RB-I00), Fundació Cellex, Fundació Mir-Puig, and Generalitat de Catalunya through CERCA. We acknowledge financial support from the Spanish Ministry of Science, Innovation and Universities (RTI2018-094830-B-100 and the Project MDM-2016-0618 of the Maria de Maeztu Units of Excellence Program) and the Basque Government (Grant Number IT1164-19). We acknowledge the Ministry of Science, Innovation and Universities through the ‘Maria de Maezt’ Programme for Units of Excellence in R&D (CEX2018-000805-M). Further, support from the Materials Engineering and Processing program of the National Science Foundation, Award Number CMMI 1538127 for h-BN crystal growth is greatly appreciated. The hBN crystals growth is also supported by an Office of Naval Research Award No. N00014-20-1-2474. I.D. acknowledges the Basque Government (Grant No. PRE_2019_2_0164). We acknowledge Project PID2020-115221GB-C41 financed by MCIN/AEI/10.13039/501100011033 and Aragon Government through Project Q-MAD.Peer reviewe

Addressing vibrational excitations in Van der Waals materials and molecular layers within electron energy loss spectroscopy

Trabajo presentado al Microscopy & Microanalysis Meeting, celebrado en Baltimore (USA) del 5 al 9 de agosto de 2018.AK acknowledges Thermo Fisher Scientific and the Czechoslovak Microscopic Society scholarship for young researchers.Peer reviewe

Enhanced light–matter interaction in 10B monoisotopic boron nitride infrared nanoresonators

Phonon-polaritons, mixed excitations of light coupled to lattice vibrations (phonons), are emerging as a powerful platform for nanophotonic applications. This is because of their ability to concentrate light into extreme sub-wavelength scales and because of their longer phonon lifetimes compared to their plasmonic counterparts. In this work, the infrared properties of phonon-polaritonic nanoresonators made of monoisotopic 10B hexagonal boron nitride (h-BN) are explored, a material with increased phonon-polariton lifetimes compared to naturally abundant h-BN due to reduced photon scattering from randomly distributed isotopes. An average relative improvement of 50% of the quality factor of monoisotopic h-BN nanoresonators is obtained with respect to nanoresonators made of naturally abundant h-BN, allowing for the sensing of nanometric-thick films of molecules through both surface-enhanced absorption spectroscopy and refractive index sensing. Further, even strong coupling between molecular vibrations and the phonon-polariton resonance in monoisotopic h-BN ribbons can be achieved.The authors acknowledge funding from the Graphene Flagship (Core2 and Core3), the Spanish Ministry of Science and Innovation (projects MDM-2016-0618 of the Maria de Maeztu Units of Excellence Programme and national projects (RTI2018-094830-B-100, RTI2018-094861-B-100, and PID2019-107432GB-I00)), and the Basque Government (project GIU18/202, Ekartek project KK-2018/00001, IT1164-19, and PhD fellowships PRE_2018_2_0253 and PRE_2017_2_0052). The h-BN crystal growth was supported by the National Science Foundation, grant CMMI 1538127 and the II-VI Foundation.Peer reviewe

Probing low-energy hyperbolic polaritons in van der Waals crystals with an electron microscope

Resumen del trabajo presentado al 8th International Workshop on Electron Energy Loss Spectroscopy and Related Techniques, celebrado en Okuma, Okinawa (Japan) del 14 al 19 de mayo de 2017.Hexagonal Boron Nitride (hBN) is a representative material of a wide class of two-dimensional (2D) systems in which individual atomic layers are only weakly coupled by van der Waals interaction, resulting in extreme optical anisotropy. The latter gives rise to hBN's hyperbolic phonon polaritons (h-PhPs) at mid-infrared (mid-IR) energies, in the range of 90-200 meV. Hyperbolic polaritons might be key to emerging technologies that rely on nanoscale light confinement and manipulation. Here we perform an experimental mapping of the spectral signature of a 2D material by analyzing the electron energy loss spectroscopy (EELS) near a hBN edge, as a function of electron beam position. We understand these excitations and the dispersion of the EELS peaks in terms of the excitation of surface h-PhPs. A theoretical description of the polaritonic losses that also considers the experimental resolution, provides an excellent agreement between theory and experiment, proving that fast electrons can couple to hyperbolic polaritons. Further technical improvements might enable this tool to become a versatile technique for infrared vibrational spectroscopy of polaritons.Peer reviewe