Electron-beam spectroscopy for nanophotonics
Source abstract
Abstract
Progress in electron-beam spectroscopies has recently enabled the study of optical excitations with combined space, energy and time resolution in the nanometre, millielectronvolt and femtosecond domain, thus providing unique access into nanophotonic structures and their detailed optical responses. These techniques rely on ~1-300 keV electron beams focused at the sample down to sub-nanometre spots, temporally compressed in wavepackets a few femtoseconds long, and in some cases controlled by ultrafast light pulses. The electrons undergo energy losses and gains (also giving rise to cathodoluminescence light emission), which are recorded to reveal the optical landscape along the beam path. This Review portraits these advances, with a focus on coherent excitations, emphasizing the increasing level of control over the electron wavefunctions and ensuing applications in the study and technological use of optically resonant modes and polaritons in nanoparticles, 2D materials and engineered nanostructures.
Source: europepmc · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Advanced Electron Microscopy Techniques and Applications · Laser-Matter Interactions and Applications · Electron and X-Ray Spectroscopy Techniques
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (100+)
Show source-provided references
1. Egerton, R. F. Electron Energy-Loss Spectroscopy in the Electron Microscope (Plenum, 1996).10.1007/978-1-4757-5099-7 ↗
2. García de Abajo, F. J. Optical excitations in electron microscopy. Rev. Mod. Phys. 82, 209–275 (2010).10.1103/RevModPhys.82.209 ↗
3. Brenny, B. J. M., Polman, A. & García de Abajo, F. J. Femtosecond plasmon and photon wave packets excited by a high-energy electron on a metal or dielectric surface. Phys. Rev. B 155412, 155412 (2016).10.1103/PhysRevB.94.155412 ↗
4. Losquin, A. et al. Unveiling nanometer scale extinction and scattering phenomena through combined electron energy loss spectroscopy and cathodoluminescence measurements. Nano Lett. 15, 1229–1237 (2015).10.1021/nl5043775 ↗
5. Yacobi, B. G. & Holt, D. B. Cathodoluminescence Microscopy of Inorganic Solids (Springer, 1990).10.1007/978-1-4757-9595-0 ↗
6. Coenen, T. & Haegel, N. M. Cathodoluminescence for the 21st century: learning more from light. Appl. Phys. Rev 4, 031103 (2017).10.1063/1.4985767 ↗
7. Kociak, M. & Zagonel, L. F. Cathodoluminescence in the scanning transmission electron microscope. Ultramicroscopy 176, 112–131 (2017).10.1016/j.ultramic.2017.03.014 ↗
8. García de Abajo, F. J. & Kociak, M. Probing the photonic local density of states with electron energy loss spectroscopy. Phys. Rev. Lett. 100, 106804 (2008).10.1103/PhysRevLett.100.106804 ↗
9. Hohenester, U., Ditlbacher, H. & Krenn, J. R. Electron-energy-loss spectra of plasmonic nanoparticles. Phys. Rev. Lett. 103, 106801 (2009).10.1103/PhysRevLett.103.106801 ↗
10. Horl, A. et al. Tomographic imaging of the photonic environment of plasmonic nanoparticles. Nat. Commun. 8, 37 (2017).10.1038/s41467-017-00051-3 ↗
11. Zuloaga, J. & Nordlander, P. On the energy shift between near-field and far-field peak intensities in localized plasmon systems. Nano Lett. 11, 1280–1283 (2011).10.1021/nl1043242 ↗
12. Ritchie, R. H. Plasma losses by fast electrons in thin films. Phys. Rev. 106, 874–881 (1957).10.1103/PhysRev.106.874 ↗
13. Zabala, N., Rivacoba, A. & Echenique, P. M. Energy loss of electrons travelling through cylindrical holes. Surf. Sci 209, 465–480 (1989).10.1016/0039-6028(89)90089-7 ↗
14. García de Abajo, F. J. Relativistic energy loss and induced photon emission in the interaction of a dielectric sphere with an external electron beam. Phys. Rev. B 59, 3095–3107 (1999).10.1103/PhysRevB.59.3095 ↗
15. Muller, D. A. & Silcox, J. Delocalization in inelastic scattering. Ultramicroscopy 59, 195–213 (1995).10.1016/0304-3991(95)00029-Z ↗
16. Schefold, J. et al. Spatial resolution of coherent cathodoluminescence super-resolution microscopy. ACS Photon. 6, 1067–1072 (2019).10.1021/acsphotonics.9b00164 ↗
17. van de Hulst, H. C. Light Scattering by Small Particles (Dover, 1981).
18. García de Abajo, F. J. & Howie, A. Retarded field calculation of electron energy loss in inhomogeneous dielectrics. Phys. Rev. B 65, 115418 (2002).10.1103/PhysRevB.65.115418 ↗
19. Waxenegger, A. J., Trügler, A. & Hohenester, U. Plasmonics simulations with the MNPBEM toolbox: consideration of substrates and layer structures. Comp. Phys. Commun 193, 138–150 (2015).10.1016/j.cpc.2015.03.023 ↗
20. Matyssek, C., Niegemann, J., Hergert, W. & Busch, K. Computing electron energy loss spectra with the Discontinuous Galerkin Time-Domain method. Photon. Nanostruct. Fundam. Appl 9, 367–373 (2011).10.1016/j.photonics.2011.04.003 ↗
21. Geuquet, N. & Henrard, L. EELS and optical response of a noble metal nanoparticle in the frame of a discrete dipole approximation. Ultramicroscopy 110, 1075–1080 (2010).10.1016/j.ultramic.2010.01.013 ↗
22. Bigelow, N. W., Vaschillo, A., Iberi, V., Camden, J. P. & Masiello, D. J. Characterization of the electron- and photon-driven plasmonic excitations of metal nanorods. ACS Nano 6, 7497–7504 (2012).10.1021/nn302980u ↗
23. Das, P., Chini, T. K. & Pond, J. Probing higher order surface plasmon modes on individual truncated tetrahedral gold nanoparticle using cathodoluminescence imaging and spectroscopy combined with FDTD simulations. J. Phys. Chem. C 116, 15610–15619 (2012).10.1021/jp3047533 ↗
24. Cao, Y., Manjavacas, A., Large, N. & Nordlander, P. Electron energy-loss spectroscopy calculation in finite-difference time-domain package. ACS Photon 2, 369–375 (2015).10.1021/ph500408e ↗
25. García de Abajo, F. J. Relativistic description of valence energy losses in the interaction of fast electrons with clusters of dielectrics: multiple-scattering approach. Phys. Rev. B 60, 6103–6112 (1999).10.1103/PhysRevB.60.6103 ↗
26. Thomas, S. et al. Application of generalized Mie theory to EELS calculations as a tool for optimization of plasmonic structures. Plasmonics 11, 865–874 (2016).10.1007/s11468-015-0120-2 ↗
27. Talebi, N. Electron-light interactions beyond the adiabatic approximation: recoil engineering and spectral interferometry. Adv. Phys. X 3, 1499438 (2018).
28. Hörl, A., Trügler, A. & Hohenester, U. Tomography of particle plasmon fields from electron energy loss spectroscopy. Phys. Rev. Lett. 111, 076801 (2013).10.1103/PhysRevLett.111.076801 ↗
29. Caldwell, J. D. et al. Low-loss, infrared and terahertz nanophotonics using surface phonon polaritons. Nanophotonics 4, 44–68 (2015).10.1515/nanoph-2014-0003 ↗
30. Lourenço-Martins, H. & Kociak, M. Vibrational surface electron-energy-loss spectroscopy probes confined surface-phonon modes. Phys. Rev. X 7, 041059 (2017).
31. Asenjo-Garcia, A. & García de Abajo, F. J. Dichroism in the interaction between vortex electron beams, plasmons, and molecules. Phys. Rev. Lett. 113, 066102 (2014).10.1103/PhysRevLett.113.066102 ↗
32. García de Abajo, F. J., Asenjo-Garcia, A. & Kociak, M. Multiphoton absorption and emission by interaction of swift electrons with evanescent light fields. Nano Lett. 10, 1859–1863 (2010).10.1021/nl100613s ↗
33. Park, S. T., Lin, M. & Zewail, A. H. Photon-induced near-field electron microscopy (PINEM): theoretical and experimental. New J. Phys. 12, 123028 (2010).10.1088/1367-2630/12/12/123028 ↗
34. Vanacore, G. M. et al. Generation and control of an ultrafast electron vortex beam via chiral plasmonic near-fields. Nat. Mater. 18, 573–579 (2019).10.1038/s41563-019-0336-1 ↗
35. Cai, W., Reinhardt, O., Kaminer, I. & García de Abajo, F. J. Efficient orbital angular momentum transfer between plasmons and free electrons. Phys. Rev. B 98, 045424 (2018).10.1103/PhysRevB.98.045424 ↗
36. Barwick, B., Flannigan, D. J. & Zewail, A. H. Photon-induced near-field electron microscopy. Nature 462, 902–906 (2009).10.1038/nature08662 ↗
37. García de Abajo, F. J. & Kociak, M. Electron energy-gain spectroscopy. New J. Phys. 10, 073035 (2008).10.1088/1367-2630/10/7/073035 ↗
38. Vanacore, G. M. et al. Attosecond coherent control of free-electron wavefunctions using semi-infinite light fields. Nat. Commun. 9, 2694 (2018).10.1038/s41467-018-05021-x ↗
39. Feist, A. et al. Quantum coherent optical phase modulation in an ultrafast transmission electron microscope. Nature 521, 200–203 (2015).10.1038/nature14463 ↗
40. Batson, P. E. Surface plasmon coupling in clusters of small spheres. Phys. Rev. Lett. 49, 936–940 (1982).10.1103/PhysRevLett.49.936 ↗
41. Batson, P. E. A new surface plasmon resonance in clusters of small aluminum spheres. 9, 277–282 (1982).10.1016/0304-3991(82)90212-1 ↗
42. Ouyang, F., Batson, P. E. & Isaacson, M. Quantum size effects in the surface-plasmon excitation of small metallic particles by electron-energy-loss spectroscopy. Phys. Rev. B 46, 15421–15425 (1992).10.1103/PhysRevB.46.15421 ↗
43. Ugarte, D., Colliex, C. & Trebbia, P. Surface- and interface-plasmon modes on small semiconducting spheres. Phys. Rev. B 45, 4332–4343 (1992).10.1103/PhysRevB.45.4332 ↗
44. Bosman, M., Keast, V. J., Watanabe, M., Maaroof, A. I. & Cortie, M. B. Mapping surface plasmons at the nanometre scale with an electron beam. Nanotechnology 18, 165505 (2007).10.1088/0957-4484/18/16/165505 ↗
45. Nelayah, J. et al. Mapping surface plasmons on a single metallic nanoparticle. Nat. Phys. 3, 348–353 (2007).10.1038/nphys575 ↗
46. Colliex, C., Kociak, M. & Stéphan, O. Electron energy loss spectroscopy imaging of surface plasmons at the nanometer scale. Ultramicroscopy 162, A1–A24 (2016).10.1016/j.ultramic.2015.11.012 ↗
47. Yamamoto, N., Araya, K. & García de Abajo, F. J. Photon emission from silver particles induced by a high-energy electron beam. Phys. Rev. B 64, 205419 (2001).10.1103/PhysRevB.64.205419 ↗
48. Vesseur, E. J. R., de Waele, R., Kuttge, M. & Polman, A. Direct observation of plasmonic modes in Au nanowires using high-resolution cathodoluminescence spectroscopy. Nano Lett. 7, 2843–2846 (2007).10.1021/nl071480w ↗
49. Coenen, T., Schoen, D. T., Brenny, B. J. M., Polman, A. & Brongersma, M. L. Combined electron energy-loss and cathodoluminescence spectroscopy on individual and composite plasmonic nanostructures. Phys. Rev. B 93, 195429 (2016).10.1103/PhysRevB.93.195429 ↗
50. Rossouw, D. & Botton, G. A. Plasmonic response of bent silver nanowires for nanophotonic subwavelength waveguiding. Phys. Rev. Lett. 110, 66801 (2013).10.1103/PhysRevLett.110.066801 ↗
51. Boltasseva, A. & Shalaev, V. M. Transdimensional photonics. ACS Photon 6, 1–3 (2019).10.1021/acsphotonics.8b01570 ↗
52. Abd El-Fattah, Z. M. et al. Plasmonics in atomically thin crystalline silver films. ACS Nano https://doi.org/10.1021/acsnano.9b01651 (2019).10.1021/acsnano.9b01651 ↗
53. Knight, M. W. et al. Aluminum plasmonic nanoantennas. Nano Lett. 12, 6000–6004 (2012).10.1021/nl303517v ↗
54. Pomarico, E. et al. meV Resolution in laser-assisted energy-filtered transmission electron microscopy. ACS Photon. 5, 759–764 (2018).10.1021/acsphotonics.7b01393 ↗
55. Martin, J. et al. High-resolution imaging and spectroscopy of multipolar plasmonic resonances in aluminum nanoantennas. Nano Lett. 14, 5517–5523 (2014).10.1021/nl501850m ↗
56. Agrawal, A. et al. Resonant coupling between molecular vibrations and localized surface plasmon resonance of faceted metal oxide nanocrystals. Nano Lett. 17, 2611–2620 (2017).10.1021/acs.nanolett.7b00404 ↗
57. Herzing, A. A. et al. Electron energy loss spectroscopy of plasmon resonances in titanium nitride thin films. Appl. Phys. Lett. 108, 171107 (2016).10.1063/1.4947442 ↗
58. Suzuki, T. & Yamamoto, N. Cathodoluminescent spectroscopic imaging of surface plasmon polaritons in a 1-dimensional plasmonic crystal. Opt. Express 17, 23664–23671 (2009).10.1364/OE.17.023664 ↗
59. Coenen, T., Vesseur, E. J. R. & Polman, A. Angle-resolved cathodoluminescence spectroscopy. Appl. Phys. Lett. 99, 4–6 (2011).10.1063/1.3644985 ↗
60. Yamamoto, N., Ohtani, S. & García de Abajo, F. J. Gap and Mie plasmons in individual silver nanospheres near a silver surface. Nano Lett. 11, 91–95 (2011).10.1021/nl102862x ↗
61. Coenen, T., Bernal Arango, F., Koenderink, A. F. & Polman, A. Directional emission from a single plasmonic scatterer. Nat. Commun. 5, 3250 (2014).10.1038/ncomms4250 ↗
62. Myroshnychenko, V., Nishio, N., García de Abajo, F. J., Förstner, J. & Yamamoto, N. Unveiling and imaging degenerate states in plasmonic nanoparticles with nanometer resolution. ACS Nano 12, 8436–8446 (2018).10.1021/acsnano.8b03926 ↗
63. Coenen, T. & Polman, A. Polarization-sensitive cathodoluminescence Fourier microscopy. Opt. Express 20, 18679–18691 (2012).10.1364/OE.20.018679 ↗
64. Osorio, C. I., Coenen, T., Brenny, B. J. M., Polman, A. & Koenderink, A. F. Angle-resolved cathodoluminescence imaging polarimetry. ACS Photon 3, 147–154 (2016).10.1021/acsphotonics.5b00596 ↗
65. Brenny, B. J. M., Coenen, T. & Polman, A. Quantifying coherent and incoherent cathodoluminescence in semiconductors and metals. J. Appl. Phys. 115, 244307 (2014).10.1063/1.4885426 ↗
66. Nicoletti, O. et al. Three-dimensional imaging of localized surface plasmon resonances of metal nanoparticles. Nature 502, 80–84 (2013).10.1038/nature12469 ↗
67. Collins, S. M. et al. Eigenmode tomography of surface charge oscillations of plasmonic nanoparticles by electron energy loss spectroscopy. ACS Photon. 2, 1628–1635 (2015).10.1021/acsphotonics.5b00421 ↗
68. Atre, A. C. et al. Nanoscale optical tomography with cathodoluminescence spectroscopy. Nat. Nanotechnol. 10, 429–436 (2015).10.1038/nnano.2015.39 ↗
69. Bashevoy, M. V. et al. Generation of traveling surface plasmon waves by free-electron impact. Nano Lett. 6, 1113–1115 (2006).10.1021/nl060941v ↗
70. van Wijngaarden, J. T. et al. Direct imaging of propagation and damping of near-resonance surface plasmon polaritons using cathodoluminescence spectroscopy. Appl. Phys. Lett. 88, 7–9 (2006).10.1063/1.2208556 ↗
71. Pettit, R. B., Silcox, J. & Vincent, R. Measurement of surface-plasmon dispersion in oxidized aluminum films. Phys. Rev. B 11, 3116–3123 (1975).10.1103/PhysRevB.11.3116 ↗
72. Gu, L. et al. Band-gap measurements of direct and indirect semiconductors using monochromated electrons. Phys. Rev. B 75, 195214 (2007).10.1103/PhysRevB.75.195214 ↗
73. Shekhar, P. et al. Momentum-resolved electron energy loss spectroscopy for mapping the photonic density of states. ACS Photon. 4, 1009–1014 (2017).10.1021/acsphotonics.7b00103 ↗
74. Hage, F. S., Hardcastle, T. P., Scott, A. J., Brydson, R. & Ramasse, Q. M. Momentum- and space-resolved high-resolution electron energy loss spectroscopy of individual single-wall carbon nanotubes. Phys. Rev. B 95, 195411 (2017).10.1103/PhysRevB.95.195411 ↗
75. Vesseur, E. J. R., Coenen, T., Caglayan, H., Engheta, N. & Polman, A. Experimental verification of n=0 structures for visible light. Phys. Rev. Lett. 110, 013902 (2013).10.1103/PhysRevLett.110.013902 ↗
76. Talebi, N. et al. Excitation of mesoscopic plasmonic tapers by relativistic electrons: phase matching versus eigenmode resonances. ACS Nano 9, 7641–7648 (2015).10.1021/acsnano.5b03024 ↗
77. Schröder, B. et al. Real-space imaging of nanotip plasmons using electron energy loss spectroscopy. Phys. Rev. B 92, 085411 (2015).10.1103/PhysRevB.92.085411 ↗
78. Takeuchi, K. & Yamamoto, N. Visualization of surface plasmon polariton waves in two-dimensional plasmonic crystal by cathodoluminescence. Opt. Express 19, 12365–12374 (2011).10.1364/OE.19.012365 ↗
79. Chen, C. H. & Silkox, J. Detection of optical surface guided modes in thin graphite films by high-energy electron scattering. Phys. Rev. 35, 390–393 (1975).
80. Terauchi, M., Tanaka, M., Matsumoto, T. & Saito, Y. Electron energy-loss spectroscopy study of the electronic structure of boron nitride nanotubes. J. Electron Microsc. 47, 319–324 (1998).10.1093/oxfordjournals.jmicro.a023598 ↗
81. Kociak, M., Henrard, L., Stephan, O., Suenaga, K. & Colliex, C. Plasmons in layered nanospheres and nanotubes investigated by spatially resolved electron energy-loss spectroscopy. Phys. Rev. B 61, 936–944 (2000).10.1103/PhysRevB.61.13936 ↗
82. Arenal, R. et al. Experimental evidence of surface-plasmon coupling in anisotropic hollow nanoparticles. Phys. Rev. Lett 87, 075501 (2001).10.1103/PhysRevLett.87.075501 ↗
83. Arenal, R. et al. Electron energy loss spectroscopy measurement of the optical gaps on individual boron nitride single-walled and multiwalled nanotubes. Phys. Rev. Lett. 95, 127601 (2005).10.1103/PhysRevLett.95.127601 ↗
84. Rossouw, D., Botton, G. A., Najafi, E., Lee, V. & Hitchcock, A. P. Metallic and semiconducting single-walled carbon nanotubes : differentiating individual SWCNTs by their carbon 1s spectra. ACS Nano 6, 10965–10972 (2012).10.1021/nn3045227 ↗
85. Talebi, N. et al. Wedge Dyakonov waves and Dyakonov plasmons in topological insulator Bi2Se3 probed by electron beams. ACS Nano 10, 6988–6994 (2016).10.1021/acsnano.6b02968 ↗
86. Hyun, J. K., Couillard, M., Rajendran, P., Liddell, C. M. & Muller, D. A. Measuring far-ultraviolet whispering gallery modes with high energy electrons. Appl. Phys. Lett. 93, 243106 (2008).10.1063/1.3046731 ↗
87. Coenen, T., van de Groep, J. & Polman, A. Resonant modes of single silicon nanocavities excited by electron irradiation. ACS Nano 7, 1689–1698 (2013).10.1021/nn3056862 ↗
88. Sapienza, R. et al. Deep-subwavelength imaging of the modal dispersion of light. Nat. Mater. 11, 781–787 (2012).10.1038/nmat3402 ↗
89. Brenny, B. J. M., Beggs, D. M., van der Wel, R. E. C., Kuipers, L. & Polman, A. Near-infrared spectroscopic cathodoluminescence imaging polarimetry on silicon photonic crystal waveguides. ACS Photon 3, 2112–2121 (2016).10.1021/acsphotonics.6b00557 ↗
90. Peng, S. et al. Probing the band structure of topological silicon photonic lattices in the visible spectrum. Phys. Rev. Lett 122, 117401 (2019).10.1103/PhysRevLett.122.117401 ↗
91. García de Abajo, F. J. et al. Cherenkov effect as a probe of photonic nanostructures. Phys. Rev. Lett. 91, 143902 (2003).10.1103/PhysRevLett.91.143902 ↗
92. Cha, J. J. et al. Mapping local optical densities of states in silicon photonic structures with nanoscale electron spectroscopy. Phys. Rev. B 81, 113102 (2010).10.1103/PhysRevB.81.113102 ↗
93. Krivanek, O. L. et al. Vibrational spectroscopy in the electron microscope. Nature 514, 209–212 (2014).10.1038/nature13870 ↗
94. Lagos, M. J., Trügler, A., Hohenester, U. & Batson, P. E. Mapping vibrational surface and bulk modes in a single nanocube. Nature 543, 529–532 (2017).10.1038/nature21699 ↗
95. Lagos, M. J. et al. Excitation of long-wavelength surface optical vibrational modes in films, cubes and film/cube composite system using an atom-sized electron beam. Microscopy 67, i3–i13 (2018).10.1093/jmicro/dfx130 ↗
96. Caldwell, J. D. et al. Low-Loss, Extreme subdiffraction photon confinement via silicon carbide localized surface phonon polariton resonators. Nano Lett. 13, 3690–3697 (2013).10.1021/nl401590g ↗
97. Forbes, B. D. & Allen, L. J. Modeling energy-loss spectra due to phonon excitation. Phys. Rev. B 94, 014110 (2016).10.1103/PhysRevB.94.014110 ↗
98. Hage, F. S., Kepaptsoglou, D. M., Ramasse, Q. M. & Allen, L. J. Phonon spectroscopy at atomic resolution. Phys. Rev. Lett. 122, 16103 (2019).10.1103/PhysRevLett.122.016103 ↗
99. Lagos, M. J. & Batson, P. E. Thermometry with subnanometer resolution in the electron microscope using the principle of detailed balancing. Nano Lett. 18, 4556–4563 (2018).10.1021/acs.nanolett.8b01791 ↗
100. Idrobo, J. C. et al. Temperature measurement by a nanoscale electron probe using energy gain and loss spectroscopy. Phys. Rev. Lett. 120, 95901 (2018).10.1103/PhysRevLett.120.095901 ↗