Single-atom vibrational spectroscopy with chemical-bonding sensitivity
Source abstract
Abstract
Correlation of lattice vibrational properties with local atomic configurations in materials is essential for elucidating functionalities that involve phonon transport in solids. Recent developments in vibrational spectroscopy in a scanning transmission electron microscope have enabled direct measurements of local phonon modes at defects and interfaces by combining high spatial and energy resolution. However, pushing the ultimate limit of vibrational spectroscopy in a scanning transmission electron microscope to reveal the impact of chemical bonding on local phonon modes requires extreme sensitivity of the experiment at the chemical-bond level. Here we demonstrate that, with improved instrument stability and sensitivity, the specific vibrational signals of the same substitutional impurity and the neighbouring carbon atoms in monolayer graphene with different chemical-bonding configurations are clearly resolved, complementary with density functional theory calculations. The present work opens the door to the direct observation of local phonon modes with chemical-bonding sensitivity, and provides more insights into the defect-induced physics in graphene.
Source: europepmc · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Electronic and Structural Properties of Oxides · Surface and Thin Film Phenomena · Force Microscopy Techniques and Applications
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (56)
Show source-provided references
1. Callaway, J. & von Baeyer, H. C. Effect of point imperfections on lattice thermal conductivity. Phys. Rev. 120, 1149–1154 (1960).10.1103/PhysRev.120.1149 ↗
2. Norris, D. J., Efros, A. L. & Erwin, S. C. Doped nanocrystals. Science 319, 1776–1779 (2008).10.1126/science.1143802 ↗
3. Hwang, H. Y. et al. Emergent phenomena at oxide interfaces. Nat. Mater. 11, 103–113 (2012).10.1038/nmat3223 ↗
4. Packan, P. A. Pushing the limits. Science 285, 2079–2081 (1999).10.1126/science.285.5436.2079 ↗
5. Wang, D. et al. Evidence for Majorana bound states in an iron-based superconductor. Science 362, 333–335 (2018).10.1126/science.aao1797 ↗
6. Lindsay, L., Broido, D. A. & Mingo, N. Flexural phonons and thermal transport in graphene. Phys. Rev. B 82, 115427 (2010).10.1103/PhysRevB.82.115427 ↗
7. Polanco, C. A. & Lindsay, L. Ab initio phonon point defect scattering and thermal transport in graphene. Phys. Rev. B 97, 014303 (2018).10.1103/PhysRevB.97.014303 ↗
8. Markussen, T., Jauho, A.-P. & Brandbyge, M. Electron and phonon transport in silicon nanowires: atomistic approach to thermoelectric properties. Phys. Rev. B 79, 035415 (2009).10.1103/PhysRevB.79.035415 ↗
9. Brun, C. et al. Remarkable effects of disorder on superconductivity of single atomic layers of lead on silicon. Nat. Phys. 10, 444–450 (2014).10.1038/nphys2937 ↗
10. Cowley, R. A. Acoustic phonon instabilities and structural phase transitions. Phys. Rev. B 13, 4877–4885 (1976).10.1103/PhysRevB.13.4877 ↗
11. Luh, D. A., Miller, T., Paggel, J. J. & Chiang, T. C. Large electron–phonon coupling at an interface. Phys. Rev. Lett. 88, 256802 (2002).10.1103/PhysRevLett.88.256802 ↗
12. Li, M. et al. Nonperturbative quantum nature of the dislocation–phonon interaction. Nano Lett. 17, 1587–1594 (2017).10.1021/acs.nanolett.6b04756 ↗
13. Rez, P. Does phonon scattering give high-resolution images? Ultramicroscopy 52, 260–266 (1993).10.1016/0304-3991(93)90034-U ↗
14. Rez, P. Is localized infrared spectroscopy now possible in the electron microscope? Microsc. Microanal. 20, 671–677 (2014).10.1017/S1431927614000129 ↗
15. Rez, P. & Singh, A. Lattice resolution of vibrational modes in the electron microscope. Ultramicroscopy 220, 113162 (2021).10.1016/j.ultramic.2020.113162 ↗
16. Krivanek, O. L. et al. Vibrational spectroscopy in the electron microscope. Nature 514, 209–212 (2014).10.1038/nature13870 ↗
17. Miyata, T. et al. Measurement of vibrational spectrum of liquid using monochromated scanning transmission electron microscopy–electron energy loss spectroscopy. Microscopy 63, 377–382 (2014).10.1093/jmicro/dfu023 ↗
18. Rez, P. et al. Damage-free vibrational spectroscopy of biological materials in the electron microscope. Nat. Commun. 7, 10945 (2016).10.1038/ncomms10945 ↗
19. Govyadinov, A. A. et al. Probing low-energy hyperbolic polaritons in van der Waals crystals with an electron microscope. Nat. Commun. 8, 95 (2017).10.1038/s41467-017-00056-y ↗
20. Li, N. et al. Direct observation of highly confined phonon polaritons in suspended monolayer hexagonal boron nitride. Nat. Mater. 20, 43–48 (2020).10.1038/s41563-020-0763-z ↗
21. Konečná, A., Li, J., Edgar, J. H., García de Abajo, F. J. & Hachtel, J. A. Revealing nanoscale confinement effects on hyperbolic phonon polaritons with an electron beam. Small 17, 2103404 (2021).10.1002/smll.202103404 ↗
22. 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 ↗
23. Idrobo, J. C. et al. Temperature measurement by a nanoscale electron probe using energy gain and loss spectroscopy. Phys. Rev. Lett. 120, 095901 (2018).10.1103/PhysRevLett.120.095901 ↗
24. 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 ↗
25. Jokisaari, J. R. et al. Vibrational spectroscopy of water with high spatial resolution. Adv. Mater. 30, 1802702 (2018).10.1002/adma.201802702 ↗
26. Hachtel, J. A. et al. Identification of site-specific isotopic labels by vibrational spectroscopy in the electron microscope. Science 363, 525–528 (2019).10.1126/science.aav5845 ↗
27. Li, X. et al. Three-dimensional vectorial imaging of surface phonon polaritons. Science 371, 1364–1367 (2021).10.1126/science.abg0330 ↗
28. Senga, R. et al. Position and momentum mapping of vibrations in graphene nanostructures. Nature 573, 247–250 (2019).10.1038/s41586-019-1477-8 ↗
29. Qi, R. et al. Four-dimensional vibrational spectroscopy for nanoscale mapping of phonon dispersion in BN nanotubes. Nat. Commun. 12, 1179 (2021).10.1038/s41467-021-21452-5 ↗
30. Qi, R. et al. Measuring phonon dispersion at an interface. Nature 599, 399–403 (2021).10.1038/s41586-021-03971-9 ↗
31. Cheng, Z. et al. Experimental observation of localized interfacial phonon modes. Nat. Commun. 12, 6901 (2021).10.1038/s41467-021-27250-3 ↗
32. Yan, X. et al. Single-defect phonons imaged by electron microscopy. Nature 589, 65–69 (2021).10.1038/s41586-020-03049-y ↗
33. Hoglund, E. R. et al. Emergent interface vibrational structure of oxide superlattices. Nature 601, 556–561 (2022).10.1038/s41586-021-04238-z ↗
34. Gadre, C. A. et al. Nanoscale imaging of phonon dynamics by electron microscopy. Nature 606, 292–297 (2022).10.1038/s41586-022-04736-8 ↗
35. Dwyer, C. Localization of high-energy electron scattering from atomic vibrations. Phys. Rev. B 89, 054103 (2014).10.1103/PhysRevB.89.054103 ↗
36. Dwyer, C. et al. Electron-beam mapping of vibrational modes with nanometer spatial resolution. Phys. Rev. Lett. 117, 256101 (2016).10.1103/PhysRevLett.117.256101 ↗
37. Hage, F. S. et al. Nanoscale momentum-resolved vibrational spectroscopy. Sci. Adv. 4, eaar7495 (2018).10.1126/sciadv.aar7495 ↗
38. Hage, F. S., Kepaptsoglou, D. M., Ramasse, Q. M. & Allen, L. J. Phonon spectroscopy at atomic resolution. Phys. Rev. Lett. 122, 016103 (2019).10.1103/PhysRevLett.122.016103 ↗
39. Venkatraman, K., Levin, B. D. A., March, K., Rez, P. & Crozier, P. A. Vibrational spectroscopy at atomic resolution with electron impact scattering. Nat. Phys. 15, 1237–1241 (2019).10.1038/s41567-019-0675-5 ↗
40. Hage, F. S., Radtke, G., Kepaptsoglou, D. M., Lazzeri, M. & Ramasse, Q. M. Single-atom vibrational spectroscopy in the scanning transmission electron microscope. Science 367, 1124–1127 (2020).10.1126/science.aba1136 ↗
41. Senga, R. et al. Imaging of isotope diffusion using atomic-scale vibrational spectroscopy. Nature 603, 68–72 (2022).10.1038/s41586-022-04405-w ↗
42. Li, Y.-H. et al. Atomic-scale probing of heterointerface phonon bridges in nitride semiconductor. Proc. Natl Acad. Sci. USA 119, e2117027119 (2022).10.1073/pnas.2117027119 ↗
43. Xu, J. et al. Determining structural and chemical heterogeneities of surface species at the single-bond limit. Science 371, 818–822 (2021).10.1126/science.abd1827 ↗
44. Yan, X., Gadre, C. A., Aoki, T. & Pan, X. Probing molecular vibrations by monochromated electron microscopy. Trends Chem. 4, 76–90 (2022).10.1016/j.trechm.2021.10.004 ↗
45. Lugg, N. R., Forbes, B. D., Findlay, S. D. & Allen, L. J. Atomic resolution imaging using electron energy-loss phonon spectroscopy. Phys. Rev. B 91, 144108 (2015).10.1103/PhysRevB.91.144108 ↗
46. Allen, L. J., Brown, H. G., Findlay, S. D. & Forbes, B. D. A quantum mechanical exploration of phonon energy-loss spectroscopy using electrons in the aloof beam geometry. Microscopy 67, i24–i29 (2017).10.1093/jmicro/dfx038 ↗
47. Zhou, W. et al. Direct determination of the chemical bonding of individual impurities in graphene. Phys. Rev. Lett. 109, 206803 (2012).10.1103/PhysRevLett.109.206803 ↗
48. Li, X. et al. Large-area synthesis of high-quality and uniform graphene films on copper foils. Science 324, 1312–1314 (2009).10.1126/science.1171245 ↗
49. Regan, W. et al. A direct transfer of layer-area graphene. Appl. Phys. Lett. 96, 113102 (2010).10.1063/1.3337091 ↗
50. Shi, J., Hu, S., Xia, Y. & Zhou, W. Laboratory design for a Nion monochromated aberration corrected scanning transmission electron microscope. J. Chin. Electron Microsc. Soc. 39, 715–721 (2020).
51. de la Peña, F. et al. hyperspy/hyperspy Hyperspy v.1.5.2. Zenodo https://doi.org/10.5281/zenodo.3396791 (2019).10.5281/zenodo.3396791 ↗
52. Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).10.1016/0927-0256(96)00008-0 ↗
53. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).10.1103/PhysRevB.54.11169 ↗
54. Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).10.1103/PhysRevB.50.17953 ↗
55. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).10.1103/PhysRevLett.77.3865 ↗
56. Perdew, J. P. et al. Atoms, molecules, solids, and surfaces: applications of the generalized gradient approximation for exchange and correlation. Phys. Rev. B 46, 6671–6687 (1992).10.1103/PhysRevB.46.6671 ↗