Vibrational spectroscopy in the electron microscope


Vibrational spectroscopies using infrared radiation1,2, Raman scattering3, neutrons4, low-energy electrons5 and inelastic electron tunnelling6 are powerful techniques that can analyse bonding arrangements, identify chemical compounds and probe many other important properties of materials. The spatial resolution of these spectroscopies is typically one micrometre or more, although it can reach a few tens of nanometres or even a few ångströms when enhanced by the presence of a sharp metallic tip6,7. If vibrational spectroscopy could be combined with the spatial resolution and flexibility of the transmission electron microscope, it would open up the study of vibrational modes in many different types of nanostructures. Unfortunately, the energy resolution of electron energy loss spectroscopy performed in the electron microscope has until now been too poor to allow such a combination. Recent developments that have improved the attainable energy resolution of electron energy loss spectroscopy in a scanning transmission electron microscope to around ten millielectronvolts now allow vibrational spectroscopy to be carried out in the electron microscope. Here we describe the innovations responsible for the progress, and present examples of applications in inorganic and organic materials, including the detection of hydrogen. We also demonstrate that the vibrational signal has both high- and low-spatial-resolution components, that the first component can be used to map vibrational features at nanometre-level resolution, and that the second component can be used for analysis carried out with the beam positioned just outside the sample—that is, for ‘aloof’ spectroscopy that largely avoids radiation damage.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Figure 1: Revealing vibrational signals in the electron microscope.
Figure 2: Vibrational spectra from various materials.
Figure 3: Profile showing the spatial variation of the vibrational signal.


  1. 1

    Stuart, B. Infrared Spectroscopy: Fundamentals and Applications (Wiley, 2004)

    Google Scholar 

  2. 2

    Griffiths, O. R. & De Haseth, J. A. Fourier Transform Infrared Spectrometry 2nd edn (Wiley, 2007)

    Google Scholar 

  3. 3

    McCreery, R. L. Raman Spectroscopy for Chemical Analysis (Wiley, 2000)

    Google Scholar 

  4. 4

    Mitchell, P. C. H., Parker, S. F., Ramirez-Cuesta, A. J. & Tomkinson, J. Vibrational Spectroscopy With Neutrons (World Scientific, 2005)

    Google Scholar 

  5. 5

    Ibach, H. & Mills, D. L. Electron Energy Loss Spectroscopy and Surface Vibrations (Academic, 1982)

    Google Scholar 

  6. 6

    Stipe, B. C., Rezaei, M. A. & Ho, W. Single molecule vibrational spectroscopy and microscopy. Science 280, 1732–1735 (1998)

    ADS  CAS  Article  Google Scholar 

  7. 7

    Dai, S. et al. Tunable photon polaritons in atomically thin van der Waals crystals of boron nitride. Science 343, 1125–1129 (2014)

    ADS  CAS  Article  Google Scholar 

  8. 8

    Haider, M., Braunshausen, G. & Schwann, E. Correction of the spherical aberration of a 200 kV TEM by means of a hexapole-corrector. Optik 99, 167–179 (1995)

    Google Scholar 

  9. 9

    Krivanek, O. L., Dellby, N., Spence, A. J., Camps, R. A. & Brown, L. M. Aberration correction in the STEM. Inst. Phys. Conf. Ser. 153, 35–40 (1997)

    Google Scholar 

  10. 10

    Haider, M. et al. Electron microscopy image enhanced. Nature 392, 768–769 (1998)

    ADS  CAS  Article  Google Scholar 

  11. 11

    Batson, P. E., Dellby, N. & Krivanek, O. L. Sub-Ångstrom resolution using aberration corrected electron optics. Nature 418, 617–620 (2002)

    ADS  CAS  Article  Google Scholar 

  12. 12

    Erni, R., Rossell, M. D., Kisielowski, C. & Dahmen, U. Atomic-resolution imaging with a sub-50-pm electron probe. Phys Rev. Lett. 102, 096101 (2009)

    ADS  Article  Google Scholar 

  13. 13

    Krivanek, O. L. et al. Atom-by-atom structural and chemical analysis by annular dark field electron microscopy. Nature 464, 571–574 (2010)

    ADS  CAS  Article  Google Scholar 

  14. 14

    Suenaga, K. & Koshino, M. Atom-by-atom spectroscopy at graphene edge. Nature 468, 1088–1090 (2010)

    ADS  CAS  Article  Google Scholar 

  15. 15

    Zhou, W. et al. Direct determination of the chemical bonding of individual impurities in graphene. Phys. Rev. Lett. 109, 206803 (2012)

    ADS  Article  Google Scholar 

  16. 16

    Ramasse, Q. M. et al. Probing the bonding and electronic structure of single atom dopants in graphene with electron energy loss spectroscopy. Nano Lett. 13, 4989–4995 (2013)

    ADS  CAS  Article  Google Scholar 

  17. 17

    Krivanek, O. L., Lovejoy, T. C., Dellby, N. & Carpenter, R. W. Monochromated STEM with a 30 meV-wide, atom-sized electron probe. Microscopy 62, 3–21 (2013)

    CAS  Article  Google Scholar 

  18. 18

    Boersch, H., Geiger, J. & Stickel, W. Interaction of 25-keV electrons with lattice vibrations in LiF. Experimental evidence for surface modes of lattice vibration. Phys. Rev. Lett. 17, 379–381 (1966)

    ADS  CAS  Article  Google Scholar 

  19. 19

    Terauchi, M., Tanaka, M., Tsuno, K. & Ishida, M. Development of a high energy-resolution electron energy loss spectroscopy microscope. J. Microsc. 194, 203–209 (1999)

    CAS  Article  Google Scholar 

  20. 20

    Walls, M. G. & Howie, A. Dielectric theory of localized energy loss spectroscopy. Ultramicroscopy 28, 40–42 (1989)

    Article  Google Scholar 

  21. 21

    Cohen, H. et al. Near-field electron energy loss spectroscopy of nanoparticles. Phys. Rev. Lett. 80, 782–785 (1998)

    ADS  CAS  Article  Google Scholar 

  22. 22

    Garcia de Abajo, F. J. & Howie, A. Electron spectroscopy from outside – aloof beam or near field? Inst. Phys. Conf. Ser. 161, 327–330 (1999)

    Google Scholar 

  23. 23

    Howie, A. & Milne, R. H. Excitations at interfaces and small particles. Ultramicroscopy 18, 427–4334 (1985)

    CAS  Article  Google Scholar 

  24. 24

    Wang, Z. L. Valence electron excitations and plasmon oscillations in thin films, surfaces, interfaces and small particles. Micron 27, 265–299 (1996)

    CAS  Article  Google Scholar 

  25. 25

    García de Abajo, F. J. Optical excitations in electron microscope. Rev. Mod. Phys. 82, 209–275 (2010)

    ADS  Article  Google Scholar 

  26. 26

    Cueva, P. & Muller, D. A. Atomic-scale optical and vibrational spectroscopy with low loss EELS. Microsc. Microanal. 19 (suppl. 2). 1130–1131 (2013)

    ADS  Article  Google Scholar 

  27. 27

    Dwyer, C. Localization of high-energy electron scattering from atomic vibrations. Phys. Rev. B 89, 054103 (2014)

    ADS  Article  Google Scholar 

  28. 28

    Rez, P. Is localised infra red spectroscopy now possible in the electron microscope? Microsc. Microanal. 20, 671–677 (2014)

    ADS  CAS  Article  Google Scholar 

  29. 29

    Lovejoy T. C et al. Energy-filtered high-angle dark field mapping of ultra-light elements. Microsc. Microanal. 20, (suppl. 3)558–559 (2014)

    Article  Google Scholar 

  30. 30

    Pennycook S. J., Nellist P. D., eds. Scanning Transmission Electron Microscopy (Springer, 2011)

  31. 31

    Spurr, A. R. A low-viscosity epoxy resin embedding medium for electron microscopy. J. Ultrastruct. Res. 26, 31–43 (1969)

    CAS  Article  Google Scholar 

  32. 32

    Egerton, R. F. Electron Energy Loss Spectroscopy in the Electron Microscope 3rd edn (Springer, 2011);

  33. 33

    Tiemeijer, P. C., van Lin, J. H. A., Freitag, B. H. & de Jong, A. F. Monochromized 200 kV (S)TEM. Microsc. Microanal. 8 (suppl. 2). 70–71 (2012)

    Article  Google Scholar 

  34. 34

    Krivanek, O. L., Gubbens, A. J., Dellby, N. & Meyer, C. E. Design and first applications of a post-column imaging filter. Microsc. Microanal. Microstruct. 3, 187–199 (1992)

    Article  Google Scholar 

  35. 35

    Gubbens, A. J. et al. The GIF Quantum, a next generation post-column imaging energy filter. Ultramicroscopy 110, 962–970 (2010)

    CAS  Article  Google Scholar 

  36. 36

    Krivanek, O. L. et al. Towards sub-10 meV energy resolution STEM-EELS. Inst. Phys. Conf. Ser. 522, 012023 (2014)

    Article  Google Scholar 

  37. 37

    Krivanek, O. L. et al. An electron microscope for the aberration-corrected era. Ultramicroscopy 108, 179–195 (2008)

    CAS  Article  Google Scholar 

  38. 38

    Krivanek, O. L., Chisholm, M. F., Dellby, N. & Murfitt, M. F. in Scanning Transmission Electron Microscopy: Imaging and Analysis (eds Pennycook, S. J. & Nellist, P. D. ) 613–656 (Springer, 2011)

    Google Scholar 

  39. 39

    Bock, J. & Gouq-Jen, S. Interpretation of the infrared spectra of fused silica. J. Am. Ceram. Soc. 53, 69–73 (1970)

    CAS  Article  Google Scholar 

  40. 40

    Oshima, C. & Nagashima, A. Ultra-thin epitaxial films of graphite and hexagonal boron nitride on solid surfaces. J. Phys. Condens. Matter 9, 1–20 (1997)

    ADS  CAS  Article  Google Scholar 

  41. 41

    Li, P. J. et al. Structural characterization of nm SiC films grown on Si. Appl. Phys. Lett. 62, 3135–3137 (1993)

    ADS  CAS  Article  Google Scholar 

  42. 42

    Bashkin, I. O. et al. Hydrogen interaction and bound multiphonon states in vibrational spectra of titanium hydrides. Z. Phys. Chem. 179, 335–342 (1993)

    CAS  Article  Google Scholar 

Download references


We thank A. Howie and J.-C. Idrobo for discussions, W. J. Bowman, J. Bruley, J. H. Butler, V. Domnich, R. A. Haber, Y. Ikuhara, M. R. Libera, D. S. Lowry and V. Nicolosi for provision of samples, J. Mardinly for help with running the instruments, our co-workers at Nion, especially N. J. Bacon, G. J. Corbin, P. J. Cramer, Z. Dellby, R. W. Hayner, P. Hrncirik, P. Phoungphidok, M. C. Sarahan, G. S. Skone, Z. Szilagyi and T. Yoo for help with the construction of the hardware, electronics and software for HERMES, and C. Trevor of Gatan Inc. for an instability-analysing script. We also acknowledge the use of facilities within the LeRoy Eyring Center for Solid State Science at Arizona State University. Financial support for the purchase of the microscopes was provided by National Science Foundation grants DMR MRI 0821796 (Arizona State University) and DMR MRI-R2 959905 (Rutgers University). Department of Energy grant DE-SC0004954 provided support for P.A.C. and microscopy performed at Arizona State University, and Department of Energy grant DE-SC0005132 provided support for P.E.B., M.J.L. and microscopy performed at Rutgers University. Additional support was provided by the Department of Energy (grant DE-SC0007694), the Natural Sciences and Engineering Council of Canada, the UK Engineering and Physical Research Council (capital equipment grant EP/J021156/1), Arizona State University, Rutgers University and Nion Co.

Author information




P.A.C., O.L.K. and P.R. initiated the project, P.A.C., O.L.K. and J.Z. prepared samples, T.A., P.E.B., N.D., O.L.K., M.J.L., T.C.L. and J.Z. obtained electron microscope spectra and images, P.A.C. and E.S. obtained infrared and Raman spectra, T.C.L., N.D., R.F.E. and J.Z. analysed EELS results, P.R. performed theoretical simulations, P.E.B., R.W.C., N.D., R.F.E., O.L.K., T.C.L. and P.R. advised on theoretical interpretation, P.E.B., O.L.K., T.C.L. and E.S. prepared the figures, and O.L.K. and P.R. wrote the paper. All the authors read and commented on the manuscript.

Corresponding authors

Correspondence to Ondrej L. Krivanek or Peter A. Crozier.

Ethics declarations

Competing interests

N.D., O.L.K. and T.C.L. have a financial interest in Nion Company.

Extended data figures and tables

Extended Data Figure 1 Analysis of total system instabilities, performed by plotting the position of the ZLP on the EEL spectrometer detector as a function of time.

a, Using the Gatan Enfinium EELS and original power supplies: 50 meV peak-to-peak and 12 meV r.m.s. instability. b, As a but with improved-stability power supplies: 18 meV peak-to-peak and 4.5 meV r.m.s. instability. c, Single magnetic sector EELS with Nion power supplies: 12 meV peak-to-peak and 3 meV r.m.s. instability. Panels a and b show the position of the ZLP on the EELS detector as a function of time, marking each position of the ZLP with a single point; c shows the whole ZLP profile, together with a blue trace that follows the instantaneous position of the centre of the profile.

Extended Data Figure 2 Raman spectrum of epoxy resin.

The major peak is centred on 2,920 cm−1 = 362 meV.

Extended Data Figure 3 Fall-off of the h-BN LO phonon signal in the vacuum, probed out to 300 nm.

a, HAADF image of an edge of a BN particle of nearly constant thickness, with the probed line indicated by a yellow arrow. b, Shown are the intensity of the BN phonon signal peak (at 173 meV) along the probed line (blue diamonds), the Ko model of the phonon signal decay in vacuum (dotted blue line), the exponential model of the same (dotted red line), and approximate sample thickness (green triangles). The edge of the particle is at R = 0.

PowerPoint slides

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Krivanek, O., Lovejoy, T., Dellby, N. et al. Vibrational spectroscopy in the electron microscope. Nature 514, 209–212 (2014).

Download citation

Further reading


By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.