Observing the individual building blocks of matter is one of the primary goals of microscopy. The invention of the scanning tunnelling microscope1 revolutionized experimental surface science in that atomic-scale features on a solid-state surface could finally be readily imaged. However, scanning tunnelling microscopy has limited applicability due to restrictions in, for example, sample conductivity, cleanliness, and data acquisition rate. An older microscopy technique, that of transmission electron microscopy (TEM)2,3, has benefited tremendously in recent years from subtle instrumentation advances, and individual heavy (high-atomic-number) atoms can now be detected by TEM4,5,6,7 even when embedded within a semiconductor material8,9. But detecting an individual low-atomic-number atom, for example carbon or even hydrogen, is still extremely challenging, if not impossible, via conventional TEM owing to the very low contrast of light elements2,3,10,11,12. Here we demonstrate a means to observe, by conventional TEM, even the smallest atoms and molecules: on a clean single-layer graphene membrane, adsorbates such as atomic hydrogen and carbon can be seen as if they were suspended in free space. We directly image such individual adatoms, along with carbon chains and vacancies, and investigate their dynamics in real time. These techniques open a way to reveal dynamics of more complex chemical reactions or identify the atomic-scale structure of unknown adsorbates. In addition, the study of atomic-scale defects in graphene may provide insights for nanoelectronic applications of this interesting material.
Subscribe to Journal
Get full journal access for 1 year
only $3.90 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
Binning, G., Rohrer, H., Gerber, Ch. & Weibel, E. Surface studies by scanning tunneling microscopy. Phys. Rev. Lett. 49, 57–61 (1982)
Spence, J. C. H. High-Resolution Electron Microscopy (Oxford Univ. Press, Oxford, UK, 2003)
Buseck, P. R., Cowley, J. M. & Eyring, L. High-Resolution Transmission Electron Microscopy (Oxford Univ. Press, Oxford, UK, 1988)
Crewe, A. V., Wall, J. & Langmore, J. Visibility of single atoms. Science 168, 1338–1340 (1970)
Hashimoto, H. et al. Visualization of single atoms in molecules and crystals by dark field electron microscopy. J. Electron Microsc. (Tokyo) 22, 123–134 (1973)
Iijima, S. Observation of single and clusters of atoms in bright field electron microscopy. Optik 48, 193–213 (1977)
Nellist, P. D. & Pennycook, S. J. Direct imaging of the atomic configuration of ultradispersed catalysts. Science 274, 413–415 (1996)
Voyles, P. M., Muller, D. A., Grazul, J. L., Citrin, P. H. & Gossmann, H.-J. L. Atomic-scale imaging of individual dopant atoms and clusters in highly n-type bulk silicon. Nature 416, 826–829 (2002)
van Benthem, K. et al. Three-dimensional imaging of individual hafnium atoms inside a semiconductor device. Appl. Phys. Lett. 87, 034104 (2005)
Doyle, P. A. & Turner, P. S. Relativistic Hartree-Fock x-ray and electron scattering factors. Acta Crystallogr. A 24, 390–397 (1968)
Kisielowski, C. et al. Imaging columns of the light elements carbon, nitrogen and oxygen with sub Angstrom resolution. Ultramicroscopy 89, 243–263 (2001)
Jia, C. L., Lentzen, M. & Urban, K. Atomic-resolution imaging of oxygen in perovskite ceramics. Science 299, 870–873 (2003)
Smith, B. W., Monthioux, M. & Luzzi, D. E. Encapsulated C in carbon nanotubes. Nature 396, 323–324 (1998)
Liu, Z. et al. Transmission electron microscopy imaging of individual functional groups of fullerene derivatives. Phys. Rev. Lett. 96, 088304 (2006)
Lui, Z., Yanagi, K., Suenaga, K., Kataura, H. & Iijima, S. Imaging the dynamic behaviour of individual retinal chromophores confined inside carbon nanotubes. Nature Nanotechnol. 2, 422–425 (2007)
Hashimoto, A., Suenaga, K., Gloter, A., Urita, K. & Iijima, S. Direct evidence for atomic defects in graphene layers. Nature 430, 870–873 (2004)
Suenaga, K. et al. Imaging active topological defects in carbon nanotubes. Nature Nanotechnol. 2, 358–360 (2007)
Meyer, J. C. et al. The structure of suspended graphene sheets. Nature 446, 60–63 (2007)
Novoselov, K. S. et al. Two-dimensional atomic crystals. Proc. Natl Acad. Sci. USA 102, 10451–10453 (2005)
Novoselov, K. S. et al. Two-dimensional gas of massless Dirac fermions in graphene. Nature 438, 197–200 (2005)
Zhang, Y., Tan, J. W., Stormer, H. L. & Kim, P. Experimental observation of the quantum Hall effect and Berry’s phase in graphene. Nature 438, 201–204 (2005)
Vainshtein, B. K. & Pinsker, Z. G. Opredelenie Polozheniya Vodoroda V Kristallicheskoi Reshetke Parafina. Dokl. Akad. Nauk SSSR 72, 53–56 (1950)
Amara, H., Latil, S., Lambin, Ph. & Charlier, J.-C. Scanning tunneling microscopy fingerprints of point defects in graphene: A theoretical prediction. Phys. Rev. B 76, 115423 (2007)
Smith, B. W. & Luzzi, E. Electron irradiation effects in single wall carbon nanotubes. J. Appl. Phys. 90, 3509–3515 (2001)
Jeloaica, L. & Sidis, V. DFT investigation of the adsorption of atomic hydrogen on a cluster-model graphite surface. Chem. Phys. Lett. 300, 157–162 (1999)
Sha, X. & Jackson, B. First-principles study of the structural and energetic properties of H atoms on a graphite (0001) surface. Surf. Sci. 496, 318–330 (2002)
Hornekaer, L. et al. Metastable structures and recombination pathways for atomic hydrogen on the graphite (0001) surface. Phys. Rev. Lett. 96, 156104 (2006)
Boukhvalov, D. W., Katsnelson, M. I. & Lichtenstein, A. I. Hydrogen on graphene: Electronic structure, total energy, structural distortions and magnetism from first-principles calculations. Phys. Rev. B 77, 035427 (2007)
Ito, A., Nakamura, H. & Takayama, A. Chemical reaction between single hydrogen atom and graphene. Preprint at 〈http://arxiv.org/abs/cond-mat/0703377〉 2007.
Nordlund, K., Keinonen, J. & Mattila, T. Formation of ion irradiation induced small-scale defects on graphite surfaces. Phys. Rev. Lett. 77, 699–702 (1996)
This work was supported by the Director, Office of Energy Research, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, of the US Department of Energy under contract DE-AC02-05CH11231. A.Z. acknowledges support from the Miller Institute of Basic Research in Science, and C.O.G. acknowledges support from an NSF Graduate Fellowship.
The file contains Supplementary Methods, Supplementary Figures S1-S3 and Supplementary Discussion: (PDF 1150 kb)
The file contains Supplementary Movie 1 showing dynamics of a linear molecule on a graphene membrane as in Figs. 4b-d of the main article. Horizontal field of view in the video is 10 nm. (MOV 243 kb)
The file contains Supplementary Movie 2 showing dynamics of a carbon chain attached between larger adsorbates. Horizontal field of view is 14 nm. (MOV 2484 kb)
About this article
Cite this article
Meyer, J., Girit, C., Crommie, M. et al. Imaging and dynamics of light atoms and molecules on graphene. Nature 454, 319–322 (2008). https://doi.org/10.1038/nature07094
Advanced Energy Materials (2020)
Advanced Materials (2020)
ACS Omega (2020)
Frontiers of Physics (2020)
Multifunctionality for the nanojunction of a rotating p-phenylene vinylene molecule between graphene leads
Physics Letters A (2020)