Gentle STEM of Single Atoms: Low keV Imaging and Analysis at Ultimate Detection Limits

Low Voltage Electron Microscopy: Principles and Applications

Volumn , Issue , 2012, Pages 119-161

  Krivanek, Ondrej L ^a   Zhou, Wu ^b,c   Chisholm, Matthew F ^c   Idrobo, Juan Carlos ^b,c   Lovejoy, Tracy C ^a   Ramasse, Quentin M ^d   Dellby, Niklas ^a  

^a Nion Co Kirkland   (United States)

^b VANDERBILT UNIVERSITY   (United States)

^c OAK RIDGE NATIONAL LABORATORY   (United States)

^d SUPERSTEM LABORATORY   (United Kingdom)

Author keywords

ADF imaging; Gentle STEM applications; Gentle STEM of single atoms; Low keV imaging; Optimizing STEM resolution; Probe current at low primary energies; Single atom fine structure EELS; Single atom imaging; STEM image formation; Ultimate detection limits

Indexed keywords

EID: 84871499348     PISSN: None     EISSN: None     Source Type: Book    
DOI: 10.1002/9781118498514.ch6     Document Type: Chapter

References (75)

1. A.V Crewe, A New Kind of Scanning Microscope, J. Microscopie, 2, 369-371 (1963).
2. A.V. Crewe, J. Wall and J. Langmore, Visibility of Single Atoms, Science, 168, 1338-1340 (1970).
3. A.V. Crewe, J.P. Langmore and M.S. Isaacson, Resolution and Contrast in the Scanning Transmission Electron Microscope, in: Physical Aspects of Electron Microscopy and Microbeam Analysis, eds. B.M. Siegel and D.R. Beaman, John Wiley & Sons, Inc., New York, NY, 47-62 (1975).
4. A.V Crewe, Direct imaging of single atoms and molecules using the STEM. Proceedings 47th Nobel Symposium, Chemica Scripta, 14, 17-20 (1979).
5. S.J Pennycook and P.D. Nellist, (eds), Scanning Transmission Electron Microscopy -Imaging and Analysis, Springer (2011).
6. T. Sasaki, H. Sawada, F. Hosokawa, et al., Performance of low-voltage STEM/TEM with delta corrector and cold field emission gun, J. Electron Microscopy, 59 (Supplement), S7-S13 (2010).
7. N. Dellby, N.J. Bacon, P. Hrncirik, et al., Dedicated STEM for 200 to 40 keV operation, Europ. Phys. J. Appl. Phys., 54, 33505 (2011).
8. O.L. Krivanek, G.J. Corbin, N. Dellby, et al., An electron microscope for the aberration-corrected era, Ultramicroscopy, 108, 179-195 (2008).
9. O.L. Krivanek, M.F. Chisholm, V. Nicolosi, et al., Atom-by-atom structural and chemical analysis by annular dark field electron microscopy, Nature, 464, 571-574 (2010).
10. K. Suenaga, M. Tence, C. Mory, et al., Element-Selective Single Atom Imaging, Science, 290, 2280-2282 (2000).
11. O.L. Krivanek, N. Dellby, M.F. Murfitt, et al., Gentle STEM: ADF imaging and EELS at low primary energies, Ultramicroscopy, 110, 935-945 (2010).
12. K. Suenaga and M. Koshino, Atom-by-atom spectroscopy at graphene edge, Nature, 468, 1088-1090 (2010).
13. K. Suenaga, Y. Iizumi and T. Okazaki, Single atom spectroscopy with reduced delocalization effect using a 30 kV-STEM, Eur. Phys. J. Appl. Phys., 54, 33508 (2011).
14. O.L. Krivanek, M.F. Chisholm, M.F. Murfitt and N. Dellby, Scanning transmission electron microscopy: Albert Crewe's vision and beyond, submitted to Ultramicroscopy (2012).
15. T.C. Lovejoy, Q.M. Ramasse, M. Falke, et al., Single Atom Identification with Energy Dispersive X-ray Spectroscopy, Appl. Phys. Letts, 100, 154101 (2012).
16. L. Reimer, Image Formation in Low-Voltage Scanning Electron Microscopy (SPIE Tutorial Text Vol. TT12, Tutorial Texts in Optical Engineering, SPIE Press, 1993) ISBN: 0819412066.
17. Y. Zhu, H. Inada, K. Nakamura and J. Wall, Imaging single atoms using secondary electrons with an aberration-corrected electron microscope, Nature Materials, 8, 808-812 (2009).
18. O.L. Krivanek, M.F. Chisholm, N. Dellby and M.F. Murfitt, Atomic-resolution STEM at low primary energies, in: Scanning Transmission ElectronMicroscopy: Imaging and Analysis, S.J. Pennycook and P.D. Nellist (ed.), Springer, New York, NY (2011).
19. J.A Lin and J.M. Cowley, Calibration of the operating parameters of an HB5 STEM instrument, Ultramicroscopy, 19, 31-42 (1986).
20. O.L. Krivanek, N. Dellby and M.F. Murfitt, Aberration Correction in Electron Microscopy, in: Handbook of Charged Particle Optics, 2nd edn, J. Orloff(ed.), CRC Press, Boca Raton, FL (2009).
21. A.R Lupini, The Electron Ronchigram, in: Scanning Transmission Electron Microscopy: Imaging and Analysis, S.J. Pennycook and P.D. Nellist (ed.), Springer, New York, NY (2011).
22. P.E. Batson, N. Dellby and O.L. Krivanek, Sub-A° ngstrom resolution using aberration-corrected electron optics, Nature, 418, 617-620 (2002).
23. J.M. LeBeau, S.D. Findlay, L.J. Allen and S. Stemmer, Quantitative Atomic Resolution Scanning Transmission Electron Microscopy, Phys. Rev Lett., 100, 206101 (2008).
24. C. Dwyer, R. Erni and J. Etheridge, Method to measure spatial coherence of subangstrom electron beams, Appl. Phys. Letts., 93, 021115 (2008).
25. H. Rose, Phase Contrast in Scanning Transmission ElectronMicroscopy, Optik, 39, 416-436 (1974).
26. J.M. Cowley, M.S. Hansen and S.-Y. Wang, Imaging modes with an annular detector in STEM, Ultramicroscopy, 58, 18-24 (1995).
27. S.D. Findlay, N. Shibata, H. Sawada, et al., Robust atomic resolution imaging of light elements using scanning transmission electron microscopy, Appl. Phys. Letts., 95, 191913 (2009).
28. Y. Oshima, H. Sawada, F. Hosokawa, et al., Direct imaging of lithium atoms in LiV2O4 by spherical aberration-corrected electron microscopy, J. Electron Micr., 59, 457-461 (2010).
29. R. Ishikawa, E. Okunishi, H. Sawada, et al., Direct imaging of hydrogenatom columns in a crystal by annular bright-field electron microscopy, Nature Materials, 10, 278-281 (2011).
30. C. Jeanguillaume and C. Colliex, Spectrum-image: The next step in EELS digital acquisition and processing, Ultramicroscopy, 28, 252-257 (1989).
31. J.M Cowley and J.C.H. Spence, Innovative Imaging and Microdiffraction in STEM, Ultramicroscopy, 3, 433-438 (1979).
32. M. Haider,A. Epstein, P. Jarron and C. Boulin, Aversatile, software configurable multichannel STEM detector for angle-resolved imaging, Ultramicroscopy, 54, 41-59 (1994).
33. N. Shibata, Y. Kohno, S.D. Findlay, et al., New area detector for atomicresolution scanning transmission electron microscopy, J. Electr. Microsc., 59, 473-479 (2010).
34. O.L. Krivanek, A.J. Gubbens, N. Dellby and C.E. Meyer, Design and first applications of a post-column imaging filter, Microsc. Microanal. Microstruct., 3, 187-199 (1992).
35. A.J. Gubbens,M. Barfels, C. Trevor, et al., The GIF Quantum, a next generation post-column imaging energy filter, Ultramicroscopy, 110, 962-970 (2010).
36. M. Bosman, V.J. Keast, J.L. Garcia-Munoz, et al., Two-Dimensional Mapping of Chemical Information at Atomic Resolution, Phys. Rev. Lett., 99, 086102 (2007).
37. D.A. Muller, L. Fitting Kourkoutis, M.F. Murfitt, et al., Atomic-Scale Chemical Imaging of Composition and Bonding by Aberration-Corrected Microscopy, Science, 319, 1073-1076 (2008).
38. K. Kimoto and K. Ishizuka, Spatially resolved diffractometry with atomiccolumn resolution, Ultramicroscopy, 111, 1111-1116 (2011).
39. H. Lichte, P. Formanek, A. Lenk, et al., Electron Holography: Applications to Materials Questions, Annual Rev. Mater. Res., 37, 539-588 (2007).
40. J.C. Meyer, F. Eder, S. Kurasch, et al., An accurate measurement of electron beam induced displacement cross sections for single-layer graphene, Phys. Rev. Letts, 108, 196102 (2012) and http://arxiv.org/abs/1203.2372.
41. K.S. Novoselov, A.K. Geim, S.V. Morozov, et al., Electric Field Effect in Atomically Thin Carbon Films, Science, 306, 666-669 (2004).
42. A.K Geim and K.S. Novoselov, The rise of graphene, Nature Materials, 6, 183-191 (2007).
43. A.K Geim, Graphene: Status and Prospects, Science, 324, 1530-1534 (2009).
44. S. Iijima. Observation of single and clusters of atoms in bright field electron microscopy, Optik, 48, 193-213 (1977).
45. J.C. Meyer, A.K. Geim, M.I. Katsnelson, et al., The structure of suspended graphene sheets, Nature, 446, 60-63 (2007).
46. J.C. Meyer, Ç.Ö. Girit, M.F. Crommie and A. Zettl, Imaging and dynamics of light atoms and molecules on graphene, Nature, 454, 319-322 (2008).
47. Ç.Ö. Girit, J.C. Meyer, R. Erniet al., Graphene at the Edge: Stability and Dynamics, Science, 323, 1705-1708 (2009).
48. J.R. Jinschek, E. Yucelena, H.A. Calderon and B. Freitag, Quantitative atomic 3-D imaging of single/double sheet graphene structure, Carbon, 49, 556-562 (2011).
49. J.C. Meyer, S. Kurasch, H.J. Park, et al., Experimental analysis of charge redistribution due to chemical bonding by high-resolution transmission electron microscopy, Nature Materials, 10, 209-215 (2011).
50. M. Isaacson, M. Ohtsuki and M. Utlaut, Can we determine the structure of thin amorphous carbon films using scanning transmission electron microscopy? Proc. 37th EMSA Meet., 498-501 (1979).
51. M.H. Gass, U. Bangert, A.L. Bleloch, et al., Free-Standing Graphene at Atomic Resolution, Nature Nanotech., 3, 676-681 (2008).
52. R. Zan, U. Bangert, Q. Ramasse and K.S. Novoselov, Metal-Graphene Interaction Studied via Atomic Resolution Scanning Transmission Electron Microscopy, Nano Letts., 11, 1087-1092 (2011).
53. R. Zan, U. Bangert, Q. Ramasse and K.S. Novoselov, Evolution of Gold Nanostructures on Graphene, Small, 7, 2868-2872 (2011).
54. P.Y. Huang, C.S. Ruiz-Vargas, A.M. van der Zande, et al., Grains and grain boundaries in single-layer graphene atomic patchwork quilts, Nature, 469, 389-392 (2011).
55. Q.M. Ramasse, R. Zan, U. Bangert, et al., Direct experimental evidence of metal-mediated graphene etching, ACS Nano, 6, 4063-4071. DOI: 10.1021/nn300452y (2012).
56. E. Stolyarova, K.T. Rim, S. Ryu, et al., High-resolution scanning tunneling microscopy imaging of mesoscopic graphene sheets on an insulating surface, Proc. Nat. Acad. Sci., 104, 9209-9212 (2007).
57. Lord Rayleigh, Investigation in Optics, with Special Reference to the Spectroscope, Philos. Mag., 8, 261-274, 403-411, 477-486(1879).
58. F. Schwierz, Graphene transistors, Nature Nanotech, 5, 487-496 (2010).
59. B. Guo, L. Fang, B. Zhang and J. R. Gong, Graphene Doping: A Review, Insciences J., 1, 80-89 (2011).
60. K. Brenner, Y. Yang and R. Murali, Edge doping of graphene sheets, Carbon, 50, 637-645 (2012).
61. L. Ci, L. Song, Ch. Jin, et al., Atomic layers of hybridized boron nitride and graphene domains, Nature Materials, 9, 430-435 (2010).
62. E.J.H. Lee, K. Balasubramanian, R.T. Weitz, et al., Contact and edge effects in graphene devices, Nature Nanotech, 3, 486-490 (2008).
63. E.J Kirkland, On the optimum probe in aberration corrected ADF-STEM, Ultramicroscopy, 111, 1523-1530 (2011).
64. W. Zhou, M.P. Oxley, A.R. Lupini et al., Single Atom Microscopy, Microscopy and Microanalysis, (to be published). The graphene sample was obtained from Graphene Supermarket (Available at https://graphene-supermarket.com).
65. M.M.J. Treacy, Z dependence of electron scattering by single atoms into annular dark-field detectors, Microsc. Microanal., 17, 847-858 (2011).
66. M. Born and E.Wolf, Principles of Optics, 7th edn, Cambridge University Press, Cambridge (1997).
67. V. Beck and A.V. Crewe, High resolution imaging properties of the STEM, Ultramicroscopy, 1, 137-144 (1975).
68. R.F Egerton, EELS in the Electron Microscope, 3rd edn, Springer, New York and Heidelberg (2011).
69. R.F Egerton, Limits to the spatial, energy and momentum resolution of electron energy-loss spectroscopy, Ultramicroscopy, 107, 575-586 (2006).
70. K. Sader, B. Schaffer, G. Vaughan, et al., Smart acquisition EELS, Ultramicroscopy, 110, 998-1003 (2010).
71. F.J Garcia de Abajo and A. Howie, Electron spectroscopy from outside-aloof beam or near field? Inst. Phys. Conf. Ser., 161, 327-330 (1999).
72. W. Zhou, M.D. Kapetanakis, M.P. Prange, et al., Direct determination of distinct atomic configurations and bonding of individual impurities in graphene, submitted to Physical Review Letters (2012).
73. W. Zhou, J. Lee, J. Nanda, et al., Atomically localized plasmon enhancement in monolayer graphene, Nature Nanotechnology, 7, 161-165 (2012); see also the supporting materials (Available at http://www.nature.com/nnano/journal/vaop /ncurrent/full/nnano.2011.252.html#/supplementary-information: accessed August 5, 2012).
74. W. Zhou, S.J. Pennycook and J.C. Idrobo, Localization of inelastic electron scattering in the low-loss energy regime, Ultramicroscopy, 119, 51-56 (2012). (DOI:10.1016/j.ultramic.2011.11.013.
75. M. Isaacson and D. Johnson, The Microanalysis of light elements using transmitted energy loss electrons, Ultramicroscopy, 1, 33-52 (1975).