Low-loss electron energy loss spectroscopy: An atomic-resolution complement to optical spectroscopies and application to graphene

Kapetanakis, Myron; Zhou, Wu; Oxley, Mark P.; Lee, Jaekwang; Prange, Micah P.; Pennycook, Stephen J.; Idrobo Tapia, Juan Carlos; Pantelides, Sokrates T.

doi:10.1103/PhysRevB.92.125147

Title: Low-loss electron energy loss spectroscopy: An atomic-resolution complement to optical spectroscopies and application to graphene

Journal Article · Fri Sep 25 00:00:00 EDT 2015 · Physical Review. B, Condensed Matter and Materials Physics

DOI:https://doi.org/10.1103/PhysRevB.92.125147· OSTI ID:1223067

Kapetanakis, Myron ^[1]; Zhou, Wu ^[2]; Oxley, Mark P. ^[1]; Lee, Jaekwang ^[3]; Prange, Micah P. ^[4]; Pennycook, Stephen J. ^[5]; Idrobo Tapia, Juan Carlos ^[2]; Pantelides, Sokrates T. ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Vanderbilt Univ., Nashville, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Pusan National Univ. (Korea)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Univ. of Tennessee, Knoxville, TN (United States); National Univ. of Singapore (Singapore)

Photon-based spectroscopies have played a central role in exploring the electronic properties of crystalline solids and thin films. Though they remain a powerful tool for probing the electronic properties of nanostructures, they are limited by lack of spatial resolution. On the other hand, electron-based spectroscopies, e.g., electron energy loss spectroscopy (EELS), are now capable of subangstrom spatial resolution. Core-loss EELS, a spatially resolved analog of x-ray absorption, has been used extensively in the study of inhomogeneous complex systems. In this paper, we demonstrate that low-loss EELS in an aberration-corrected scanning transmission electron microscope, which probes low-energy excitations, combined with a theoretical framework for simulating and analyzing the spectra, is a powerful tool to probe low-energy electron excitations with atomic-scale resolution. The theoretical component of the method combines density functional theory–based calculations of the excitations with dynamical scattering theory for the electron beam. We apply the method to monolayer graphene in order to demonstrate that atomic-scale contrast is inherent in low-loss EELS even in a perfectly periodic structure. The method is a complement to optical spectroscopy as it probes transitions entailing momentum transfer. The theoretical analysis identifies the spatial and orbital origins of excitations, holding the promise of ultimately becoming a powerful probe of the structure and electronic properties of individual point and extended defects in both crystals and inhomogeneous complex nanostructures. The method can be extended to probe magnetic and vibrational properties with atomic resolution.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science; Vanderbilt Univ., Nashville, TN (United States); University of California, Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725; FG02-09ER46554; AC02-05CH11231

OSTI ID:: 1223067

Alternate ID(s):: OSTI ID: 1224631; OSTI ID: 1597697

Journal Information:: Physical Review. B, Condensed Matter and Materials Physics, Vol. 92, Issue 12; ISSN 1098-0121

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 29 works

Citation information provided by
Web of Science

References (39)

Atom-by-atom structural and chemical analysis by annular dark-field electron microscopy Krivanek, Ondrej L.; Chisholm, Matthew F.; Nicolosi, Valeria Nature, Vol. 464, Issue 7288 https://doi.org/10.1038/nature08879	journal	March 2010
Two-Dimensional Mapping of Chemical Information at Atomic Resolution Bosman, M.; Keast, V. J.; García-Muñoz, J. L. Physical Review Letters, Vol. 99, Issue 8 https://doi.org/10.1103/PhysRevLett.99.086102	journal	August 2007
Dielectric matrix calculation of the differential cross section for plasmon excitation and application to electron diffraction Josefsson, T. W.; Cobal, R. L.; Allen, L. J. Physical Review B, Vol. 54, Issue 18 https://doi.org/10.1103/PhysRevB.54.12873	journal	November 1996
Signatures of Short-Range Many-Body Effects in the Dielectric Function of Silicon for Finite Momentum Transfer Weissker, Hans-Christian; Serrano, Jorge; Huotari, Simo Physical Review Letters, Vol. 97, Issue 23 https://doi.org/10.1103/PhysRevLett.97.237602	journal	December 2006
Preservation of electron microscope image contrast after inelastic scattering Cundy, S. L.; Howie, A.; Valdrè, U. Philosophical Magazine, Vol. 20, Issue 163 https://doi.org/10.1080/14786436908228542	journal	July 1969
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Achieving 63 pm Resolution in Scanning Transmission Electron Microscope with Spherical Aberration Corrector Sawada, Hidetaka; Hosokawa, Fumio; Kaneyama, Toshikatsu Japanese Journal of Applied Physics, Vol. 46, Issue No. 23 https://doi.org/10.1143/JJAP.46.L568	journal	June 2007
Delocalization in inelastic scattering Muller, D. A.; Silcox, J. Ultramicroscopy, Vol. 59, Issue 1-4 https://doi.org/10.1016/0304-3991(95)00029-Z	journal	July 1995
Interpreting atomic-resolution spectroscopic images Oxley, M. P.; Varela, M.; Pennycook, T. J. Physical Review B, Vol. 76, Issue 6 https://doi.org/10.1103/PhysRevB.76.064303	journal	August 2007
Advanced Computing in Electron Microscopy Kirkland, Earl J. https://doi.org/10.1007/978-1-4419-6533-2	book	January 2010
Atomic-Scale Chemical Imaging of Composition and Bonding by Aberration-Corrected Microscopy Muller, D. A.; Kourkoutis, L. F.; Murfitt, M. Science, Vol. 319, Issue 5866 https://doi.org/10.1126/science.1148820	journal	February 2008
Limits to the spatial, energy and momentum resolution of electron energy-loss spectroscopy Egerton, R. F. Ultramicroscopy, Vol. 107, Issue 8 https://doi.org/10.1016/j.ultramic.2006.11.005	journal	August 2007
Single Atom Microscopy Zhou, Wu; Oxley, Mark P.; Lupini, Andrew R. Microscopy and Microanalysis, Vol. 18, Issue 6 https://doi.org/10.1017/S1431927612013335	journal	November 2012
Modeling Atomic-Resolution Scanning Transmission Electron Microscopy Images Findlay, Scott D.; Oxley, Mark P.; Allen, Leslie J. Microscopy and Microanalysis, Vol. 14, Issue 1 https://doi.org/10.1017/S1431927608080112	journal	December 2007
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Excitonic Effects on the Optical Response of Graphene and Bilayer Graphene Yang, Li; Deslippe, Jack; Park, Cheol-Hwan Physical Review Letters, Vol. 103, Issue 18 https://doi.org/10.1103/PhysRevLett.103.186802	journal	October 2009
Nanoscale chemical mapping using three-dimensional adiabatic compression of surface plasmon polaritons De Angelis, Francesco; Das, Gobind; Candeloro, Patrizio Nature Nanotechnology, Vol. 5, Issue 1 https://doi.org/10.1038/nnano.2009.348	journal	November 2009
Suppression of Octahedral Tilts and Associated Changes in Electronic Properties at Epitaxial Oxide Heterostructure Interfaces Borisevich, A. Y.; Chang, H. J.; Huijben, M. Physical Review Letters, Vol. 105, Issue 8 https://doi.org/10.1103/PhysRevLett.105.087204	journal	August 2010
Simulation of Spatially Resolved Electron Energy Loss Near-Edge Structure for Scanning Transmission Electron Microscopy Prange, M. P.; Oxley, M. P.; Varela, M. Physical Review Letters, Vol. 109, Issue 24 https://doi.org/10.1103/PhysRevLett.109.246101	journal	December 2012
Study of atomic resolved plasmon-loss image by spherical aberration-corrected STEM-EELS method Yamazaki, Takashi; Kotaka, Yasutoshi; Tsukada, Mineharu Ultramicroscopy, Vol. 110, Issue 9 https://doi.org/10.1016/j.ultramic.2010.04.011	journal	August 2010
Plasmon holographic experiments: theoretical framework Verbeeck, J.; van Dyck, D.; Lichte, H. Ultramicroscopy, Vol. 102, Issue 3 https://doi.org/10.1016/j.ultramic.2004.10.005	journal	February 2005
Simulation of annular dark field stem images using a modified multislice method Kirkland, Earl J.; Loane, Russell F.; Silcox, John Ultramicroscopy, Vol. 23, Issue 1, p. 77-96 https://doi.org/10.1016/0304-3991(87)90229-4	journal	January 1987
Atomic resolution mapping of phonon excitations in STEM-EELS experiments Egoavil, R.; Gauquelin, N.; Martinez, G. T. Ultramicroscopy, Vol. 147 https://doi.org/10.1016/j.ultramic.2014.04.011	journal	December 2014
Atomic-resolution imaging of oxidation states in manganites Varela, M.; Oxley, M. P.; Luo, W. Physical Review B, Vol. 79, Issue 8 https://doi.org/10.1103/PhysRevB.79.085117	journal	February 2009
Atomic-Resolution Imaging with a Sub-50-pm Electron Probe Erni, Rolf; Rossell, Marta D.; Kisielowski, Christian Physical Review Letters, Vol. 102, Issue 9 https://doi.org/10.1103/PhysRevLett.102.096101	journal	March 2009
Atomically localized plasmon enhancement in monolayer graphene Zhou, Wu; Lee, Jaekwang; Nanda, Jagjit Nature Nanotechnology, Vol. 7, Issue 3 https://doi.org/10.1038/nnano.2011.252	journal	January 2012
The scattering of electrons by atoms and crystals. I. A new theoretical approach Cowley, J. M.; Moodie, A. F. Acta Crystallographica, Vol. 10, Issue 10, p. 609-619 https://doi.org/10.1107/S0365110X57002194	journal	October 1957
Valence electron energy loss study of Fe-doped SrTiO3 and a Σ13 boundary: electronic structure and dispersion forces van Benthem, K.; French, R. H.; Sigle, W. Ultramicroscopy, Vol. 86, Issue 3-4 https://doi.org/10.1016/S0304-3991(00)00121-2	journal	February 2001
Optical properties of semiconductors using projector-augmented waves Adolph, B.; Furthmüller, J.; Bechstedt, F. Physical Review B, Vol. 63, Issue 12 https://doi.org/10.1103/PhysRevB.63.125108	journal	March 2001
Z-Contrast Transmission Electron Microscopy: Direct Atomic Imaging of Materials Pennycook, S. J. Annual Review of Materials Science, Vol. 22, Issue 1 https://doi.org/10.1146/annurev.ms.22.080192.001131	journal	August 1992
Localization of inelastic electron scattering in the low-loss energy regime Zhou, Wu; Pennycook, Stephen J.; Idrobo, Juan-Carlos Ultramicroscopy, Vol. 119 https://doi.org/10.1016/j.ultramic.2011.11.013	journal	August 2012
Spectroscopic Imaging of Single Atoms Within a Bulk Solid Varela, M.; Findlay, S. D.; Lupini, A. R. Physical Review Letters, Vol. 92, Issue 9 https://doi.org/10.1103/PhysRevLett.92.095502	journal	March 2004
Simulation of Probe Position-Dependent Electron Energy-Loss Fine Structure Oxley, Mark P.; Kapetanakis, Myron D.; Prange, Micah P. Microscopy and Microanalysis, Vol. 20, Issue 3 https://doi.org/10.1017/S1431927614000610	journal	March 2014
Plasmonic Materials Murray, W. A.; Barnes, W. L. Advanced Materials, Vol. 19, Issue 22 https://doi.org/10.1002/adma.200700678	journal	November 2007
Visualizing and identifying single atoms using electron energy-loss spectroscopy with low accelerating voltage Suenaga, Kazu; Sato, Yuta; Liu, Zheng Nature Chemistry, Vol. 1, Issue 5 https://doi.org/10.1038/nchem.282	journal	July 2009
Element-Selective Single Atom Imaging Suenaga, K. Science, Vol. 290, Issue 5500 https://doi.org/10.1126/science.290.5500.2280	journal	December 2000
Towards atomic column-by-column spectroscopy Rafferty, B.; Pennycook, S. J. Ultramicroscopy, Vol. 78, Issue 1-4 https://doi.org/10.1016/S0304-3991(99)00033-9	journal	June 1999
Sub-ångstrom resolution using aberration corrected electron optics Batson, P. E.; Dellby, N.; Krivanek, O. L. Nature, Vol. 418, Issue 6898 https://doi.org/10.1038/nature00972	journal	August 2002

Cited By (8)

Atomic‐Scale Spectroscopic Imaging of the Extreme‐UV Optical Response of B‐ and N‐Doped Graphene Hage, Fredrik S.; Kapetanakis, Myron D.; Idrobo, Juan‐Carlos Advanced Functional Materials https://doi.org/10.1002/adfm.201901819	journal	May 2019
The impact of substrate surface defects on the properties of two-dimensional van der Waals heterostructures Kim, Se-Yang; Kim, Jung Hwa; Lee, Sungwoo Nanoscale, Vol. 10, Issue 40 https://doi.org/10.1039/c8nr03777a	journal	January 2018
Measuring the practical particle-in-a-box: orthorhombic perovskite nanocrystals Mitchell, Brandon; Herrmann, Eric; Lin, Junhao European Journal of Physics, Vol. 39, Issue 5 https://doi.org/10.1088/1361-6404/aac808	journal	June 2018
Energy losses and transition radiation produced by the interaction of charged particles with a graphene sheet Mišković, Zoran L.; Segui, Silvina; Gervasoni, Juana L. Physical Review B, Vol. 94, Issue 12 https://doi.org/10.1103/physrevb.94.125414	journal	September 2016
Molecular polarizability of water from local dielectric response theory Ge, Xiaochuan; Lu, Deyu Physical Review B, Vol. 96, Issue 7 https://doi.org/10.1103/physrevb.96.075114	journal	August 2017
Material structure, properties, and dynamics through scanning transmission electron microscopy Pennycook, Stephen J.; Li, Changjian; Li, Mengsha Journal of Analytical Science and Technology, Vol. 9, Issue 1 https://doi.org/10.1186/s40543-018-0142-4	journal	April 2018
Molecular Polarizability of Water from the Local Dielectric Response Theory Ge, Xiaochuan; Lu, Deyu arXiv https://doi.org/10.48550/arxiv.1706.01075	text	January 2017
Materials Structure, Properties and Dynamics through Scanning Transmission Electron Microscopy Pennycook, Stephen J.; Li, Changjian; Li, Mengsha arXiv https://doi.org/10.48550/arxiv.1908.07238	text	January 2019

Similar Records

Continuous Wave Resonant Photon Stimulated Electron Energy-Gain and Electron Energy-Loss Spectroscopy of Individual Plasmonic Nanoparticles

Journal Article · Wed Aug 28 00:00:00 EDT 2019 · ACS Photonics · OSTI ID:1223067

Liu, Chenze; Wu, Yueying; Hu, Zhongwei; +9 more

Signatures of distinct impurity configurations in atomic-resolution valence electron-energy-loss spectroscopy: Application to graphene

Journal Article · Mon Oct 31 00:00:00 EDT 2016 · Physical Review B · OSTI ID:1223067

Kapetanakis, Myron D.; Oxley, Mark P.; Zhou, Wu; +3 more

Aberration corrected scanning transmission electron microscopy and electron energy loss spectroscopy studies of epitaxial Fe/MgO/(001)Ge heterostructures

Journal Article · Sat Jan 01 00:00:00 EST 2011 · Journal of Materials Science · OSTI ID:1223067

Gazquez Alabart, Jaume; Varela del Arco, Maria; Petti, D.; +4 more

Related Subjects

75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY

Title: Low-loss electron energy loss spectroscopy: An atomic-resolution complement to optical spectroscopies and application to graphene

Citation Formats

References (39)

Cited By (8)

Similar Records

Related Subjects