Mapping Photoemission and Hot-Electron Emission from Plasmonic Nanoantennas
Abstract
Understanding plasmon-mediated electron emission and energy transfer on the nanometer length scale is critical to controlling light–matter interactions at nanoscale dimensions. In a high-resolution lithographic material, electron emission and energy transfer lead to chemical transformations. Here, we employ such chemical transformations in two different high-resolution electron-beam lithography resists, poly(methyl methacrylate) (PMMA) and hydrogen silsesquioxane (HSQ), to map local electron emission and energy transfer with nanometer resolution from plasmonic nanoantennas excited by femtosecond laser pulses. We observe exposure of the electron-beam resists (both PMMA and HSQ) in regions on the surface of nanoantennas where the local field is significantly enhanced. Exposure in these regions is consistent with previously reported optical-field-controlled electron emission from plasmonic hotspots as well as earlier work on low-electron-energy scanning probe lithography. For HSQ, in addition to exposure in hotspots, we observe resist exposure at the centers of rod-shaped nanoantennas in addition to exposure in plasmonic hotspots. Optical field enhancement is minimized at the center of nanorods suggesting that exposure in these regions involves a different mechanism to that in plasmonic hotspots. Our simulations suggest that exposure at the center of nanorods results from the emission of hot electrons produced via plasmon decay in the nanorods. Our resultsmore »
- Authors:
-
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Research Lab. of Electronics; Trinity College, Dublin (Ireland). Centre for Research on Adapative Nanostructures and Nanodevices (CRANN), Advanced Materials Bio-Engineering Resarch Center (AMBER)
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Research Lab. of Electronics; Univ. of Hamburg (Germany). Dept. of Physics, Center for Ultrafast Imaging; Northrop Grumman, Redondo Beach, CA (United States)
- Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany). Center for Free-Electron Laser Science
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Research Lab. of Electronics
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Research Lab. of Electronics; Univ. of Hamburg (Germany). Dept. of Physics, Center for Ultrafast Imaging; Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany). Center for Free-Electron Laser Science
- Publication Date:
- Research Org.:
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1395006
- Grant/Contract Number:
- SC0001088
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Nano Letters
- Additional Journal Information:
- Journal Volume: 17; Journal ID: ISSN 1530-6984
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 77 NANOSCIENCE AND NANOTECHNOLOGY; charge transfer; hot electrons; Nanoantennas; photoemission; plasmon decay; plasmonics
Citation Formats
Hobbs, Richard G., Putnam, William P., Fallahi, Arya, Yang, Yujia, Kärtner, Franz X., and Berggren, Karl K. Mapping Photoemission and Hot-Electron Emission from Plasmonic Nanoantennas. United States: N. p., 2017.
Web. doi:10.1021/acs.nanolett.7b02495.
Hobbs, Richard G., Putnam, William P., Fallahi, Arya, Yang, Yujia, Kärtner, Franz X., & Berggren, Karl K. Mapping Photoemission and Hot-Electron Emission from Plasmonic Nanoantennas. United States. https://doi.org/10.1021/acs.nanolett.7b02495
Hobbs, Richard G., Putnam, William P., Fallahi, Arya, Yang, Yujia, Kärtner, Franz X., and Berggren, Karl K. 2017.
"Mapping Photoemission and Hot-Electron Emission from Plasmonic Nanoantennas". United States. https://doi.org/10.1021/acs.nanolett.7b02495. https://www.osti.gov/servlets/purl/1395006.
@article{osti_1395006,
title = {Mapping Photoemission and Hot-Electron Emission from Plasmonic Nanoantennas},
author = {Hobbs, Richard G. and Putnam, William P. and Fallahi, Arya and Yang, Yujia and Kärtner, Franz X. and Berggren, Karl K.},
abstractNote = {Understanding plasmon-mediated electron emission and energy transfer on the nanometer length scale is critical to controlling light–matter interactions at nanoscale dimensions. In a high-resolution lithographic material, electron emission and energy transfer lead to chemical transformations. Here, we employ such chemical transformations in two different high-resolution electron-beam lithography resists, poly(methyl methacrylate) (PMMA) and hydrogen silsesquioxane (HSQ), to map local electron emission and energy transfer with nanometer resolution from plasmonic nanoantennas excited by femtosecond laser pulses. We observe exposure of the electron-beam resists (both PMMA and HSQ) in regions on the surface of nanoantennas where the local field is significantly enhanced. Exposure in these regions is consistent with previously reported optical-field-controlled electron emission from plasmonic hotspots as well as earlier work on low-electron-energy scanning probe lithography. For HSQ, in addition to exposure in hotspots, we observe resist exposure at the centers of rod-shaped nanoantennas in addition to exposure in plasmonic hotspots. Optical field enhancement is minimized at the center of nanorods suggesting that exposure in these regions involves a different mechanism to that in plasmonic hotspots. Our simulations suggest that exposure at the center of nanorods results from the emission of hot electrons produced via plasmon decay in the nanorods. Our results provide a means to map both optical-field-controlled electron emission and hot-electron transfer from nanoparticles via chemical transformations produced locally in lithographic materials.},
doi = {10.1021/acs.nanolett.7b02495},
url = {https://www.osti.gov/biblio/1395006},
journal = {Nano Letters},
issn = {1530-6984},
number = ,
volume = 17,
place = {United States},
year = {Tue Sep 19 00:00:00 EDT 2017},
month = {Tue Sep 19 00:00:00 EDT 2017}
}
Web of Science
Figures / Tables:
Works referenced in this record:
Nano-optics from sensing to waveguiding
journal, November 2007
- Lal, Surbhi; Link, Stephan; Halas, Naomi J.
- Nature Photonics, Vol. 1, Issue 11
The Promise of Plasmonics
journal, April 2007
- Atwater, Harry A.
- Scientific American, Vol. 296, Issue 4
Plasmonics-A Route to Nanoscale Optical Devices
journal, September 2001
- Maier, S. A.; Brongersma, M. L.; Kik, P. G.
- Advanced Materials, Vol. 13, Issue 19, p. 1501-1505
Plasmon-induced hot carrier science and technology
journal, January 2015
- Brongersma, Mark L.; Halas, Naomi J.; Nordlander, Peter
- Nature Nanotechnology, Vol. 10, Issue 1
Plasmonic hot electron transport drives nano-localized chemistry
journal, March 2017
- Cortés, Emiliano; Xie, Wei; Cambiasso, Javier
- Nature Communications, Vol. 8, Issue 1
Biosensing with plasmonic nanosensors
journal, June 2008
- Anker, Jeffrey N.; Hall, W. Paige; Lyandres, Olga
- Nature Materials, Vol. 7, Issue 6
Multiwavelength Photoacoustic Imaging and Plasmon Resonance Coupling of Gold Nanoparticles for Selective Detection of Cancer
journal, August 2009
- Mallidi, Srivalleesha; Larson, Timothy; Tam, Justina
- Nano Letters, Vol. 9, Issue 8
Visualizing Electromagnetic Fields at the Nanoscale by Single Molecule Localization
journal, April 2015
- Steuwe, Christian; Erdelyi, Miklos; Szekeres, G.
- Nano Letters, Vol. 15, Issue 5
Control and Near-Field Detection of Surface Plasmon Interference Patterns
journal, May 2013
- Dvořák, Petr; Neuman, Tomáš; Břínek, Lukáš
- Nano Letters, Vol. 13, Issue 6
Erratum: Plasmonics for improved photovoltaic devices
journal, September 2010
- Atwater, Harry A.; Polman, Albert
- Nature Materials, Vol. 9, Issue 10
Plasmoelectric potentials in metal nanostructures
journal, October 2014
- Sheldon, M. T.; van de Groep, J.; Brown, A. M.
- Science, Vol. 346, Issue 6211
A Plasmonic Photocatalyst Consisting of Silver Nanoparticles Embedded in Titanium Dioxide
journal, February 2008
- Awazu, Koichi; Fujimaki, Makoto; Rockstuhl, Carsten
- Journal of the American Chemical Society, Vol. 130, Issue 5
Visible-light-enhanced catalytic oxidation reactions on plasmonic silver nanostructures
journal, May 2011
- Christopher, Phillip; Xin, Hongliang; Linic, Suljo
- Nature Chemistry, Vol. 3, Issue 6
Controlling Nanowire Growth by Light
journal, October 2015
- Martino, G. Di; Michaelis, F. B.; Salmon, A. R.
- Nano Letters, Vol. 15, Issue 11
Visualization of Active Sites for Plasmon-Induced Electron Transfer Reactions Using Photoelectrochemical Polymerization of Pyrrole
journal, May 2016
- Minamimoto, Hiro; Toda, Takahiro; Futashima, Ryo
- The Journal of Physical Chemistry C, Vol. 120, Issue 29
Plasmon-Enhanced Single Photon Emission from a Nanoassembled Metal−Diamond Hybrid Structure at Room Temperature
journal, April 2009
- Schietinger, Stefan; Barth, Michael; Aichele, Thomas
- Nano Letters, Vol. 9, Issue 4
Plasmonic Pumping of Excitonic Photoluminescence in Hybrid MoS 2 –Au Nanostructures
journal, November 2014
- Najmaei, Sina; Mlayah, Adnen; Arbouet, Arnaud
- ACS Nano, Vol. 8, Issue 12
Surface plasmon-enhanced photoluminescence from a single quantum well
journal, September 1999
- Hecker, N. E.; Höpfel, R. A.; Sawaki, N.
- Applied Physics Letters, Vol. 75, Issue 11
Nanoshell-Enabled Photothermal Cancer Therapy: Impending Clinical Impact
journal, December 2008
- Lal, Surbhi; Clare, Susan E.; Halas, Naomi J.
- Accounts of Chemical Research, Vol. 41, Issue 12, p. 1842-1851
High-Yield, Ultrafast, Surface Plasmon-Enhanced, Au Nanorod Optical Field Electron Emitter Arrays
journal, November 2014
- Hobbs, Richard G.; Yang, Yujia; Fallahi, Arya
- ACS Nano, Vol. 8, Issue 11
Ultrafast Strong-Field Photoemission from Plasmonic Nanoparticles
journal, January 2013
- Dombi, Péter; Hörl, Anton; Rácz, Péter
- Nano Letters, Vol. 13, Issue 2
Attosecond control of electrons emitted from a nanoscale metal tip
journal, July 2011
- Krüger, Michael; Schenk, Markus; Hommelhoff, Peter
- Nature, Vol. 475, Issue 7354
Tip-Enhanced Strong-Field Photoemission
journal, September 2010
- Bormann, R.; Gulde, M.; Weismann, A.
- Physical Review Letters, Vol. 105, Issue 14
Terahertz control of nanotip photoemission
journal, May 2014
- Wimmer, L.; Herink, G.; Solli, D. R.
- Nature Physics, Vol. 10, Issue 6
Optical-field-controlled photoemission from plasmonic nanoparticles
journal, December 2016
- Putnam, William P.; Hobbs, Richard G.; Keathley, Phillip D.
- Nature Physics, Vol. 13, Issue 4
Anomalous ultrafast dynamics of hot plasmonic electrons in nanostructures with hot spots
journal, August 2015
- Harutyunyan, Hayk; Martinson, Alex B. F.; Rosenmann, Daniel
- Nature Nanotechnology, Vol. 10, Issue 9
Theoretical predictions for hot-carrier generation from surface plasmon decay
journal, December 2014
- Sundararaman, Ravishankar; Narang, Prineha; Jermyn, Adam S.
- Nature Communications, Vol. 5, Issue 1
Photochemical transformations on plasmonic metal nanoparticles
journal, May 2015
- Linic, Suljo; Aslam, Umar; Boerigter, Calvin
- Nature Materials, Vol. 14, Issue 6
Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy
journal, November 2011
- Linic, Suljo; Christopher, Phillip; Ingram, David B.
- Nature Materials, Vol. 10, Issue 12
Hot Electrons Do the Impossible: Plasmon-Induced Dissociation of H 2 on Au
journal, December 2012
- Mukherjee, Shaunak; Libisch, Florian; Large, Nicolas
- Nano Letters, Vol. 13, Issue 1
Plasmon-induced hot-electron generation at nanoparticle/metal-oxide interfaces for photovoltaic and photocatalytic devices
journal, January 2014
- Clavero, César
- Nature Photonics, Vol. 8, Issue 2
A circuit model for plasmonic resonators
journal, January 2014
- Zhu, Di; Bosman, Michel; Yang, Joel K. W.
- Optics Express, Vol. 22, Issue 8
Mapping Heat Origin in Plasmonic Structures
journal, April 2010
- Baffou, Guillaume; Girard, Christian; Quidant, Romain
- Physical Review Letters, Vol. 104, Issue 13
PolyMethyl Methacrylate Thin-Film-Based Field Emission Microscope
journal, May 2012
- Sun, Yonghai; Jaffray, David A.; Chen, Liang-Yih
- IEEE Transactions on Nanotechnology, Vol. 11, Issue 3
Near-Field Mapping of Plasmonic Antennas by Multiphoton Absorption in Poly(methyl methacrylate)
journal, January 2012
- Volpe, Giorgio; Noack, Monika; Aćimović, Srdjan S.
- Nano Letters, Vol. 12, Issue 9
Vibrational near-field mapping of planar and buried three-dimensional plasmonic nanostructures
journal, July 2013
- Dregely, Daniel; Neubrech, Frank; Duan, Huigao
- Nature Communications, Vol. 4, Issue 1
Nonlinear Plasmonics: Four-photon Near-field Photolithography using Optical Antennas
journal, June 2013
- Jiang, Hao; Gordon, Reuven
- Plasmonics, Vol. 8, Issue 4
High-density Au nanorod optical field-emitter arrays
journal, October 2014
- Hobbs, R. G.; Yang, Y.; Keathley, P. D.
- Nanotechnology, Vol. 25, Issue 46
Polarization-Dependent Scanning Photoionization Microscopy: Ultrafast Plasmon-Mediated Electron Ejection Dynamics in Single Au Nanorods
journal, April 2011
- Schweikhard, Volker; Grubisic, Andrej; Baker, Thomas A.
- ACS Nano, Vol. 5, Issue 5
Surface plasmon assisted electron acceleration in photoemission from gold nanopillars
journal, March 2013
- Nagel, Phillip M.; Robinson, Joseph S.; Harteneck, Bruce D.
- Chemical Physics, Vol. 414
Heat generation in plasmonic nanostructures: Influence of morphology
journal, April 2009
- Baffou, G.; Quidant, R.; Girard, C.
- Applied Physics Letters, Vol. 94, Issue 15
Observing Plasmon Damping Due to Adhesion Layers in Gold Nanostructures Using Electron Energy Loss Spectroscopy
journal, January 2017
- Madsen, Steven J.; Esfandyarpour, Majid; Brongersma, Mark L.
- ACS Photonics, Vol. 4, Issue 2
Quantitative electron spectroscopy of surfaces: A standard data base for electron inelastic mean free paths in solids
journal, February 1979
- Seah, M. P.; Dench, W. A.
- Surface and Interface Analysis, Vol. 1, Issue 1
Metrology for electron-beam lithography and resist contrast at the sub-10 nm scale
journal, November 2010
- Duan, Huigao; Manfrinato, Vitor R.; Yang, Joel K. W.
- Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phenomena, Vol. 28, Issue 6
On the mean inner potential in high- and low-energy electron diffraction
journal, October 1994
- Saldin, D. K.; Spence, J. C. H.
- Ultramicroscopy, Vol. 55, Issue 4
Characteristics of electron inelastic interactions in organic compounds and water over the energy range 20–10 000 eV
journal, November 1999
- Akkerman, A.; Akkerman, E.
- Journal of Applied Physics, Vol. 86, Issue 10
Sub-10-nm half-pitch electron-beam lithography by using poly(methyl methacrylate) as a negative resist
journal, November 2010
- Duan, Huigao; Winston, Donald; Yang, Joel K. W.
- Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phenomena, Vol. 28, Issue 6
Nanostructured Ultrafast Silicon-Tip Optical Field-Emitter Arrays
journal, August 2014
- Swanwick, Michael E.; Keathley, Phillip D.; Fallahi, Arya
- Nano Letters, Vol. 14, Issue 9
Field-based DGTD/PIC technique for general and stable simulation of interaction between light and electron bunches
journal, November 2014
- Fallahi, Arya; Kärtner, Franz
- Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 47, Issue 23
Lift-off metallization using poly(methyl methacrylate) exposed with a scanning tunneling microscope
journal, January 1988
- McCord, M. A.
- Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 6, Issue 1
Direct Photocatalysis by Plasmonic Nanostructures
journal, December 2013
- Kale, Matthew J.; Avanesian, Talin; Christopher, Phillip
- ACS Catalysis, Vol. 4, Issue 1
Plasmon-induced resonance energy transfer for solar energy conversion
journal, August 2015
- Li, Jiangtian; Cushing, Scott K.; Meng, Fanke
- Nature Photonics, Vol. 9, Issue 9
Energy transfer in plasmonic photocatalytic composites
journal, February 2016
- Ma, Xiang-Chao; Dai, Ying; Yu, Lin
- Light: Science & Applications, Vol. 5, Issue 2
Mechanism of Charge Transfer from Plasmonic Nanostructures to Chemically Attached Materials
journal, May 2016
- Boerigter, Calvin; Aslam, Umar; Linic, Suljo
- ACS Nano, Vol. 10, Issue 6
Evidence and implications of direct charge excitation as the dominant mechanism in plasmon-mediated photocatalysis
journal, January 2016
- Boerigter, Calvin; Campana, Robert; Morabito, Matthew
- Nature Communications, Vol. 7, Issue 1
Precursors of Solvated Electrons in Radiobiological Physics and Chemistry
journal, June 2012
- Alizadeh, Elahe; Sanche, Léon
- Chemical Reviews, Vol. 112, Issue 11
Fundamental Mechanisms of Desorption and Fragmentation Induced by Electronic Transitions at Surfaces
journal, October 1989
- Avouris, P.; Walkup, R. E.
- Annual Review of Physical Chemistry, Vol. 40, Issue 1
Ultra-violet and X-ray photoelectron spectroscopy (UPS and XPS) of CO, CO2, O2 and H2O on molybdenum and gold films
journal, January 1974
- Atkinson, S. J.; Brundle, C. R.; Roberts, M. W.
- Faraday Discussions of the Chemical Society, Vol. 58
The Electronic Structures of Condensed Materials Studied by Ultraviolet Photoelectron Spectroscopy
journal, January 1981
- Takahashi, Takashi; Harada, Yoshiya
- Bulletin of the Chemical Society of Japan, Vol. 54, Issue 1
Cross Sections and Interpretation of Dissociative Attachment Reactions Producing OH − , O − , and H − in H 2 O
journal, November 1972
- Melton, Charles E.
- The Journal of Chemical Physics, Vol. 57, Issue 10
Dissociative electron attachment in nanoscale ice films: Temperature and morphology effects
journal, November 1997
- Simpson, W. C.; Sieger, M. T.; Orlando, T. M.
- The Journal of Chemical Physics, Vol. 107, Issue 20
Quantum Mode Selectivity of Plasmon-Induced Water Splitting on Gold Nanoparticles
journal, May 2016
- Yan, Lei; Wang, Fangwei; Meng, Sheng
- ACS Nano, Vol. 10, Issue 5
A study of acid diffusion in chemically amplified deep ultraviolet resist
journal, November 1996
- Itani, Toshiro
- Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 14, Issue 6
Surface patterning of nanoparticles with polymer patches
journal, August 2016
- Choueiri, Rachelle M.; Galati, Elizabeth; Thérien-Aubin, Héloïse
- Nature, Vol. 538, Issue 7623
Works referencing / citing this record:
Transport of hot carriers in plasmonic nanostructures
journal, July 2019
- Jermyn, Adam S.; Tagliabue, Giulia; Atwater, Harry A.
- Physical Review Materials, Vol. 3, Issue 7
Plasma physics of liquids—A focused review
journal, September 2018
- Vanraes, Patrick; Bogaerts, Annemie
- Applied Physics Reviews, Vol. 5, Issue 3
Ultrafast Field‐Emission Electron Sources Based on Nanomaterials
journal, February 2019
- Zhou, Shenghan; Chen, Ke; Cole, Matthew Thomas
- Advanced Materials, Vol. 31, Issue 45
Vanishing carrier-envelope-phase-sensitive response in optical-field photoemission from plasmonic nanoantennas
journal, August 2019
- Keathley, P. D.; Putnam, W. P.; Vasireddy, P.
- Nature Physics, Vol. 15, Issue 11
Tracing the Origin of Visible Light Enhanced Oxygen Evolution Reaction
journal, December 2018
- Cai, Chao; Han, Shaobo; Caiyang, Weinan
- Advanced Materials Interfaces, Vol. 6, Issue 3
Plasmon‐Induced Hot Carrier Separation across Dual Interface in Gold–Nickel Phosphide Heterojunction for Photocatalytic Water Splitting
journal, December 2019
- Mondal, Indranil; Lee, Hyunhwa; Kim, Heeyoung
- Advanced Functional Materials, Vol. 30, Issue 11
Plasmonic hot charge carriers activated Ni centres of metal–organic frameworks for the oxygen evolution reaction
journal, January 2019
- Hu, Wen-Chao; Shi, Yi; Zhou, Yue
- Journal of Materials Chemistry A, Vol. 7, Issue 17
Two-color multiphoton emission for comprehensive reveal of ultrafast plasmonic field distribution
journal, July 2018
- Ji, Boyu; Song, Xiaowei; Dou, Yinping
- New Journal of Physics, Vol. 20, Issue 7
Attosecond physics phenomena at nanometric tips
journal, August 2018
- Krüger, Michael; Lemell, Christoph; Wachter, Georg
- Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 51, Issue 17
Vanishing carrier-envelope-phase-sensitive response in optical-field photoemission from plasmonic nanoantennas
text, January 2019
- Keathley, Phillip; Putman, Wp; Vasireddy, P.
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Terahertz-driven polymerization of resists in nanoantennas
journal, May 2018
- Park, Woongkyu; Lee, Youjin; Kang, Taehee
- Scientific Reports, Vol. 8, Issue 1
Vanishing carrier-envelope-phase-sensitive response in optical-field photoemission from plasmonic nanoantennas
text, January 2019
- Keathley, Phillip; Putman, Wp; Vasireddy, P.
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Figures / Tables found in this record: