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Title: Direct-write liquid phase transformations with a scanning transmission electron microscope

Abstract

The highly energetic electron beam from a scanning transmission electron microscope (STEM) can induce local changes in the state of matter, ranging from local knock-out and atomic movement, to amorphization/crystallization, and chemical/electrochemical reactions occuring at localized liquid-solid and gas-solid interfaces. To date, fundamental studies of e-beam induced phenomena and practical applications have been limited by conventional e-beam rastering modes that allow only for uniform e-beam exposures. Here we develop an automated liquid phase nanolithography method that is capable of directly writing nanometer scaled features within silicon nitride encapsulated liquid cells. An external beam control system, connected to the scan coils of an aberration-corrected STEM, is used to precisely control the position, dwell time, and scan velocity of a sub-nanometer STEM probe. Site-specific locations in a sealed liquid cell containing an aqueous solution of H2PdCl4 are irradiated to controllably deposit palladium onto silicon nitride membranes. We determine the threshold electron dose required for the radiolytic deposition of metallic palladium, explore the influence of electron dose on the feature size and morphology of nanolithographically patterned nanostructures, and propose a feedback-controlled monitoring method for active control of the nanofabricated structures through STEM detector signal monitoring. As a result, this approach enables both fundamentalmore » studies of electron beam induced interactions with matter, as well as opens a pathway to fabricate nanostructures with tailored architectures and chemistries via shape-controlled nanolithographic patterning from liquid phase precursors.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1333640
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Nanoscale
Additional Journal Information:
Journal Volume: 8; Journal Issue: 34; Journal ID: ISSN 2040-3364
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 43 PARTICLE ACCELERATORS

Citation Formats

Unocic, Raymond R., Lupini, Andrew R., Borisevich, Albina Y., Cullen, David A., Kalinin, Sergei V., and Jesse, Stephen. Direct-write liquid phase transformations with a scanning transmission electron microscope. United States: N. p., 2016. Web. doi:10.1039/C6NR04994J.
Unocic, Raymond R., Lupini, Andrew R., Borisevich, Albina Y., Cullen, David A., Kalinin, Sergei V., & Jesse, Stephen. Direct-write liquid phase transformations with a scanning transmission electron microscope. United States. doi:10.1039/C6NR04994J.
Unocic, Raymond R., Lupini, Andrew R., Borisevich, Albina Y., Cullen, David A., Kalinin, Sergei V., and Jesse, Stephen. Wed . "Direct-write liquid phase transformations with a scanning transmission electron microscope". United States. doi:10.1039/C6NR04994J. https://www.osti.gov/servlets/purl/1333640.
@article{osti_1333640,
title = {Direct-write liquid phase transformations with a scanning transmission electron microscope},
author = {Unocic, Raymond R. and Lupini, Andrew R. and Borisevich, Albina Y. and Cullen, David A. and Kalinin, Sergei V. and Jesse, Stephen},
abstractNote = {The highly energetic electron beam from a scanning transmission electron microscope (STEM) can induce local changes in the state of matter, ranging from local knock-out and atomic movement, to amorphization/crystallization, and chemical/electrochemical reactions occuring at localized liquid-solid and gas-solid interfaces. To date, fundamental studies of e-beam induced phenomena and practical applications have been limited by conventional e-beam rastering modes that allow only for uniform e-beam exposures. Here we develop an automated liquid phase nanolithography method that is capable of directly writing nanometer scaled features within silicon nitride encapsulated liquid cells. An external beam control system, connected to the scan coils of an aberration-corrected STEM, is used to precisely control the position, dwell time, and scan velocity of a sub-nanometer STEM probe. Site-specific locations in a sealed liquid cell containing an aqueous solution of H2PdCl4 are irradiated to controllably deposit palladium onto silicon nitride membranes. We determine the threshold electron dose required for the radiolytic deposition of metallic palladium, explore the influence of electron dose on the feature size and morphology of nanolithographically patterned nanostructures, and propose a feedback-controlled monitoring method for active control of the nanofabricated structures through STEM detector signal monitoring. As a result, this approach enables both fundamental studies of electron beam induced interactions with matter, as well as opens a pathway to fabricate nanostructures with tailored architectures and chemistries via shape-controlled nanolithographic patterning from liquid phase precursors.},
doi = {10.1039/C6NR04994J},
journal = {Nanoscale},
number = 34,
volume = 8,
place = {United States},
year = {2016},
month = {8}
}

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Cited by: 7 works
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Works referenced in this record:

Atomic-Level Sculpting of Crystalline Oxides: Toward Bulk Nanofabrication with Single Atomic Plane Precision
journal, October 2015


Writing Silica Structures in Liquid with Scanning Transmission Electron Microscopy
journal, September 2014

  • van de Put, Marcel W. P.; Carcouët, Camille C. M. C.; Bomans, Paul H. H.
  • Small, Vol. 11, Issue 5
  • DOI: 10.1002/smll.201400913

Atom-by-atom structural and chemical analysis by annular dark-field electron microscopy
journal, March 2010

  • Krivanek, Ondrej L.; Chisholm, Matthew F.; Nicolosi, Valeria
  • Nature, Vol. 464, Issue 7288
  • DOI: 10.1038/nature08879

Electron microscopy of specimens in liquid
journal, October 2011

  • de Jonge, Niels; Ross, Frances M.
  • Nature Nanotechnology, Vol. 6, Issue 11, p. 695-704
  • DOI: 10.1038/nnano.2011.161

Gas-assisted focused electron beam and ion beam processing and fabrication
journal, January 2008

  • Utke, Ivo; Hoffmann, Patrik; Melngailis, John
  • Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 26, Issue 4
  • DOI: 10.1116/1.2955728

Real-Time Imaging of Pt3Fe Nanorod Growth in Solution
journal, May 2012


Electron beam induced deposition of silicon nanostructures from a liquid phase precursor
journal, September 2012


Bubble and Pattern Formation in Liquid Induced by an Electron Beam
journal, December 2013

  • Grogan, Joseph M.; Schneider, Nicholas M.; Ross, Frances M.
  • Nano Letters, Vol. 14, Issue 1
  • DOI: 10.1021/nl404169a

Controlled Growth of Nanoparticles from Solution with In Situ Liquid Transmission Electron Microscopy
journal, July 2011

  • Evans, James E.; Jungjohann, Katherine L.; Browning, Nigel D.
  • Nano Letters, Vol. 11, Issue 7
  • DOI: 10.1021/nl201166k

Atomic-Scale Chemical Imaging of Composition and Bonding by Aberration-Corrected Microscopy
journal, February 2008


In situ Study of Oxidative Etching of Palladium Nanocrystals by Liquid Cell Electron Microscopy
journal, June 2014

  • Jiang, Yingying; Zhu, Guomin; Lin, Fang
  • Nano Letters, Vol. 14, Issue 7
  • DOI: 10.1021/nl500670q

Observation of Single Colloidal Platinum Nanocrystal Growth Trajectories
journal, June 2009


Direct in Situ Observation of Nanoparticle Synthesis in a Liquid Crystal Surfactant Template
journal, March 2012

  • Parent, Lucas R.; Robinson, David B.; Woehl, Taylor J.
  • ACS Nano, Vol. 6, Issue 4
  • DOI: 10.1021/nn300671g

Direct Observation of Aggregative Nanoparticle Growth: Kinetic Modeling of the Size Distribution and Growth Rate
journal, December 2013

  • Woehl, Taylor J.; Park, Chiwoo; Evans, James E.
  • Nano Letters, Vol. 14, Issue 1
  • DOI: 10.1021/nl4043328

In Situ Liquid Cell Electron Microscopy of the Solution Growth of Au–Pd Core–Shell Nanostructures
journal, May 2013

  • Jungjohann, K. L.; Bliznakov, S.; Sutter, P. W.
  • Nano Letters, Vol. 13, Issue 6
  • DOI: 10.1021/nl4014277

Mapping Irreversible Electrochemical Processes on the Nanoscale: Ionic Phenomena in Li Ion Conductive Glass Ceramics
journal, October 2011

  • Arruda, Thomas M.; Kumar, Amit; Kalinin, Sergei V.
  • Nano Letters, Vol. 11, Issue 10
  • DOI: 10.1021/nl202039v

Flexible metallic nanowires with self-adaptive contacts to semiconducting transition-metal dichalcogenide monolayers
journal, April 2014


Direct in Situ Determination of the Mechanisms Controlling Nanoparticle Nucleation and Growth
journal, September 2012

  • Woehl, Taylor J.; Evans, James E.; Arslan, Ilke
  • ACS Nano, Vol. 6, Issue 10
  • DOI: 10.1021/nn303371y

Factors influencing quantitative liquid (scanning) transmission electron microscopy
journal, January 2014

  • Abellan, P.; Woehl, T. J.; Parent, L. R.
  • Chem. Commun., Vol. 50, Issue 38
  • DOI: 10.1039/C3CC48479C

Facet development during platinum nanocube growth
journal, August 2014


The Probe Profile and Lateral Resolution of Scanning Transmission Electron Microscopy of Thick Specimens
journal, May 2012

  • Demers, Hendrix; Ramachandra, Ranjan; Drouin, Dominique
  • Microscopy and Microanalysis, Vol. 18, Issue 3
  • DOI: 10.1017/S1431927612000232

Determining the Resolution Limits of Electron-Beam Lithography: Direct Measurement of the Point-Spread Function
journal, June 2014

  • Manfrinato, Vitor R.; Wen, Jianguo; Zhang, Lihua
  • Nano Letters, Vol. 14, Issue 8
  • DOI: 10.1021/nl5013773

Electron–Water Interactions and Implications for Liquid Cell Electron Microscopy
journal, September 2014

  • Schneider, Nicholas M.; Norton, Michael M.; Mendel, Brian J.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 38
  • DOI: 10.1021/jp507400n

Direct Observation of Dopant Atom Diffusion in a Bulk Semiconductor Crystal Enhanced by a Large Size Mismatch
journal, October 2014


Probing Local Ionic Dynamics in Functional Oxides at the Nanoscale
journal, July 2013

  • Strelcov, Evgheni; Kim, Yunseok; Jesse, Stephen
  • Nano Letters, Vol. 13, Issue 8
  • DOI: 10.1021/nl400780d

Opportunities and challenges in liquid cell electron microscopy
journal, December 2015


Microfluidic System for Transmission Electron Microscopy
journal, August 2010


Nanoscale ferroelectrics: processing, characterization and future trends
journal, July 2006


Intrinsic single-domain switching in ferroelectric materials on a nearly ideal surface
journal, December 2007

  • Kalinin, S. V.; Rodriguez, B. J.; Jesse, S.
  • Proceedings of the National Academy of Sciences, Vol. 104, Issue 51
  • DOI: 10.1073/pnas.0709316104

Creating pure nanostructures from electron-beam-induced deposition using purification techniques: a technology perspective
journal, August 2009


Direct visualization of reversible dynamics in a Si6 cluster embedded in a graphene pore
journal, April 2013

  • Lee, Jaekwang; Zhou, Wu; Pennycook, Stephen J.
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms2671

The partially reversible formation of Li-metal particles on a solid Li electrolyte: applications toward nanobatteries
journal, July 2012


Impact of Membrane-Induced Particle Immobilization on Seeded Growth Monitored by In Situ Liquid Scanning Transmission Electron Microscopy
journal, April 2016

  • Weiner, Rebecca G.; Chen, Dennis P.; Unocic, Raymond R.
  • Small, Vol. 12, Issue 20
  • DOI: 10.1002/smll.201502974

Substrate effects on the electron-beam-induced deposition of platinum from a liquid precursor
journal, January 2011

  • Donev, Eugenii U.; Schardein, Gregory; Wright, John C.
  • Nanoscale, Vol. 3, Issue 7
  • DOI: 10.1039/c1nr10026b

    Works referencing / citing this record:

    Atom-by-atom fabrication with electron beams
    journal, June 2019

    • Dyck, Ondrej; Ziatdinov, Maxim; Lingerfelt, David B.
    • Nature Reviews Materials, Vol. 4, Issue 7
    • DOI: 10.1038/s41578-019-0118-z

    Atom-by-atom fabrication with electron beams
    journal, June 2019

    • Dyck, Ondrej; Ziatdinov, Maxim; Lingerfelt, David B.
    • Nature Reviews Materials, Vol. 4, Issue 7
    • DOI: 10.1038/s41578-019-0118-z