Arranging atoms one by one the way we want them

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ARRANGING ATOMS
ONE-BY-ONE
THE WAY WE WANT THEM
Ondrej Dyck
Jacob Swett
Mina Yoon
Andrew R. Lupini
Stephen Jesse
Maxim Ziatdinov
David Lingerfelt
Ray Unocic
Beth Hudak
Sergei Kalinin
Albina Borisevich
Songkil Kim
Cheng Zhang
Philip Rack
Jason Fowlkes
Bobby Sumpter
Elisa Jimenez-Izal
Anastasia Alexandrova
Lizhi Zhang
Sinchul Yeom
Sarah Dillender
Dale Hensley
Jan Mol
Ivan Kravchenko
Leslie Wilson
Ivan Vlassiouk

4
Overarching Vision
• Moore’s law = smaller devices
• No intrinsic operational difference in smaller devices
• Devices based on single atoms are fundamentally different
• How does one actually do it?
Electron Spin Qubit Piano
Patrik Recher and Bj¨orn Trauzettel
DOI: 10.1088/0957-4484/21/30/302001
arXiv:1004.2136
Spin-up and spin-down
local density of states
Charge and Spin Rectifier
Yao-Jun Dong, Xue-Feng Wang, Shuo-
Wang Yang & Xue-Mei Wu
Scientific Reports volume 4, Article number:
6157 (2014)
Graphene Quantum Dot
Quantum Phase Engineering of Two-Dimensional Post-Transition Metals by
Substrates: Toward a High-Temperature Quantum Anomalous Hall Insulator,
L. Zhang, C. Park, and M. Yoon, Nano Lett. 20 (10), 7186–7192 (2020)
Magnetic ordering and topological
edge states controlled by strain

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Kalinin, Borisevich, Jesse, Nature 539, 485–487 (24
November 2016) doi:10.1038/539485a
Dyck, O., Ziatdinov, M.,
Lingerfelt, D.B. et al. Atom-
by-atom fabrication with
electron beams. Nat Rev
Mater 4, 497–507 (2019).
https://doi.org/10.1038/s415
78-019-0118-z
STEM Platform
• High-precision beam
(~1 Å)
• Large energy (30-300
kV)
• Can access material
interior

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Unintended Transformations Mitigated
vacuum mitigates unintended hydrocarbon
deposition
Strategies for mitigating beam damage
(aberration correction and low kV resolution)

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(1) van Dorp, W. F.; van Someren, B.; Hagen, C. W.; Kruit, P.; Crozier, P. A. Approaching the Resolution
Limit of Nanometer-Scale Electron Beam-Induced Deposition. Nano Lett. 2005, 5 (7), 1303–1307.
https://doi.org/10.1021/nl050522i.
(2) van Dorp, W. F.; Beyer, A.; Mainka, M.; Gölzhäuser, A.; Hansen, T. W.; Wagner, J. B.; Hagen, C. W.;
De Hosson, J. T. M. Focused Electron Beam Induced Processing and the Effect of Substrate Thickness
Revisited. Nanotechnology 2013, 24 (34), 345301. https://doi.org/10.1088/0957-4484/24/34/345301.
(3) van Dorp, W. F.; Zhang, X.; Feringa, B. L.; Hansen, T. W.; Wagner, J. B.; De Hosson, J. T. M.
Molecule-by-Molecule Writing Using a Focused Electron Beam. ACS Nano 2012, 6 (11), 10076–10081.
https://doi.org/10.1021/nn303793w.
(4) W. F. van Dorp; X. Zhang; B. L. Feringa; J. B. Wagner; T. W. Hansen; J. Th M De Hosson.
Nanometer-Scale Lithography on Microscopically Clean Graphene. Nanotechnology 2011, 22 (50),
505303.
(5) van Dorp, W. F.; Lazić, I.; Beyer, A.; Gölzhäuser, A.; Wagner, J. B.; Hansen, T. W.; Hagen, C. W.
Ultrahigh Resolution Focused Electron Beam Induced Processing: The Effect of Substrate Thickness.
Nanotechnology 2011, 22 (11), 115303. https://doi.org/10.1088/0957-4484/22/11/115303.
2005-2013
Van Dorp
Cretu, O.; Rodríguez-Manzo, J. A.; Demortière, A.; Banhart, F. Electron Beam-Induced
Formation and Displacement of Metal Clusters on Graphene, Carbon Nanotubes and
Amorphous Carbon. Carbon 2012, 50 (1), 259–264.
https://doi.org/10.1016/j.carbon.2011.08.043.
Jesse, S.; He, Q.; Lupini, A. R.; Leonard, D. N.; Oxley, M. P.; Ovchinnikov, O.;
Unocic, R. R.; Tselev, A.; Fuentes-Cabrera, M.; Sumpter, B. G.; Pennycook, S. J.;
Kalinin, S. V.; Borisevich, A. Y. Atomic-Level Sculpting of Crystalline Oxides: Toward
Bulk Nanofabrication with Single Atomic Plane Precision. Small 2015, 11 (44), 5895–
5900. https://doi.org/10.1002/smll.201502048.
Unocic, R. R.; Lupini, A. R.; Borisevich, A. Y.; Cullen, D. A.; Kalinin, S. V.; Jesse, S.
Direct-Write Liquid Phase Transformations with a Scanning Transmission Electron
Microscope. Nanoscale 2016, 8 (34), 15581–15588.
https://doi.org/10.1039/C6NR04994J.
Beam Dragging
Deposition
Automated Material Transformations
Cretu 2012
Jesse
2015-2016

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The Atom Forge
Ambitious
Ignores many important details
What transformations?
What materials?
What signals will we look for?

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• E-beam Induced Deposition
• How to deposit a single atom
• Can we “deposit” any type of atom?
• Atomic precision requires atomic cleanliness
• The role of temperature on vacancy diffusion
• Evaporation for long range delivery of atoms
• The Synthescope—a new perspective on in situ microscopy; synthesis in a STEM
• An evaporation platform for in situ synthesis
From THE ATOM FORGE To THE SYNTHESCOPE

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11
Substrate
Gas injection system
E-beam Induced Deposition (EBID)

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E-Beam

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16

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Fowlkes, J. D.; Winkler, R.; Lewis, B. B.; Stanford, M. G.; Plank, H.;
Rack, P. D. Simulation-Guided 3D Nanomanufacturing via Focused
Electron Beam Induced Deposition. ACS Nano 2016, 10 (6), 6163–
6172. https://doi.org/10.1021/acsnano.6b02108.

19

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Carden, W. G.; Lu, H.; Spencer, J. A.; Fairbrother, D. H.; McElwee-White, L. Mechanism-Based Design of Precursors for
Focused Electron Beam-Induced Deposition. MRS Communications 2018, 8 (2), 343–357. https://doi.org/10.1557/mrc.2018.77.
Chemical reactivity of molecular fragments are
critical for driving EBID deposition
Precursor
s

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Scaling to AN ATOM on an atomically pristine
substrate requires rethinking deposition
Precursor
s

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An atom on an atomically pristine substrate is just an
adatom – not what one usually considers “deposition”
Precursor
s

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Delivering chemically pure precursor material (i.e.
single atoms) precludes dissociation
Precursor
s

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Delivering chemically pure precursor material (i.e.
single atoms) precludes dissociation
To achieve strong chemical bonding, the
SUBSTRATE must be modified
Precursor
s

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Dopant Insertion
Dyck, O.; Kim, S.; Kalinin, S. V.; Jesse, S. Placing Single Atoms in Graphene with a Scanning Transmission Electron Microscope.
Appl. Phys. Lett. 2017, 111 (11), 113104. https://doi.org/10.1063/1.4998599.
https://youtu.be/Gg9BAkVBw6Q Paper summary on youtube!

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Dopant Insertion

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Dopant Insertion

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Dopant Insertion

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Dopant Insertion

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Dopant Insertion

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Extending to other elements
O. Dyck, C. Zhang, P. D. Rack, J. D. Fowlkes, B. Sumpter, A. R. Lupini,
S. V. Kalinin, S. Jesse, Electron-beam introduction of heteroatomic Pt–Si
structures in graphene,Carbon, 161, 2020, Pages 750-757, ISSN 0008-
6223, https://doi.org/10.1016/j.carbon.2020.01.042.
Pt Insertion
https://youtu.be/HUXRirt6yJg Paper summary on youtube!

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Pt Insertion Cr Insertion
Ondrej Dyck, Mina Yoon, Lizhi Zhang, Andrew R.
Lupini, Jacob L. Swett, and Stephen Jesse ACS
Applied Nano Materials 2020 3 (11), 10855-10863 DOI:
10.1021/acsanm.0c02118
https://youtu.be/BZ0UKf286UE

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Pt Insertion Cr Insertion
Ondrej Dyck, Mina Yoon, Lizhi Zhang, Andrew R.
Lupini, Jacob L. Swett, and Stephen Jesse ACS
Applied Nano Materials 2020 3 (11), 10855-10863 DOI:
10.1021/acsanm.0c02118
General Insertion
O. Dyck, L. Zhang, M. Yoon, J. L. Swett, D. Hensley, C. Zhang, P. D.
Rack, J. D. Fowlkes, A. R. Lupini, S. Jesse, Doping transition-metal
atoms in graphene for atomic-scale tailoring of electronic, magnetic,
and quantum topological properties, Carbon, 173, 2021, ISSN 0008-
Si
Ti
Cr
Fe
Co
Ni
Cu
Pd
Ag
Pt

39

40
Google
graphene
Real world graphene

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Requires
source material reservoir
(somewhere else)
Dirty Graphene Clean Graphene
Requires reliable
cleaning step
in the microscope
Vacancy must be stable
until adatom attaches
It turns out, none of these steps are trivial when
we try to use larger areas.
One dopant is not
a pattern. We need to
automate.

42
Dyck, O., Ziatdinov, M., Lingerfelt, D.B. et
al. Atom-by-atom fabrication with electron
beams. Nat Rev Mater 4, 497–507 (2019).
https://doi.org/10.1038/s41578-019-0118-z
Manufacturing
Proof of principle

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Dirty Graphene Clean Graphene
Requires reliable
cleaning step
in the microscope

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Rapid Thermal Cleaning
Dyck, O.; Kim, S.; Kalinin, S. V.; Jesse, S. Mitigating E-Beam-Induced Hydrocarbon
Deposition on Graphene for Atomic-Scale Scanning Transmission Electron Microscopy
Studies. Journal of Vacuum Science & Technology, B: Nanotechnology &
Microelectronics: Materials, Processing, Measurement, & Phenomena 2018, 36 (1),
011801. https://doi.org/10.1116/1.5003034.
https://youtu.be/3koezsd02bQ

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Understanding: Hydrocarbon diffusion
Dyck, O.; Lupini, A. R.; Rack, P. D.; Fowlkes, J.; Jesse, S. Controlling Hydrocarbon Transport and Electron Beam Induced Deposition on
Single Layer Graphene: Toward Atomic Scale Synthesis in the Scanning Transmission Electron Microscope. Nano Select 2022, 3 (3),
643–654. https://doi.org/10.1002/nano.202100188.

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Vacancy must be stable
until adatom attaches
One dopant is not
a pattern. We need to
automate.

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Automation: Feedback Control
Dyck, O.; Yeom, S.; Dillender, S.; Lupini, A. R.; Yoon, M.; Jesse, S. The Role of Temperature on Defect Diffusion and Nanoscale
Patterning in Graphene. Carbon 2023, 201, 212–221. https://doi.org/10.1016/j.carbon.2022.09.006.

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Unexpected radiation resistance

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Vacancy diffusion

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Defect chain formation

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Maybe we need a constant supply of material to
incorporate.
Maybe we need to stabilize the vacancies.

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Dyck, O.; Yeom, S.; Lupini, A. R.; Swett, J. L.; Hensley, D.; Yoon, M.; Jesse, S. Top-down Fabrication of Atomic Patterns in Twisted
Bilayer Graphene. arXiv January 4, 2023. https://doi.org/10.48550/arXiv.2301.01674.

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Cr and Cu on bilayer graphene

59

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(a) (b) (c)
8 nm
Original proposal Acquired during write up of final summary document

61

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• The Synthescope—a new perspective on in situ microscopy; synthesis in a
STEM

63
W. F. van Dorp; X. Zhang; B. L.
Feringa; J. B. Wagner; T. W.
Hansen; J. Th M De Hosson.
Nanometer-Scale Lithography on
Microscopically Clean Graphene.
Nanotechnology 2011, 22 (50),
505303.

66
A special case of synthesis

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Future Directions: The Synthescope
Dyck, O.; Lupini, A. R.; Jesse, S. A Platform for in Situ Synthesis in a STEM. arXiv February 27, 2023.
https://doi.org/10.48550/arXiv.2302.14000.

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Requires
source material reservoir
(somewhere else)
What we have
What we want

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77 Dyck, O.; Lupini, A. R.; Jesse, S. Atom-by-Atom Direct Writing. Nano Lett. 2023. https://doi.org/10.1021/acs.nanolett.3c00114.
Direct Writing with Sn Atoms

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• Control:
• Source temperature/evaporation rate
• Source species
• Sample temperature
• Electrical bias and transport
• E-beam position, current, energy
• Real-time observation and characterization during
fabrication and growth processes
• Chamberless synthesis environment the size of an
atom
Chamberless
Synthesis
Environment
Dyck, O.; Lupini, A. R.; Jesse, S. The Synthescope: A Vision for
Combining Synthesis with Atomic Fabrication. arXiv February 16, 2023.

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Center for Nanophase Materials Sciences
A DOE User Facility for Creating, Characterizing,
and Understanding Nanomaterials
Proposals:
• Simple, two-page
narrative
• Two general calls per
year
• Short-term projects
accepted continuously
• Joint proposals with
neutron sources (SNS,
HFIR)
Research areas:
• Synthesis – Soft matter (precision synthesis, selective deuteration), 2D materials, hybrid structures,
epitaxial oxides
• Nanofabrication – Direct-write (3D) fabrication, e-beam lithography, multiscale fluidics,
10,000 sq. ft. cleanroom
• Advanced Microscopy – AFM, STM, aberration-corrected and in situ TEM/STEM, He-ion microscopy,
atom-probe tomography
• Chemical Imaging – Multiple approaches based on mass spectrometry or optical spectroscopies
• Functional Characterization – Laser spectroscopy, transport, magnetism, electromechanical
phenomena
• Theory/Modeling, Data Analytics – Including interactions and co-development with leadership-class,
high-performance computing
• Gateway to Neutron Sciences – deuterated materials, sample environments, multimodal
measurements
Providing free access to staff expertise and equipment if intent is to publish results.
cnms.ornl.gov

82
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Arranging atoms one by one the way we want them

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