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Title: High-Resolution Three-Dimensional Sculpting of Two-Dimensional Graphene Oxide by E-Beam Direct Write

Abstract

On demand switchable additive/subtractive patterning of 2D nanomaterials is an essential capability for developing new concepts of functional nanomaterials and their device realizations. Traditionally, this is performed via a multi-step process using photoresist coating and patterning by conventional photo or electron beam lithography, which is followed by bulk dry/wet etch or deposition. This limits the range of functionalities and structural topologies that can be achieved, as well as increases the complexity, cost, and possibility of contamination which are significant barriers to device fabrication from highly sensitive 2D materials. Focused electron beam induced processing (FEBIP) enables a material chemistry/site-specific, high-resolution multi-mode atomic scale processing and provides unprecedented opportunities for direct-write, single-step surface patterning of 2D nanomaterials with an in-situ imaging capability. It allows for realizing a rapid multi-scale/multi-mode approach, ranging from an atomic scale manipulation (e.g., via targeted defect introduction as an active site) to a large-area surface modification on nano and micro scales, including patterned doping and material removal/deposition with 2D (in-plane)/3D (out-of-plane) control. In this work, we report on a new capability of FEBIP for nanoscale patterning of graphene oxide via removal of oxygenated carbon moieties with no use of reactive gas required for etching complemented by carbon atommore » deposition using focused electron beam. The mechanism of experimentally observed phenomena is explored using the density functional theory (DFT) calculations, revealing that interactions of e-beam liberated reactive oxygen radicals with carbon atoms on graphene basal plane lead to creation of atomic vacancies in the material. The reaction by-products are volatile carbon di-oxides, which are dissociated and volatilized from the graphene oxide surface functional groups by interactions with an energetic focused electron beam. Along with selective “subtractive” patterning of graphene oxide, the same electron beam with increased irradiation doses can deposit out-of-plane 3D carbon nanostructures on top of or around the 2D etched pattern, thus forming a hybrid 2D/3D nanocomposite with feature control down to a few nanometers. This in-operando dual nanofabrication capability of FEBIP is unmatched by any other nanopatterning techniques and opens a new design window for forming 2D/3D complex nanostructures and functional nanodevices.« less

Authors:
ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [2]
  1. Pusan National University, Busan (South Korea)
  2. Georgia Institute of Technology, Atlanta, GA (United States)
Publication Date:
Research Org.:
Georgia Institute of Technology, Atlanta, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Contributing Org.:
Pusan University, South Korea
OSTI Identifier:
1646665
Alternate Identifier(s):
OSTI ID: 1656921; OSTI ID: 1773741
Grant/Contract Number:  
SC0010729
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 12; Journal Issue: 35; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; Graphene oxide; focused electron beam induced processing (FEBIP); reactive gas-free etching; in-operando dual nanofabrication; hybrid 2D/3D nanocomposites; graphene oxide, focused electron beam induced processing (FEBIP), reactive gas-free etching, in-operando dual nanofabrication, hybrid 2D/3D nanocomposite

Citation Formats

Kim, Songkil, Jung, SungYeb, Lee, Jaekwang, Kim, Seokjun, and Fedorov, Andrei G. High-Resolution Three-Dimensional Sculpting of Two-Dimensional Graphene Oxide by E-Beam Direct Write. United States: N. p., 2020. Web. https://doi.org/10.1021/acsami.0c11053.
Kim, Songkil, Jung, SungYeb, Lee, Jaekwang, Kim, Seokjun, & Fedorov, Andrei G. High-Resolution Three-Dimensional Sculpting of Two-Dimensional Graphene Oxide by E-Beam Direct Write. United States. https://doi.org/10.1021/acsami.0c11053
Kim, Songkil, Jung, SungYeb, Lee, Jaekwang, Kim, Seokjun, and Fedorov, Andrei G. Fri . "High-Resolution Three-Dimensional Sculpting of Two-Dimensional Graphene Oxide by E-Beam Direct Write". United States. https://doi.org/10.1021/acsami.0c11053. https://www.osti.gov/servlets/purl/1646665.
@article{osti_1646665,
title = {High-Resolution Three-Dimensional Sculpting of Two-Dimensional Graphene Oxide by E-Beam Direct Write},
author = {Kim, Songkil and Jung, SungYeb and Lee, Jaekwang and Kim, Seokjun and Fedorov, Andrei G.},
abstractNote = {On demand switchable additive/subtractive patterning of 2D nanomaterials is an essential capability for developing new concepts of functional nanomaterials and their device realizations. Traditionally, this is performed via a multi-step process using photoresist coating and patterning by conventional photo or electron beam lithography, which is followed by bulk dry/wet etch or deposition. This limits the range of functionalities and structural topologies that can be achieved, as well as increases the complexity, cost, and possibility of contamination which are significant barriers to device fabrication from highly sensitive 2D materials. Focused electron beam induced processing (FEBIP) enables a material chemistry/site-specific, high-resolution multi-mode atomic scale processing and provides unprecedented opportunities for direct-write, single-step surface patterning of 2D nanomaterials with an in-situ imaging capability. It allows for realizing a rapid multi-scale/multi-mode approach, ranging from an atomic scale manipulation (e.g., via targeted defect introduction as an active site) to a large-area surface modification on nano and micro scales, including patterned doping and material removal/deposition with 2D (in-plane)/3D (out-of-plane) control. In this work, we report on a new capability of FEBIP for nanoscale patterning of graphene oxide via removal of oxygenated carbon moieties with no use of reactive gas required for etching complemented by carbon atom deposition using focused electron beam. The mechanism of experimentally observed phenomena is explored using the density functional theory (DFT) calculations, revealing that interactions of e-beam liberated reactive oxygen radicals with carbon atoms on graphene basal plane lead to creation of atomic vacancies in the material. The reaction by-products are volatile carbon di-oxides, which are dissociated and volatilized from the graphene oxide surface functional groups by interactions with an energetic focused electron beam. Along with selective “subtractive” patterning of graphene oxide, the same electron beam with increased irradiation doses can deposit out-of-plane 3D carbon nanostructures on top of or around the 2D etched pattern, thus forming a hybrid 2D/3D nanocomposite with feature control down to a few nanometers. This in-operando dual nanofabrication capability of FEBIP is unmatched by any other nanopatterning techniques and opens a new design window for forming 2D/3D complex nanostructures and functional nanodevices.},
doi = {10.1021/acsami.0c11053},
journal = {ACS Applied Materials and Interfaces},
number = 35,
volume = 12,
place = {United States},
year = {2020},
month = {8}
}

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