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Title: Graphene Microcapsule Arrays for Combinatorial Electron Microscopy and Spectroscopy in Liquids

Abstract

Atomic-scale thickness, molecular impermeability, low atomic number, and mechanical strength make graphene an ideal electron-transparent membrane for material characterization in liquids and gases with scanning electron microscopy and spectroscopy. Here in this paper, we present a novel sample platform made of an array of thousands of identical isolated graphene-capped microchannels with high aspect ratio. A combination of a global wide field of view with high resolution local imaging of the array allows for high throughput in situ studies as well as for combinatorial screening of solutions, liquid interfaces, and immersed samples. We demonstrate the capabilities of this platform by studying a pure water sample in comparison with alkali halide solutions, a model electrochemical plating process, and beam-induced crystal growth in liquid electrolyte. Spectroscopic characterization of liquid interfaces and immersed objects with Auger and X-ray fluorescence analysis through the graphene membrane are also demonstrated.

Authors:
 [1];  [2];  [3];  [4]; ORCiD logo [5]; ORCiD logo [4]
  1. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Nanoscale Science and Technology; Univ. of Maryland, College Park, MD (United States). Dept. of Materials Science and Engineering; Univ. of Maryland, College Park, MD (United States). Maryland NanoCenter
  2. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Nanoscale Science and Technology; Univ. of Maryland, College Park, MD (United States). Maryland NanoCenter
  3. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Nanoscale Science and Technology; Univ. of Maryland, College Park, MD (United States). Maryland NanoCenter
  4. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Nanoscale Science and Technology
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1399453
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 9; Journal Issue: 31; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ambient pressure electron microscopy; Auger; electrochemistry; graphene; liquid cell

Citation Formats

Yulaev, Alexander, Guo, Hongxuan, Strelcov, Evgheni, Chen, Lei, Vlassiouk, Ivan, and Kolmakov, Andrei. Graphene Microcapsule Arrays for Combinatorial Electron Microscopy and Spectroscopy in Liquids. United States: N. p., 2017. Web. doi:10.1021/acsami.7b02824.
Yulaev, Alexander, Guo, Hongxuan, Strelcov, Evgheni, Chen, Lei, Vlassiouk, Ivan, & Kolmakov, Andrei. Graphene Microcapsule Arrays for Combinatorial Electron Microscopy and Spectroscopy in Liquids. United States. https://doi.org/10.1021/acsami.7b02824
Yulaev, Alexander, Guo, Hongxuan, Strelcov, Evgheni, Chen, Lei, Vlassiouk, Ivan, and Kolmakov, Andrei. Thu . "Graphene Microcapsule Arrays for Combinatorial Electron Microscopy and Spectroscopy in Liquids". United States. https://doi.org/10.1021/acsami.7b02824. https://www.osti.gov/servlets/purl/1399453.
@article{osti_1399453,
title = {Graphene Microcapsule Arrays for Combinatorial Electron Microscopy and Spectroscopy in Liquids},
author = {Yulaev, Alexander and Guo, Hongxuan and Strelcov, Evgheni and Chen, Lei and Vlassiouk, Ivan and Kolmakov, Andrei},
abstractNote = {Atomic-scale thickness, molecular impermeability, low atomic number, and mechanical strength make graphene an ideal electron-transparent membrane for material characterization in liquids and gases with scanning electron microscopy and spectroscopy. Here in this paper, we present a novel sample platform made of an array of thousands of identical isolated graphene-capped microchannels with high aspect ratio. A combination of a global wide field of view with high resolution local imaging of the array allows for high throughput in situ studies as well as for combinatorial screening of solutions, liquid interfaces, and immersed samples. We demonstrate the capabilities of this platform by studying a pure water sample in comparison with alkali halide solutions, a model electrochemical plating process, and beam-induced crystal growth in liquid electrolyte. Spectroscopic characterization of liquid interfaces and immersed objects with Auger and X-ray fluorescence analysis through the graphene membrane are also demonstrated.},
doi = {10.1021/acsami.7b02824},
journal = {ACS Applied Materials and Interfaces},
number = 31,
volume = 9,
place = {United States},
year = {Thu Apr 27 00:00:00 EDT 2017},
month = {Thu Apr 27 00:00:00 EDT 2017}
}

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Cited by: 22 works
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Works referenced in this record:

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

The Nanoaquarium: A Platform for In Situ Transmission Electron Microscopy in Liquid Media
journal, August 2010


Monolithic Chip System with a Microfluidic Channel for In Situ Electron Microscopy of Liquids
journal, April 2014

  • Jensen, Eric; Burrows, Andrew; Mølhave, Kristian
  • Microscopy and Microanalysis, Vol. 20, Issue 2
  • DOI: 10.1017/S1431927614000300

High-Resolution Imaging and Spectroscopy at High Pressure: A Novel Liquid Cell for the Transmission Electron Microscope
journal, December 2015

  • Tanase, Mihaela; Winterstein, Jonathan; Sharma, Renu
  • Microscopy and Microanalysis, Vol. 21, Issue 6
  • DOI: 10.1017/S1431927615015482

An apparatus for imaging liquids, cells, and other wet samples in the scanning electron microscopy
journal, July 2004

  • Thiberge, S.; Zik, O.; Moses, E.
  • Review of Scientific Instruments, Vol. 75, Issue 7
  • DOI: 10.1063/1.1763262

The Atmospheric Scanning Electron Microscope with open sample space observes dynamic phenomena in liquid or gas
journal, December 2011


In-situ SEM microchip setup for electrochemical experiments with water based solutions
journal, June 2013


Design and Application of Variable Temperature Setup for Scanning Electron Microscopy in Gases and Liquids at Ambient Conditions
journal, June 2015


Electron Microscopy of Living Cells During in Situ Fluorescence Microscopy
journal, December 2015

  • Liv, Nalan; van Oosten Slingeland, Daan S. B.; Baudoin, Jean-Pierre
  • ACS Nano, Vol. 10, Issue 1
  • DOI: 10.1021/acsnano.5b03970

Calculations of electron inelastic mean free paths. IX. Data for 41 elemental solids over the 50 eV to 30 keV range
journal, February 2011

  • Tanuma, S.; Powell, C. J.; Penn, D. R.
  • Surface and Interface Analysis, Vol. 43, Issue 3
  • DOI: 10.1002/sia.3522

Photoelectron spectroscopy of wet and gaseous samples through graphene membranes
journal, January 2014

  • Kraus, Jürgen; Reichelt, Robert; Günther, Sebastian
  • Nanoscale, Vol. 6, Issue 23
  • DOI: 10.1039/C4NR03561E

Electron transparent graphene windows for environmental scanning electron microscopy in liquids and dense gases
journal, November 2012


High-Resolution EM of Colloidal Nanocrystal Growth Using Graphene Liquid Cells
journal, April 2012


High-Resolution Electron Microscopy and Spectroscopy of Ferritin in Biocompatible Graphene Liquid Cells and Graphene Sandwiches
journal, February 2014

  • Wang, Canhui; Qiao, Qiao; Shokuhfar, Tolou
  • Advanced Materials, Vol. 26, Issue 21
  • DOI: 10.1002/adma.201306069

Electron Microscopy in Air: Transparent Atomic Membranes and Imaging Modes
journal, August 2015


Impermeable Atomic Membranes from Graphene Sheets
journal, August 2008

  • Bunch, J. Scott; Verbridge, Scott S.; Alden, Jonathan S.
  • Nano Letters, Vol. 8, Issue 8
  • DOI: 10.1021/nl801457b

Graphene Membranes for Atmospheric Pressure Photoelectron Spectroscopy
journal, April 2016

  • Weatherup, Robert S.; Eren, Baran; Hao, Yibo
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 9
  • DOI: 10.1021/acs.jpclett.6b00640

Photoelectron Spectroscopy at the Graphene-Liquid Interface Reveals the Electronic Structure of an Electrodeposited Cobalt/Graphene Electrocatalyst
journal, October 2015

  • Velasco-Velez, Juan J.; Pfeifer, Verena; Hävecker, Michael
  • Angewandte Chemie International Edition, Vol. 54, Issue 48
  • DOI: 10.1002/anie.201506044

Transfer of CVD-Grown Monolayer Graphene onto Arbitrary Substrates
journal, August 2011

  • Suk, Ji Won; Kitt, Alexander; Magnuson, Carl W.
  • ACS Nano, Vol. 5, Issue 9
  • DOI: 10.1021/nn201207c

Three-dimensional electron microscopy simulation with the CASINO Monte Carlo software
journal, May 2011

  • Demers, Hendrix; Poirier-Demers, Nicolas; Couture, Alexandre Réal
  • Scanning, Vol. 33, Issue 3
  • DOI: 10.1002/sca.20262

Scanning Electron Microscopy and X-ray Microanalysis
book, January 2003


Nanofiltration across Defect-Sealed Nanoporous Monolayer Graphene
journal, April 2015


Implications of Permeation through Intrinsic Defects in Graphene on the Design of Defect-Tolerant Membranes for Gas Separation
journal, December 2013

  • Boutilier, Michael S. H.; Sun, Chengzhen; O’Hern, Sean C.
  • ACS Nano, Vol. 8, Issue 1, p. 841-849
  • DOI: 10.1021/nn405537u

Selective Molecular Transport through Intrinsic Defects in a Single Layer of CVD Graphene
journal, October 2012

  • O’Hern, Sean C.; Stewart, Cameron A.; Boutilier, Michael S. H.
  • ACS Nano, Vol. 6, Issue 11, p. 10130-10138
  • DOI: 10.1021/nn303869m

Hydrogen bonding in liquid water probed by resonant Auger-electron spectroscopy
journal, September 2007

  • Winter, Bernd; Hergenhahn, Uwe; Faubel, Manfred
  • The Journal of Chemical Physics, Vol. 127, Issue 9
  • DOI: 10.1063/1.2770457

Soft X-ray microscopes and their biological applications
journal, February 1995

  • Kirz, Janos; Jacobsen, Chris; Howells, Malcolm
  • Quarterly Reviews of Biophysics, Vol. 28, Issue 1
  • DOI: 10.1017/S0033583500003139

Relaxation Processes in Aqueous Systems upon X-ray Ionization: Entanglement of Electronic and Nuclear Dynamics
journal, January 2016

  • Slavíček, Petr; Kryzhevoi, Nikolai V.; Aziz, Emad F.
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 2
  • DOI: 10.1021/acs.jpclett.5b02665

Ultrafast energy transfer between water molecules
journal, January 2010

  • Jahnke, T.; Sann, H.; Havermeier, T.
  • Nature Physics, Vol. 6, Issue 2
  • DOI: 10.1038/nphys1498

Enabling Photoemission Electron Microscopy in Liquids via Graphene-Capped Microchannel Arrays
journal, January 2017


Sensitivity Enhancement for Quantitative Electrochemical Determination of a Trace Amount of Accelerator in Copper Plating Solutions
journal, January 2011

  • Chiu, Yong-Da; Dow, Wei-Ping; Huang, Su-Mei
  • Journal of The Electrochemical Society, Vol. 158, Issue 5
  • DOI: 10.1149/1.3560479

Accelerator Screening by Cyclic Voltammetry for Microvia Filling by Copper Electroplating
journal, January 2013

  • Chiu, Yong-Da; Dow, Wei-Ping
  • Journal of The Electrochemical Society, Vol. 160, Issue 12
  • DOI: 10.1149/2.006312jes

Electron-Beam-Induced Deposition of Platinum from a Liquid Precursor
journal, July 2009

  • Donev, Eugenii U.; Hastings, J. Todd
  • Nano Letters, Vol. 9, Issue 7
  • DOI: 10.1021/nl9012216

Control of Electron Beam-Induced Au Nanocrystal Growth Kinetics through Solution Chemistry
journal, July 2015


Direct-write liquid phase transformations with a scanning transmission electron microscope
journal, January 2016

  • Unocic, Raymond R.; Lupini, Andrew R.; Borisevich, Albina Y.
  • Nanoscale, Vol. 8, Issue 34
  • DOI: 10.1039/C6NR04994J

Real-Time Observation of Water-Soluble Mineral Precipitation in Aqueous Solution by In Situ High-Resolution Electron Microscopy
journal, December 2015


Estimation of Setchenow constants for nonpolar gases in aqueous solutions of common salts at moderate temperatures
journal, February 1983

  • Pawlikowski, Ellen M.; Prausnitz, John M.
  • Industrial & Engineering Chemistry Fundamentals, Vol. 22, Issue 1
  • DOI: 10.1021/i100009a015

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

Quantitative Description of Crystal Nucleation and Growth from in Situ Liquid Scanning Transmission Electron Microscopy
journal, October 2015


Graphene nanobubbles on TiO 2 for in-operando electron spectroscopy of liquid-phase chemistry
journal, January 2017

  • Nappini, S.; Matruglio, A.; Naumenko, D.
  • Nanoscale, Vol. 9, Issue 13
  • DOI: 10.1039/C6NR09061C

Role of Hydrogen in Chemical Vapor Deposition Growth of Large Single-Crystal Graphene
journal, July 2011

  • Vlassiouk, Ivan; Regmi, Murari; Fulvio, Pasquale
  • ACS Nano, Vol. 5, Issue 7, p. 6069-6076
  • DOI: 10.1021/nn201978y

Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils
journal, May 2009


Works referencing / citing this record:

Studies of surface of metal nanoparticles in a flowing liquid with XPS
journal, January 2018

  • Nguyen, Luan; Tao, Paul (Pengcheng); Liu, Huimin
  • Chemical Communications, Vol. 54, Issue 71
  • DOI: 10.1039/c8cc03497d

State-of-the-Art and Future Prospects for Atomically Thin Membranes from 2D Materials
journal, August 2018