Using Single-Crystal Graphene to Form Arrays of Nanocapsules Enabling the Observation of Light Elements in Liquid Cell Transmission Electron Microscopy.

We have designed and fabricated a TEM (transmission electron microscopy) liquid cell with hundreds of graphene nanocapsules arranged in a stack of two Si3N4-x membranes. These graphene nanocapsules are formed on arrays of nanoholes patterned on the Si3N4-x membrane by focused ion beam milling, allowing for better resolution than for the conventional graphene liquid cells, which enables the observation of light elements, such as atomic structures of silicon. We suggest that multiple nanocapsules provide opportunities for consecutive imaging under the same conditions in a single liquid cell. The use of single-crystal graphene windows offers an excellent signal-to-noise ratio and high spatial resolution. The motion of silicon nanoparticles (a low atomic number (Z) material) interacting with nanobubbles was observed, and analyzed, in detail. Our approach will help advance liquid-phase TEM observations by providing a straightforward method to encapsulate liquid between monolayers of various 2-dimensional materials.

[1]  H. Peng,et al.  Graphene Membranes for Multi‐Dimensional Electron Microscopy Imaging: Preparation, Application, and Prospect , 2022, Advanced Functional Materials.

[2]  Zhongfan Liu,et al.  Intrinsic Wettability in Pristine Graphene , 2021, Advanced materials.

[3]  R. Ruoff,et al.  Single-crystal, large-area, fold-free monolayer graphene , 2021, Nature.

[4]  Maarten J. M. Wirix,et al.  Mapping and Controlling Liquid Layer Thickness in Liquid-Phase (Scanning) Transmission Electron Microscopy. , 2021, Small methods.

[5]  Won Chul Lee,et al.  Nanobubble Dynamics in Aqueous Surfactant Solutions Studied by Liquid-Phase Transmission Electron Microscopy , 2021 .

[6]  Hyun‐Wook Lee,et al.  The Role of Polymer and Inorganic Coatings to Enhance Interparticle Connections Diagnosed by In Situ Techniques. , 2021, Nano letters.

[7]  A. Koster,et al.  Graphene Liquid Cells Assembled through Loop‐Assisted Transfer Method and Located with Correlated Light‐Electron Microscopy , 2020, Advanced Functional Materials.

[8]  Yi Cui,et al.  Robust ultraclean atomically thin membranes for atomic-resolution electron microscopy , 2020, Nature Communications.

[9]  I. Grigorieva,et al.  Limits on gas impermeability of graphene , 2019, Nature.

[10]  R. Ruoff,et al.  Adlayer‐Free Large‐Area Single Crystal Graphene Grown on a Cu(111) Foil , 2019, Advanced materials.

[11]  N. de Jonge,et al.  Liquid-Phase Electron Microscopy with Controllable Liquid Thickness. , 2019, Nano letters.

[12]  Jiwoong Yang,et al.  Dynamic behavior of nanoscale liquids in graphene liquid cells revealed by in situ transmission electron microscopy. , 2019, Micron.

[13]  L. Frey,et al.  Unravelling the Mechanisms of Gold-Silver Core-Shell Nanostructure Formation by in Situ TEM Using an Advanced Liquid Cell Design. , 2018, Nano letters.

[14]  Bin Wang,et al.  Colossal grain growth yields single-crystal metal foils by contact-free annealing , 2018, Science.

[15]  Bin Wang,et al.  Camphor‐Enabled Transfer and Mechanical Testing of Centimeter‐Scale Ultrathin Films , 2018, Advanced materials.

[16]  N. de Jonge,et al.  Strategies for Preparing Graphene Liquid Cells for Transmission Electron Microscopy. , 2018, Nano letters.

[17]  R. Ruoff,et al.  Highly Oriented Monolayer Graphene Grown on a Cu/Ni(111) Alloy Foil. , 2018, ACS nano.

[18]  S. Haigh,et al.  Nanometer Resolution Elemental Mapping in Graphene-Based TEM Liquid Cells , 2017, Nano letters.

[19]  N. de Jonge,et al.  Resolution and aberration correction in liquid cell transmission electron microscopy , 2018, Nature Reviews Materials.

[20]  W. Dang,et al.  Clean Transfer of Large Graphene Single Crystals for High‐Intactness Suspended Membranes and Liquid Cells , 2017, Advanced materials.

[21]  R. Nair,et al.  Dependence of the shape of graphene nanobubbles on trapped substance , 2017, Nature Communications.

[22]  C. Wadell,et al.  Nanocuvette: A Functional Ultrathin Liquid Container for Transmission Electron Microscopy. , 2017, ACS nano.

[23]  M. Bazant,et al.  Liquid cell transmission electron microscopy observation of lithium metal growth and dissolution: Root growth, dead lithium and lithium flotsams , 2017 .

[24]  R. Klie,et al.  Precise In Situ Modulation of Local Liquid Chemistry via Electron Irradiation in Nanoreactors Based on Graphene Liquid Cells , 2016, Advanced materials.

[25]  Yi Cui,et al.  Perspectives in in situ transmission electron microscopy studies on lithium battery electrodes , 2016 .

[26]  Y. Sasaki,et al.  Efficient preparation of graphene liquid cell utilizing direct transfer with large-area well-stitched graphene , 2016 .

[27]  F. Ross Opportunities and challenges in liquid cell electron microscopy , 2015, Science.

[28]  David T. Limmer,et al.  3D structure of individual nanocrystals in solution by electron microscopy , 2015, Science.

[29]  K. Novoselov,et al.  Growth dynamics and gas transport mechanism of nanobubbles in graphene liquid cells , 2014, Nature Communications.

[30]  Lin-Wang Wang,et al.  Facet development during platinum nanocube growth , 2014, Science.

[31]  G. Duscher,et al.  Synthesis of millimeter-size hexagon-shaped graphene single crystals on resolidified copper. , 2013, ACS nano.

[32]  Daniel J. Hellebusch,et al.  High-Resolution EM of Colloidal Nanocrystal Growth Using Graphene Liquid Cells , 2012, Science.

[33]  H. Xin,et al.  In situ observation of oscillatory growth of bismuth nanoparticles. , 2012, Nano letters.

[34]  D. Dikin,et al.  Drop-casted self-assembling graphene oxide membranes for scanning electron microscopy on wet and dense gaseous samples. , 2011, ACS nano.

[35]  Christoph Bräuchle,et al.  Single-particle tracking as a quantitative microscopy-based approach to unravel cell entry mechanisms of viruses and pharmaceutical nanoparticles. , 2011, Molecular therapy : the journal of the American Society of Gene Therapy.

[36]  Rolf Erni,et al.  Determination of the Local Chemical Structure of Graphene Oxide and Reduced Graphene Oxide , 2010, Advanced materials.

[37]  Kwang S. Kim,et al.  Roll-to-roll production of 30-inch graphene films for transparent electrodes. , 2010, Nature nanotechnology.

[38]  Franklin Kim,et al.  Graphene Oxide: Surface Activity and Two‐Dimensional Assembly , 2010, Advanced materials.

[39]  Zhenhua Ni,et al.  Probing layer number and stacking order of few-layer graphene by Raman spectroscopy. , 2010, Small.

[40]  Julio Gómez-Herrero,et al.  Chemical Vapor Deposition Repair of Graphene Oxide: A Route to Highly‐Conductive Graphene Monolayers , 2009 .

[41]  Quan-hong Yang,et al.  Self‐Assembled Free‐Standing Graphite Oxide Membrane , 2009 .

[42]  A. Reina,et al.  Large area, few-layer graphene films on arbitrary substrates by chemical vapor deposition. , 2009, Nano letters.

[43]  D. Peckys,et al.  Electron microscopy of whole cells in liquid with nanometer resolution , 2009, Proceedings of the National Academy of Sciences.

[44]  U. Starke,et al.  Raman spectra of epitaxial graphene on SiC and of epitaxial graphene transferred to SiO2. , 2008, Nano letters.

[45]  J. Kysar,et al.  Measurement of the Elastic Properties and Intrinsic Strength of Monolayer Graphene , 2008, Science.

[46]  Jannik C. Meyer,et al.  The structure of suspended graphene sheets , 2007, Nature.

[47]  S. Siboni,et al.  Contact angle analysis on polymethylmethacrylate and commercial wax by using an environmental scanning electron microscope. , 2007, Scanning.

[48]  J. Philip,et al.  Young's modulus of silicon nitride used in scanning force microscope cantilevers , 2004 .