Abstract
Controlled fabrication of nanopores in 2D materials offer the means to create robust membranes needed for ion transport and nanofiltration. Techniques for creating nanopores have relied upon either plasma etching or direct irradiation; however, aberration-corrected scanning transmission electron microscopy (STEM) offers the advantage of combining a sub-Å sized electron beam for atomic manipulation along with atomic resolution imaging. Here, a method for automated nanopore fabrication is utilized with real-time atomic visualization to enhance the mechanistic understanding of beam-induced transformations. Additionally, an electron beam simulation technique, Electron-Beam Simulator (E-BeamSim) is developed to observe the atomic movements and interactions resulting from electron beam irradiation. Using the MXene Ti3C2Tx, the influence of temperature on nanopore fabrication is explored by tracking atomic transformations and find that at room temperature the electron beam irradiation induces random displacement and results in titanium pileups at the nanopore edge, which is confirmed by E-BeamSim. At elevated temperatures, after removal of the surface functional groups and with the increased mobility of atoms results in atomic transformations that lead to the selective removal of atoms layer by layer. This work can lead to the development of defect engineering techniques within functionalized MXene layers and other 2D materials.
| Original language | English |
|---|---|
| Article number | 2400203 |
| Journal | Small Methods |
| Volume | 8 |
| Issue number | 12 |
| DOIs | |
| State | Published - Dec 19 2024 |
Funding
STEM experiments were performed at and supported by the Center for Nanophase Materials Sciences at Oak Ridge National Laboratory, which was a Department of Energy (DOE) Office of Science User Facility. Development of the scan control customization was supported by the U.S. DOE, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering. MXene synthesis and development of E-beam Sim was supported by the Fluid Interface, Reactions, Structures and Transport (FIRST) Center, an Energy Frontier Research Center (EFRC) funded by the U.S. DOE, Office of Science, Office of Basic Energy Sciences. Additional support for the development of the E-beam Sim code and its connectivity to ReaxFF was provided by the National Science Foundation (NSF) through the Pennsylvania State University 2D Crystal Consortium\u2013Materials Innovation Platform (2DCC-MIP) under NSF cooperative agreement numbers DMR-1539916 and DMR-2039351. DFT calculations were supported by INTERSECT Initiative as part of the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory, managed by UT-Battelle, LLC, for the U.S. DOE under contract DE-AC05-00OR22725. This manuscript has been authored by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan). STEM experiments were performed at and supported by the Center for Nanophase Materials Sciences at Oak Ridge National Laboratory, which was a Department of Energy (DOE) Office of Science User Facility. Development of the scan control customization was supported by the U.S. DOE, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering. MXene synthesis and development of E\u2010beam Sim was supported by the Fluid Interface, Reactions, Structures and Transport (FIRST) Center, an Energy Frontier Research Center (EFRC) funded by the U.S. DOE, Office of Science, Office of Basic Energy Sciences. Additional support for the development of the E\u2010beam Sim code and its connectivity to ReaxFF was provided by the National Science Foundation (NSF) through the Pennsylvania State University 2D Crystal Consortium\u2013Materials Innovation Platform (2DCC\u2010MIP) under NSF cooperative agreement numbers DMR\u20101539916 and DMR\u20102039351. DFT calculations were supported by INTERSECT Initiative as part of the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory, managed by UT\u2010Battelle, LLC, for the U.S. DOE under contract DE\u2010AC05\u201000OR22725. This manuscript has been authored by UT\u2010Battelle, LLC, under contract DE\u2010AC05\u201000OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid\u2010up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe\u2010public\u2010access\u2010plan ).
Keywords
- DFT and AIMD simulations
- MXenes
- automated experimentation
- defect fabrication
- scanning transmission electron microscopy