Scientists at the Department of Energy's Oak Ridge National Laboratory induced a two-dimensional material to cannibalize itself for atomic "building blocks" from which stable structures formed.
The findings, reported in Nature Communications, provide insights that may improve design of 2D materials for fast-charging energy-storage and electronic devices.
"Under our experimental conditions, titanium and carbon atoms can spontaneously form an atomically thin layer of 2D transition-metal carbide, which was never observed before," said Xiahan Sang of ORNL.
He and ORNL's Raymond Unocic led a team that performed in situ experiments using state-of-the-art scanning transmission electron microscopy (STEM), combined with theory-based simulations, to reveal the mechanism's atomistic details.
"This study is about determining the atomic-level mechanisms and kinetics that are responsible for forming new structures of a 2D transition-metal carbide such that new synthesis methods can be realized for this class of materials," Unocic added.
The starting material was a 2D ceramic called a MXene (pronounced "max een"). Unlike most ceramics, MXenes are good electrical conductors because they are made from alternating atomic layers of carbon or nitrogen sandwiched within transition metals like titanium.
The research was a project of the Fluid Interface Reactions, Structures and Transport (FIRST) Center, a DOE Energy Frontier Research Center that explores fluid-solid interface reactions that have consequences for energy transport in everyday applications.
Scientists conducted experiments to synthesize and characterize advanced materials and performed theory and simulation work to explain observed structural and functional properties of the materials. New knowledge from FIRST projects provides guideposts for future studies.
The high-quality material used in these experiments was synthesized by Drexel University scientists, in the form of five-ply single-crystal monolayer flakes of MXene. The flakes were taken from a parent crystal called "MAX," which contains a transition metal denoted by "M"; an element such as aluminum or silicon, denoted by "A"; and either a carbon or nitrogen atom, denoted by "X." The researchers used an acidic solution to etch out the monoatomic aluminum layers, exfoliate the material and delaminate it into individual monolayers of a titanium carbide MXene (Ti3C2).
The ORNL scientists suspended a large MXene flake on a heating chip with holes drilled in it so no support material, or substrate, interfered with the flake. Under vacuum, the suspended flake was exposed to heat and irradiated with an electron beam to clean the MXene surface and fully expose the layer of titanium atoms.
MXenes are typically inert because their surfaces are covered with protective functional groups--oxygen, hydrogen and fluorine atoms that remain after acid exfoliation. After protective groups are removed, the remaining material activates. Atomic-scale defects--"vacancies" created when titanium atoms are removed during etching--are exposed on the outer ply of the monolayer. "These atomic vacancies are good initiation sites," Sang said. "It's favorable for titanium and carbon atoms to move from defective sites to the surface." In an area with a defect, a pore may form when atoms migrate.
"Once those functional groups are gone, now you're left with a bare titanium layer (and underneath, alternating carbon, titanium, carbon, titanium) that's free to reconstruct and form new structures on top of existing structures," Sang said.
High-resolution STEM imaging proved that atoms moved from one part of the material to another to build structures. Because the material feeds on itself, the growth mechanism is cannibalistic.
"The growth mechanism is completely supported by density functional theory and reactive molecular dynamics simulations, thus opening up future possibilities to use these theory tools to determine the experimental parameters required for synthesizing specific defect structures," said Adri van Duin of Penn State.
Most of the time, only one additional layer [of carbon and titanium] grew on a surface. The material changed as atoms built new layers. Ti3C2 turned into Ti4C3, for example.
"These materials are efficient at ionic transport, which lends itself well to battery and supercapacitor applications," Unocic said. "How does ionic transport change when we add more layers to nanometer-thin MXene sheets?" This question may spur future studies.
"Because MXenes containing molybdenum, niobium, vanadium, tantalum, hafnium, chromium and other metals are available, there are opportunities to make a variety of new structures containing more than three or four metal atoms in cross-section (the current limit for MXenes produced from MAX phases)," Yury Gogotsi of Drexel University added. "Those materials may show different useful properties and create an array of 2D building blocks for advancing technology."
At ORNL's Center for Nanophase Materials Sciences (CNMS), Yu Xie, Weiwei Sun and Paul Kent performed first-principles theory calculations to explain why these materials grew layer by layer instead of forming alternate structures, such as squares. Xufan Li and Kai Xiao helped understand the growth mechanism, which minimizes surface energy to stabilize atomic configurations. Penn State scientists conducted large-scale dynamical reactive force field simulations showing how atoms rearranged on surfaces, confirming defect structures and their evolution as observed in experiments.
The researchers hope the new knowledge will help others grow advanced materials and generate useful nanoscale structures.
The title of the paper is "In situ atomistic insight into the growth mechanisms of single layer 2D transition metal carbides."
Research was supported as part of the FIRST Center, an Energy Frontier Research Center funded by the U.S. Department of Energy Office of Science. In situ aberration-corrected STEM imaging was conducted at CNMS, a U.S. Department of Energy Office of Science User Facility at ORNL. The research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility at Lawrence Berkeley National Laboratory.
UT-Battelle manages ORNL for DOE's Office of Science. The single largest supporter of basic research in the physical sciences in the United States, the Office of Science is working to address some of the most pressing challenges of our time. For more information, please visit https:/
Dawn Levy | EurekAlert!
Capturing 3D microstructures in real time
03.04.2020 | DOE/Argonne National Laboratory
Graphene-based actuator swarm enables programmable deformation
02.04.2020 | Science China Press
Electrolytes play a key role in many areas: They are crucial for the storage of energy in our body as well as in batteries. In order to release energy, ions - charged atoms - must move in a liquid such as water. Until now the precise mechanism by which they move through the atoms and molecules of the electrolyte has, however, remained largely unknown. Scientists at the Max Planck Institute for Polymer Research have now shown that the electrical resistance of an electrolyte, which is determined by the motion of ions, can be traced back to microscopic vibrations of these dissolved ions.
In chemistry, common table salt is also known as sodium chloride. If this salt is dissolved in water, sodium and chloride atoms dissolve as positively or...
Drops of water falling on or sliding over surfaces may leave behind traces of electrical charge, causing the drops to charge themselves. Scientists at the Max Planck Institute for Polymer Research (MPI-P) in Mainz have now begun a detailed investigation into this phenomenon that accompanies us in every-day life. They developed a method to quantify the charge generation and additionally created a theoretical model to aid understanding. According to the scientists, the observed effect could be a source of generated power and an important building block for understanding frictional electricity.
Water drops sliding over non-conducting surfaces can be found everywhere in our lives: From the dripping of a coffee machine, to a rinse in the shower, to an...
90 million-year-old forest soil provides unexpected evidence for exceptionally warm climate near the South Pole in the Cretaceous
An international team of researchers led by geoscientists from the Alfred Wegener Institute, Helmholtz Centre for Polar and Marine Research (AWI) have now...
The bacteria that cause tuberculosis need iron to survive. Researchers at the University of Zurich have now solved the first detailed structure of the transport protein responsible for the iron supply. When the iron transport into the bacteria is inhibited, the pathogen can no longer grow. This opens novel ways to develop targeted tuberculosis drugs.
One of the most devastating pathogens that lives inside human cells is Mycobacterium tuberculosis, the bacillus that causes tuberculosis. According to the...
An international team with the participation of Prof. Dr. Michael Kues from the Cluster of Excellence PhoenixD at Leibniz University Hannover has developed a new method for generating quantum-entangled photons in a spectral range of light that was previously inaccessible. The discovery can make the encryption of satellite-based communications much more secure in the future.
A 15-member research team from the UK, Germany and Japan has developed a new method for generating and detecting quantum-entangled photons at a wavelength of...
06.04.2020 | Event News
02.04.2020 | Event News
26.03.2020 | Event News
06.04.2020 | Life Sciences
06.04.2020 | Power and Electrical Engineering
06.04.2020 | Social Sciences