Nanostructures
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A 20-year-old puzzle solved: KAIST research team reveals the 'three-dimensional vortex' of zero-dimensional ferroelectrics
Materials that can maintain a magnetized state by themselves without an external magnetic field (i.e., permanent magnets) are called ferromagnets. Ferroelectrics can be thought of as the electric counterpart to ferromagnets, as they maintain a polarized state without an external electric field. It is well-known that ferromagnets lose their magnetic properties when reduced to nano sizes below a certain threshold. What happens when ferroelectrics are similarly made extremely small in all directions (i.e., into a zero-dimensional structure such as nanoparticles) has been a topic of controversy for a long time.
< (From left) Professor Yongsoo Yang, the corresponding author, and Chaehwa Jeong, the first author studying in the integrated master’s and doctoral program, of the KAIST Department of Physics >
The research team led by Dr. Yongsoo Yang from the Department of Physics at KAIST has, for the first time, experimentally clarified the three-dimensional, vortex-shaped polarization distribution inside ferroelectric nanoparticles through international collaborative research with POSTECH, SNU, KBSI, LBNL and University of Arkansas.
About 20 years ago, Prof. Laurent Bellaiche (currently at University of Arkansas) and his colleagues theoretically predicted that a unique form of polarization distribution, arranged in a toroidal vortex shape, could occur inside ferroelectric nanodots. They also suggested that if this vortex distribution could be properly controlled, it could be applied to ultra-high-density memory devices with capacities over 10,000 times greater than existing ones. However, experimental clarification had not been achieved due to the difficulty of measuring the three-dimensional polarization distribution within ferroelectric nanostructures.
The research team at KAIST successfully solved this 20-year-old challenge by implementing a technique called atomic electron tomography. This technique works by acquiring atomic-resolution transmission electron microscope images of the nanomaterials from multiple tilt angles, and then reconstructing them back into three-dimensional structures using advanced reconstruction algorithms. Electron tomography can be understood as essentially the same method with the CT scans used in hospitals to view internal organs in three dimensions; the KAIST team adapted it uniquely for nanomaterials, utilizing an electron microscope at the single-atom level.
< Figure 1. Three-dimensional polarization distribution of BaTiO3 nanoparticles revealed by atomic electron tomography. >(Left) Schematic of the electron tomography technique, which involves acquiring transmission electron microscope images at multiple tilt angles and reconstructing them into 3D atomic structures.(Center) Experimentally determined three-dimensional polarization distribution inside a BaTiO3 nanoparticle via atomic electron tomography. A vortex-like structure is clearly visible near the bottom (blue dot).(Right) A two-dimensional cross-section of the polarization distribution, thinly sliced at the center of the vortex, with the color and arrows together indicating the direction of the polarization. A distinct vortex structure can be observed.
Using atomic electron tomography, the team completely measured the positions of cation atoms inside barium titanate (BaTiO3) nanoparticles, a well-known ferroelectric material, in three dimensions. From the precisely determined 3D atomic arrangements, they were able to further calculate the internal three-dimensional polarization distribution at the single-atom level. The analysis of the polarization distribution revealed, for the first time experimentally, that topological polarization orderings including vortices, anti-vortices, skyrmions, and a Bloch point occur inside the 0-dimensional ferroelectrics, as theoretically predicted 20 years ago. Furthermore, it was also found that the number of internal vortices can be controlled depending on their sizes.
Prof. Sergey Prosandeev and Prof. Bellaiche (who proposed with other co-workers the polar vortex ordering theoretically 20 years ago), joined this collaboration and further proved that the vortex distribution results obtained from experiments are consistent with theoretical calculations.
By controlling the number and orientation of these polarization distributions, it is expected that this can be utilized into next-generation high-density memory device that can store more than 10,000 times the amount of information in the same-sized device compared to existing ones.
Dr. Yang, who led the research, explained the significance of the results: “This result suggests that controlling the size and shape of ferroelectrics alone, without needing to tune the substrate or surrounding environmental effects such as epitaxial strain, can manipulate ferroelectric vortices or other topological orderings at the nano-scale. Further research could then be applied to the development of next-generation ultra-high-density memory.”
This research, with Chaehwa Jeong from the Department of Physics at KAIST as the first author, was published online in Nature Communications on May 8th (Title: Revealing the Three-Dimensional Arrangement of Polar Topology in Nanoparticles).
The study was mainly supported by the National Research Foundation of Korea (NRF) Grants funded by the Korean Government (MSIT).
2024.05.31 View 3636 -
Hierarchically-Porous Polymers with Fast Absorption
KAIST's Professor Myungeun Seo and his research team from the Graduate School of Nanoscience and Technology has developed a method to form micropores of less than 2 nanometers within porous polymers where 10 nanometers long mesopores connect like a net. The advantage of the porous polymers is fast absorption of molecules.
Porous polymers with micropores of less than 2 nanometers, like a zeolite, have a large surface area. They are used as a means to store hydrogen-based molecules or as a catalytic support that can be used as a surface to convert a material into a desired form. However, because the size of the pores in its path was too small for the molecules, it took a long time to spread into the pores and reach the surface.
To reach the surface efficiently, a lung cell or the vein of a leaf has a structure wherein the pores are subdivided into different sizes so that the molecule can spread throughout the organ. A technology that can create not only micropores but also bigger pores was necessary in order to create such structure.
The research team solved the issue by implementing a "self-assembly" of block polymers to easily form a net-like nanostructure from mesopores of 10 nanometers.
The team created hierarchically-porous polymers consisting of two different types of pores by using a hypercrosslinking reaction along with the "self-assembly" method. The reaction creates micropores within the chain after the polymer chain is confined by a chemical bond.
This porous polymer has micropores that are smaller than 2 nanometers on the walls of mesopores while 10 nanometers long mesopores forming 3-dimensional net structures. Because of the "self-assembly" method, the size of mesopores can be adjusted within the range of 6 to 15 nanometers.
This is the first case where a porous polymer has both well-defined mesopores and micropores. The research team verified the effect of hierarchically-porous structures on absorption of molecules by confirming that the porous polymer had faster absorption speeds than a polymer consisting only of micropores.
Professor Seo said, “The study has found a simple way to create different sizes of pores within a polymer.” He expected that the hierarchically-porous polymers can be used as a catalytic support in which fast diffusion of molecules is essential, or for molecule collection.
The research was sponsored by National Research Foundation of Korea and published online in the Journal of the American Chemical Society.
Figure 1 – Net-like Structure of Hierarchically-Porous Polymers with Mesopores and Micropores on the walls of Mesopores.
Figure 2 - Hierarchically-Porous Polymers
Figure 3 – Comparison of Porous-Polymers consisting of Mesopores only (left), and Mesopores and Micropores (right)
2015.01.13 View 8090