Tag Archives: Kwanpyo Kim

A nano big bang event

Here’s what you’re seeing (from the YouTube entry),

Berkeley Lab scientists and collaborators took advantage of one of the best microscopes in the world – the TEAM I electron microscope at the Molecular Foundry – to watch how individual gold atoms organized themselves into crystals on top of graphene. The research team observed as groups of gold atoms formed and broke apart many times, trying out different configurations, before finally stabilizing. The discovery of this fast-changing and reversible process was possible thanks to these high-speed images captured at atomic resolution. Credit: Berkeley Lab

The work was announced in a March 25, 2021 news item on phys.org,

When we grow crystals, atoms first group together into small clusters—a process called nucleation. But understanding exactly how such atomic ordering emerges from the chaos of randomly moving atoms has long eluded scientists.

Classical nucleation theory suggests that crystals form one atom at a time, steadily increasing the level of order. Modern studies have also observed a two-step nucleation process, where a temporary, high-energy structure forms first, which then changes into a stable crystal. But according to an international research team co-led by the Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab), the real story is even more complicated.

Their findings, recently reported in the journal Science, reveal that rather than grouping together one-by-one or making a single irreversible transition, gold atoms will instead self-organize, fall apart, regroup, and then reorganize many times before establishing a stable, ordered crystal. Using an advanced electron microscope, the researchers witnessed this rapid, reversible nucleation process for the first time. Their work provides tangible insights into the early stages of many growth processes such as thin-film deposition and nanoparticle formation.

A March 25, 2021 DOE [US Dept. of Energy]/Lawrence Berkeley National Laboratory news release (also on EurekAlert) by Clarissa Bhargava, which originated the news item, expands on the topic,

“As scientists seek to control matter at smaller length scales to produce new materials and devices, this study helps us understand exactly how some crystals form,” said Peter Ercius, one of the study’s lead authors and a staff scientist at Berkeley Lab’s Molecular Foundry.

In line with scientists’ conventional understanding, once the crystals in the study reached a certain size, they no longer returned to the disordered, unstable state. Won Chul Lee, one of the professors guiding the project, describes it this way: if we imagine each atom as a Lego brick, then instead of building a house one brick at a time, it turns out that the bricks repeatedly fit together and break apart again until they are finally strong enough to stay together. Once the foundation is set, however, more bricks can be added without disrupting the overall structure.

The unstable structures were only visible because of the speed of newly developed detectors on the TEAM I [Transmission Electron Aberration-corrected Microscope], one of the world’s most powerful electron microscopes. A team of in-house experts guided the experiments at the National Center for Electron Microscopy in Berkeley Lab’s Molecular Foundry. Using the TEAM I microscope, researchers captured real-time, atomic-resolution images at speeds up to 625 frames per second, which is exceptionally fast for electron microcopy and about 100 times faster than previous studies. The researchers observed individual gold atoms as they formed into crystals, broke apart into individual atoms, and then reformed again and again into different crystal configurations before finally stabilizing.

“Slower observations would miss this very fast, reversible process and just see a blur instead of the transitions, which explains why this nucleation behavior has never been seen before,” said Ercius.

The reason behind this reversible phenomenon is that crystal formation is an exothermic process – that is, it releases energy. In fact, the very energy released when atoms attach to the tiny nuclei can raise the local “temperature” and melt the crystal. In this way, the initial crystal formation process works against itself, fluctuating between order and disorder many times before building a nucleus that is stable enough to withstand the heat. The research team validated this interpretation of their experimental observations by performing calculations of binding reactions between a hypothetical gold atom and a nanocrystal.

Now, scientists are developing even faster detectors which could be used to image the process at higher speeds. This could help them understand if there are more features of nucleation hidden in the atomic chaos. The team is also hoping to spot similar transitions in different atomic systems to determine whether this discovery reflects a general process of nucleation.

One of the study’s lead authors, Jungwon Park, summarized the work: “From a scientific point of view, we discovered a new principle of crystal nucleation process, and we proved it experimentally.”

Here’s a link to and a citation for the paper,

Reversible disorder-order transitions in atomic crystal nucleation by Sungho Jeon, Taeyeong Heo, Sang-Yeon Hwang, Jim Ciston, Karen C. Bustillo, Bryan W. Reed, Jimin Ham, Sungsu Kang, Sungin Kim, Joowon Lim, Kitaek Lim, Ji Soo Kim, Min-Ho Kang, Ruth S. Bloom, Sukjoon Hong, Kwanpyo Kim, Alex Zettl, Woo Youn Kim, Peter Ercius, Jungwon Park, Won Chul Lee. Science 29 Jan 2021: Vol. 371, Issue 6528, pp. 498-503 DOI: 10.1126/science.aaz7555

This paper is behind a paywall.

A new type of diode from South Korea’s Ulsan National Institute of Science and Technology

A Feb. 8, 2017 news item on phys.org features a ‘dream’ diode from Ulsan National Institute of Science and Technology,

A team of researchers, affiliated with UNIST [Ulsan National Institute of Science and Technology] has created a new technique that greatly enhances the performance of Schottky Diodes (metal-semiconductor junction) used in electronic devices. Their research findings have attracted considerable attention within the scientific community by solving the contact resistance problem of metal-semiconductor, which had remained unsolved for almost 50 years.

As described in the January [2017] issue of Nano Letters, the researchers have created a new type of diode with a graphene insertion layer sandwiched between metal and semiconductor. This new technique blows all previous attemps out the water, as it is expected to significantly contribute to the semiconductor industry’s growth.

A Jan. 27, 2017 UNIST press release, (also on EurekAlert), which originated the news item, describes the research in greater detail,

The Schottky diode is one of the oldest and most representative semiconductor devices, formed by the junction of a semiconductor with a metal.  However, due to the atomic intermixing along the interface between two materials, it has been impossible to produce an ideal diode. (An ideal diode acts like a perfect conductor when voltage is applied forward biased and like a perfect insulator when voltage is applied reverse biased.)

graphene interlayer 2

The schematic view of internal photoemission (IPE) measurements on metal/n-Si(001) junctions with Ni, Pt, and Ti electrodes for with and without a graphene insertion layer.

Professor Kibog Park of Natural Science solved this problem by inserting a graphene layer at the metal-semiconductor interface. In the study, the research team demonstrated that this graphene layer, consisting of a single layer of carbon atoms can not only suppress the material intermixing substantially, but also matches well with the theoretical prediction.

“The sheets of graphene in graphite have a space between each sheet that shows a high electron density of quantum mechanics in that no atoms can pass through,” says Professor Park. “Therefore, with this single-layer graphene sandwiched between metal and semiconductor, it is possible to overcome the inevitable atomic diffusion problem.”

The study also has the physiological meaning of confirming the theoretical prediction that “In the case of silicon semiconductors, the electrical properties of the junction surfaces hardly change regardless of the type of metal they use,” according to Hoon Hahn Yoon (Combined M.S./Ph.D. student of Natural Science), the first author of the study.

The internal photoemission method was used to measure the electronic energy barrier of the newly-fabricated metal/graphene/n-Si(001) junction diodes. The Internal Photoemission (IPE) Measurement System in the image shown above has contributed greatly to these experiments. This system has been developed by four UNIST graduate students (Hoon Han Yoon, Sungchul Jung, Gahyun Choi, and Junhyung Kim), which was carried out as part of an undergraduate research project in 2012 and was supported by the Korea Foundation for the Advancement of Science and Creativity (KOFAC).

This is the internal photoemission (IPE) measurement system, developed by Hoon Hahn Yoon of Physics at UNIST.

Shown above is the Internal Photoemission (IPE) Measurement System, developed by Hoon Hahn Yoon, combined M.S./Ph.D. student of Natural Science at UNIST.

“Students have teamed up and carried out all the necessary steps for the research since they were undergraduates,” Professor Park says. “Therefore, this research is a perfect example of time, persistence, and patience paying off.”

This study has been jointly conducted by Professor Hu Young Jeong of the UNIST Central Research Facilities (UCRF), Professor Kwanpyo Kim of Natural Science, Professor Soon-Yong Kwon of Materials Science and Engineering, and Professor Yong Soo Kim of Ulsan University. It has been also supported by the National Research Foundation of Korea, Nuclear Research Basis Expansion Project, as well as the Global Ph.D Fellowship (GPF).

Here’s a link to and a citation for the paper,

Strong Fermi-Level Pinning at Metal/n-Si(001) Interface Ensured by Forming an Intact Schottky Contact with a Graphene Insertion Layer by Hoon Hahn Yoon, Sungchul Jung, Gahyun Choi, Junhyung Kim, Youngeun Jeon, Yong Soo Kim, Hu Young Jeong, Kwanpyo Kim, Soon-Yong Kwon, and Kibog Park. Nano Lett., 2017, 17 (1), pp 44–49 DOI: 10.1021/acs.nanolett.6b03137 Publication Date (Web): December 14, 2016

Copyright © 2016 American Chemical Society

This paper is behind a paywall.

SINGLE (3D Structure Identification of Nanoparticles by Graphene Liquid Cell Electron Microscopy) and the 3D structures of two individual platinum nanoparticles in solution

It seems to me there’s been an explosion of new imaging techniques lately. This one from the Lawrence Berkelely National Laboratory is all about imaging colloidal nanoparticles (nanoparticles in solution), from a July 20, 2015 news item on Azonano,

Just as proteins are one of the basic building blocks of biology, nanoparticles can serve as the basic building blocks for next generation materials. In keeping with this parallel between biology and nanotechnology, a proven technique for determining the three dimensional structures of individual proteins has been adapted to determine the 3D structures of individual nanoparticles in solution.

A multi-institutional team of researchers led by the U.S. Department of Energy (DOE)’s Lawrence Berkeley National Laboratory (Berkeley Lab), has developed a new technique called “SINGLE” that provides the first atomic-scale images of colloidal nanoparticles. SINGLE, which stands for 3D Structure Identification of Nanoparticles by Graphene Liquid Cell Electron Microscopy, has been used to separately reconstruct the 3D structures of two individual platinum nanoparticles in solution.

A July 16, 2015 Berkeley Lab news release, which originated the news item, reveals more details about the reason for the research and the research itself,

“Understanding structural details of colloidal nanoparticles is required to bridge our knowledge about their synthesis, growth mechanisms, and physical properties to facilitate their application to renewable energy, catalysis and a great many other fields,” says Berkeley Lab director and renowned nanoscience authority Paul Alivisatos, who led this research. “Whereas most structural studies of colloidal nanoparticles are performed in a vacuum after crystal growth is complete, our SINGLE method allows us to determine their 3D structure in a solution, an important step to improving the design of nanoparticles for catalysis and energy research applications.”

Alivisatos, who also holds the Samsung Distinguished Chair in Nanoscience and Nanotechnology at the University of California Berkeley, and directs the Kavli Energy NanoScience Institute at Berkeley (Kavli ENSI), is the corresponding author of a paper detailing this research in the journal Science. The paper is titled “3D Structure of Individual Nanocrystals in Solution by Electron Microscopy.” The lead co-authors are Jungwon Park of Harvard University, Hans Elmlund of Australia’s Monash University, and Peter Ercius of Berkeley Lab. Other co-authors are Jong Min Yuk, David Limmer, Qian Chen, Kwanpyo Kim, Sang Hoon Han, David Weitz and Alex Zettl.

Colloidal nanoparticles are clusters of hundreds to thousands of atoms suspended in a solution whose collective chemical and physical properties are determined by the size and shape of the individual nanoparticles. Imaging techniques that are routinely used to analyze the 3D structure of individual crystals in a material can’t be applied to suspended nanomaterials because individual particles in a solution are not static. The functionality of proteins are also determined by their size and shape, and scientists who wanted to image 3D protein structures faced a similar problem. The protein imaging problem was solved by a technique called “single-particle cryo-electron microscopy,” in which tens of thousands of 2D transmission electron microscope (TEM) images of identical copies of an individual protein or protein complex frozen in random orientations are recorded then computationally combined into high-resolution 3D reconstructions. Alivisatos and his colleagues utilized this concept to create their SINGLE technique.

“In materials science, we cannot assume the nanoparticles in a solution are all identical so we needed to develop a hybrid approach for reconstructing the 3D structures of individual nanoparticles,” says co-lead author of the Science paper Peter Ercius, a staff scientist with the National Center for Electron Microscopy (NCEM) at the Molecular Foundry, a DOE Office of Science User Facility.

“SINGLE represents a combination of three technological advancements from TEM imaging in biological and materials science,” Ercius says. “These three advancements are the development of a graphene liquid cell that allows TEM imaging of nanoparticles rotating freely in solution, direct electron detectors that can produce movies with millisecond frame-to-frame time resolution of the rotating nanocrystals, and a theory for ab initio single particle 3D reconstruction.”

The graphene liquid cell (GLC) that helped make this study possible was also developed at Berkeley Lab under the leadership of Alivisatos and co-author Zettl, a physicist who also holds joint appointments with Berkeley Lab, UC Berkeley and Kavli ENSI. TEM imaging uses a beam of electrons rather than light for illumination and magnification but can only be used in a high vacuum because molecules in the air disrupt the electron beam. Since liquids evaporate in high vacuum, samples in solutions must be hermetically sealed in special solid containers – called cells – with a very thin viewing window before being imaged with TEM. In the past, liquid cells featured silicon-based viewing windows whose thickness limited resolution and perturbed the natural state of the sample materials. The GLC developed at Berkeley lab features a viewing window made from a graphene sheet that is only a single atom thick.

“The GLC provides us with an ultra-thin covering of our nanoparticles while maintaining liquid conditions in the TEM vacuum,” Ercius says. “Since the graphene surface of the GLC is inert, it does not adsorb or otherwise perturb the natural state of our nanoparticles.”

Working at NCEM’s TEAM I, the world’s most powerful electron microscope, Ercius, Alivisatos and their colleagues were able to image in situ the translational and rotational motions of individual nanoparticles of platinum that were less than two nanometers in diameter. Platinum nanoparticles were chosen because of their high electron scattering strength and because their detailed atomic structure is important for catalysis.

“Our earlier GLC studies of platinum nanocrystals showed that they grow by aggregation, resulting in complex structures that are not possible to determine by any previously developed method,” Ercius says. “Since SINGLE derives its 3D structures from images of individual nanoparticles rotating freely in solution, it enables the analysis of heterogeneous populations of potentially unordered nanoparticles that are synthesized in solution, thereby providing a means to understand the structure and stability of defects at the nanoscale.”

The next step for SINGLE is to recover a full 3D atomic resolution density map of colloidal nanoparticles using a more advanced camera installed on TEAM I that can provide 400 frames-per-second and better image quality.

“We plan to image defects in nanoparticles made from different materials, core shell particles, and also alloys made of two different atomic species,” Ercius says. [emphasis mine]

“Two different atomic species?”, they really are pushing that biology analogy.

Here’s a link to and a citation for the paper,

3D structure of individual nanocrystals in solution by electron microscopy by Jungwon Park, Hans Elmlund, Peter Ercius, Jong Min Yuk, David T. Limme, Qian Chen, Kwanpyo Kim, Sang Hoon Han, David A. Weitz, A. Zettl, A. Paul Alivisatos. Science 17 July 2015: Vol. 349 no. 6245 pp. 290-295 DOI: 10.1126/science.aab1343

This paper is behind a paywall.