Tag Archives: Jim Ciston

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.

Nanoscale imaging gets rough

Smooth is easier than rough when imaging at the nanoscale according to a June 17, 2015 Northwestern University news release by Megan Fellman (also on EurekAlert),

A multi-institutional team of scientists has taken an important step in understanding where atoms are located on the surfaces of rough materials, information that could be very useful in diverse commercial applications, such as developing green energy and understanding how materials rust.

Researchers from Northwestern University, Brookhaven National Laboratory, Lawrence Berkeley National Laboratory and the University of Melbourne, Australia, have developed a new imaging technique that uses atomic resolution secondary electron images in a quantitative way to determine the arrangement of atoms on the surface.

Many important processes take place at surfaces, ranging from the catalysis used to generate energy-dense fuels from sunlight and carbon dioxide to how bridges and airplanes corrode, or rust. Every material interacts with the world through its surface, which is often different in both structure and chemistry from the bulk of the material.

The real focus of the work is on corrosion, according to the news release,

“We are excited by the possibilities of applying our imaging technique to corrosion and catalysis problems,” said Laurence Marks, a co-author of the paper and a professor of materials science and engineering at Northwestern’s McCormick School of Engineering and Applied Science. “The cost of corrosion to industry and the military is enormous, and we do not understand everything that is taking place. We must learn more, so we can produce materials that will last longer.”

To understand these processes and improve material performance, it is vital to know how the atoms are arranged on surfaces. While there are many good methods for obtaining this information for rather flat surfaces, most currently available tools are limited in what they can reveal when the surfaces are rough.

Scanning electron microscopes are widely used to produce images of many different materials, and roughness of the surface is not that important. Until very recently, instruments could not obtain clear atomic images of surfaces until a group at Brookhaven managed in 2011 to get the first images that seemed to show the surfaces very clearly. However, it was not clear to what extent they really were able to image the surface, as there was no theory for the imaging and many uncertainties.

The new work has answered all these questions, Marks said, providing a definitive way of understanding the surfaces in detail. What was needed was to use a carefully controlled sample of strontium titanate and perform a large range of different types of imaging to unravel the precise details of how secondary electron images are produced.

“We started this work by investigating a well-studied material,” said Jim Ciston, a staff scientist at Lawrence Berkeley National Laboratory and the lead author of the paper, who obtained the experimental images. “This new technique is so powerful that we had to revise much of what was already thought to be well-known. This is an exciting prospect because the surface of every material can act as its own nanomaterial coating, which can greatly change the chemistry and behavior.”

“The beauty of the technique is that we can image surface atoms and bulk atoms simultaneously,” said Yimei Zhu, a scientist at Brookhaven National Laboratory. “Currently, no existing methods can achieve that.”

Les Allen, who led the theoretical and modeling aspects of the new imaging technique in Melbourne, said, “We now have a sophisticated understanding of what the images mean. It now will be full steam ahead to apply them to many different types of problems.”

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

Surface determination through atomically resolved secondary-electron imaging by J. Ciston, H. G. Brown, A. J. D’Alfonso, P. Koirala, C. Ophus, Y. Lin, Y. Suzuki, H. Inada, Y. Zhu, L. J. Allen, & L. D. Marks. Nature Communications 6, Article number: 7358 doi:10.1038/ncomms8358 Published 17 June 2015

This paper is open access.