Tag Archives: copper

A deep look at atomic switches

A July 19, 2019 news item on phys.org describes research that may result in a substantive change for information technology,

A team of researchers from Tokyo Institute of Technology has gained unprecedented insight into the inner workings of an atomic switch. By investigating the composition of the tiny metal ‘bridge’ that forms inside the switch, their findings may spur the design of atomic switches with improved performance.

A July 22, 2019 Tokyo Institute of Technology press release (also on EurekAlert but published July 19, 2019), which originated the news item, explains how this research could have such an important impact,

Atomic switches are hailed as the tiniest of electrochemical switches that could change the face of information technology. Due to their nanoscale dimensions and low power consumption, they hold promise for integration into next-generation circuits that could drive the development of artificial intelligence (AI) and Internet of Things (IoT) devices.

Although various designs have emerged, one intriguing question concerns the nature of the metallic filament, or bridge, that is key to the operation of the switch. The bridge forms inside a metal sulfide layer sandwiched between two electrodes [see figure below], and is controlled by applying a voltage that induces an electrochemical reaction. The formation and annihilation of this bridge determines whether the switch is on or off.

Now, a research group including Akira Aiba and Manabu Kiguchi and colleagues at Tokyo Institute of Technology’s Department of Chemistry has found a useful way to examine precisely what the bridge is composed of.

By cooling the atomic switch enough so as to be able to investigate the bridge using a low-temperature measurement technique called point contact spectroscopy (PCS) [2], their study revealed that the bridge is made up of metal atoms from both the electrode and the metal sulfide layer. This surprising finding controverts the prevailing notion that the bridge derives from the electrode only, Kiguchi explains.

The team compared atomic switches with different combinations of electrodes (Pt and Ag, or Pt and Cu) and metal sulfide layers (Cu2S and Ag2S). In both cases, they found that the bridge is mainly composed of Ag.

The reason behind the dominance of Ag in the bridge is likely due to “the higher mobility of Ag ions compared to Cu ions”, the researchers say in their paper published in ACS Applied Materials & Interfaces.

They conclude that “it would be better to use metals with low mobility” for designing atomic switches with higher stability.

Much remains to be explored in the advancement of atomic switch technologies, and the team is continuing to investigate which combination of elements would be the most effective in improving performance.


Technical terms
[1] Atomic switch: The idea behind an atomic switch — one that can be controlled by the motion of a single atom — was introduced by Donald Eigler and colleagues at the IBM Almaden Research Center in 1991. Interest has since focused on how to realize and harness the potential of such extremely small switches for use in logic circuits and memory devices. Over the past two decades, researchers in Japan have taken a world-leading role in the development of atomic switch technologies.
[2] Point contact spectroscopy: A method of measuring the properties or excitations of single atoms at low temperature.

Caption: The ‘bridge’ that forms within the metal sulfide layer, connecting two metal electrodes, results in the atomic switch being turned on. Credit: Manabu Kiguchi

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

Investigation of Ag and Cu Filament Formation Inside the Metal Sulfide Layer of an Atomic Switch Based on Point-Contact Spectroscopy by A. Aiba, R. Koizumi, T. Tsuruoka, K. Terabe, K. Tsukagoshi, S. Kaneko, S. Fujii, T. Nishino, M. Kiguchi. ACS Appl. Mater. Interfaces 2019 XXXXXXXXXX-XXX DOI: https://doi.org/10.1021/acsami.9b05523 Publication Date:July 5, 2019 Copyright © 2019 American Chemical Society

This paper is behind a paywall.

For anyone who might need a bit of a refresher for the chemical elements, Pt is platinum, Ag is silver, and Cu is copper. So, with regard to the metal sulfide layers Cu2S is copper sulfide and Ag2S is silver sulfide.

Borophene and next generation electronics?

2D materials as signified by the ‘ene’ suffix are, as far as I can tell, always associated with electronics—initially. Borophene is not an exception.

This borophene news was announced in a December 3, 2018 news item on ScienceDaily,

Borophene — two-dimensional (2-D) atom-thin-sheets of boron, a chemical element traditionally found in fiberglass insulation — is anything but boring. Though boron is a nonmetallic semiconductor in its bulk (3-D) form, it becomes a metallic conductor in 2-D. Borophene is extremely flexible, strong, and lightweight — even more so than its carbon-based analogue, graphene. [Providing a little competition to the Europeans who are seriously pursuing nanotechnology-enabled electronics and other applications with graphene?] These unique electronic and mechanical properties make borophene a promising material platform for next-generation electronic devices such as wearables, biomolecule sensors, light detectors, and quantum computers.

Now, physicists from the U.S. Department of Energy’s (DOE) Brookhaven National Laboratory and Yale University have synthesized borophene on copper substrates with large-area (ranging in size from 10 to 100 micrometers) single-crystal domains (for reference, a strand of human hair is about 100 micrometers wide). Previously, only nanometer-size single-crystal flakes of borophene had been produced. The advance, reported on Dec. 3 [2018] in Nature Nanotechnology, represents an important step in making practical borophene-based devices possible.

A December 3, 2018 Brookhaven National Laboratory (BNL) news release (also on EurekAlert), which originated the news item, provides more detail about 2D materials and the specifics of this borophene research,

For electronic applications, high-quality single crystals–periodic arrangements of atoms that continue throughout the entire crystal lattice without boundaries or defects–must be distributed over large areas of the surface material (substrate) on which they are grown. For example, today’s microchips use single crystals of silicon and other semiconductors. Device fabrication also requires an understanding of how different substrates and growth conditions impact a material’s crystal structure, which determines its properties.

“We increased the size of the single-crystal domains by a factor of a million,” said co-author and project lead Ivan Bozovic, senior scientist and Molecular Beam Epitaxy Group Leader in Brookhaven Lab’s Condensed Matter Physics and Materials Science (CMPMS) Department and adjunct professor of applied physics at Yale University. “Large domains are required to fabricate next-generation electronic devices with high electron mobility. Electrons that can easily and quickly move through a crystal structure are key to improving device performance.”

A new 2-D material

Since the 2004 discovery of graphene–a single sheet of carbon atoms, which can be peeled from graphite, the core component of pencils, with Scotch tape–scientists have been on the hunt for other 2-D materials with remarkable properties. The chemical bonds between carbon atoms that impart graphene with its strength make manipulating its structure difficult.

Theorists predicted that boron (next to carbon on the Periodic Table, with one less electron) deposited on an appropriately chosen substrate could form a 2-D material similar to graphene. But this prediction was not experimentally confirmed until three years ago, when scientists synthesized borophene for the very first time. They deposited boron onto silver substrates under ultrahigh-vacuum conditions through molecular beam epitaxy (MBE), a precisely controlled atomic layer-by-layer crystal growth technique. Soon thereafter, another group of scientists grew borophene on silver, but they proposed an entirely different crystal structure.

“Borophene is structurally similar to graphene, with a hexagonal network made of boron (instead of carbon) atoms on each of the six vertices defining the hexagon,” said Bozovic. “However, borophene is different in that it periodically has an extra boron atom in the center of the hexagon. The crystal structure tends to be theoretically stable when about four out of every five center positions are occupied and one is vacant.”

According to theory, while the number of vacancies is fixed, their arrangement is not. As long as the vacancies are distributed in a way that maintains the most stable (lowest energy) structure, they can be rearranged. Because of this flexibility, borophene can have multiple configurations.

A small step toward device fabrication

In this study, the scientists first investigated the real-time growth of borophene on silver surfaces at various temperatures. They grew the samples at Yale in an ultra-high vacuum low-energy electron microscope (LEEM) equipped with an MBE system. During and after the growth process, they bombarded the sample with a beam of electrons at low energy and analyzed the low-energy electron diffraction (LEED) patterns produced as electrons were reflected from the crystal surface and projected onto a detector. Because the electrons have low energy, they can only reach the first few atomic layers of the material. The distance between the reflected electrons (“spots” in the diffraction patterns) is related to the distance between atoms on the surface, and from this information, scientists can reconstruct the crystal structure.

In this case, the patterns revealed that the single-crystal borophene domains were only tens of nanometers in size–too small for fabricating devices and studying fundamental physical properties–for all growth conditions. They also resolved the controversy about borophene’s structure: both structures exist, but they form at different temperatures. The scientists confirmed their LEEM and LEED results through atomic force microscopy (AFM). In AFM, a sharp tip is scanned over a surface, and the measured force between the tip and atoms on the surface is used to map the atomic arrangement.

To promote the formation of larger crystals, the scientists then switched the substrate from silver to copper, applying the same LEEM, LEED, and AFM techniques. Brookhaven scientists Percy Zahl and Ilya Drozdov also imaged the surface structure at high resolution using a custom-built scanning tunneling microscope (STM) with a carbon monoxide probe tip at Brookhaven’s Center for Functional Nanomaterials (CFN)–a U.S. Department of Energy (DOE) Office of Science User Facility. Yale theorists Stephen Eltinge and Sohrab Ismail-Beigi performed calculations to determine the stability of the experimentally obtained structures. After identifying which structures were most stable, they simulated the electron diffraction spectra and STM images and compared them to the experimental data. This iterative process continued until theory and experiment were in agreement.

“From theoretical insights, we expected copper to produce larger single crystals because it interacts more strongly with borophene than silver,” said Bozovic. “Copper donates some electrons to stabilize borophene, but the materials do not interact too much as to form a compound. Not only are the single crystals larger, but the structures of borophene on copper are different from any of those grown on silver.”

Because there are several possible distributions of vacancies on the surface, various crystal structures of borophene can emerge. This study also showed how the structure of borophene can be modified by changing the substrate and, in some cases, the temperature or deposition rate.

The next step is to transfer the borophene sheets from the metallic copper surfaces to insulating device-compatible substrates. Then, scientists will be able to accurately measure resistivity and other electrical properties important to device functionality. Bozovic is particularly excited to test whether borophene can be made superconducting. Some theorists have speculated that its unusual electronic structure may even open a path to lossless transmission of electricity at room temperature, as opposed to the ultracold temperatures usually required for superconductivity. Ultimately, the goal in 2-D materials research is to be able to fine-tune the properties of these materials to suit particular applications.

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

Large-area single-crystal sheets of borophene on Cu(111) surfaces by Rongting Wu, Ilya K. Drozdov, Stephen Eltinge, Percy Zahl, Sohrab Ismail-Beigi, Ivan Božović & Adrian Gozar. Nature Nanotechnology (2018) DOI: https://doi.org/10.1038/s41565-018-0317-6Published 03 December 2018

This paper is behind a paywall.

Mixing the unmixable for all new nanoparticles

This news comes out of the University of Maryland and the discovery could led to nanoparticles that have never before been imagined. From a March 29, 2018 news item on ScienceDaily,

Making a giant leap in the ‘tiny’ field of nanoscience, a multi-institutional team of researchers is the first to create nanoscale particles composed of up to eight distinct elements generally known to be immiscible, or incapable of being mixed or blended together. The blending of multiple, unmixable elements into a unified, homogenous nanostructure, called a high entropy alloy nanoparticle, greatly expands the landscape of nanomaterials — and what we can do with them.

This research makes a significant advance on previous efforts that have typically produced nanoparticles limited to only three different elements and to structures that do not mix evenly. Essentially, it is extremely difficult to squeeze and blend different elements into individual particles at the nanoscale. The team, which includes lead researchers at University of Maryland, College Park (UMD)’s A. James Clark School of Engineering, published a peer-reviewed paper based on the research featured on the March 30 [2018] cover of Science.

A March 29, 2018 University of Maryland press release (also on EurekAlert), which originated the news item, delves further (Note: Links have been removed),

“Imagine the elements that combine to make nanoparticles as Lego building blocks. If you have only one to three colors and sizes, then you are limited by what combinations you can use and what structures you can assemble,” explains Liangbing Hu, associate professor of materials science and engineering at UMD and one of the corresponding authors of the paper. “What our team has done is essentially enlarged the toy chest in nanoparticle synthesis; now, we are able to build nanomaterials with nearly all metallic and semiconductor elements.”

The researchers say this advance in nanoscience opens vast opportunities for a wide range of applications that includes catalysis (the acceleration of a chemical reaction by a catalyst), energy storage (batteries or supercapacitors), and bio/plasmonic imaging, among others.

To create the high entropy alloy nanoparticles, the researchers employed a two-step method of flash heating followed by flash cooling. Metallic elements such as platinum, nickel, iron, cobalt, gold, copper, and others were exposed to a rapid thermal shock of approximately 3,000 degrees Fahrenheit, or about half the temperature of the sun, for 0.055 seconds. The extremely high temperature resulted in uniform mixtures of the multiple elements. The subsequent rapid cooling (more than 100,000 degrees Fahrenheit per second) stabilized the newly mixed elements into the uniform nanomaterial.

“Our method is simple, but one that nobody else has applied to the creation of nanoparticles. By using a physical science approach, rather than a traditional chemistry approach, we have achieved something unprecedented,” says Yonggang Yao, a Ph.D. student at UMD and one of the lead authors of the paper.

To demonstrate one potential use of the nanoparticles, the research team used them as advanced catalysts for ammonia oxidation, which is a key step in the production of nitric acid (a liquid acid that is used in the production of ammonium nitrate for fertilizers, making plastics, and in the manufacturing of dyes). They were able to achieve 100 percent oxidation of ammonia and 99 percent selectivity toward desired products with the high entropy alloy nanoparticles, proving their ability as highly efficient catalysts.

Yao says another potential use of the nanoparticles as catalysts could be the generation of chemicals or fuels from carbon dioxide.

“The potential applications for high entropy alloy nanoparticles are not limited to the field of catalysis. With cross-discipline curiosity, the demonstrated applications of these particles will become even more widespread,” says Steven D. Lacey, a Ph.D. student at UMD and also one of the lead authors of the paper.

This research was performed through a multi-institutional collaboration of Prof. Liangbing Hu’s group at the University of Maryland, College Park; Prof. Reza Shahbazian-Yassar’s group at University of Illinois at Chicago; Prof. Ju Li’s group at the Massachusetts Institute of Technology; Prof. Chao Wang’s group at Johns Hopkins University; and Prof. Michael Zachariah’s group at the University of Maryland, College Park.

What outside experts are saying about this research:

“This is quite amazing; Dr. Hu creatively came up with this powerful technique, carbo-thermal shock synthesis, to produce high entropy alloys of up to eight different elements in a single nanoparticle. This is indeed unthinkable for bulk materials synthesis. This is yet another beautiful example of nanoscience!,” says Peidong Yang, the S.K. and Angela Chan Distinguished Professor of Energy and professor of chemistry at the University of California, Berkeley and member of the American Academy of Arts and Sciences.

“This discovery opens many new directions. There are simulation opportunities to understand the electronic structure of the various compositions and phases that are important for the next generation of catalyst design. Also, finding correlations among synthesis routes, composition, and phase structure and performance enables a paradigm shift toward guided synthesis,” says George Crabtree, Argonne Distinguished Fellow and director of the Joint Center for Energy Storage Research at Argonne National Laboratory.

More from the research coauthors:

“Understanding the atomic order and crystalline structure in these multi-element nanoparticles reveals how the synthesis can be tuned to optimize their performance. It would be quite interesting to further explore the underlying atomistic mechanisms of the nucleation and growth of high entropy alloy nanoparticle,” says Reza Shahbazian-Yassar, associate professor at the University of Illinois at Chicago and a corresponding author of the paper.

“Carbon metabolism drives ‘living’ metal catalysts that frequently move around, split, or merge, resulting in a nanoparticle size distribution that’s far from the ordinary, and highly tunable,” says Ju Li, professor at the Massachusetts Institute of Technology and a corresponding author of the paper.

“This method enables new combinations of metals that do not exist in nature and do not otherwise go together. It enables robust tuning of the composition of catalytic materials to optimize the activity, selectivity, and stability, and the application will be very broad in energy conversions and chemical transformations,” says Chao Wang, assistant professor of chemical and biomolecular engineering at Johns Hopkins University and one of the study’s authors.

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

Carbothermal shock synthesis of high-entropy-alloy nanoparticles by Yonggang Yao, Zhennan Huang, Pengfei Xie, Steven D. Lacey, Rohit Jiji Jacob, Hua Xie, Fengjuan Chen, Anmin Nie, Tiancheng Pu, Miles Rehwoldt, Daiwei Yu, Michael R. Zachariah, Chao Wang, Reza Shahbazian-Yassar, Ju Li, Liangbing Hu. Science 30 Mar 2018: Vol. 359, Issue 6383, pp. 1489-1494 DOI: 10.1126/science.aan5412

This paper is behind a paywall.

Refining metals more sustainably

We don’t just extract and refine metals from the earth, increasingly, we extract and refine them from consumer goods. Researchers from McGill University (Montréal, Québec, Canada) have devised a ‘greener’ technique to do this. From a June 7, 2017 McGill University news release (received via email and also on EurekAlert),

A team of chemists in Canada has developed a way to process metals without using toxic solvents and reagents.

The system, which also consumes far less energy than conventional techniques, could greatly shrink the environmental impact of producing metals from raw materials or from post-consumer electronics.

“At a time when natural deposits of metals are on the decline, there is a great deal of interest in improving the efficiency of metal refinement and recycling, but few disruptive technologies are being put forth,” says Jean-Philip Lumb, an associate professor in McGill University’s Department of Chemistry. “That’s what makes our advance so important.”

The discovery stems from a collaboration between Lumb and Tomislav Friscic at McGill in Montreal, and Kim Baines of Western University in London, Ont. In an article published recently in Science Advances, the researchers outline an approach that uses organic molecules, instead of chlorine and hydrochloric acid, to help purify germanium, a metal used widely in electronic devices. Laboratory experiments by the researchers have shown that the same technique can be used with other metals, including zinc, copper, manganese and cobalt.

The research could mark an important milestone for the “green chemistry” movement, which seeks to replace toxic reagents used in conventional industrial manufacturing with more environmentally friendly alternatives. Most advances in this area have involved organic chemistry – the synthesis of carbon-based compounds used in pharmaceuticals and plastics, for example.

“Applications of green chemistry lag far behind in the area of metals,” Lumb says. “Yet metals are just as important for sustainability as any organic compound. For example, electronic devices require numerous metals to function.”

Taking a page from biology

There is no single ore rich in germanium, so it is generally obtained from mining operations as a minor component in a mixture with many other materials. Through a series of processes, that blend of matter can be reduced to germanium and zinc.

“Currently, in order to isolate germanium from zinc, it’s a pretty nasty process,” Baines explains. The new approach developed by the McGill and Western chemists “enables you to get germanium from zinc, without those nasty processes.”

To accomplish this, the researchers took a page from biology. Lumb’s lab for years has conducted research into the chemistry of melanin, the molecule in human tissue that gives skin and hair their color. Melanin also has the ability to bind to metals. “We asked the question: ‘Here’s this biomaterial with exquisite function, would it be possible to use it as a blueprint for new, more efficient technologies?'”

The scientists teamed up to synthesize a molecule that mimics some of the qualities of melanin. In particular, this “organic co-factor” acts as a mediator that helps to extract germanium at room temperature, without using solvents.

Next step: industrial scale

The system also taps into Friscic’s expertise in mechanochemistry, an emerging branch of chemistry that relies on mechanical force – rather than solvents and heat – to promote chemical reactions. Milling jars containing stainless-steel balls are shaken at high speeds to help purify the metal.

“This shows how collaborations naturally can lead to sustainability-oriented innovation,” Friscic says. “Combining elegant new chemistry with solvent-free mechanochemical techniques led us to a process that is cleaner by virtue of circumventing chlorine-based processing, but also eliminates the generation of toxic solvent waste”

The next step in developing the technology will be to show that it can be deployed economically on industrial scales, for a range of metals.

“There’s a tremendous amount of work that needs to be done to get from where we are now to where we need to go,” Lumb says. “But the platform works on many different kinds of metals and metal oxides, and we think that it could become a technology adopted by industry. We are looking for stakeholders with whom we can partner to move this technology forward.”

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

A chlorine-free protocol for processing germanium by Martin Glavinovic, Michael Krause, Linju Yang, John A. McLeod, Lijia Liu, Kim M. Baines, Tomislav Friščić, and Jean-Philip Lumb. Science Advances 05 May 2017: Vol. 3, no. 5, e1700149 DOI: 10.1126/sciadv.1700149

This paper is open access.

ETA June 9, 2017 at 1700 hours PDT: I have to give them marks for creativity. Here’s the image being used to illustrate the work,

Caption: Strategy for reducing the environmental impact of a refining process: replace hazardous chemicals with more benign and recyclable compounds. Credit: Michael J. Krause (Western University)

Nuclear magnetic resonance microscope breaks records

Dutch researchers have found a way to apply the principles underlying magnetic resonance imaging (MRI) to a microscope designed *for* examining matter and life at the nanoscale. From a July 15, 2016 news item on phys.org,

A new nuclear magnetic resonance (NMR) microscope gives researchers an improved instrument to study fundamental physical processes. It also offers new possibilities for medical science—for example, to better study proteins in Alzheimer’s patients’ brains. …

A Leiden Institute of Physics press release, which originated the news item, expands on the theme,

If you get a knee injury, physicians use an MRI machine to look right through the skin and see what exactly is the problem. For this trick, doctors make use of the fact that our body’s atomic nuclei are electrically charged and spin around their axis. Just like small electromagnets they induce their own magnetic field. By placing the knee in a uniform magnetic field, the nuclei line up with their axis pointing in the same direction. The MRI machine then sends a specific type of radio waves through the knee, causing some axes to flip. After turning off this signal, those nuclei flip back after some time, under excitation of a small radio wave. Those waves give away the atoms’ location, and provide physicians with an accurate image of the knee.


MRI is the medical application of Nuclear Magnetic Resonance (NMR), which is based on the same principle and was invented by physicists to conduct fundamental research on materials. One of the things they study with NMR is the so-called relaxation time. This is the time scale at which the nuclei flip back and it gives a lot of information about a material’s properties.


To study materials on the smallest of scales as well, physicists go one step further and develop NMR microscopes, with which they study the mechanics behind physical processes at the level of a group of atoms. Now Leiden PhD students Jelmer Wagenaar and Arthur de Haan have built an NMR microscope, together with principal investigator Tjerk Oosterkamp, that operates at a record temperature of 42 milliKelvin—close to absolute zero. In their article in Physical Review Applied they prove it works by measuring the relaxation time of copper. They achieved a thousand times higher sensitivity than existing NMR microscopes—also a world record.


With their microscope, they give physicists an instrument to conduct fundamental research on many physical phenomena, like systems displaying strange behavior in extreme cold. And like NMR eventually led to MRI machines in hospitals, NMR microscopes have great potential too. Wagenaar: ‘One example is that you might be able to use our technique to study Alzheimer patients’ brains at the molecular level, in order to find out how iron is locked up in proteins.’

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

Probing the Nuclear Spin-Lattice Relaxation Time at the Nanoscale by J. J. T. Wagenaar, A. M. J. den Haan, J. M. de Voogd, L. Bossoni, T. A. de Jong, M. de Wit, K. M. Bastiaans, D. J. Thoen, A. Endo, T. M. Klapwijk, J. Zaanen, and T. H. Oosterkamp. Phys. Rev. Applied 6, 014007 DOI:http://dx.doi.org/10.1103/PhysRevApplied.6.014007 Published 15 July 2016

This paper is open access.

*’fro’ changed to ‘for’ on Aug. 3, 2016.

Ultimate discovery tool?

For anyone familiar with the US nanomedicine scene, Chad Mirkin’s appearance in this announcement from Northwestern University isn’t much of a surprise.  From a June 23, 2016 news item on ScienceDaily,

The discovery power of the gene chip is coming to nanotechnology. A Northwestern University research team is developing a tool to rapidly test millions and perhaps even billions or more different nanoparticles at one time to zero in on the best particle for a specific use.

When materials are miniaturized, their properties—optical, structural, electrical, mechanical and chemical—change, offering new possibilities. But determining what nanoparticle size and composition are best for a given application, such as catalysts, biodiagnostic labels, pharmaceuticals and electronic devices, is a daunting task.

“As scientists, we’ve only just begun to investigate what materials can be made on the nanoscale,” said Northwestern’s Chad A. Mirkin, a world leader in nanotechnology research and its application, who led the study. “Screening a million potentially useful nanoparticles, for example, could take several lifetimes. Once optimized, our tool will enable researchers to pick the winner much faster than conventional methods. We have the ultimate discovery tool.”

A June 23, 2016 Northwestern University news release (also on EurekAlert), which originated the news item, describes the work in more detail,

Using a Northwestern technique that deposits materials on a surface, Mirkin and his team figured out how to make combinatorial libraries of nanoparticles in a very controlled way. (A combinatorial library is a collection of systematically varied structures encoded at specific sites on a surface.) Their study will be published June 24 by the journal Science.

The nanoparticle libraries are much like a gene chip, Mirkin says, where thousands of different spots of DNA are used to identify the presence of a disease or toxin. Thousands of reactions can be done simultaneously, providing results in just a few hours. Similarly, Mirkin and his team’s libraries will enable scientists to rapidly make and screen millions to billions of nanoparticles of different compositions and sizes for desirable physical and chemical properties.

“The ability to make libraries of nanoparticles will open a new field of nanocombinatorics, where size — on a scale that matters — and composition become tunable parameters,” Mirkin said. “This is a powerful approach to discovery science.”

“I liken our combinatorial nanopatterning approach to providing a broad palette of bold colors to an artist who previously had been working with a handful of dull and pale black, white and grey pastels,” said co-author Vinayak P. Dravid, the Abraham Harris Professor of Materials Science and Engineering in the McCormick School of Engineering.

Using five metallic elements — gold, silver, cobalt, copper and nickel — Mirkin and his team developed an array of unique structures by varying every elemental combination. In previous work, the researchers had shown that particle diameter also can be varied deliberately on the 1- to 100-nanometer length scale.

Some of the compositions can be found in nature, but more than half of them have never existed before on Earth. And when pictured using high-powered imaging techniques, the nanoparticles appear like an array of colorful Easter eggs, each compositional element contributing to the palette.

To build the combinatorial libraries, Mirkin and his team used Dip-Pen Nanolithography, a technique developed at Northwestern in 1999, to deposit onto a surface individual polymer “dots,” each loaded with different metal salts of interest. The researchers then heated the polymer dots, reducing the salts to metal atoms and forming a single nanoparticle. The size of the polymer dot can be varied to change the size of the final nanoparticle.

This control of both size and composition of nanoparticles is very important, Mirkin stressed. Having demonstrated control, the researchers used the tool to systematically generate a library of 31 nanostructures using the five different metals.

To help analyze the complex elemental compositions and size/shape of the nanoparticles down to the sub-nanometer scale, the team turned to Dravid, Mirkin’s longtime friend and collaborator. Dravid, founding director of Northwestern’s NUANCE Center, contributed his expertise and the advanced electron microscopes of NUANCE to spatially map the compositional trajectories of the combinatorial nanoparticles.

Now, scientists can begin to study these nanoparticles as well as build other useful combinatorial libraries consisting of billions of structures that subtly differ in size and composition. These structures may become the next materials that power fuel cells, efficiently harvest solar energy and convert it into useful fuels, and catalyze reactions that take low-value feedstocks from the petroleum industry and turn them into high-value products useful in the chemical and pharmaceutical industries.

Here’s a diagram illustrating the work,

 Caption: A combinatorial library of polyelemental nanoparticles was developed using Dip-Pen Nanolithography. This novel nanoparticle library opens up a new field of nanocombinatorics for rapid screening of nanomaterials for a multitude of properties. Credit: Peng-Cheng Chen/James Hedrick

Caption: A combinatorial library of polyelemental nanoparticles was developed using Dip-Pen Nanolithography. This novel nanoparticle library opens up a new field of nanocombinatorics for rapid screening of nanomaterials for a multitude of properties. Credit: Peng-Cheng Chen/James Hedrick

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

Polyelemental nanoparticle libraries by Peng-Cheng Chen, Xiaolong Liu, James L. Hedrick, Zhuang Xie, Shunzhi Wang, Qing-Yuan Lin, Mark C. Hersam, Vinayak P. Dravid, Chad A. Mirkin. Science  24 Jun 2016: Vol. 352, Issue 6293, pp. 1565-1569 DOI: 10.1126/science.aaf8402

This paper is behind a paywall.

Measuring the van der Waals forces between individual atoms for the first time

A May 13, 2016 news item on Nanowerk heralds the first time measuring the van der Waals forces between individual atoms,

Physicists at the Swiss Nanoscience Institute and the University of Basel have succeeded in measuring the very weak van der Waals forces between individual atoms for the first time. To do this, they fixed individual noble gas atoms within a molecular network and determined the interactions with a single xenon atom that they had positioned at the tip of an atomic force microscope. As expected, the forces varied according to the distance between the two atoms; but, in some cases, the forces were several times larger than theoretically calculated.

A May 13, 2016 University of Basel press release (also on EurekAlert), which originated the news item, provides an explanation of van der Waals forces (the most comprehensive I’ve seen) and technical details about how the research was conducted,

Van der Waals forces act between non-polar atoms and molecules. Although they are very weak in comparison to chemical bonds, they are hugely significant in nature. They play an important role in all processes relating to cohesion, adhesion, friction or condensation and are, for example, essential for a gecko’s climbing skills.

Van der Waals interactions arise due to a temporary redistribution of electrons in the atoms and molecules. This results in the occasional formation of dipoles, which in turn induce a redistribution of electrons in closely neighboring molecules. Due to the formation of dipoles, the two molecules experience a mutual attraction, which is referred to as a van der Waals interaction. This only exists temporarily but is repeatedly re-formed. The individual forces are the weakest binding forces that exist in nature, but they add up to reach magnitudes that we can perceive very clearly on the macroscopic scale – as in the example of the gecko.

Fixed within the nano-beaker

To measure the van der Waals forces, scientists in Basel used a low-temperature atomic force microscope with a single xenon atom on the tip. They then fixed the individual argon, krypton and xenon atoms in a molecular network. This network, which is self-organizing under certain experimental conditions, contains so-called nano-beakers of copper atoms in which the noble gas atoms are held in place like a bird egg. Only with this experimental set-up is it possible to measure the tiny forces between microscope tip and noble gas atom, as a pure metal surface would allow the noble gas atoms to slide around.

Compared with theory

The researchers compared the measured forces with calculated values and displayed them graphically. As expected from the theoretical calculations, the measured forces fell dramatically as the distance between the atoms increased. While there was good agreement between measured and calculated curve shapes for all of the noble gases analyzed, the absolute measured forces were larger than had been expected from calculations according to the standard model. Above all for xenon, the measured forces were larger than the calculated values by a factor of up to two.

The scientists are working on the assumption that, even in the noble gases, charge transfer occurs and therefore weak covalent bonds are occasionally formed, which would explain the higher values.

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

Van der Waals interactions and the limits of isolated atom models at interfaces by Shigeki Kawai, Adam S. Foster, Torbjörn Björkman, Sylwia Nowakowska, Jonas Björk, Filippo Federici Canova, Lutz H. Gade, Thomas A. Jung, & Ernst Meyer. Nature Communications 7, Article number: 11559  doi:10.1038/ncomms11559 Published 13 May 2016

This is an open access paper.

Weaving at the nanoscale

A Jan. 21, 2016 news item on ScienceDaily announces a brand new technique,

For the first time, scientists have been able to weave a material at molecular level. The research is led by University of California Berkeley, in cooperation with Stockholm University. …

A Jan. 21, 2016 Stockholm University press release, which originated the news item, provides more information,

Weaving is a well-known way of making fabric, but has until now never been used at the molecular level. Scientists have now been able to weave organic threads into a three-dimensional material, using copper as a template. The new material is a COF, covalent organic framework, and is named COF-505. The copper ions can be removed and added without changing the underlying structure, and at the same time the elasticity can be reversibly changed.

– It almost looks like a molecular version of the Vikings chain-armour. The material is very flexible, says Peter Oleynikov, researcher at the Department of Materials and Environmental Chemistry at Stockholm University.

COF’s are like MOF’s porous three-dimensional crystals with a very large internal surface that can adsorb and store enormous quantities of molecules. A potential application is capture and storage of carbon dioxide, or using COF’s as a catalyst to make useful molecules from carbon dioxide.

Complex structure determined in Stockholm

The research is led by Professor Omar Yaghi at University of California Berkeley. At Stockholm University Professor Osamu Terasaki, PhD Student Yanhang Ma and Researcher Peter Oleynikov have contributed to determine the structure of COF-505 at atomic level from a nano-crystal, using electron crystallography methods.

– It is a difficult, complicated structure and it was very demanding to resolve. We’ve spent lot of time and efforts on the structure solution. Now we know exactly where the copper is and we can also replace the metal. This opens up many possibilities to make other materials, says Yanhang Ma, PhD Student at the Department of Materials and Environmental Chemistry at Stockholm University.

Another of the collaborating institutions, US Department of Energy Lawrence Berkeley National Laboratory issued a Jan. 21, 2016 news release on EurekAlert, providing a different perspective and some additional details,

There are many different ways to make nanomaterials but weaving, the oldest and most enduring method of making fabrics, has not been one of them – until now. An international collaboration led by scientists at the U.S. Department of Energy (DOE)’s Lawrence Berkeley National Laboratory (Berkeley Lab) and the University of California (UC) Berkeley, has woven the first three-dimensional covalent organic frameworks (COFs) from helical organic threads. The woven COFs display significant advantages in structural flexibility, resiliency and reversibility over previous COFs – materials that are highly prized for their potential to capture and store carbon dioxide then convert it into valuable chemical products.

“Weaving in chemistry has been long sought after and is unknown in biology,” Yaghi says [Omar Yaghi, chemist who holds joint appointments with Berkeley Lab’s Materials Sciences Division and UC Berkeley’s Chemistry Department and is the co-director of the Kavli Energy NanoScience Institute {Kavli-ENSI}]. “However, we have found a way of weaving organic threads that enables us to design and make complex two- and three-dimensional organic extended structures.”

COFs and their cousin materials, metal organic frameworks (MOFs), are porous three-dimensional crystals with extraordinarily large internal surface areas that can absorb and store enormous quantities of targeted molecules. Invented by Yaghi, COFs and MOFs consist of molecules (organics for COFs and metal-organics for MOFs) that are stitched into large and extended netlike frameworks whose structures are held together by strong chemical bonds. Such frameworks show great promise for, among other applications, carbon sequestration.

Through another technique developed by Yaghi, called “reticular chemistry,” these frameworks can also be embedded with catalysts to carry out desired functions: for example, reducing carbon dioxide into carbon monoxide, which serves as a primary building block for a wide range of chemical products including fuels, pharmaceuticals and plastics.

In this latest study, Yaghi and his collaborators used a copper(I) complex as a template for bringing threads of the organic compound “phenanthroline” into a woven pattern to produce an immine-based framework they dubbed COF-505. Through X-ray and electron diffraction characterizations, the researchers discovered that the copper(I) ions can be reversibly removed or restored to COF-505 without changing its woven structure. Demetalation of the COF resulted in a tenfold increase in its elasticity and remetalation restored the COF to its original stiffness.

“That our system can switch between two states of elasticity reversibly by a simple operation, the first such demonstration in an extended chemical structure, means that cycling between these states can be done repeatedly without degrading or altering the structure,” Yaghi says. “Based on these results, it is easy to imagine the creation of molecular cloths that combine unusual resiliency, strength, flexibility and chemical variability in one material.”

Yaghi says that MOFs can also be woven as can all structures based on netlike frameworks. In addition, these woven structures can also be made as nanoparticles or polymers, which means they can be fabricated into thin films and electronic devices.

“Our weaving technique allows long threads of covalently linked molecules to cross at regular intervals,” Yaghi says. “These crossings serve as points of registry, so that the threads have many degrees of freedom to move away from and back to such points without collapsing the overall structure, a boon to making materials with exceptional mechanical properties and dynamics.”


This research was primarily supported by BASF (Germany) and King Abdulaziz City for Science and Technology (KACST).

It’s unusual that neither Stockholm University not the Lawrence Berkeley National Laboratory list all of the institutions involved. To get a sense of this international collaboration’s size, I’m going to list them,

  • 1Department of Chemistry, University of California, Berkeley, Materials Sciences Division, Lawrence Berkeley National Laboratory, and Kavli Energy NanoSciences Institute, Berkeley, CA 94720, USA.
  • 2Department of Materials and Environmental Chemistry, Stockholm University, SE-10691 Stockholm, Sweden.
  • 3Department of New Architectures in Materials Chemistry, Materials Science Institute of Madrid, Consejo Superior de Investigaciones Científicas, Madrid 28049, Spain.
  • 4Nanomaterials Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba 305-8565, Japan.
  • 5NSF Nanoscale Science and Engineering Center (NSEC), University of California at Berkeley, 3112 Etcheverry Hall, Berkeley, CA 94720, USA.
  • 6Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
  • 7King Abdulaziz City of Science and Technology, Post Office Box 6086, Riyadh 11442, Saudi Arabia.
  • 8Material Sciences Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, CA 94720, USA.
  • 9School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China.

Given that some of the money came from a German company, I’m surprised not one German institution was involved.

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

Weaving of organic threads into a crystalline covalent organic framework by Yuzhong Liu, Yanhang Ma, Yingbo Zhao, Xixi Sun, Felipe Gándara, Hiroyasu Furukawa, Zheng Liu, Hanyu Zhu, Chenhui Zhu, Kazutomo Suenaga, Peter Oleynikov, Ahmad S. Alshammari, Xiang Zhang, Osamu Terasaki, Omar M. Yaghi. Science  22 Jan 2016: Vol. 351, Issue 6271, pp. 365-369 DOI: 10.1126/science.aad4011

This paper is behind a paywall.

Self-assembly with porphine molecules

A Jan. 12, 2016 American Institute of Physics (AIP) news release by John Arnst (also on EurekAlert but dated Jan. 14, 2016) describes computational research into self-assembling nanodevices based on porphine molecules,

As we continue to shrink electronic components, top-down manufacturing methods begin to approach a physical limit at the nanoscale. Rather than continue to chip away at this limit, one solution of interest involves using the bottom-up self-assembly of molecular building blocks to build nanoscale devices.

Successful self-assembly is an elaborately choreographed dance, in which the attractive and repulsive forces within molecules, between each molecule and its neighbors, and between molecules and the surface that supports them, have to all be taken into account. To better understand the self-assembly process, researchers at the Technical University of Munich have characterized the contributions of all interaction components, such as covalent bonding and van der Waals interactions between molecules and between molecules and a surface.

“In an ideal case, the smallest possible device has the size of a single atom or molecule,” said Katharina Diller, who worked as a postdoctoral researcher in the group of Karsten Reuter at the Technical University of Munich. Reuter and his colleagues present their work this week in The Journal of Chemical Physics, from AIP Publishing.

One such example is a single-porphyrin switch, which occupies a surface area of only one square nanometer. [emphasis mine] The porphine molecule, which was the object of this study, is even smaller than this. Porphyrins are a group of ringed chemical compounds which notably include heme – responsible for transporting oxygen and carbon dioxide in the bloodstream – and chlorophyll. In synthetically-derived applications, porphyrins are studied for their potential uses as sensors, light-sensitive dyes in organic solar cells, and molecular magnets.

The researchers from TU Munich assessed the interactions of the porphyrin molecule 2H-porphine by using density functional theory, a quantum mechanical computational modelling method used to describe the electronic properties of molecules and materials. Their simulations were performed at the high-performance supercomputer SuperMUC at Leibniz-Rechenzentrum in Garching.

The metallic substrates the researchers chose for the porphyrin molecules to assemble on, the close packed single crystal surfaces of copper and silver, are widely used as substrates in surface science. This is due to the densely packed nature of the surfaces, which allow the molecules to exhibit a smooth adsorption environment. Additionally, copper and silver each react differently with porhyrins – the molecule adsorbs more strongly on copper, whereas silver does a better job of keeping the electronic structure of the molecule intact – allowing the researchers to monitor a variety of competing effects for future applications.

In their simulation, porphyrin molecules were placed on a copper or silver slab, which was repeated periodically to simulate an extended surface. After finding the optimal geometry in which the molecules would adsorb on the surface, the researchers altered the size of the metal slab to increase or decrease the distance between molecules, thus simulating different molecular coverages. The computational setup gave them a switch to turn the energy contributions of neighboring molecules on and off, in order to observe the interplay of the individual interactions.

Diller and Reuter, along with colleagues Reinhard Maurer and Moritz Müller, who is first author on the paper, found that the weak long-range van der Waals interactions yielded the largest contribution to the molecule-surface interaction, and showed that the often employed methods to quantify the electronic charges in the system have to be used with caution. Surprisingly, while interactions directly between molecules are negligible, the researcher found indications for surface-mediated molecule-molecule interactions at higher molecular coverages.

“The analysis of the electronic structure and the individual interaction components allows us to better understand the self-assembly of porphine adsorbed on copper and silver, and additionally enables predictions for more complex porphyrine analogues,” Diller said. “These conclusions, however, come without yet considering the effects of atomic motion at finite temperature, which we did not study in this work.”

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

Interfacial charge rearrangement and intermolecular interactions: Density-functional theory study of free-base porphine adsorbed on Ag(111) and Cu(111) by Moritz Müller, Katharina Diller, Reinhard J. Maurer, and Karsten Reuter. J. Chem. Phys. 144, 024701 (2016); http://dx.doi.org/10.1063/1.4938259

This paper appears to be open access.

Finally, the researchers have made this illustrative diagram titled ‘Energy’ available,

Caption: Schematic depiction of different energy terms contributing to the adsorption energy, and charge density difference of 2H-P after adsorption onto Cu(111) at 12.8 Angstrom separation. Credit: M. Müller/TU Munich

Caption: Schematic depiction of different energy terms contributing to the adsorption energy, and charge density difference of 2H-P after adsorption onto Cu(111) at 12.8 Angstrom separation. Credit: M. Müller/TU Munich

Green tech with single atom platinum catalyst?

There’s something mind boggling to me about the notion of a single atom catalyst. Luckily, an Oct. 5, 2015 news item on Nanowerk describes the research (Note: A link has been removed),

A new generation of platinum-copper catalysts that require very low concentrations of platinum in the form of individual atoms to cleanly and cheaply perform important chemical reactions is reported today by Tufts University researchers in the journal Nature Communications (“Selective hydrogenation of butadiene on platinum copper alloys at the single atom limit”).

An Oct. 9, 2015 Tufts University news release on EurekAlert, which originated the news item, describes the nature of the problem the researchers were trying to resolve and their solution,

Platinum is used as a catalyst in fuel cells, in automobile converters and in the chemical industry because of its remarkable ability to facilitate a wide range of chemical reactions. However, its future potential uses are significantly limited by scarcity and cost, as well as the fact that platinum readily binds with carbon monoxide, which “poisons” the desired reactions, for example in polymer electrolyte membrane (PEM) fuel cells, which are the leading contenders for small-scale and mobile power generation not based on batteries or combustion engines.

The Tufts researchers discovered that dispersing individual, isolated platinum atoms in much less costly copper surfaces can create a highly effective and cost-efficient catalyst for the selective hydrogenation of 1,3 butadiene, a chemical produced by steam cracking of naphtha or by catalytic cracking of gas oil. Butadiene is an impurity in propene streams that must be removed from the stream through hydrogenation in order to facilitate downstream polymer production. The current industrial catalyst for butadiene hydrogenation uses palladium and silver.

Like Sugar in Coffee

Copper, while a relatively cheap metal, is not nearly as catalytically powerful as platinum, noted Professor of Chemistry Charles Sykes, Ph.D., one of the senior authors on the paper. “We wanted to find a way to improve its performance.”

The researchers first conducted surface science experiments to study precisely how platinum and copper metals mix. “We were excited to find that the platinum metal dissolved in copper, just like sugar in hot coffee, all the way down to single atoms. We call such materials single atom alloys,” said Sykes.

The Tufts chemists used a specialized low temperature scanning tunneling microscope to visualize the single platinum atoms and their interaction with hydrogen. “We found that even at temperatures as low as minus 300 degrees F these platinum atoms were capable of splitting hydrogen molecules into atoms, indicating that the platinum atoms would be very good at activating hydrogen for a chemical reaction,” Sykes said.

With that knowledge, Sykes and his fellow chemists turned to long-time Tufts collaborator Maria Flytzani-Stephanopoulos, Ph.D., the Robert and Marcy Haber Endowed Professor in Energy Sustainability at the School of Engineering, to determine which hydrogenation reaction would be most significant for industrial applications. The answer, she said, was butadiene.

The model catalyst performed effectively for that reaction in vacuum conditions in the laboratory, so Flytzani-Stephanopoulos’s team took the study to the next level. They synthesized small quantities of realistic catalysts, such as platinum-copper single atom alloy nanoparticles supported on an alumina substrate, and then tested them under industrial pressure and temperatures.

“To our delight, these catalysts worked very well and their performance was steady for many days,” said Flytzani-Stephanopoulos. “While we had previously shown that palladium would do related reactions in a closed reactor system, this work with platinum is our first demonstration of operation in a flow reactor at industrially relevant conditions. We believe this approach is also applicable to other precious metals if added as minority components in copper.”

Further, the researchers found that the reaction actually became less efficient when they used more platinum, because clusters of platinum atoms have inferior selectivity compared with individual atoms. “In this case, less is more,” said Flytzani-Stephanopoulos, “which is a very good thing.”

Environmental Benefits

Because platinum is at the center of many clean energy and green chemicals production technologies, such as fuel cells, catalytic converters, and value-added chemicals from bio-renewable feedstocks, the new, less expensive platinum-copper catalysts could facilitate broader adoption of such environmentally friendly devices and processes, she added.

The news release goes on to describe this cross-disciplinary partnership,

The work is the latest fruit from a long cross-disciplinary partnership between Sykes and Flytzani-Stephanopoulos.

“Maria and I met more than seven years ago and talked regularly about how to combine our fairly different fields of research into an effective collaboration across the schools of Arts and Sciences and Engineering,” said Sykes. “I had a state-of-the-art microscope that could see and manipulate atoms and molecules, and I wanted to use its unique capabilities to gain insight into industrially important chemical reactions. In the early 2000s, Maria’s group had pioneered the single-atom approach for metals anchored on oxide supports as the exclusive active sites for the water-gas shift reaction to upgrade hydrogen streams for fuel cell use. Catalyst design know-how already existed in her lab. In retrospect, it seems obvious that combining forces would be a ‘natural’ development. Together we embarked on a new direction involving single atom alloys as catalysts for selective hydrogenation reactions. Our microscope was uniquely suited for characterizing the atomic composition of surfaces. We got funding from the National Science Foundation, U.S. Department of Energy and the Tufts Collaborates initiative to pursue this new area of research.”

Sykes and Flytzani-Stephanopoulos have used this approach to design a variety of single atom alloy catalysts that have, in the last two years, sparked international interest.

“Traditionally catalyst development happens by trial and error and screening many materials,” said Flytzani-Stephanopoulos. “In this study we took a fundamental approach to understanding the atomic scale structure and properties of single atom alloy surfaces and then applied this knowledge to develop a working catalyst. Armed with this knowledge, we are now ready to compare the stability of these single atom alloy catalysts to single atom catalysts supported on various oxide or carbon surfaces. This may give us very useful criteria for industrial catalyst design.”

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

Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit by Felicia R. Lucci, Jilei Liu, Matthew D. Marcinkowski, Ming Yang, Lawrence F. Allard, Maria Flytzani-Stephanopoulos, & E. Charles H. Sykes. Nature Communications 6, Article number: 8550 doi:10.1038/ncomms9550 Published 09 October 2015

This is an open access paper.