Tag Archives: SLAC National Accelerator Laboratory

X-rays reveal memristor workings

A June 14, 2016 news item on ScienceDaily focuses on memristors. (It’s been about two months since my last memristor posting on April 22, 2016 regarding electronic synapses and neural networks). This piece announces new insight into how memristors function at the atomic scale,

In experiments at two Department of Energy national labs — SLAC National Accelerator Laboratory and Lawrence Berkeley National Laboratory — scientists at Hewlett Packard Enterprise (HPE) [also referred to as HP Labs or Hewlett Packard Laboratories] have experimentally confirmed critical aspects of how a new type of microelectronic device, the memristor, works at an atomic scale.

This result is an important step in designing these solid-state devices for use in future computer memories that operate much faster, last longer and use less energy than today’s flash memory. …

“We need information like this to be able to design memristors that will succeed commercially,” said Suhas Kumar, an HPE scientist and first author on the group’s technical paper.

A June 13, 2016 SLAC news release, which originated the news item, offers a brief history according to HPE and provides details about the latest work,

The memristor was proposed theoretically [by Dr. Leon Chua] in 1971 as the fourth basic electrical device element alongside the resistor, capacitor and inductor. At its heart is a tiny piece of a transition metal oxide sandwiched between two electrodes. Applying a positive or negative voltage pulse dramatically increases or decreases the memristor’s electrical resistance. This behavior makes it suitable for use as a “non-volatile” computer memory that, like flash memory, can retain its state without being refreshed with additional power.

Over the past decade, an HPE group led by senior fellow R. Stanley Williams has explored memristor designs, materials and behavior in detail. Since 2009 they have used intense synchrotron X-rays to reveal the movements of atoms in memristors during switching. Despite advances in understanding the nature of this switching, critical details that would be important in designing commercially successful circuits  remained controversial. For example, the forces that move the atoms, resulting in dramatic resistance changes during switching, remain under debate.

In recent years, the group examined memristors made with oxides of titanium, tantalum and vanadium. Initial experiments revealed that switching in the tantalum oxide devices could be controlled most easily, so it was chosen for further exploration at two DOE Office of Science User Facilities – SLAC’s Stanford Synchrotron Radiation Lightsource (SSRL) and Berkeley Lab’s Advanced Light Source (ALS).

At ALS, the HPE researchers mapped the positions of oxygen atoms before and after switching. For this, they used a scanning transmission X-ray microscope and an apparatus they built to precisely control the position of their sample and the timing and intensity of the 500-electronvolt ALS X-rays, which were tuned to see oxygen.

The experiments revealed that even weak voltage pulses create a thin conductive path through the memristor. During the pulse the path heats up, which creates a force that pushes oxygen atoms away from the path, making it even more conductive. Reversing the voltage pulse resets the memristor by sucking some of oxygen atoms back into the conducting path, thereby increasing the device’s resistance. The memristor’s resistance changes between 10-fold and 1 million-fold, depending on operating parameters like the voltage-pulse amplitude. This resistance change is dramatic enough to exploit commercially.

To be sure of their conclusion, the researchers also needed to understand if the tantalum atoms were moving along with the oxygen during switching. Imaging tantalum required higher-energy, 10,000-electronvolt X-rays, which they obtained at SSRL’s Beam Line 6-2. In a single session there, they determined that the tantalum remained stationary.

“That sealed the deal, convincing us that our hypothesis was correct,” said HPE scientist Catherine Graves, who had worked at SSRL as a Stanford graduate student. She added that discussions with SLAC experts were critical in guiding the HPE team toward the X-ray techniques that would allow them to see the tantalum accurately.

Kumar said the most promising aspect of the tantalum oxide results was that the scientists saw no degradation in switching over more than a billion voltage pulses of a magnitude suitable for commercial use. He added that this knowledge helped his group build memristors that lasted nearly a billion switching cycles, about a thousand-fold improvement.

“This is much longer endurance than is possible with today’s flash memory devices,” Kumar said. “In addition, we also used much higher voltage pulses to accelerate and observe memristor failures, which is also important in understanding how these devices work. Failures occurred when oxygen atoms were forced so far away that they did not return to their initial positions.”

Beyond memory chips, Kumar says memristors’ rapid switching speed and small size could make them suitable for use in logic circuits. Additional memristor characteristics may also be beneficial in the emerging class of brain-inspired neuromorphic computing circuits.

“Transistors are big and bulky compared to memristors,” he said. “Memristors are also much better suited for creating the neuron-like voltage spikes that characterize neuromorphic circuits.”

The researchers have provided an animation illustrating how memristors can fail,

This animation shows how millions of high-voltage switching cycles can cause memristors to fail. The high-voltage switching eventually creates regions that are permanently rich (blue pits) or deficient (red peaks) in oxygen and cannot be switched back. Switching at lower voltages that would be suitable for commercial devices did not show this performance degradation. These observations allowed the researchers to develop materials processing and operating conditions that improved the memristors’ endurance by nearly a thousand times. (Suhas Kumar) Courtesy: SLAC

This animation shows how millions of high-voltage switching cycles can cause memristors to fail. The high-voltage switching eventually creates regions that are permanently rich (blue pits) or deficient (red peaks) in oxygen and cannot be switched back. Switching at lower voltages that would be suitable for commercial devices did not show this performance degradation. These observations allowed the researchers to develop materials processing and operating conditions that improved the memristors’ endurance by nearly a thousand times. (Suhas Kumar) Courtesy: SLAC

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

Direct Observation of Localized Radial Oxygen Migration in Functioning Tantalum Oxide Memristors by Suhas Kumar, Catherine E. Graves, John Paul Strachan, Emmanuelle Merced Grafals, Arthur L. David Kilcoyne3, Tolek Tyliszczak, Johanna Nelson Weker, Yoshio Nishi, and R. Stanley Williams. Advanced Materials, First published: 2 February 2016; Print: Volume 28, Issue 14 April 13, 2016 Pages 2772–2776 DOI: 10.1002/adma.201505435

This paper is behind a paywall.

Some of the ‘memristor story’ is contested and you can find a brief overview of the discussion in this Wikipedia memristor entry in the section on ‘definition and criticism’. There is also a history of the memristor which dates back to the 19th century featured in my May 22, 2012 posting.

Oily nanodiamonds

Nanodiamonds if successfully extracted from oil could be used for imaging and communications and the world’s leading program for extracting nanodiamonds (also known as diamondoids) is in California (US). From a May 12, 2016 news item on Nanowerk,

Stanford and SLAC National Accelerator Laboratory jointly run the world’s leading program for isolating and studying diamondoids — the tiniest possible specks of diamond. Found naturally in petroleum fluids, these interlocking carbon cages weigh less than a billionth of a billionth of a carat (a carat weighs about the same as 12 grains of rice); the smallest ones contain just 10 atoms.

Over the past decade, a team led by two Stanford-SLAC faculty members — Nick Melosh, an associate professor of materials science and engineering and of photon science, and Zhi-Xun Shen, a professor of photon science and of physics and applied physics – has found potential roles for diamondoids in improving electron microscope images, assembling materials and printing circuits on computer chips. The team’s work takes place within SIMES, the Stanford Institute for Materials and Energy Sciences, which is run jointly with SLAC.

Close-up of purified diamondoids on a lab bench. Too small to see with the naked eye, diamondoids are visible only when they clump together in fine, sugar-like crystals like these. Photo: Christopher Smith, SLAC National Accelerator Laboratory

Close-up of purified diamondoids on a lab bench. Too small to see with the naked eye, diamondoids are visible only when they clump together in fine, sugar-like crystals like these. Photo: Christopher Smith, SLAC National Accelerator Laboratory

A March 31, 2016 Stanford University news release by Glennda Chui, which originated the news item, describes the work in more detail,

Before they can do that [use nanodiamonds in imaging and other applications], though, just getting the diamondoids is a technical feat. It starts at the nearby Chevron refinery in Richmond, California, with a railroad tank car full of crude oil from the Gulf of Mexico. “We analyzed more than a thousand oils from around the world to see which had the highest concentrations of diamondoids,” says Jeremy Dahl, who developed key diamondoid isolation techniques with fellow Chevron researcher Robert Carlson before both came to Stanford — Dahl as a physical science research associate and Carlson as a visiting scientist.

The original isolation steps were carried out at the Chevron refinery, where the selected crudes were boiled in huge pots to concentrate the diamondoids. Some of the residue from that work came to a SLAC lab, where small batches are repeatedly boiled to evaporate and isolate molecules of specific weights. These fluids are then forced at high pressure through sophisticated filtration systems to separate out diamondoids of different sizes and shapes, each of which has different properties.

The diamondoids themselves are invisible to the eye; the only reason we can see them is that they clump together in fine, sugar-like crystals. “If you had a spoonful,” Dahl says, holding a few in his palm, “you could give 100 billion of them to every person on Earth and still have some left over.”

Recently, the team started using diamondoids to seed the growth of flawless, nano-sized diamonds in a lab at Stanford. By introducing other elements, such as silicon or nickel, during the growing process, they hope to make nanodiamonds with precisely tailored flaws that can produce single photons of light for next-generation optical communications and biological imaging.

Early results show that the quality of optical materials grown from diamondoid seeds is consistently high, says Stanford’s Jelena Vuckovic, a professor of electrical engineering who is leading this part of the research with Steven Chu, professor of physics and of molecular and cellular physiology.

“Developing a reliable way of growing the nanodiamonds is critical,” says Vuckovic, who is also a member of Stanford Bio-X. “And it’s really great to have that source and the grower right here at Stanford. Our collaborators grow the material, we characterize it and we give them feedback right away. They can change whatever we want them to change.”

Split some water molecules and save solar and wind (energy) for a future day

Professor Ted Sargent’s research team at the University of Toronto has a developed a new technique for saving the energy harvested by sun and wind farms according to a March 28, 2016 news item on Nanotechnology Now,

We can’t control when the wind blows and when the sun shines, so finding efficient ways to store energy from alternative sources remains an urgent research problem. Now, a group of researchers led by Professor Ted Sargent at the University of Toronto’s Faculty of Applied Science & Engineering may have a solution inspired by nature.

The team has designed the most efficient catalyst for storing energy in chemical form, by splitting water into hydrogen and oxygen, just like plants do during photosynthesis. Oxygen is released harmlessly into the atmosphere, and hydrogen, as H2, can be converted back into energy using hydrogen fuel cells.

Discovering a better way of storing energy from solar and wind farms is “one of the grand challenges in this field,” Ted Sargent says (photo above by Megan Rosenbloom via flickr) Courtesy: University of Toronto

Discovering a better way of storing energy from solar and wind farms is “one of the grand challenges in this field,” Ted Sargent says (photo above by Megan Rosenbloom via flickr) Courtesy: University of Toronto

A March 24, 2016 University of Toronto news release by Marit Mitchell, which originated the news item, expands on the theme,

“Today on a solar farm or a wind farm, storage is typically provided with batteries. But batteries are expensive, and can typically only store a fixed amount of energy,” says Sargent. “That’s why discovering a more efficient and highly scalable means of storing energy generated by renewables is one of the grand challenges in this field.”

You may have seen the popular high-school science demonstration where the teacher splits water into its component elements, hydrogen and oxygen, by running electricity through it. Today this requires so much electrical input that it’s impractical to store energy this way — too great proportion of the energy generated is lost in the process of storing it.

This new catalyst facilitates the oxygen-evolution portion of the chemical reaction, making the conversion from H2O into O2 and H2 more energy-efficient than ever before. The intrinsic efficiency of the new catalyst material is over three times more efficient than the best state-of-the-art catalyst.

Details are offered in the news release,

The new catalyst is made of abundant and low-cost metals tungsten, iron and cobalt, which are much less expensive than state-of-the-art catalysts based on precious metals. It showed no signs of degradation over more than 500 hours of continuous activity, unlike other efficient but short-lived catalysts. …

“With the aid of theoretical predictions, we became convinced that including tungsten could lead to a better oxygen-evolving catalyst. Unfortunately, prior work did not show how to mix tungsten homogeneously with the active metals such as iron and cobalt,” says one of the study’s lead authors, Dr. Bo Zhang … .

“We invented a new way to distribute the catalyst homogenously in a gel, and as a result built a device that works incredibly efficiently and robustly.”

This research united engineers, chemists, materials scientists, mathematicians, physicists, and computer scientists across three countries. A chief partner in this joint theoretical-experimental studies was a leading team of theorists at Stanford University and SLAC National Accelerator Laboratory under the leadership of Dr. Aleksandra Vojvodic. The international collaboration included researchers at East China University of Science & Technology, Tianjin University, Brookhaven National Laboratory, Canadian Light Source and the Beijing Synchrotron Radiation Facility.

“The team developed a new materials synthesis strategy to mix multiple metals homogeneously — thereby overcoming the propensity of multi-metal mixtures to separate into distinct phases,” said Jeffrey C. Grossman, the Morton and Claire Goulder and Family Professor in Environmental Systems at Massachusetts Institute of Technology. “This work impressively highlights the power of tightly coupled computational materials science with advanced experimental techniques, and sets a high bar for such a combined approach. It opens new avenues to speed progress in efficient materials for energy conversion and storage.”

“This work demonstrates the utility of using theory to guide the development of improved water-oxidation catalysts for further advances in the field of solar fuels,” said Gary Brudvig, a professor in the Department of Chemistry at Yale University and director of the Yale Energy Sciences Institute.

“The intensive research by the Sargent group in the University of Toronto led to the discovery of oxy-hydroxide materials that exhibit electrochemically induced oxygen evolution at the lowest overpotential and show no degradation,” said University Professor Gabor A. Somorjai of the University of California, Berkeley, a leader in this field. “The authors should be complimented on the combined experimental and theoretical studies that led to this very important finding.”

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

Homogeneously dispersed, multimetal oxygen-evolving catalysts by Bo Zhang, Xueli Zheng, Oleksandr Voznyy, Riccardo Comin, Michal Bajdich, Max García-Melchor, Lili Han, Jixian Xu, Min Liu, Lirong Zheng, F. Pelayo García de Arquer, Cao Thang Dinh, Fengjia Fan, Mingjian Yuan, Emre Yassitepe, Ning Chen, Tom Regier, Pengfei Liu, Yuhang Li, Phil De Luna, Alyf Janmohamed, Huolin L. Xin, Huagui Yang, Aleksandra Vojvodic, Edward H. Sargent. Science  24 Mar 2016: DOI: 10.1126/science.aaf1525

This paper is behind a paywall.

Nanoparticle snapshots with femtosecond photography

Caption: Here are "stills" from an X-ray "movie" of an exploding nanoparticle. The nanoparticle is superheated with an intense optical pulse and subsequently explodes (left). A series of ultrafast x-ray diffraction images (right) maps the process and contains information how the explosion starts with surface softening and proceeds from the outside in. Credit: Christoph Bostedt

Caption: Here are “stills” from an X-ray “movie” of an exploding nanoparticle. The nanoparticle is superheated with an intense optical pulse and subsequently explodes (left). A series of ultrafast x-ray diffraction images (right) maps the process and contains information how the explosion starts with surface softening and proceeds from the outside in. Credit: Christoph Bostedt

A Feb. 10, 2016 news item on Nanotechnology Now provides more information about the ‘snapshots,

Just as a photographer needs a camera with a split-second shutter speed to capture rapid motion, scientists looking at the behavior of tiny materials need special instruments with the capacity to see changes that happen in the blink of an eye.

An international team of researchers led by X-ray scientist Christoph Bostedt of the U.S. Department of Energy’s (DOE) Argonne National Laboratory and Tais Gorkhover of DOE’s SLAC National Accelerator Laboratory used two special lasers to observe the dynamics of a small sample of xenon as it was heated to a plasma.

A Feb. 10, 2016 Argonne National Laboratory news release (also on EurekAlert) by Jared Sagoff, which originated the news item, provides more technical details,

Bostedt and Gorkhover were able to use the Linac Coherent Light Source (LCLS) at SLAC to make observations of the sample in time steps of approximately a hundred femtoseconds – a femtosecond being one millionth of a billionth of a second [emphasis mine]. The exposure time of the individual images was so short that the quickly moving particles in the gas phase appeared frozen. “The advantage of a machine like the LCLS is that it gives us the equivalent of high-speed flash photography as opposed to a pinhole camera,” Bostedt said. The LCLS is a DOE Office of Science User Facility.

The researchers used an optical laser to heat the sample cluster and an X-ray laser to probe the dynamics of the cluster as it changed over time. As the laser heated the cluster, the photons freed electrons initially bound to the atoms; however, these electrons still remained loosely bound to the cluster.

By imaging exploding nanoparticles, the team was able to make measurements of how they change over time in extreme environments. “Ultimately, we want to understand how the energy from the light affects the system,” Gorkhover said.

“There are really no other techniques that give us this good a resolution in both time and space simultaneously,” she added. “Other methods require us to take averages over many different ‘exposures,’ which can obscure relevant details. Additionally, techniques like electron microscopy involve a substrate material that can interfere with the behavior of the sample.”

According to Bostedt, the research could also impact the study of aerosols in the environment or in combustion, as the dual-laser “pump and probe” model could be adapted to study materials in the gas phase. “Although our material goes from solid to plasma very quickly, there are other types of materials you could study with this or a similar technique,” he said.

I marvel at how very brief the time intervals are at the femtoscale and for that matter, the other subatomic scales.

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

Femtosecond and nanometre visualization of structural dynamics in superheated nanoparticles by Tais Gorkhover, Sebastian Schorb, Ryan Coffee, Marcus Adolph, Lutz Foucar, Daniela Rupp, Andrew Aquila, John D. Bozek, Sascha W. Epp, Benjamin Erk, Lars Gumprecht, Lotte Holmegaard, Andreas Hartmann, Robert Hartmann, Günter Hauser, Peter Holl, Andre Hömke, Per Johnsson, Nils Kimmel, Kai-Uwe Kühnel, Marc Messerschmidt, Christian Reich, Arnaud Rouzée, Benedikt Rudek, Carlo Schmidt et al. Nature Photonics 10, 93–97 (2016) doi:10.1038/nphoton.2015.264 Published online 25 January 2016

This paper is behind a paywall.

Stress makes quantum dots ‘breathe’

A March 19, 2015 news item on ScienceDaily describes some new research on quantum dots,

Researchers at the Department of Energy’s SLAC National Accelerator Laboratory watched nanoscale semiconductor crystals expand and shrink in response to powerful pulses of laser light. This ultrafast “breathing” provides new insight about how such tiny structures change shape as they start to melt — information that can help guide researchers in tailoring their use for a range of applications.

In the experiment using SLAC’s Linac Coherent Light Source (LCLS) X-ray laser, a DOE Office of Science User Facility, researchers first exposed the nanocrystals to a burst of laser light, followed closely by an ultrabright X-ray pulse that recorded the resulting structural changes in atomic-scale detail at the onset of melting.

“This is the first time we could measure the details of how these ultrasmall materials react when strained to their limits,” said Aaron Lindenberg, an assistant professor at SLAC and Stanford who led the experiment. The results were published March 12 [2015] in Nature Communications.

A March 18, 2015 SLAC news release, which originated the news item, provides a general description of quantum dots,

The crystals studied at SLAC are known as “quantum dots” because they display unique traits at the nanoscale that defy the classical physics governing their properties at larger scales. The crystals can be tuned by changing their size and shape to emit specific colors of light, for example.

So scientists have worked to incorporate them in solar panels to make them more efficient and in computer displays to improve resolution while consuming less battery power. These materials have also been studied for potential use in batteries and fuel cells and for targeted drug delivery.

Scientists have also discovered that these and other nanomaterials, which may contain just tens or hundreds of atoms, can be far more damage-resistant than larger bits of the same materials because they exhibit a more perfect crystal structure at the tiniest scales. This property could prove useful in battery components, for example, as smaller particles may be able to withstand more charging cycles than larger ones before degrading.

The news release then goes on to describe the latest research showing the dots ‘breathe’ (Note: A link has been removed),

In the LCLS experiment, researchers studied spheres and nanowires made of cadmium sulfide and cadmium selenide that were just 3 to 5 nanometers, or billionths of a meter, across. The nanowires were up to 25 nanometers long. By comparison, amino acids – the building blocks of proteins – are about 1 nanometer in length, and individual atoms are measured in tenths of nanometers.

By examining the nanocrystals from many different angles with X-ray pulses, researchers reconstructed how they change shape when hit with an optical laser pulse. They were surprised to see the spheres and nanowires expand in width by about 1 percent and then quickly contract within femtoseconds, or quadrillionths of a second. They also found that the nanowires don’t expand in length, and showed that the way the crystals respond to strain was coupled to how their structure melts.

In an earlier, separate study, another team of researchers had used LCLS to explore the response of larger gold particles on longer timescales.

“In the future, we want to extend these experiments to more complex and technologically relevant nanostructures, and also to enable X-ray exploration of nanoscale devices while they are operating,” Lindenberg said. “Knowing how materials change under strain can be used together with simulations to design new materials with novel properties.”

Participating researchers were from SLAC, Stanford and two of their joint institutes, the Stanford Institute for Materials and Energy Sciences (SIMES) and Stanford PULSE Institute; University of California, Berkeley; University of Duisburg-Essen in Germany; and Argonne National Laboratory. The work was supported by the DOE Office of Science and the German Research Council.

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

Visualization of nanocrystal breathing modes at extreme strains by Erzsi Szilagyi, Joshua S. Wittenberg, Timothy A. Miller, Katie Lutker, Florian Quirin, Henrik Lemke, Diling Zhu, Matthieu Chollet, Joseph Robinson, Haidan Wen, Klaus Sokolowski-Tinten, & Aaron M. Lindenberg. Nature Communications 6, Article number: 6577 doi:10.1038/ncomms7577 Published 12 March 2015

This paper is behind a paywall but there is a free preview available through ReadCube Access.

Nanoparticles in 3D courtesy of x-rays

A Feb. 4, 2015 Deutsches Elektronen-Synchrotron (DESY) press release (also on EurekAlert) announces a 3D first,

For the first time, a German-American research team has determined the three-dimensional shape of free-flying silver nanoparticles, using DESY’s X-ray laser FLASH. The tiny particles, hundreds of times smaller than the width of a human hair, were found to exhibit an unexpected variety of shapes, as the physicists from the Technical University (TU) Berlin, the University of Rostock, the SLAC National Accelerator Laboratory in the United States and from DESY report in the scientific journal Nature Communications. Besides this surprise, the results open up new scientific routes, such as direct observation of rapid changes in nanoparticles.

The press release goes on to describe the work in more detail,

“The functionality of nanoparticles is linked to their geometric form, which is often very difficult to determine experimentally,” explains Dr. Ingo Barke from the University of Rostock. “This is particularly challenging when they are present as free particles, that is, in the absence of contact with a surface or a liquid.”

The nanoparticle shape can be revealed from the characteristic way how it scatters X-ray light. Therefore, X-ray sources like DESY’s FLASH enable a sort of super microscope into the nano-world. So far, the spatial structure of nanoparticles has been reconstructed from multiple two-dimensional images, which were taken from different angles. This procedure is uncritical for particles on solid substrates, as the images can be taken from many different angles to uniquely reconstruct their three-dimensional shape.

“Bringing nanoparticles into contact with a surface or a liquid can significantly alter the particles, such that you can no longer see their actual form,” says Dr. Daniela Rupp from the TU Berlin. A free particle, however, can only be measured one time in flight before it either escapes or is destroyed by the intense X-ray light. Therefore, the scientists looked for a way to record the entire structural information of a nanoparticle with a single X-ray laser pulse.

To achieve this goal, the scientists led by Prof. Thomas Möller from the TU Berlin and Prof. Karl-Heinz Meiwes-Broer and Prof. Thomas Fennel from the University of Rostock employed a trick. Instead of taking usual small-angle scattering images, the physicists recorded the scattered X-rays in a wide angular range. “This approach virtually captures the structure from many different angles simultaneously from a single laser shot,” explains Fennel.

The researchers tested this method on free silver nanoparticles with diameters of 50 to 250 nanometres (0.00005 to 0.00025 millimetres). The experiment did not only verify the feasibility of the tricky method, but also uncovered the surprising result that large nanoparticles exhibit a much greater variety of shapes than expected.

The shape of free nanoparticles is a result of different physical principles, particularly the particles’ effort to minimize their energy. Consequently, large particles composed of thousands or millions of atoms often yield predictable shapes, because the atoms can only be arranged in a particular way to obtain an energetically favourable state.

In their experiment, however, the researchers observed numerous highly symmetrical three-dimensional shapes, including several types known as Platonic and Archimedean bodies. Examples include the truncated octahedron (a body consisting of eight regular hexagons and six squares) and the icosahedron (a body made up of twenty equilateral triangles). The latter is actually only favourable for extremely small particles consisting of few atoms, and its occurrence with free particles of this size was previously unknown. “The results show that metallic nanoparticles retain a type of memory of their structure, from the early stages of growth to a yet unexplored size range,” emphasizes Barke.

Due to the large variety of shapes, it was especially important to use a fast computational method so that the researchers were capable of mapping the shape of each individual particle. The scientists used a two-step process: the rough shape was determined first and then refined using more complex simulations on a super computer. This approach turned out to be so efficient that it could not only determine various shapes reliably, but could also differentiate between varying orientations of the same shape.

This new method for determining the three-dimensional shape and orientation of nanoparticles with a single X-ray laser shot opens up a wide spectrum of new research directions. In future projects, particles could be directly “filmed” in three dimensions during growth or during phase changes. “The ability to directly film the reaction of a nanoparticle to an intense flash of X-ray light has been a dream for many physicists – this dream could now come true, even in 3D!,” emphasises Rupp.

The researchers have provided an image showing their work,

Caption: This is a wide-angle X-ray diffraction image of a truncated twinned tetrahedra nanoparticle. Credit: Hannes Hartmann/University of Rostock

Caption: This is a wide-angle X-ray diffraction image of a truncated twinned tetrahedra nanoparticle.
Credit: Hannes Hartmann/University of Rostock

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

The 3D-architecture of individual free ​silver nanoparticles captured by X-ray scattering by Ingo Barke, Hannes Hartmann, Daniela Rupp, Leonie Flückiger, Mario Sauppe, Marcus Adolph, Sebastian Schorb, Christoph Bostedt, Rolf Treusch, Christian Peltz, Stephan Bartling, Thomas Fennel, Karl-Heinz Meiwes-Broer, & Thomas Möller. Nature Communications 6, Article number: 6187 doi:10.1038/ncomms7187 Published 04 February 2015

This article is open access.

Buckydiamondoids steer electron flow

One doesn’t usually think about buckyballs (Buckminsterfullerenes) and diamondoids as being together in one molecule but that has not stopped scientists from trying to join them and, in this case, successfully. From a Sept. 9, 2014 news item on ScienceDaily,

Scientists have married two unconventional forms of carbon — one shaped like a soccer ball, the other a tiny diamond — to make a molecule that conducts electricity in only one direction. This tiny electronic component, known as a rectifier, could play a key role in shrinking chip components down to the size of molecules to enable faster, more powerful devices.

Here’s an illustration the scientists have provided,

Illustration of a buckydiamondoid molecule under a scanning tunneling microscope (STM). In this study the STM made images of the buckydiamondoids and probed their electronic properties.

Illustration of a buckydiamondoid molecule under a scanning tunneling microscope (STM). In this study the STM made images of the buckydiamondoids and probed their electronic properties.

A Sept. 9, 2014 Stanford University news release by Glenda Chui (also on EurekAlert), which originated the news item, provides some information about this piece of international research along with background information on buckyballs and diamondoids (Note: Links have been removed),

“We wanted to see what new, emergent properties might come out when you put these two ingredients together to create a ‘buckydiamondoid,'” said Hari Manoharan of the Stanford Institute for Materials and Energy Sciences (SIMES) at the U.S. Department of Energy’s SLAC National Accelerator Laboratory. “What we got was basically a one-way valve for conducting electricity – clearly more than the sum of its parts.”

The research team, which included scientists from Stanford University, Belgium, Germany and Ukraine, reported its results Sept. 9 in Nature Communications.

Many electronic circuits have three basic components: a material that conducts electrons; rectifiers, which commonly take the form of diodes, to steer that flow in a single direction; and transistors to switch the flow on and off. Scientists combined two offbeat ingredients – buckyballs and diamondoids – to create the new diode-like component.

Buckyballs – short for buckminsterfullerenes – are hollow carbon spheres whose 1985 discovery earned three scientists a Nobel Prize in chemistry. Diamondoids are tiny linked cages of carbon joined, or bonded, as they are in diamonds, with hydrogen atoms linked to the surface, but weighing less than a billionth of a billionth of a carat. Both are subjects of a lot of research aimed at understanding their properties and finding ways to use them.

In 2007, a team led by researchers from SLAC and Stanford discovered that a single layer of diamondoids on a metal surface can emit and focus electrons into a tiny beam. Manoharan and his colleagues wondered: What would happen if they paired an electron-emitting diamondoid with another molecule that likes to grab electrons? Buckyballs are just that sort of electron-grabbing molecule.

Details are then provided about this specific piece of research (from the Stanford news release),

For this study, diamondoids were produced in the SLAC laboratory of SIMES researchers Jeremy Dahl and Robert Carlson, who are world experts in extracting the tiny diamonds from petroleum. The diamondoids were then shipped to Germany, where chemists at Justus-Liebig University figured out how to attach them to buckyballs.

The resulting buckydiamondoids, which are just a few nanometers long, were tested in SIMES laboratories at Stanford. A team led by graduate student Jason Randel and postdoctoral researcher Francis Niestemski used a scanning tunneling microscope to make images of the hybrid molecules and measure their electronic behavior. They discovered that the hybrid is an excellent rectifier: The electrical current flowing through the molecule was up to 50 times stronger in one direction, from electron-spitting diamondoid to electron-catching buckyball, than in the opposite direction. This is something neither component can do on its own.

While this is not the first molecular rectifier ever invented, it’s the first one made from just carbon and hydrogen, a simplicity researchers find appealing, said Manoharan, who is an associate professor of physics at Stanford. The next step, he said, is to see if transistors can be constructed from the same basic ingredients.

“Buckyballs are easy to make – they can be isolated from soot – and the type of diamondoid we used here, which consists of two tiny cages, can be purchased commercially,” he said. “And now that our colleagues in Germany have figured out how to bind them together, others can follow the recipe. So while our research was aimed at gaining fundamental insights about a novel hybrid molecule, it could lead to advances that help make molecular electronics a reality.”

Other research collaborators came from the Catholic University of Louvain in Belgium and Kiev Polytechnic Institute in Ukraine. The primary funding for the work came from U.S. the Department of Energy Office of Science (Basic Energy Sciences, Materials Sciences and Engineering Divisions).

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

Unconventional molecule-resolved current rectification in diamondoid–fullerene hybrids by Jason C. Randel, Francis C. Niestemski,    Andrés R. Botello-Mendez, Warren Mar, Georges Ndabashimiye, Sorin Melinte, Jeremy E. P. Dahl, Robert M. K. Carlson, Ekaterina D. Butova, Andrey A. Fokin, Peter R. Schreiner, Jean-Christophe Charlier & Hari C. Manoharan. Nature Communications 5, Article number: 4877 doi:10.1038/ncomms5877 Published 09 September 2014

This paper is open access. The scientists provided not only a standard illustration but a pretty picture of the buckydiamondoid,

Caption: An international team led by researchers at SLAC National Accelerator Laboratory and Stanford University joined two offbeat carbon molecules -- diamondoids, the square cages at left, and buckyballs, the soccer-ball shapes at right -- to create "buckydiamondoids," center. These hybrid molecules function as rectifiers, conducting electrons in only one direction, and could help pave the way to molecular electronic devices. Credit: Manoharan Lab/Stanford University

Caption: An international team led by researchers at SLAC National Accelerator Laboratory and Stanford University joined two offbeat carbon molecules — diamondoids, the square cages at left, and buckyballs, the soccer-ball shapes at right — to create “buckydiamondoids,” center. These hybrid molecules function as rectifiers, conducting electrons in only one direction, and could help pave the way to molecular electronic devices.
Credit: Manoharan Lab/Stanford University

Not ageing gracefully; the lithium-ion battery story

There’s an alphabet soup’s worth of agencies involved in research on lithium-ion battery ageing which has resulted in two papers as noted in a May 30, 2014 news item Azonano,

Batteries do not age gracefully. The lithium ions that power portable electronics cause lingering structural damage with each cycle of charge and discharge, making devices from smartphones to tablets tick toward zero faster and faster over time. To stop or slow this steady degradation, scientists must track and tweak the imperfect chemistry of lithium-ion batteries with nanoscale precision.

In two recent Nature Communications papers, scientists from several U.S. Department of Energy national laboratories—Lawrence Berkeley, Brookhaven, SLAC, and the National Renewable Energy Laboratory—collaborated to map these crucial billionths-of-a-meter dynamics and lay the foundation for better batteries.

A May 29, 2014 Brookhaven National Laboratory news release by Justin Eure, which originated the news item, describes the research techniques in more detail,

“We discovered surprising and never-before-seen evolution and degradation patterns in two key battery materials,” said Huolin Xin, a materials scientist at Brookhaven Lab’s Center for Functional Nanomaterials (CFN) and coauthor on both studies. “Contrary to large-scale observation, the lithium-ion reactions actually erode the materials non-uniformly, seizing upon intrinsic vulnerabilities in atomic structure in the same way that rust creeps unevenly across stainless steel.”

Xin used world-leading electron microscopy techniques in both studies to directly visualize the nanoscale chemical transformations of battery components during each step of the charge-discharge process. In an elegant and ingenious setup, the collaborations separately explored a nickel-oxide anode and a lithium-nickel-manganese-cobalt-oxide cathode—both notable for high capacity and cyclability—by placing samples inside common coin-cell batteries running under different voltages.

“Armed with a precise map of the materials’ erosion, we can plan new ways to break the patterns and improve performance,” Xin said.

In these experiments, lithium ions traveled through an electrolyte solution, moving into an anode when charging and a cathode when discharging. The processes were regulated by electrons in the electrical circuit, but the ions’ journeys—and the battery structures—subtly changed each time.

The news release first describes the research involving the nickel-oxide anode, one of the two areas of interest,

For the nickel-oxide anode, researchers submerged the batteries in a liquid organic electrolyte and closely controlled the charging rates. They stopped at predetermined intervals to extract and analyze the anode. Xin and his collaborators rotated 20-nanometer-thick sheets of the post-reaction material inside a carefully calibrated transmission electron microscope (TEM) grid at CFN to catch the contours from every angle—a process called electron tomography.

To see the way the lithium-ions reacted with the nickel oxide, the scientists used a suite of custom-written software to digitally reconstruct the three-dimensional nanostructures with single-nanometer resolution. Surprisingly, the reactions sprang up at isolated spatial points rather than sweeping evenly across the surface.

“Consider the way snowflakes only form around tiny particles or bits of dirt in the air,” Xin said. “Without an irregularity to glom onto, the crystals cannot take shape. Our nickel oxide anode only transforms into metallic nickel through nanoscale inhomogeneities or defects in the surface structure, a bit like chinks in the anode’s armor.”

The electron microscopy provided a crucial piece of the larger puzzle assembled in concert with Berkeley Lab materials scientists and soft x-ray spectroscopy experiments conducted at SLAC’s Stanford Synchrotron Radiation Lightsource (SSRL). The combined data covered the reactions on the nano-, meso-, and microscales.

Next, there’s this about the second area of interest, a lithium-nickel-manganese-cobalt-oxide (NMC) cathode (from the news release),

In the other study, scientists sought the voltage sweet-spot for the high-performing lithium-nickel-manganese-cobalt-oxide (NMC) cathode: How much power can be stored, at what intensity, and across how many cycles?

The answers hinged on intrinsic material qualities and the structural degradation caused by cycles at 4.7 volts and 4.3 volts, as measured against a lithium metal standard.

As revealed through another series of coin-cell battery tests, 4.7 volts caused rapid decomposition of the electrolytes and poor cycling—the higher power comes at a price. A 4.3-volt battery, however, offered a much longer cycling lifetime at the cost of lower storage and more frequent recharges.

In both cases, the chemical evolution exhibited sprawling surface asymmetries, though not without profound patterns.

“As the lithium ions race through the reaction layers, they cause clumping crystallization—a kind of rock-salt matrix builds up over time and begins limiting performance,” Xin said. “We found that these structures tended to form along the lithium-ion reaction channels, which we directly visualized under the TEM. The effect was even more pronounced at higher voltages, explaining the more rapid deterioration.”

Identifying this crystal-laden reaction pathways hints at a way forward in battery design.

“It may be possible to use atomic deposition to coat the NMC cathodes with elements that resist crystallization, creating nanoscale boundaries within the micron-sized powders needed at the cutting-edge of industry,” Xin said. “In fact, Berkeley Lab battery experts Marca Doeff and Feng Lin are working on that now.”

Shirley Meng, a professor at UC San Diego’s Department of NanoEngineering, added, “This beautiful study combines several complementary tools that probe both the bulk and surface of the NMC layered oxide—one of the most promising cathode materials for high-voltage operation that enables higher energy density in lithium-ion batteries. The meaningful insights provided by this study will significantly impact the optimization strategies for this type of cathode material.”

The TEM measurements revealed the atomic structures while electron energy loss spectroscopy helped pinpoint the chemical evolution—both carried out at the CFN….

The scientists next want to observe these changes in real-time which will necessitate the custom design of some new equipment (“electrochemical contacts and liquid flow holders”).

Here are links to and citations for the papers,

Phase evolution for conversion reaction electrodes in lithium-ion batteries by Feng Lin, Dennis Nordlund, Tsu-Chien Weng, Ye Zhu, Chunmei Ban, Ryan M. Richards, & Huolin L. Xin. Nature Communications 5, Article number: 3358 doi:10.1038/ncomms4358 Published 24 February 2014

Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries by Feng Lin, Isaac M. Markus, Dennis Nordlund, Tsu-Chien Weng, Mark D. Asta, Huolin L. Xin & Marca M. Doeff. Nature Communications 5, Article number: 3529 doi:10.1038/ncomms4529 Published 27 March 2014

Both of these articles are behind a paywall and they both offer previews via ReadCube Access.

Accelerator-on-a-chip at Stanford University’s SLAC National Accelerator Laboratory

For anyone who’s ever seen a picture of the accelerators at CERN’s (European Particle Physics Laboratory) Large Hadron Collider, the notion of an accelerator-on-a-chip seems unbelievable. Scientists at Stanford’s SLAC National Accelerator Laboratory thought otherwise according to a Sept. 27, 2013 SLAC news release (also on EurekAlert),

In an advance that could dramatically shrink particle accelerators for science and medicine, researchers used a laser to accelerate electrons at a rate 10 times higher than conventional technology in a nanostructured glass chip smaller than a grain of rice.

“We still have a number of challenges before this technology becomes practical for real-world use, but eventually it would substantially reduce the size and cost of future high-energy particle colliders for exploring the world of fundamental particles and forces,” said Joel England, the SLAC physicist who led the experiments. “It could also help enable compact accelerators and X-ray devices for security scanning, medical therapy and imaging, and research in biology and materials science.”

Because it employs commercial lasers and low-cost, mass-production techniques, the researchers believe it will set the stage for new generations of “tabletop” accelerators.

At its full potential, the new “accelerator on a chip” could match the accelerating power of SLAC’s 2-mile-long linear accelerator in just 100 feet, and deliver a million more electron pulses per second. [emphasis mine]

The news release goes on to describe how the researchers have achieved a more efficient acceleration,

Particles are generally accelerated in two stages. First they are boosted to nearly the speed of light. Then any additional acceleration increases their energy, but not their speed; this is the challenging part.

In the accelerator-on-a-chip experiments, electrons are first accelerated to near light-speed in a conventional accelerator. Then they are focused into a tiny, half-micron-high channel within a fused silica glass chip just half a millimeter long. The channel had been patterned with precisely spaced nanoscale ridges. Infrared laser light shining on the pattern generates electrical fields that interact with the electrons in the channel to boost their energy.

The researchers’ have produced an animation which illustrates their work,

Caption: This animation explains how the accelerator on a chip uses infrared laser light to accelerate electrons to increasingly higher energies. Credit:  (Greg Stewart/SLAC)

Here’s a citation for and a link to the  research paper (‘near final version as of Sept. 30, 2013),

Demonstration of electron acceleration in a laser-driven dielectric microstructure by E. A. Peralta, K. Soong, R. J. England, E. R. Colby, Z. Wu, B. Montazeri, C. McGuinness, J. McNeur, K. J. Leedle, D. Walz, E. B. Sozer, B. Cowan, B. Schwartz, G. Travish, & R. L. Byer. Nature (2013) doi:10.1038/nature12664  Published online 27 September 2013

It is behind a paywall although you can get reading access via ReadCube.

Finally, here’s what the chip looks like,

Nanofabricated chips of fused silica just 3 millimeters long were used to accelerate electrons at a rate 10 times higher than conventional particle accelerator technology. (Brad Plummer/SLAC)

Nanofabricated chips of fused silica just 3 millimeters long were used to accelerate electrons at a rate 10 times higher than conventional particle accelerator technology. (Brad Plummer/SLAC)

Keeping it together—new glue for lithium-ion batteries

Glue isn’t the first component that comes to my mind when discussing ways to make lithium-ion (Li-ion) batteries more efficient but researchers at SLAC National Accelerator Laboratory at Stanford University have proved that the glue used to bind a Li-ion battery together can make a difference to its efficiency (from the Aug. 20, 2013 news item on phys.org),

When it comes to improving the performance of lithium-ion batteries, no part should be overlooked – not even the glue that binds materials together in the cathode, researchers at SLAC and Stanford have found.

Tweaking that material, which binds lithium sulfide and carbon particles together, created a cathode that lasted five times longer than earlier designs, according to a report published last month in Chemical Science. The research results are some of the earliest supported by the Department of Energy’s Joint Center for Energy Storage Research.

“We were very impressed with how important this binder was in improving the lifetime of our experimental battery,” said Yi Cui, an associate professor at SLAC and Stanford who led the research.

The Aug. 19, 2013 SLAC news release by Mike Ross, which originated the news item, provides context for this accidental finding about glue and Li-ion batteries,

Researchers worldwide have been racing to improve lithium-ion batteries, which are one of the most promising technologies for powering increasingly popular devices such as mobile electronics and electric vehicles. In theory, using silicon and sulfur as the active elements in the batteries’ terminals, called the anode and cathode, could allow lithium-ion batteries to store up to five times more energy than today’s best versions. But finding specific forms and formulations of silicon and sulfur that will last for several thousand charge-discharge cycles during real-life use has been difficult.

Cui’s group was exploring how to create a better cathode by using lithium sulfide rather than sulfur. The lithium atoms it contains can provide the ions that shuttle between anode and cathode during the battery’s charge/discharge cycle; this in turn means the battery’s other electrode can be made from a non-lithium material, such as silicon. Unfortunately, lithium sulfide is also electrically insulating, which greatly reduces any battery’s performance. To overcome this, electrically conducting carbon particles can be mixed with the sulfide; a glue-like material – the binder – holds it all together.

Scientists in Cui’s [Yi Cui, an associate professor at SLAC and Stanford who led the research] group devised a new binder that is particularly well-suited for use with a lithium sulfide cathode ­– and that also binds strongly with intermediate polysulfide molecules that dissolve out of the cathode and diminish the battery’s storage capacity and useful lifetime.

The experimental battery using the new binder, known by the initials PVP, retained 94 percent of its original energy-storage capacity after 100 charge/discharge cycles, compared with 72 percent for cells using a conventionally-used binder, known as PVDF. After 500 cycles, the PVP battery still had 69 percent of its initial capacity.

Cui said the improvement was due to PVP’s much stronger affinity for lithium sulfide; together they formed a fine-grained lithium sulfide/carbon composite that made it easier for lithium ions to penetrate and reach all of the active material within the cathode. In contrast, the previous binder, PVDF, caused the composite to grow into large clumps, which hindered the lithium ions’ penetration and ruined the battery within 100 cycles

Even the best batteries lose some energy-storage capacity with each charge/discharge cycle. Researchers aim to reduce such losses as much as possible. Further enhancements to the PVP/lithium sulfide cathode combination will be needed to extend its lifetime to more than 1,000 cycles, but Cui said he finds it encouraging that improving the usually overlooked binder material produced such dramatic benefits.

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

Stable cycling of lithium sulfide cathodes through strong affinity with a bifunctional binder by Zhi Wei Seh, Qianfan Zhang, Weiyang Li, Guangyuan Zheng, Hongbin Yaoa, and Yi Cui. Chem. Sci., 2013,4, 3673-3677 DOI: 10.1039/C3SC51476E First published online 11 Jul 2013

There’s a note on the website stating the article is free but the instructions for accessing the article are confusing seeming to suggest you need a subscription of some sort or you need to register for the site.

I have written about Yi Cui’s work with lithium-ion batteries before including this Jan. 9, 2013 posting, How is an eggshell like a lithium-ion battery?, which also features a news release by Mike Ross.