Tag Archives: crystals

Formation of a time (temporal) crystal

It’s a crystal arranged in time according to a March 8, 2017 University of Texas at Austin news release (also on EurekAlert), Note: Links have been removed,

Salt, snowflakes and diamonds are all crystals, meaning their atoms are arranged in 3-D patterns that repeat. Today scientists are reporting in the journal Nature on the creation of a phase of matter, dubbed a time crystal, in which atoms move in a pattern that repeats in time rather than in space.

The atoms in a time crystal never settle down into what’s known as thermal equilibrium, a state in which they all have the same amount of heat. It’s one of the first examples of a broad new class of matter, called nonequilibrium phases, that have been predicted but until now have remained out of reach. Like explorers stepping onto an uncharted continent, physicists are eager to explore this exotic new realm.

“This opens the door to a whole new world of nonequilibrium phases,” says Andrew Potter, an assistant professor of physics at The University of Texas at Austin. “We’ve taken these theoretical ideas that we’ve been poking around for the last couple of years and actually built it in the laboratory. Hopefully, this is just the first example of these, with many more to come.”

Some of these nonequilibrium phases of matter may prove useful for storing or transferring information in quantum computers.

Potter is part of the team led by researchers at the University of Maryland who successfully created the first time crystal from ions, or electrically charged atoms, of the element ytterbium. By applying just the right electrical field, the researchers levitated 10 of these ions above a surface like a magician’s assistant. Next, they whacked the atoms with a laser pulse, causing them to flip head over heels. Then they hit them again and again in a regular rhythm. That set up a pattern of flips that repeated in time.

Crucially, Potter noted, the pattern of atom flips repeated only half as fast as the laser pulses. This would be like pounding on a bunch of piano keys twice a second and notes coming out only once a second. This weird quantum behavior was a signature that he and his colleagues predicted, and helped confirm that the result was indeed a time crystal.

The team also consists of researchers at the National Institute of Standards and Technology, the University of California, Berkeley and Harvard University, in addition to the University of Maryland and UT Austin.

Frank Wilczek, a Nobel Prize-winning physicist at the Massachusetts Institute of Technology, was teaching a class about crystals in 2012 when he wondered whether a phase of matter could be created such that its atoms move in a pattern that repeats in time, rather than just in space.

Potter and his colleague Norman Yao at UC Berkeley created a recipe for building such a time crystal and developed ways to confirm that, once you had built such a crystal, it was in fact the real deal. That theoretical work was announced publically last August and then published in January in the journal Physical Review Letters.

A team led by Chris Monroe of the University of Maryland in College Park built a time crystal, and Potter and Yao helped confirm that it indeed had the properties they predicted. The team announced that breakthrough—constructing a working time crystal—last September and is publishing the full, peer-reviewed description today in Nature.

A team led by Mikhail Lukin at Harvard University created a second time crystal a month after the first team, in that case, from a diamond.

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

Observation of a discrete time crystal by J. Zhang, P. W. Hess, A. Kyprianidis, P. Becker, A. Lee, J. Smith, G. Pagano, I.-D. Potirniche, A. C. Potter, A. Vishwanath, N. Y. Yao, & C. Monroe. Nature 543, 217–220 (09 March 2017) doi:10.1038/nature21413 Published online 08 March 2017

This paper is behind a paywall.

Snow reveals the truth about crystalline growth

A Jan. 24, 2014 news item on Nanowerk has a beautiful and timely (given the snowy, frigid weather in Eastern Canada and the US) opening for a story about crystals and metallic nanorods,

This time of year it’s not hard to imagine the world buried under a smooth blanket of snow. A picnic table on a flat lawn eventually vanishes as trillions of snowflakes collect around it, a crystalline sheet obscuring the normall – visible peaks and valleys of our summertime world.

This is basically how scientists understand the classical theory of crystalline growth. Height steps gradually disappear as atoms of a given material—be it snow or copper or aluminum—collect on a surface and then tumble down to lower heights to fill in the gaps. The only problem with this theory is that it totally falls apart when applied to extremely small situations—i.e., the nanoscale.

The Jan. 23, 2014 Northeastern University news release by Angela Herring, which originated the news item, goes on to provide some context and describe this work concerning nanorods,

Hanchen Huang, pro­fessor and chair of the Depart­ment of Mechan­ical and Indus­trial Engi­neering [Northeastern University located in Massachusetts, US], has spent the last 10 years revising the clas­sical theory of crystal growth that accounts for his obser­va­tions of nanorod crys­tals. His work has gar­nered the con­tinued sup­port of the U.S, Depart­ment of Energy’s Basic Energy Sci­ence Core Program.

Nanorods are minis­cule fibers grown per­pen­dic­ular to a sub­strate, each one about 100,000 times thinner than a human hair. Sur­face steps, or the minor vari­a­tions in the ver­tical land­scape of that sub­strate, deter­mine how the rods will grow.

“Even if some sur­face steps are closer and others more apart at the start, with time the clas­sical theory pre­dicts they become more equal­ized,” Huang said. “But we found that the clas­sical theory missed a pos­i­tive feed­back mechanism.”

This mech­a­nism, he explained, causes the steps to “cluster,” making it more dif­fi­cult for atoms to fall from a higher step to a lower one. So, instead of filling in the height gaps of a vari­able sur­face, atoms in a nanorod crystal localize to the highest levels.

“The taller region gets taller,” Huang said. “It’s like, if you ever play bas­ket­ball, you know the taller guys will get more rebounds.” That’s basi­cally what hap­pens with nanorod growth.

Huang’s theory, which was pub­lished in the journal Phys­ical Review Let­ters this year, rep­re­sents the first time anyone has pro­vided a the­o­ret­ical frame­work for under­standing nanorod crystal growth. “Lots of money has been spent over the past decades on nanoscience and nan­otech­nology,” Huang said. “But we can only turn that into real-​​world appli­ca­tions if we under­stand the science.”

Indeed, his con­tri­bu­tion to under­standing the sci­ence allowed him and his col­leagues to pre­dict the smallest pos­sible size for copper nanorods and then suc­cess­fully syn­the­size them. Not only are they the smallest nanorods ever pro­duced, but with Huang’s theory he can con­fi­dently say they are the smallest nanorods pos­sible using phys­ical vapor deposition.

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

Smallest Metallic Nanorods Using Physical Vapor Deposition by Xiaobin Niu, Stephen P. Stagon, Hanchen Huang, J. Kevin Baldwin, and Amit Misra. Phys. Rev. Lett. 110 (no. 13), 136102 (2013) [5 pages] DoI:

This paper is behind a paywall.

Bejweled and bedazzled but not bewitched, bothered, or bewildered at Northwestern University

When discussing DNA (deoxyribonucleic acid) one doesn’t usually expect to encounter gems as one does in a Nov. 28, 2013 news item on Azonano,

Nature builds flawless diamonds, sapphires and other gems. Now a Northwestern University [located in Chicago, Illinois, US] research team is the first to build near-perfect single crystals out of nanoparticles and DNA, using the same structure favored by nature.

The Nov. 27, 2013 Northwestern University news release by Megan Fellman (also on EurekAlert), which originated the news item,, explains why single crystals are of such interest,

“Single crystals are the backbone of many things we rely on — diamonds for beauty as well as industrial applications, sapphires for lasers and silicon for electronics,” said nanoscientist Chad A. Mirkin. “The precise placement of atoms within a well-defined lattice defines these high-quality crystals.

“Now we can do the same with nanomaterials and DNA, the blueprint of life,” Mirkin said. “Our method could lead to novel technologies and even enable new industries, much as the ability to grow silicon in perfect crystalline arrangements made possible the multibillion-dollar semiconductor industry.”

His research group developed the “recipe” for using nanomaterials as atoms, DNA as bonds and a little heat to form tiny crystals. This single-crystal recipe builds on superlattice techniques Mirkin’s lab has been developing for nearly two decades.

(I wrote about Mirkin’s nanoparticle DNA work in the context of his proposed periodic table of modified nucleic acid nanoparticles in a July 5, 2013 posting.) The news release goes on to describe Mirkin’s most recent work,

In this recent work, Mirkin, an experimentalist, teamed up with Monica Olvera de la Cruz, a theoretician, to evaluate the new technique and develop an understanding of it. Given a set of nanoparticles and a specific type of DNA, Olvera de la Cruz showed they can accurately predict the 3-D structure, or crystal shape, into which the disordered components will self-assemble.

The general set of instructions gives researchers unprecedented control over the type and shape of crystals they can build. The Northwestern team worked with gold nanoparticles, but the recipe can be applied to a variety of materials, with potential applications in the fields of materials science, photonics, electronics and catalysis.

A single crystal has order: its crystal lattice is continuous and unbroken throughout. The absence of defects in the material can give these crystals unique mechanical, optical and electrical properties, making them very desirable.

In the Northwestern study, strands of complementary DNA act as bonds between disordered gold nanoparticles, transforming them into an orderly crystal. The researchers determined that the ratio of the DNA linker’s length to the size of the nanoparticle is critical.

“If you get the right ratio it makes a perfect crystal — isn’t that fun?” said Olvera de la Cruz, who also is a professor of chemistry in the Weinberg College of Arts and Sciences. “That’s the fascinating thing, that you have to have the right ratio. We are learning so many rules for calculating things that other people cannot compute in atoms, in atomic crystals.”

The ratio affects the energy of the faces of the crystals, which determines the final crystal shape. Ratios that don’t follow the recipe lead to large fluctuations in energy and result in a sphere, not a faceted crystal, she explained. With the correct ratio, the energies fluctuate less and result in a crystal every time.

“Imagine having a million balls of two colors, some red, some blue, in a container, and you try shaking them until you get alternating red and blue balls,” Mirkin explained. “It will never happen.

“But if you attach DNA that is complementary to nanoparticles — the red has one kind of DNA, say, the blue its complement — and now you shake, or in our case, just stir in water, all the particles will find one another and link together,” he said. “They beautifully assemble into a three-dimensional crystal that we predicted computationally and realized experimentally.”

To achieve a self-assembling single crystal in the lab, the research team reports taking two sets of gold nanoparticles outfitted with complementary DNA linker strands. Working with approximately 1 million nanoparticles in water, they heated the solution to a temperature just above the DNA linkers’ melting point and then slowly cooled the solution to room temperature, which took two or three days.

The very slow cooling process encouraged the single-stranded DNA to find its complement, resulting in a high-quality single crystal approximately three microns wide. “The process gives the system enough time and energy for all the particles to arrange themselves and find the spots they should be in,” Mirkin said.

The researchers determined that the length of DNA connected to each gold nanoparticle can’t be much longer than the size of the nanoparticle. In the study, the gold nanoparticles varied from five to 20 nanometers in diameter; for each, the DNA length that led to crystal formation was about 18 base pairs and six single-base “sticky ends.”

“There’s no reason we can’t grow extraordinarily large single crystals in the future using modifications of our technique,” said Mirkin, who also is a professor of medicine, chemical and biological engineering, biomedical engineering and materials science and engineering and director of Northwestern’s International Institute for Nanotechnology.

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

DNA-mediated nanoparticle crystallization into Wulff polyhedra by Evelyn Auyeung, Ting I. N. G. Li, Andrew J. Senesi, Abrin L. Schmucker, Bridget C. Pals, Monica Olvera de la Cruz, & Chad A. Mirkin. Nature (2013) doi:10.1038/nature12739 Published online 27 November 2013

This article is behind a paywall.

Points to anyone who recognized the song title (Bewitched, Bothered and Bewildered) embedded in the head for this posting.

Controlling crystal growth for plastic electronics

A July 4, 2013 news item on Nanowerk highlights research into plastic electronics taking place at Imperial College London (ICL), Note: A link has been removed,

Scientists have discovered a way to better exploit a process that could revolutionise the way that electronic products are made.

The scientists from Imperial College London say improving the industrial process, which is called crystallisation, could revolutionise the way we produce electronic products, leading to advances across a whole range of fields; including reducing the cost and improving the design of plastic solar cells.

The process of making many well-known products from plastics involves controlling the way that microscopic crystals are formed within the material. By controlling the way that these crystals are grown engineers can determine the properties they want such as transparency and toughness. Controlling the growth of these crystals involves engineers adding small amounts of chemical additives to plastic formulations. This approach is used in making food boxes and other transparent plastic containers, but up until now it has not been used in the electronics industry.

The team from Imperial have now demonstrated that these additives can also be used to improve how an advanced type of flexible circuitry called plastic electronics is made.

The team found that when the additives were included in the formulation of plastic electronic circuitry they could be printed more reliably and over larger areas, which would reduce fabrication costs in the industry.

The team reported their findings this month in the journal Nature Materials (“Microstructure formation in molecular and polymer semiconductors assisted by nucleation agents”).

The June 7, 2013 Imperial College London news release by Joshua Howgego, which originated the news item, describes the researchers and the process in more detail,

Dr Natalie Stingelin, the leader of the study from the Department of Materials and Centre of Plastic Electronics at Imperial, says:

“Essentially, we have demonstrated a simple way to gain control over how crystals grow in electrically conducting ‘plastic’ semiconductors. Not only will this help industry fabricate plastic electronic devices like solar cells and sensors more efficiently. I believe it will also help scientists experimenting in other areas, such as protein crystallisation, an important part of the drug development process.”

Dr Stingelin and research associate Neil Treat looked at two additives, sold under the names IrgaclearÒ XT 386 and MilladÒ 3988, which are commonly used in industry. These chemicals are, for example, some of the ingredients used to improve the transparency of plastic drinking bottles. The researchers experimented with adding tiny amounts of these chemicals to the formulas of several different electrically conducting plastics, which are used in technologies such as security key cards, solar cells and displays.

The researchers found the additives gave them precise control over where crystals would form, meaning they could also control which parts of the printed material would conduct electricity. In addition, the crystallisations happened faster than normal. Usually plastic electronics are exposed to high temperatures to speed up the crystallisation process, but this can degrade the materials. This heat treatment treatment is no longer necessary if the additives are used.

Another industrially important advantage of using small amounts of the additives was that the crystallisation process happened more uniformly throughout the plastics, giving a consistent distribution of crystals.  The team say this could enable circuits in plastic electronics to be produced quickly and easily with roll-to-roll printing procedures similar to those used in the newspaper industry. This has been very challenging to achieve previously.

Dr Treat says: “Our work clearly shows that these additives are really good at controlling how materials crystallise. We have shown that printed electronics can be fabricated more reliably using this strategy. But what’s particularly exciting about all this is that the additives showed fantastic performance in many different types of conducting plastics. So I’m excited about the possibilities that this strategy could have in a wide range of materials.”

Dr Stingelin and Dr Treat collaborated with scientists from the University of California Santa Barbara (UCSB), and the National Renewable Energy Laboratory in Golden, US, and the Swiss Federal Institute of Technology on this study. The team are planning to continue working together to see if subtle chemical changes to the additives improve their effects – and design new additives.

There are some big plans for this discovery, from the news release,

They [the multinational team from ICL, UCSB, National Renewable Energy Laboratory, and Swiss Federal Institute of Technology]  will be working with the new Engineering and Physical Sciences Research Council (EPSRC)-funded Centre for Innovative Manufacturing in Large Area Electronics in order to drive the industrial exploitation of their process. The £5.6 million of funding for this centre, to be led by researchers from Cambridge University, was announced earlier this year [2013]. They are also exploring collaborations with printing companies with a view to further developing their circuit printing technique.

For the curious, here’s a link to and a citation for the published paper,

Microstructure formation in molecular and polymer semiconductors assisted by nucleation agents by Neil D. Treat, Jennifer A. Nekuda Malik, Obadiah Reid, Liyang Yu, Christopher G. Shuttle, Garry Rumbles, Craig J. Hawker, Michael L. Chabinyc, Paul Smith, & Natalie Stingelin. Nature Materials 12, 628–633 (2013) doi:10.1038/nmat3655 Published online 02 June 2013

This article is open access (at least for now).

Turning my world upside down: a new view on entropy

Entropy as a state of increasing disorder (or everything falls apart) is a concept introduced to me during a high school chemistry class. I think the teacher was having a bad day because the concept was couched in the most depressive terms possible. However, that may the reason a very strong impression was made, so news that entropy may lead to organization definitely piqued my interest. From the July 26, 2012 news item on Nanowerk (Note: I have removed a link),

Researchers trying to herd tiny particles into useful ordered formations have found an unlikely ally: entropy, a tendency generally described as “disorder.”

Computer simulations by University of Michigan scientists and engineers show that the property can nudge particles to form organized structures. By analyzing the shapes of the particles beforehand, they can even predict what kinds of structures will form.

The findings, published in this week’s edition of Science (“Predictive Self-Assembly of Polyhedra into Complex Structures”), help lay the ground rules for making designer materials with wild capabilities such as shape-shifting skins to camouflage a vehicle or optimize its aerodynamics.

More information can be found in the University of Michigan July 26, 2012 news release by Nicole Casal Moore,

One of the major challenges is persuading the nanoparticles to create the intended structures, but recent studies by Glotzer’s [professor Sharon Glotzer] group and others showed that some simple particle shapes do so spontaneously as the particles are crowded together. The team wondered if other particle shapes could do the same.

“We studied 145 different shapes, and that gave us more data than anyone has ever had on these types of potential crystal-formers,” Glotzer SAID. “With so much information, we could begin to see just how many structures are possible from particle shape alone, and look for trends.”

Using computer code written by chemical engineering research investigator Michael Engel, applied physics graduate student Pablo Damasceno ran thousands of virtual experiments, exploring how each shape behaved under different levels of crowding. The program could handle any polyhedral shape, such as dice with any number of sides.

Left to their own devices, drifting particles find the arrangements with the highest entropy. That arrangement matches the idea that entropy is a disorder if the particles have enough space: they disperse, pointed in random directions. But crowded tightly, the particles began forming crystal structures like atoms do—even though they couldn’t make bonds. These ordered crystals had to be the high-entropy arrangements, too.

However, this isn’t a simple reversal of the  entropy concept at the nanoscale (from the Moore news release),

Glotzer explains that this isn’t really disorder creating order—entropy needs its image updated. Instead, she describes it as a measure of possibilities. If you could turn off gravity and empty a bag full of dice into a jar, the floating dice would point every which way. However, if you keep adding dice, eventually space becomes so limited that the dice have more options to align face-to-face. The same thing happens to the nanoparticles, which are so small that they feel entropy’s influence more strongly than gravity’s.

“It’s all about options. In this case, ordered arrangements produce the most possibilities, the most options. It’s counterintuitive, to be sure,” Glotzer said.

The simulation results showed that nearly 70 percent of the shapes tested produced crystal-like structures under entropy alone. But the shocker was how complicated some of these structures were, with up to 52 particles involved in the pattern that repeated throughout the crystal.

Here’s an illustration the scientists have provided,

Shapes can arrange themselves into crystal structures through entropy alone, new research from the University of Michigan shows. Image credit: P. Damasceno, M. Engel, S. Glotzer

This excerpt includes a bit more about the crystals and two of the remaining mysteries (from the Moore news release),

The particle shapes produced three crystal types: regular crystals like salt, liquid crystals as found in some flat-screen TVs and plastic crystals in which particles can spin in place. By analyzing the shape of the particle and how groups of them behave before they crystallize, Damasceno said that it is possible to predict which type of crystal the particles would make.

“The geometry of the particles themselves holds the secret for their assembly behavior,” he said.

Why the other 30 percent never formed crystal structures, remaining as disordered glasses, is a mystery.

“These may still want to form crystals but got stuck. What’s neat is that for any particle that gets stuck, we had other, awfully similar shapes forming crystals,” Glotzer said.

In addition to finding out more about how to coax nanoparticles into structures, her team will also try to discover why some shapes resist order.