Tag Archives: Xiang Zhang

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.”

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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.

Shhhh! IBM practices nanoscience in its brand new quiet room

I am intrigued. It looks like IBM’s new nano research quiet room (which opened this Oct. 16, 2013) was announced some five years ago in 2008. Let’s start with the 2013 story, from the Oct. 18, 2013 article by Stephen Shankland for CNET,

…  IBM has just finished building new noise-free labs at its Binnig and Rohrer Nanotechnology Center. The labs, which IBM showed off Wednesday during a news media tour at its research facilities here, are designed to block out just about every kind of disturbance to IBM’s super-precise microscopes — vibrations, audio and radio noise, magnetic fields, and even turbulent air.

It doesn’t come cheap. The rooms cost about $50,000 per square foot to build, IBM researchers said in a paper published this August [2013] in the journal Nanoscale.

Duncan Graham-Rowe writing a June 27, 2008 article for MIT (Massachusetts Institute of Technology) Review described the plans for IBM’s nano quiet room and offered some responses to the idea,

This week, IBM announced plans to build the world’s largest “noise free” nanoelectronic fabrication facilities in Switzerland. By shielding equipment from external electromagnetic, thermal, and seismic noise, the new facilities should help advance research in a wide range of fields, such as spintronics, carbon-based devices, and nanophotonics, says IBM.

“What we’re trying to get to is something that is truly noise free, shielding against all these influences,” says Kaiserswerth [Matthias Kaiserswerth, director of the IBM Zurich Research Laboratory]. Eventually, Kaiserswerth says, these kinds of facilities will become for nanoelectronics what clean rooms are for conventional silicon electronics.

Henry Smith, codirector of MIT’s Nanostructures Laboratory, is not so sure. “There is no firm evidence that such facilities are needed,” he says. “Active isolation of vibration is a better solution and at much lower cost.”

But Xiang Zhang, director of the Nano-Scale Science and Engineering Center at the University of California, Berkeley, says that it’s precisely IBM’s willingness to take risks with its new facility that will create excitement in the nanotech community. “This is a good sign,” he says.

Getting back to Shankland’s article, here’s one of the room’s features he describes,

One device the specialized environment enables is a spin-polarized scanning electron microscope (spin-SEM), which can be used to study the precise orientation of electrons so researchers can deduce properties of magnetic materials. Another is a transmission electron microscope, which can pick out features measuring less than one 10 billionth of a meter — the width of a hydrogen atom — so scientists can understand things like the types of individual chemical bonds.

It’s been a busy year for this IBM center which received a William Tell medal from the Swiss government in March 2013 (as mentioned in my March 18, 2013 posting).

Space-time crystals and everlasting clocks

Apparently, a space-time crystal could be useful for such things as studying the many-body problem in physics.  Since I hadn’t realized the many-body problem existed and have no idea how this might affect me or anyone else, I will have to take the utility of a space-time crystal on trust.As for the possibility of an everlasting clock, how will I ever know the truth since I’m not everlasting?

The Sept. 24, 2012 news item on Nanowerk about a new development makes the space-time crystal sound quite fascinating,

Imagine a clock that will keep perfect time forever, even after the heat-death of the universe. This is the “wow” factor behind a device known as a “space-time crystal,” a four-dimensional crystal that has periodic structure in time as well as space. However, there are also practical and important scientific reasons for constructing a space-time crystal. With such a 4D crystal, scientists would have a new and more effective means by which to study how complex physical properties and behaviors emerge from the collective interactions of large numbers of individual particles, the so-called many-body problem of physics. A space-time crystal could also be used to study phenomena in the quantum world, such as entanglement, in which an action on one particle impacts another particle even if the two particles are separated by vast distances. [emphasis mine]

While I’m most interested in the possibility of studying entanglement, it seems to me the scientists are guessing since the verb ‘could’ is being used where they used ‘would’ previously for studying the many body problem.

The Sept. 24, 2012 news release by Lynn Yarris for the Lawrence Berkeley National Laboratory  (Berkeley Lab), which originated the news item, provides detail on the latest space-time crystal development,

A space-time crystal, however, has only existed as a concept in the minds of theoretical scientists with no serious idea as to how to actually build one – until now. An international team of scientists led by researchers with the U.S. Department of Energy (DOE)’s Lawrence Berkeley National Laboratory (Berkeley Lab) has proposed the experimental design of a space-time crystal based on an electric-field ion trap and the Coulomb repulsion of particles that carry the same electrical charge.

“The electric field of the ion trap holds charged particles in place and Coulomb repulsion causes them to spontaneously form a spatial ring crystal,” says Xiang Zhang, a faculty scientist  with Berkeley Lab’s Materials Sciences Division who led this research. “Under the application of a weak static magnetic field, this ring-shaped ion crystal will begin a rotation that will never stop. The persistent rotation of trapped ions produces temporal order, leading to the formation of a space-time crystal at the lowest quantum energy state.”

Because the space-time crystal is already at its lowest quantum energy state, its temporal order – or timekeeping – will theoretically persist even after the rest of our universe reaches entropy, thermodynamic equilibrium or “heat-death.”

This new development builds on some work done earlier this year at the Massachusetts Institute of Technology (MIT), from the Yarris news release,

The concept of a crystal that has discrete order in time was proposed earlier this year by Frank Wilczek, the Nobel-prize winning physicist at the Massachusetts Institute of Technology. While Wilczek mathematically proved that a time crystal can exist, how to physically realize such a time crystal was unclear. Zhang and his group, who have been working on issues with temporal order in a different system since September 2011, have come up with an experimental design to build a crystal that is discrete both in space and time – a space-time crystal.

Traditional crystals are 3D solid structures made up of atoms or molecules bonded together in an orderly and repeating pattern. Common examples are ice, salt and snowflakes. Crystallization takes place when heat is removed from a molecular system until it reaches its lower energy state. At a certain point of lower energy, continuous spatial symmetry breaks down and the crystal assumes discrete symmetry, meaning that instead of the structure being the same in all directions, it is the same in only a few directions.

“Great progress has been made over the last few decades in exploring the exciting physics of low-dimensional crystalline materials such as two-dimensional graphene, one-dimensional nanotubes, and zero-dimensional buckyballs,” says Tongcang Li, lead author of the PRL paper and a post-doc in Zhang’s research group. “The idea of creating a crystal with dimensions higher than that of conventional 3D crystals is an important conceptual breakthrough in physics and it is very exciting for us to be the first to devise a way to realize a space-time crystal.”

Just as a 3D crystal is configured at the lowest quantum energy state when continuous spatial symmetry is broken into discrete symmetry, so too is symmetry breaking expected to configure the temporal component of the space-time crystal. Under the scheme devised by Zhang and Li and their colleagues, a spatial ring of trapped ions in persistent rotation will periodically reproduce itself in time, forming a temporal analog of an ordinary spatial crystal. With a periodic structure in both space and time, the result is a space-time crystal.

Here’s an image created by team at the Berkeley Lab to represent their work on the space-time crystal,

Imagine a clock that will keep perfect time forever or a device that opens new dimensions into quantum phenomena such as emergence and entanglement. (courtesy of Xiang Zhang group[?] at Berkeley Lab)

For anyone who’s interested in this work, I suggest reading either the news item on Nanowerk or the Berkeley Lab news release in full. I will leave you with Natalie Cole and Everlasting Love,

Flipping chirality at the Lawrence Berkeley National Laboratory

First, it might be a good idea to define chirality. From the Lawrence Berkeley National Laboratory (Berkeley Lab) July 10, 2012 news release by LynnYarris,

Chirality is the distinct left/right orientation or “handedness” of some types of molecules, meaning the molecule can take one of two mirror image forms. The right-handed and left-handed forms of such molecules, called “enantiomers,” can exhibit strikingly different properties. For example, one enantiomer of the chiral molecule limonene smells of lemon, the other smells of orange. The ability to observe or even switch the chirality of molecules using terahertz (trillion-cycles-per-second) electromagnetic radiation is a much coveted asset in the world of high technology.

As for why anyone would want  to flip molecules back and forth between left- and right-handedness (from the news release),

A multi-institutional team of researchers that included scientists with the U.S. Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab) has created the first artificial molecules whose chirality can be rapidly switched from a right-handed to a left-handed orientation with a  beam of light. This holds potentially important possibilities for the application of terahertz technologies across a wide range of fields, including reduced energy use for data-processing, homeland security and ultrahigh-speed communications.

Here’s how the technique works, from the July 10, 2012 news item on physorg.com,

Working with terahertz (THz) metamaterials engineered from nanometer-sized gold strips with air as the dielectric – Zhang [Xiang Zhang, one of the leaders of this research and a principal investigator with Berkeley Lab’s Materials Sciences Division] and his colleagues fashioned a delicate artificial chiral molecule which they then incorporated with a photoactive silicon medium. Through photoexcitation of their metamolecules with an external beam of light, the researchers observed handedness flipping in the form of circularly polarized emitted THz light. Furthermore, the photoexcitation enabled this chirality flipping and the circular polarization of THz light to be dynamically controlled.

“In contrast to previous demonstrations where chirality was merely switched on or off in metamaterials using photoelectric stimulation, we used an optical switch to actually reverse the chirality of our THz metamolecules,” Zhang says.

The researchers describe in more detail the potential for this new technique,

“The observed giant switchable chirality we can engineer into our metamaterials provides a viable approach towards creating high performance polarimetric devices that are largely not available at terahertz frequencies,” says corresponding author Antoinette Taylor. “This frequency range is particularly interesting because it uniquely reveals information about physical phenomena such as the interactions between or within biologically relevant molecules, and may enable control of electronic states in novel material systems, such as cyclotron resonances in graphene and topological insulators.”

Taylor and her co-authors say that the general design principle of their optically switchable chiral THz metamolecules is not limited to handedness switching but could also be applied to the dynamic reversing of other electromagnetic properties.

From what I understand metamaterials are very expensive and difficult to produce which means this exciting advance is likely to remain in the laboratory of at least 10 years.