Tag Archives: Daniel Shechtman

A method for producing two-dimensional quasicrystals from metal organic networks

A July 13, 2016 news item on ScienceDaily highlights an advance where quasicrystals are concerned,

Unlike classical crystals, quasicrystals do not comprise periodic units, even though they do have a superordinate structure. The formation of the fascinating mosaics that they produce is barely understood. In the context of an international collaborative effort, researchers at the Technical University of Munich (TUM) have now presented a methodology that allows the production of two-dimensional quasicrystals from metal-organic networks, opening the door to the development of promising new materials.

A July 13, 2016 TUM press release (also on EurekAlert), which originated the news item, explains further,

Physicist Daniel Shechtman [emphasis mine] merely put down three question marks in his laboratory journal, when he saw the results of his latest experiment one day in 1982. He was looking at a crystalline pattern that was considered impossible at the time. According to the canonical tenet of the day, crystals always had so-called translational symmetry. They comprise a single basic unit, the so-called elemental cell, that is repeated in the exact same form in all spatial directions.

Although Shechtman’s pattern did contain global symmetry, the individual building blocks could not be mapped onto each other merely by translation. The first quasicrystal had been discovered. In spite of partially stark criticism by reputable colleagues, Shechtman stood fast by his new concept and thus revolutionized the scientific understanding of crystals and solid bodies. In 2011 he ultimately received the Nobel Prize in Chemistry. To this day, both the basic conditions and mechanisms by which these fascinating structures are formed remain largely shrouded in mystery.

A toolbox for quasicrystals

Now a group of scientists led by Wilhelm Auwärter and Johannes Barth, both professors in the Department of Surface Physics at TU Munich, in collaboration with Hong Kong University of Science and Technology (HKUST, Prof. Nian Lin, et al) and the Spanish research institute IMDEA Nanoscience (Dr. David Écija), have developed a new basis for producing two-dimensional quasicrystals, which might bring them a good deal closer to understanding these peculiar patterns.

The TUM doctoral candidate José Ignacio Urgel made the pioneering measurements in the course of a research fellowship at HKUST. “We now have a new set of building blocks that we can use to assemble many different new quasicrystalline structures. This diversity allows us to investigate on how quasicrystals are formed,” explain the TUM physicists.

The researchers were successful in linking europium – a metal atom in the lanthanide series – with organic compounds, thereby constructing a two-dimensional quasicrystal that even has the potential to be extended into a three-dimensional quasicrystal. To date, scientists have managed to produce many periodic and in part highly complex structures from metal-organic networks, but never a quasicrystal.

The researchers were also able to thoroughly elucidate the new network geometry in unparalleled resolution using a scanning tunnelling microscope. They found a mosaic of four different basic elements comprising triangles and rectangles distributed irregularly on a substrate. Some of these basic elements assembled themselves to regular dodecagons that, however, cannot be mapped onto each other through parallel translation. The result is a complex pattern, a small work of art at the atomic level with dodecagonal symmetry.

Interesting optical and magnetic properties

In their future work, the researchers are planning to vary the interactions between the metal centers and the attached compounds using computer simulation and experiments in order to understand the conditions under which two-dimensional quasicrystals form. This insight could facilitate the future development of new tailored quasicrystalline layers.

These kinds of materials hold great promise. After all, the new metal-organic quasicrystalline networks may have properties that make them interesting in a wide variety of application. “We have discovered a new playing field on which we can not only investigate quasicrystallinity, but also create new functionalities, especially in the fields of optics and magnetism,” says Dr. David Écija of IMDEA Nanoscience.

For one, scientists could one day use the new methodology to create quasicrystalline coatings that influence photons in such a manner that they are transmitted better or that only certain wavelengths can pass through the material.

In addition, the interactions of the lanthanide building blocks in the new quasicrystals could facilitate the development of magnetic systems with very special properties, so-called “frustrated systems”. Here, the individual atoms in a crystalline grid interfere with each other in a manner that prevents grid points from achieving a minimal energy state. The result: exotic magnetic ground states that can be investigated as information stores for future quantum computers.

The researchers have made an image available,

The quasicrystalline network built up with europium atoms linked with para-quaterphenyl–dicarbonitrile on a gold surface (yellow) - Image: Carlos A. Palma / TUM

The quasicrystalline network built up with europium atoms linked with para-quaterphenyl–dicarbonitrile on a gold surface (yellow) – Image: Carlos A. Palma / TUM

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

Quasicrystallinity expressed in two-dimensional coordination networks by José I. Urgel, David Écija, Guoqing Lyu, Ran Zhang, Carlos-Andres Palma, Willi Auwärter, Nian Lin, & Johannes V. Barth. Nature Chemistry 8, 657–662 (2016) doi:10.1038/nchem.2507 Published online 16 May 2016

This paper is behind a paywall.

For anyone interested in more about the Daniel Schechter story and how he was reviled for his discovery of quasicrystals, there’s more in my Dec. 24, 2013 posting (scroll down about 60% of the way).

Single-element quasicrystal created in laboratory for the first time

There’s a background story which gives this breakthrough a fabulous aspect but, first, here’s the research breakthrough from a Dec. 24, 2013 news item on Nanowerk (Note: A link has been removed),

A research group led by Assistant Professor Kazuki Nozawa and Professor Yasushi Ishii from the Department of Physics, Faculty of Science and Engineering, Chuo University, Chief Researcher Masahiko Shimoda from the National Institute for Materials Science (NIMS) and Professor An-Pang Tsai from the Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, succeeded for the first time in the world in fabricating a three-dimensional structure of a quasicrystal composed of a single element, through joint research with a group led by Dr. Hem Raj Sharma from the University of Liverpool, the United Kingdom.

The Dec. 2, 2013 National Institute for Materials Science (NIMS; Japan) press release, which originated the news item, describes quasicrystals and the reasons why this particular achievement is such a breakthrough,

Quasicrystals are substances discovered in 1984 by Dr. Dan Shechtman (who was awarded the Nobel Prize in Chemistry in 2011). [emphasis mine] To date, quasicrystals have been found in more than one hundred kinds of alloy, polymer and nanoparticle systems. However, a quasicrystal composed of a single element has not been found yet. Quasicrystals have a beautiful crystalline structure which is closely related to the golden ratio, called a quasiperiodic structure. This structure is made of a pentagonal or decagonal atomic arrangement that is not found in ordinary periodic crystals (see the reference illustrations). Due to the complexity of the crystalline structure and chemical composition, much about quasicrystals is still veiled in mystery, including the mechanism for stabilizing a quasiperiodic structure and the novel properties of this unique type of crystalline structure. For these reasons, efforts have been made for a long time in the quest for a chemically simple type of quasicrystal composed only of a single element. The joint research group has recently succeeded in growing a crystal of lead with a quasiperiodic structure which is modeled on the structure of a substrate quasicrystal, by vapor-depositing lead atoms on the quasicrystal substrate of an existing alloy made of silver (Ag), indium (In) and ytterbium (Yb). Success using this approach had been reported for fabricating a single-element quasiperiodic film consisting of a single atomic layer (two-dimensional structure), but there had been no successful case of fabricating a single-element quasiperiodic structure consisting of multiple atomic layers (three-dimensional structure). This recent success by the joint research group is a significant step forward toward achieving single-element quasicrystals. It is also expected to lead to advancement in various fields, such as finding properties unique to quasiperiodic structures that cannot be found in periodic crystals and elucidating the mechanism of stabilization of quasiperiodic structures.

Here’s an image illustrating the researchers’ achievement,

Illustrations of the deposition structure of lead. The Tsai cluster in the substrate quasicrystal which is near the surface of the substrate is cut at the point where it contacts the surface. While lead usually has a face-centered cubic structure, it is deposited on the quasicrystal substrate in a manner that it recovers Tsai clusters which are cut near the surface of the substrate. This indicates that a crystal of lead is grown with the same structure as the structure of the quasicrystal substrate. (Courtesy National Institute for Materials Science, Japan)

Illustrations of the deposition structure of lead. The Tsai cluster in the substrate quasicrystal which is near the surface of the substrate is cut at the point where it contacts the surface. While lead usually has a face-centered cubic structure, it is deposited on the quasicrystal substrate in a manner that it recovers Tsai clusters which are cut near the surface of the substrate. This indicates that a crystal of lead is grown with the same structure as the structure of the quasicrystal substrate. (Courtesy National Institute for Materials Science, Japan)

I suggested earlier that this achievement has a fabulous quality and the Daniel Schechtman backstory is the reason. The winner of the 2011 Nobel Prize for Chemistry, Schechtman was reviled for years within his scientific community as Ian Sample notes in his Oct. 5, 2011 article on the announcement of Schechtman’s Nobel win written for the Guardian newspaper (Note: A link has been removed),

A scientist whose work was so controversial he was ridiculed and asked to leave his research group has won the Nobel Prize in Chemistry.

Daniel Shechtman, 70, a researcher at Technion-Israel Institute of Technology in Haifa, received the award for discovering seemingly impossible crystal structures in frozen gobbets of metal that resembled the beautiful patterns seen in Islamic mosaics.

Images of the metals showed their atoms were arranged in a way that broke well-establised rules of how crystals formed, a finding that fundamentally altered how chemists view solid matter.

On the morning of 8 April 1982, Shechtman saw something quite different while gazing at electron microscope images of a rapidly cooled metal alloy. The atoms were packed in a pattern that could not be repeated. Shechtman said to himself in Hebrew, “Eyn chaya kazo,” which means “There can be no such creature.”

The bizarre structures are now known as “quasicrystals” and have been seen in a wide variety of materials. Their uneven structure means they do not have obvious cleavage planes, making them particularly hard.

In an interview this year with the Israeli newspaper, Haaretz, Shechtman said: “People just laughed at me.” He recalled how Linus Pauling, a colossus of science and a double Nobel laureate, mounted a frightening “crusade” against him. After telling Shechtman to go back and read a crystallography textbook, the head of his research group asked him to leave for “bringing disgrace” on the team. “I felt rejected,” Shachtman said.

It takes a lot to persevere when most, if not all, of your colleagues are mocking and rejecting your work so bravo to Schechtman! And,bravo to the Japan-UK project researchers who have persevered to help solve at least part of a complex problem requiring that our basic notions of matter be rethought.

I encourage you to read Sample’s article in its entirety as it is well written and I’ve excerpted only bits of the story as it relates to a point I’m making in this post, i.e., perseverance in the face of extreme resistance.