Tag Archives: europium

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).

Purple promises and bioimaging from Singapore’s A*STAR

A May 7, 2014 news item on Nanowerk describes a promising new approach to bioimaging,

Labeling biomolecules with light-emitting nanoparticles is a powerful technique for observing cell movement and signaling under realistic, in vivo conditions. The small size of these probes, however, often limits their optical capabilities. In particular, many nanoparticles have trouble producing high-energy light with wavelengths in the violet to ultraviolet range, which can trigger critical biological reactions.

Now, an international team led by Xiaogang Liu from the A*STAR Institute of Materials Research and Engineering and the National University of Singapore has discovered a novel class of rare-earth nanocrystals that preserve excited energy inside their atomic framework, resulting in unusually intense violet emissions …

A May 7, 2014 A*STAR (Agency for Science, Technology and Research) news release (h/t Imagist), which originated the news item, describes the problems with current bioimaging techniques and the new approach in more detail (Note: Links have been removed)

Nanocrystals selectively infused, or ‘doped’, with rare-earth ions have attracted the attention of researchers, because of their low toxicity and ability to convert low-energy laser light into violet-colored luminescence emissions — a process known as photon upconversion. Efforts to improve the intensity of these emissions have focused on ytterbium (Yb) rare-earth dopants, as they are easily excitable with standard lasers. Unfortunately, elevated amounts of Yb dopants can rapidly diminish, or ‘quench’, the generated light.

This quenching probably arises from the long-range migration of laser-excited energy states from Yb and toward defects in the nanocrystal. Most rare-earth nanocrystals have relatively uniform dopant distributions, but Liu and co-workers considered that a different crystal arrangement — clustering dopants into multi-atom arrays separated by large distances — could produce localized excited states that do not undergo migratory quenching.

The team screened numerous nanocrystals with different symmetries before discovering a material that met their criteria: a potassium fluoride crystal doped with Yb and europium rare earths (KYb2F7:Eu). Experiments revealed that the isolated Yb ‘energy clusters’ inside this pill-shaped nanocrystal (see image) enabled substantially higher dopant concentrations than usual — Yb accounted for up to 98 per cent of the crystal’s mass — and helped initiate multiphoton upconversion that yielded violet light with an intensity eight times higher than previously seen.

The researchers then explored the biological applications of their nanocrystals by using them to detect alkaline phosphatases, enzymes that frequently indicate bone and liver diseases. When the team brought the nanocrystals close to an alkaline phosphate-catalyzed reaction, they saw the violet emissions diminish in direct proportion to a chemical indicator produced by the enzyme. This approach enables swift and sensitive detection of this critical biomolecule at microscale concentration levels.

“We believe that the fundamental aspects of these findings — that crystal structures can greatly influence luminescence properties — could allow upconversion nanocrystals to eventually outperform conventional fluorescent biomarkers,” says Liu.

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

Enhancing multiphoton upconversion through energy clustering at sublattice level by Juan Wang, Renren Deng, Mark A. MacDonald, Bolei Chen, Jikang Yuan, Feng Wang, Dongzhi Chi, Tzi Sum Andy Hor, Peng Zhang, Guokui Liu, Yu Han, & Xiaogang Liu. Nature Materials 13, 157–162 (2014) doi:10.1038/nmat3804 Published online 24 November 2013

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