Tag Archives: Pavel Sorokin

Deriving graphene-like films from salt

This research comes from Russia (mostly). A July 29, 2016 news item on ScienceDaily describes a graphene-like structure derived from salt,

Researchers from Moscow Institute of Physics and Technology (MIPT), Skolkovo Institute of Science and Technology (Skoltech), the Technological Institute for Superhard and Novel Carbon Materials (TISNCM), the National University of Science and Technology MISiS (Russia), and Rice University (USA) used computer simulations to find how thin a slab of salt has to be in order for it to break up into graphene-like layers. Based on the computer simulation, they derived the equation for the number of layers in a crystal that will produce ultrathin films with applications in nanoelectronics. …

Caption: Transition from a cubic arrangement into several hexagonal layers. Credit: authors of the study

Caption: Transition from a cubic arrangement into several hexagonal layers. Credit: authors of the study

A July 29, 2016 Moscow Institute of Physics and Technology press release on EurekAlert, which originated the news item,  provides more technical detail,

From 3D to 2D

Unique monoatomic thickness of graphene makes it an attractive and useful material. Its crystal lattice resembles a honeycombs, as the bonds between the constituent atoms form regular hexagons. Graphene is a single layer of a three-dimensional graphite crystal and its properties (as well as properties of any 2D crystal) are radically different from its 3D counterpart. Since the discovery of graphene, a large amount of research has been directed at new two-dimensional materials with intriguing properties. Ultrathin films have unusual properties that might be useful for applications such as nano- and microelectronics.

Previous theoretical studies suggested that films with a cubic structure and ionic bonding could spontaneously convert to a layered hexagonal graphitic structure in what is known as graphitisation. For some substances, this conversion has been experimentally observed. It was predicted that rock salt NaCl can be one of the compounds with graphitisation tendencies. Graphitisation of cubic compounds could produce new and promising structures for applications in nanoelectronics. However, no theory has been developed that would account for this process in the case of an arbitrary cubic compound and make predictions about its conversion into graphene-like salt layers.

For graphitisation to occur, the crystal layers need to be reduced along the main diagonal of the cubic structure. This will result in one crystal surface being made of sodium ions Na? and the other of chloride ions Cl?. It is important to note that positive and negative ions (i.e. Na? and Cl?)–and not neutral atoms–occupy the lattice points of the structure. This generates charges of opposite signs on the two surfaces. As long as the surfaces are remote from each other, all charges cancel out, and the salt slab shows a preference for a cubic structure. However, if the film is made sufficiently thin, this gives rise to a large dipole moment due to the opposite charges of the two crystal surfaces. The structure seeks to get rid of the dipole moment, which increases the energy of the system. To make the surfaces charge-neutral, the crystal undergoes a rearrangement of atoms.

Experiment vs model

To study how graphitisation tendencies vary depending on the compound, the researchers examined 16 binary compounds with the general formula AB, where A stands for one of the four alkali metals lithium Li, sodium Na, potassium K, and rubidium Rb. These are highly reactive elements found in Group 1 of the periodic table. The B in the formula stands for any of the four halogens fluorine F, chlorine Cl, bromine Br, and iodine I. These elements are in Group 17 of the periodic table and readily react with alkali metals.

All compounds in this study come in a number of different structures, also known as crystal lattices or phases. If atmospheric pressure is increased to 300,000 times its normal value, an another phase (B2) of NaCl (represented by the yellow portion of the diagram) becomes more stable, effecting a change in the crystal lattice. To test their choice of methods and parameters, the researchers simulated two crystal lattices and calculated the pressure that corresponds to the phase transition between them. Their predictions agree with experimental data.

Just how thin should it be?

The compounds within the scope of this study can all have a hexagonal, “graphitic”, G phase (the red in the diagram) that is unstable in 3D bulk but becomes the most stable structure for ultrathin (2D or quasi-2D) films. The researchers identified the relationship between the surface energy of a film and the number of layers in it for both cubic and hexagonal structures. They graphed this relationship by plotting two lines with different slopes for each of the compounds studied. Each pair of lines associated with one compound has a common point that corresponds to the critical slab thickness that makes conversion from a cubic to a hexagonal structure energetically favourable. For example, the critical number of layers was found to be close to 11 for all sodium salts and between 19 and 27 for lithium salts.

Based on this data, the researchers established a relationship between the critical number of layers and two parameters that determine the strength of the ionic bonds in various compounds. The first parameter indicates the size of an ion of a given metal–its ionic radius. The second parameter is called electronegativity and is a measure of the ? atom’s ability to attract the electrons of element B. Higher electronegativity means more powerful attraction of electrons by the atom, a more pronounced ionic nature of the bond, a larger surface dipole, and a lower critical slab thickness.

And there’s more

Pavel Sorokin, Dr. habil., [sic] is head of the Laboratory of New Materials Simulation at TISNCM. He explains the importance of the study, ‘This work has already attracted our colleagues from Israel and Japan. If they confirm our findings experimentally, this phenomenon [of graphitisation] will provide a viable route to the synthesis of ultrathin films with potential applications in nanoelectronics.’

The scientists intend to broaden the scope of their studies by examining other compounds. They believe that ultrathin films of different composition might also undergo spontaneous graphitisation, yielding new layered structures with properties that are even more intriguing.

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

Ionic Graphitization of Ultrathin Films of Ionic Compounds by A. G. Kvashnin, E. Y. Pashkin, B. I. Yakobson, and P. B. Sorokin. J. Phys. Chem. Lett., 2016, 7 (14), pp 2659–2663 DOI: 10.1021/acs.jpclett.6b01214 Publication Date (Web): June 23, 2016

Copyright © 2016 American Chemical Society

This paper is behind a paywall.

Diamane—a no pressure road map

Russian and US researchers have produced a road map for creating ‘diamane’, according to a Feb. 3, 2014  Rice University (Texas) news release (available on EurekAlert and also as a Feb. 4, 2014 news item on Azonano),

Perfect sheets of diamond a few atoms thick appear to be possible even without the big squeeze that makes natural gems.

Scientists have speculated about it and a few labs have even seen signs of what they call diamane, an extremely thin film of diamond that has all of diamond’s superior semiconducting and thermal properties.

Now researchers at Rice University and in Russia have calculated a “phase diagram” for the creation of diamane. The diagram is a road map. It lays out the conditions – temperature, pressure and other factors – that would be necessary to turn stacked sheets of graphene into a flawless diamond lattice.

In the process, the researchers determined diamane could be made completely chemically, with no pressure at all, under some circumstances.

The news release provides more into the researchers’ theories and road map,

“Diamanes have a wide potential range of application,” Sorokin [Pavel Sorokin, a former postdoctoral associate at Rice and now a senior researcher at the Technological Institute for Superhard and Novel Carbon Materials in Moscow] said. “They can be applied as very thin, dielectric hard films in nanocapacitors or mechanically stiff, nanothick elements in nanoelectronics. Also, diamanes have potential for application in nano-optics.

“The possibility of obtaining such a quasi-two-dimensional object is intriguing, but available experimental data prevents the expectation of its fabrication using traditional methods. However, the ‘bottom-up’ approach proposed by Richard Feynman allows the fabrication of diamanes from smaller objects, such as graphene.”

The researchers built computer models to simulate the forces applied by every atom involved in the process. That includes the graphene, the single-atom-thick form of carbon and one of the strongest substances in the universe, as well as the hydrogen (or, alternately, a halogen) that promotes the reaction.

Conditions, they learned, need to be just right for a short stack of graphene pancakes to collapse into a diamond matrix – or vice versa – via chemistry.

“A phase diagram shows you which phase dominates the ground state for each pressure and temperature,” Yakobson [Rice theoretical physicist Boris Yakobson] said. “In the case of diamane, the diagram is unusual because the result also depends on thickness, the number of layers of graphene. So we have a new parameter.”

Hydrogen isn’t the only possible catalyst, he said, but it’s the one they used in their calculations. “When the hydrogen attacks, it takes one electron from a carbon atom in graphene. As a result, a bond is broken and another electron is left hanging on the other side of the graphene layer. It’s now free to connect to a carbon atom on the adjacent sheet with little or no pressure.

“If you have several layers, you get a domino effect, where hydrogen starts a reaction on top and it propagates through the bonded carbon system,” he said. “Once it zips all the way through, the phase transition is complete and the crystal structure is that of diamond.”

Yakobson said the paper doesn’t cover a possible deal-breaker. “The conversion from one phase to another starts from a small seed, a nucleation site, and in this process there’s always what is called a nucleation barrier. We don’t calculate that here.” He said carbon normally prefers to be graphite (the bulk form of carbon used as pencil lead) rather than diamond, but a high nucleation barrier prevents diamond from making the transition.

“Thermodynamically, an existing diamond should become graphite, but it doesn’t happen for exactly this reason,” Yakobson said. “So sometimes it’s a good thing. But if we want to make flat diamond, we need to find ways to circumvent this barrier.”

He said the manufacture of synthetic diamond, which was first reliably made in the 1950s, requires very high pressures of about 725,000 pounds per square inch. Manufactured diamonds are used in hardened tools for cutting, as abrasives and even as high-quality gemstones grown via techniques that simulate the temperatures and pressures found deep in Earth, where natural diamond is forged.

Diamond films are also routinely made via chemical vapor deposition, “but they’re always very poor quality because they’re polycrystalline,” Yakobson said. “For mechanical purposes, like very expensive sandpaper, they’re perfect. But for electronics, you would need high quality for it to serve as a wide-band gap semiconductor.”

This image illustrates the conditions necessary to create diamane,

The phase diagram developed by scientists at Rice University and in Moscow describes the conditions necessary for the chemical creation of thin films of diamond from stacks of single-atomic-layer graphene. (Credit: Pavel Sorokin/Technological Institute for Superhard and Novel Carbon Materials)

The phase diagram developed by scientists at Rice University and in Moscow describes the conditions necessary for the chemical creation of thin films of diamond from stacks of single-atomic-layer graphene. (Credit: Pavel Sorokin/Technological Institute for Superhard and Novel Carbon Materials)

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

Phase Diagram of Quasi-Two-Dimensional Carbon, From Graphene to Diamond by Alexander G. Kvashnin, Leonid A. Chernozatonskii, Boris I. Yakobson, and Pavel B. Sorokin. Nano Lett., Article ASAP DOI: 10.1021/nl403938g Publication Date (Web): January 17, 2014
Copyright © 2014 American Chemical Society

This paper is behind a paywall.