Brookhaven Lab scientists Percy Zahl (left), Ivan Bozovic (center) and Ilya Drozdov (right) at the Center for Functional Nanomaterials. They are using a custom-built scanning tunneling microscope to image the surface structure of 2D atom-thin sheets of boron on copper. Image: Brookhaven National Laboratory.
Brookhaven Lab scientists Percy Zahl (left), Ivan Bozovic (center) and Ilya Drozdov (right) at the Center for Functional Nanomaterials. They are using a custom-built scanning tunneling microscope to image the surface structure of 2D atom-thin sheets of boron on copper. Image: Brookhaven National Laboratory.

Borophene – two-dimensional (2D) atom-thin-sheets of boron, a chemical element traditionally found in fiberglass insulation – is anything but boring. Though boron is a non-metallic semiconductor in its bulk, three-dimensional (3D) form, it becomes a metallic conductor in 2D. Borophene is also extremely flexible, strong and lightweight – even more so than its carbon-based analogue, graphene. These unique electronic and mechanical properties make borophene a promising material platform for next-generation electronic devices such as wearables, biomolecule sensors, light detectors and quantum computers.

Now, physicists from the US Department of Energy's (DOE) Brookhaven National Laboratory and Yale University have managed to synthesize borophene with large-area single-crystal domains (ranging in size from 10µm to 100µm) on copper substrates. Previously, only nanometer-size single-crystal flakes of borophene had been produced. This advance, reported in a paper in Nature Nanotechnology, represents an important step in making practical borophene-based devices possible.

For electronic applications, high-quality single crystals – periodic arrangements of atoms that continue throughout the entire crystal lattice without boundaries or defects – must be distributed over large areas of the surface material (substrate) on which they are grown. For example, today's microchips use single crystals of silicon and other semiconductors. Device fabrication also requires an understanding of how different substrates and growth conditions impact a material's crystal structure, which determines its properties.

"We increased the size of the single-crystal domains by a factor of a million," said co-author and project lead Ivan Bozovic, senior scientist and Molecular Beam Epitaxy group leader in Brookhaven Lab's Condensed Matter Physics and Materials Science (CMPMS) department and adjunct professor of applied physics at Yale University. "Large domains are required to fabricate next-generation electronic devices with high electron mobility. Electrons that can easily and quickly move through a crystal structure are key to improving device performance."

Since the 2004 discovery of graphene – a single sheet of carbon atoms that can be peeled from graphite, the core component of pencils, with Scotch tape – scientists have been on the hunt for other 2D materials with remarkable properties. The chemical bonds between carbon atoms that impart graphene with its strength make manipulating its structure difficult.

Theorists predicted that boron (next to carbon on the Periodic Table, with one less electron) deposited on an appropriately chosen substrate could form a 2D material similar to graphene. But this prediction was not experimentally confirmed until three years ago, when scientists synthesized borophene for the very first time. They deposited boron onto a silver substrate under ultrahigh-vacuum conditions using molecular beam epitaxy (MBE), a precisely controlled, atomic, layer-by-layer crystal growth technique. Soon thereafter, another group of scientists grew borophene on silver, but they proposed an entirely different crystal structure.

"Borophene is structurally similar to graphene, with a hexagonal network made of boron (instead of carbon) atoms on each of the six vertices defining the hexagon," explained Bozovic. "However, borophene is different in that it periodically has an extra boron atom in the center of the hexagon. The crystal structure tends to be theoretically stable when about four out of every five center positions are occupied and one is vacant."

According to theory, while the number of vacancies is fixed, their arrangement is not. As long as the vacancies are distributed in a way that maintains the most stable (lowest energy) structure, they can be rearranged. Because of this flexibility, borophene can have multiple configurations.

In this study, the scientists first investigated the real-time growth of borophene on silver surfaces at various temperatures. They grew the samples at Yale in an ultra-high vacuum low-energy electron microscope (LEEM) equipped with an MBE system. During and after the growth process, they bombarded the sample with a beam of electrons at low energy and analyzed the low-energy electron diffraction (LEED) patterns produced as electrons were reflected from the crystal surface and projected onto a detector.

Because the electrons have low energy, they can only reach the first few atomic layers of the material. The distance between the reflected electrons (‘spots’ in the diffraction patterns) is related to the distance between atoms on the surface, and, from this information, scientists can reconstruct the crystal structure.

In this case, the patterns revealed that the single-crystal borophene domains were only tens of nanometers in size – too small for fabricating devices and studying fundamental physical properties – for all growth conditions. They also resolved the controversy about borophene's structure: both structures exist, but they form at different temperatures. The scientists confirmed their LEEM and LEED results with atomic force microscopy (AFM). In AFM, a sharp tip is scanned over a surface, and the measured force between the tip and atoms on the surface is used to map the atomic arrangement.

To promote the formation of larger crystals, the scientists then switched the substrate from silver to copper, applying the same LEEM, LEED and AFM techniques. Brookhaven scientists Percy Zahl and Ilya Drozdov also imaged the surface structure at high resolution using a custom-built scanning tunneling microscope (STM) with a carbon monoxide probe tip at Brookhaven's Center for Functional Nanomaterials (CFN).

Yale theorists Stephen Eltinge and Sohrab Ismail-Beigi performed calculations to determine the stability of the experimentally obtained structures. After identifying which structures were most stable, they simulated the electron diffraction spectra and STM images and compared them to the experimental data. This iterative process continued until theory and experiment were in agreement.

"From theoretical insights, we expected copper to produce larger single crystals because it interacts more strongly with borophene than silver," said Bozovic. "Copper donates some electrons to stabilize borophene, but the materials do not interact too much as to form a compound. Not only are the single crystals larger, but the structures of borophene on copper are different from any of those grown on silver."

Because there are several possible distributions of vacancies on the surface, various crystal structures of borophene can emerge. This study also showed how the structure of borophene can be modified by changing the substrate and, in some cases, the temperature or deposition rate.

The next step is to transfer the borophene sheets from the metallic copper surfaces to insulating, device-compatible substrates. Then scientists will be able to accurately measure resistivity and other electrical properties important to device functionality.

Bozovic is particularly excited to test whether borophene can be made superconducting. Some theorists have speculated that borophene’s unusual electronic structure may open a path to lossless transmission of electricity at room temperature, as opposed to the ultracold temperatures usually required for superconductivity. Ultimately, the goal in 2D materials research is to be able to fine-tune the properties of these materials to suit particular applications.

This story is adapted from material from Brookhaven National Laboratory, with editorial changes made by Materials Today. The views expressed in this article do not necessarily represent those of Elsevier. Link to original source.