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2D Materials May Be Brittle

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By Ed Korczynski, Sr. Technical Editor

International researchers using a novel in situ quantitative tensile testing platform have tested the uniform in-plane loading of freestanding membranes of 2D materials inside a scanning electron microscope (SEM). Led by materials researchers at Rice University, the in situ tensile testing reveals the brittle fracture of large-area molybdenum diselenide (MoSe2) crystals and measures their fracture strength for the first time. Borophene monolayers with a wavy topography are more flexible.

A communication to Advanced Materials online (DOI: 10.1002/adma.201604201) titled “Brittle Fracture of 2D MoSe2” by Yinchao Yang et al. disclosed work by researchers from the USA and China led by Department of Materials Science and NanoEngineering Professor Jun Lou at Rice University, Houston, Texas. His team found that MoSe2 is more brittle than expected, and that flaws as small as one missing atom can initiate catastrophic cracking under strain.

“It turns out not all 2D crystals are equal. Graphene is a lot more robust compared with some of the others we’re dealing with right now, like this molybdenum diselenide,” says Lou. “We think it has something to do with defects inherent to these materials. It’s very hard to detect them. Even if a cluster of vacancies makes a bigger hole, it’s difficult to find using any technique.” The team has posted a short animation online showing crack propagation.

2D Materials in a 3D World -222

While all real physical things in our world are inherently built as three-dimensional (3D) structures, a single layer of flat atoms approximates a two-dimensional (2D) structure. Except for special superconducting crystals frozen below the Curie temperature, when electrons flow through 3D materials there are always collisions which increase resistance and heat. However, certain single layers of crystals have atoms aligned such that electron transport is essentially confined within the 2D plane, and those electrons may move “ballistically” without being slowed by collisions.

MoSe2 is a dichalcogenide, a 2D semiconducting material that appears as a graphene-like hexagonal array from above but is actually a sandwich of Mo atoms between two layers of Se chalcogen atoms. MoSe2 is being considered for use as transistors and in next-generation solar cells, photodetectors, and catalysts as well as electronic and optical devices.

The Figure shows the micron-scale sample holder inside a SEM, where natural van der Waals forces held the sample in place on springy cantilever arms that measured the applied stress. Lead-author Yang is a postdoctoral researcher at Rice who developed a new dry-transfer process to exfoliate MoSe2 from the surface upon which it had been grown by chemical vapor deposition (CVD).

Custom built micron-scale mechanical jig used to test mechanical properties of nano-scale materials. (Source: Lou Group/Rice University)

The team measured the elastic modulus—the amount of stretching a material can handle and still return to its initial state—of MoSe2 at 177.2 (plus or minus 9.3) gigapascals (GPa). Graphene is more than five times as elastic. The fracture strength—amount of stretching a material can handle before breaking—was measured at 4.8 (plus or minus 2.9) GPa. Graphene is nearly 25 times stronger.

“The important message of this work is the brittle nature of these materials,” Lou says. “A lot of people are thinking about using 2D crystals because they’re inherently thin. They’re thinking about flexible electronics because they are semiconductors and their theoretical elastic strength should be very high. According to our calculations, they can be stretched up to 10 percent. The samples we have tested so far broke at 2 to 3 percent (of the theoretical maximum) at most.”

Borophene

“Wavy” borophene might be better, according to finding of other Rice University scientists. The Rice lab of theoretical physicist Boris Yakobson and experimental collaborators observed examples of naturally undulating metallic borophene—an atom-thick layer of boron—and suggested that transferring it onto an elastic surface would preserve the material’s stretchability along with its useful electronic properties.

Highly conductive graphene has promise for flexible electronics, but it is too stiff for devices that must repeatably bend, stretch, compress, or even twist. The Rice researchers found that borophene deposited on a silver substrate develops nanoscale corrugations, and due to weak binding to the silver can be exfoliated for transfer to a flexible surface. The research appeared recently in the American Chemical Society journal Nano Letters.

Rice University has been one of the world’s leading locations for the exploration of 1D and 2D materials research, ever since it was lucky enough to get a visionary genius like Richard Smalley to show up in 1976, so we should expect excellent work from people in their department of Materials Science and NanoEngineering (CSNE). Still, this ground-breaking work is being done in labs using tools capable of handling micron-scale substrates, so even after a metaphorical “path” has been found it will take a lot of work to build up a manufacturing roadway capable of fabricating meter-scale substrates.

—E.K.



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