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Two-Dimensional Covalent Crystals by Chemical Conversion of Thin van der Waals Materials.

ABSTRACT: Most of the studied two-dimensional (2D) materials have been obtained by exfoliation of van der Waals crystals. Recently, there has been growing interest in fabricating synthetic 2D crystals which have no layered bulk analogues. These efforts have been focused mainly on the surface growth of molecules in high vacuum. Here, we report an approach to making 2D crystals of covalent solids by chemical conversion of van der Waals layers. As an example, we used 2D indium selenide (InSe) obtained by exfoliation and converted it by direct fluorination into indium fluoride (InF₃), which has a nonlayered, rhombohedral structure and therefore cannot possibly be obtained by exfoliation. The conversion of InSe into InF₃ is found to be feasible for thicknesses down to three layers of InSe, and the obtained stable InF₃ layers are doped with selenium. We study this new 2D material by optical, electron transport, and Raman measurements and show that it is a semiconductor with a direct bandgap of 2.2 eV, exhibiting high optical transparency across the visible and infrared spectral ranges. We also demonstrate the scalability of our approach by chemical conversion of large-area, thin InSe laminates obtained by liquid exfoliation, into InF₃ films. The concept of chemical conversion of cleavable thin van der Waals crystals into covalently bonded noncleavable ones opens exciting prospects for synthesizing a wide variety of novel atomically thin covalent crystals.

SUBMITTER: Sreepal V

PROVIDER: S-EPMC6814286 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature

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Two-Dimensional Covalent Crystals by Chemical Conversion of Thin van der Waals Materials.

Sreepal Vishnu V Yagmurcukardes Mehmet M Vasu Kalangi S KS Kelly Daniel J DJ Taylor Sarah F R SFR Kravets Vasyl G VG Kudrynskyi Zakhar Z Kovalyuk Zakhar D ZD Patanè Amalia A Grigorenko Alexander N AN Haigh Sarah J SJ Hardacre Christopher C Eaves Laurence L Sahin Hasan H Geim Andre K AK Peeters Francois M FM Nair Rahul R RR

Nano letters 20190826 9

Most of the studied two-dimensional (2D) materials have been obtained by exfoliation of van der Waals crystals. Recently, there has been growing interest in fabricating synthetic 2D crystals which have no layered bulk analogues. These efforts have been focused mainly on the surface growth of molecules in high vacuum. Here, we report an approach to making 2D crystals of covalent solids by chemical conversion of van der Waals layers. As an example, we used 2D indium selenide (InSe) obtained by exf ...[more]

PMID: 31426634

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Project description:Liquid-phase deposition of exfoliated 2D nanosheets is the basis for emerging technologies that include writable electronic inks, molecular barriers, selective membranes, and protective coatings against fouling or corrosion. These nanosheet thin films have complex internal structures that are discontinuous assemblies of irregularly tiled micron-scale sheets held together by van der Waals (vdW) forces. On stiff substrates, nanosheet vdW films are stable to many common stresses, but can fail by internal delamination under shear stress associated with handling or abrasion. This "re-exfoliation" pathway is an intrinsic feature of stacked vdW films and can limit nanosheet-based technologies. Here we investigate the shear stability of graphene oxide and MoSe2 nanosheet vdW films through lap shear experiments on polymer-nanosheet-polymer laminates. These sandwich laminate structures fail in mixed cohesive and interfacial mode with critical shear forces from 40 - 140 kPa and fracture energies ranging from 0.2 - 6 J/m2. Surprisingly these energies are higher than delamination energies reported for smooth peeling of ordered stacks of continuous 2D sheets, which we propose is due to energy dissipation and chaotic crack motion during nanosheet film disassembly at the crack tip. Experiment results also show that film thickness plays a key role in determining critical shear force (maximum load before failure) and dissipated energy for different nanosheet vdW films. Using a mechanical model with an edge crack in the thin nanosheet film, we propose a shear-to-tensile failure mode transition to explain a maximum in critical shear force for graphene oxide films but not MoSe2 films. This transition reflects a weakening of the substrate confinement effect and increasing rotational deformation near the film edge as the film thickness increases. For graphene oxide, the critical shear force can be increased by electrostatic cross-linking achieved through interlayer incorporation of metal cations. These results have important implications for the stability of functional devices that employ 2D nanosheet coatings.

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Two-Dimensional Covalent Crystals by Chemical Conversion of Thin van der Waals Materials.

Publications

Two-Dimensional Covalent Crystals by Chemical Conversion of Thin van der Waals Materials.

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