Microwave-Driven Exfoliation of Bulk 2H-MoS₂ after Acetonitrile Prewetting Produces Large-Area Ultrathin Flakes with Exceptionally High Yield

2D materials display exciting properties in numerous fields, but the development of applications is hindered by the low yields, high processing times, and impaired quality of current exfoliation methods. In this work we have used the excellent MW absorption properties of MoS2 to induce a fast heating that produces the near-instantaneous evaporation of an adsorbed, low boiling point solvent. The sudden evaporation creates an internal pressure that separates the MoS2 layers with high efficiency, and these are kept separated by the action of the dispersion solvent. Our fast method (90 s) gives high yields (47% at 0.2 mg/mL, 35% at 1 mg/mL) of highly exfoliated material (90% under 4 layers), large area (up to several μm2), and excellent quality (no significant MoO3 detected)

Fabrication of devices featuring covalently linked MoS2–graphene heterostructures

The most widespread method for the synthesis of 2D–2D heterostructures is the direct growth of one material on top of the other. Alternatively, flakes of different materials can be manually stacked on top of each other. Both methods typically involve stacking 2D layers through van der Waals forces—such that these materials are often referred to as van der Waals heterostructures—and are stacked one crystal or one device at a time. Here we describe the covalent grafting of 2H-MoS2 flakes onto graphene monolayers embedded in field-effect transistors. A bifunctional molecule featuring a maleimide and a diazonium functional group was used, known to connect to sulfide- and carbon-based materials, respectively. MoS2 flakes were exfoliated, functionalized by reaction with the maleimide moieties and then anchored to graphene by the diazonium groups. This approach enabled the simultaneous functionalization of several devices. The electronic properties of the resulting heterostructure are shown to be dominated by the MoS2–graphene interface.The authors acknowledge European Research Council (ERC-PoC- 842606 (E.M.P.); ERC-AdG-742684 (J. S.) and the MSCA program MSCA-IF-2019-892667 (N.M.S.), MINECO (CTQ2017-86060-P (E.M.P.) and CTQ2016-79419-R), Ministerio de Ciencia e Innovación (RTI2018-096075-A-C22 (E.B.), RYC2019-028429-I (E.B.)) the Comunidad de Madrid (MAD2D-CM S2013/ MIT-3007 (E.M.P.), Y2018/NMT-4783 (A.D.)) and the Programa de Atracción del Talento Investigador 2017-T1/IND-5562 (E.B.)). CzechNanoLab Research Infrastructure supported by MEYS CR (LM2018110) are gratefully acknowledged. IMDEA Nanociencia acknowledges support from the Severo Ochoa Programme for Centres of Excellence in R&D (MINECO, grant no. SEV-2016-0686).Peer reviewe

Controlled covalent functionalization of 2 H‐MoS2 with molecular or polymeric adlayers

Special Issue: Chemical Functionalization of 2D Materials. This article also appears in: Chemical Functionalization of 2D Materials Society Volumes: Czech Republic.Most air‐stable 2D materials are relatively inert, which makes their chemical modification difficult. In particular, in the case of MoS2, the semiconducting 2 H‐MoS2 is much less reactive than its metallic counterpart, 1T‐MoS2. As a consequence, there are hardly any reliable methods for the covalent modification of 2 H‐MoS2. An ideal method for the chemical functionalization of such materials should be both mild, not requiring the introduction of a large number of defects, and versatile, allowing for the decoration with as many different functional groups as possible. Herein, a comprehensive study on the covalent functionalization of 2 H‐MoS2 with maleimides is presented. The use of a base (Et3N) leads to the in situ formation of a succinimide polymer layer, covalently connected to MoS2. In contrast, in the absence of base, functionalization stops at the molecular level. Moreover, the functionalization protocol is mild (occurs at room temperature), fast (nearly complete in 1 h), and very flexible (11 different solvents and 10 different maleimides tested). In practical terms, the procedures described here allow for the chemist to manipulate 2 H‐MoS2 in a very flexible way, decorating it with polymers or molecules, and with a wide range of functional groups for subsequent modification. Conceptually, the spurious formation of an organic polymer might be general to other methods of functionalization of 2D materials, where a large excess of molecular reagents is typically used.The European Research Council (ERC‐StG‐307609; ERC‐PoC‐ ERC‐AdG‐742684), MINECO (CTQ2017‐86060‐P and CTQ2016‐79419‐R) the Comunidad de Madrid (MAD2D‐CM S2013/ MIT‐3007) are gratefully acknowledged. IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV‐ 2016‐0686). Part of the work was carried out with the support of CEITEC Nano Research Infrastructure (ID LM2015041, MEYS CR, 2016–2019), CEITEC Brno University of Technology.Peer reviewe

A Chemical Approach to 2D-2D Heterostructures Beyond Van Der Waals: High-Throughput On-Device Covalent Connection of MoS2 and Graphene

The most widespread method for the synthesis of 2D-2D heterostructures is the direct growth of one material on top of the other. Alternatively, one can manually stack flakes of different materials. Both methods are limited to one crystal/device at a time and involve interfacing the 2D materials through van der Waals forces, to the point that all these materials are known as van der Waals heterostructures. Synthetic chemistry is the paradigm of atomic-scale control, yet its toolbox remains unexplored for the construction of 2D-2D heterostructures. Here, we describe how to covalently connect 2H-MoS2 flakes to several single-layer graphene field-effect transistors simultaneously, and show that the final electronic properties of the MoS2-graphene heterostructure are dominated by the molecular interface. We use a bifunctional molecule with two chemically orthogonal anchor points, selective for sulphides and carbon-based materials. Our experiments highlight the potential of the chemical approach to build 2D-2D heterostructures beyond van der Waals. </p

2D 2D covalent heterostructures: High-throughput on-device connection of MoS2 and graphene

Resumen del póster presentado a la XXXVIII Reunión Bienal de la Real Sociedad Española de Química, celebrada en el Palacio de Congresos de Granada, del 27 de junio al 30 de junio de 2022.The most widespread method for the synthesis of 2D-2D heterostructures is the direct growth of one material on top of the other. Alternatively, one can manually stack flakes of different materials. Both methods are limited to one crystal/device at a time and involve interfacing the 2D materials through van der Waals forces, to the point that all these materials are known as van der Waals heterostructures. Synthetic chemistry is the paradigm of atomic-scale control, yet its toolbox remains unexplored for the construction of 2D-2D heterostructures. Here, we describe how to covalently connect 2H-MoS2 flakes to several single-layer graphene field-effect transistors simultaneously, and show that the final electronic properties of the MoS2-graphene heterostructure are dominated by the molecular interface. We use a bifunctional molecule with two chemically orthogonal anchor points, selective for sulfides and carbon-based materials: On one hand, we exploit the chemistry of maleimide described by our group to functionalize sulfide-based materials under mild conditions. On the other hand, we use a diazonium salt, which is the most common method for the covalent modification graphene. The solvents play a key role to activate a specific part of the molecule for the covalent anchoring. In order to measure the electrical properties of the heterostructure, we have fabricated a number of f-MoS2@graphene field effect transistors (FET) on Si/SiO2 substrates. The electronic properties of the functionalized devices are dominated by the chemical interface, resulting in p-doped devices in which the charge mobility is conserved after reaction, and the degree of doping can be controlled by increasing the degree of functionalization. The results described here show the power of the chemical approach to build functional 2D-2D heterostructures beyond van der Waals. Figure 1: Experimental procedure for the production of MoS2@Graphene covalent heterostructures.Peer reviewe