The isolation of graphene in 2004 from graphite was a defining moment for the "birth" of a field: two-dimensional (2D) materials. In recent years, there has been a rapidly increasing number of papers focusing on non-graphene layered materials, including transition-metal dichalcogenides (TMDs), because of the new properties and applications that emerge upon 2D confinement. Here, we review significant recent advances and important new developments in 2D materials "beyond graphene". We provide insight into the theoretical modeling and understanding of the van der Waals (vdW) forces that hold together the 2D layers in bulk solids, as well as their excitonic properties and growth morphologies. Additionally, we highlight recent breakthroughs in TMD synthesis and characterization and discuss the newest families of 2D materials, including monoelement 2D materials (i.e., silicene, phosphorene, etc.) and transition metal carbide- and carbon nitride-based MXenes. We then discuss the doping and functionalization of 2D materials beyond graphene that enable device applications, followed by advances in electronic, optoelectronic, and magnetic devices and theory. Finally, we provide perspectives on the future of 2D materials beyond graphene.

Research in stretchable conductors is fuelled by diverse technological needs. Flexible electronics, neuroprosthetic and cardiostimulating implants, soft robotics and other curvilinear systems require materials with high conductivity over a tensile strain of 100 per cent (refs 1-3). Furthermore, implantable devices or stretchable displays need materials with conductivities a thousand times higher while retaining a strain of 100 per cent. However, the molecular mechanisms that operate during material deformation and stiffening make stretchability and conductivity fundamentally difficult properties to combine. The macroscale stretching of solids elongates chemical bonds, leading to the reduced overlap and delocalization of electronic orbitals. This conductivity-stretchability dilemma can be exemplified by liquid metals, in which conduction pathways are retained on large deformation but weak interatomic bonds lead to compromised strength. The best-known stretchable conductors use polymer matrices containing percolated networks of high-aspect-ratio nanometre-scale tubes or nanowires to address this dilemma to some extent. Further improvements have been achieved by using fillers (the conductive component) with increased aspect ratio, of all-metallic composition, or with specific alignment (the way the fillers are arranged in the matrix). However, the synthesis and separation of high-aspect-ratio fillers is challenging, stiffness increases with the volume content of metallic filler, and anisotropy increases with alignment. Pre-strained substrates, buckled microwires and three-dimensional microfluidic polymer networks have also been explored. Here we demonstrate stretchable conductors of polyurethane containing spherical nanoparticles deposited by either layer-by-layer assembly or vacuum-assisted flocculation. High conductivity and stretchability were observed in both composites despite the minimal aspect ratio of the nanoparticles. These materials also demonstrate the electronic tunability of mechanical properties, which arise from the dynamic self-organization of the nanoparticles under stress. A modified percolation theory incorporating the self-assembly behaviour of nanoparticles gave an excellent match with the experimental data.

Stable dispersions of nanofibers are virtually unknown for synthetic polymers. They can complement analogous dispersions of inorganic components, such as nanoparticles, nanowires, nanosheets, etc as a fundamental component of a toolset for design of nanostructures and metamaterials via numerous solvent-based processing methods. As such, strong flexible polymeric nanofibers are very desirable for the effective utilization within composites of nanoscale inorganic components such as nanowires, carbon nanotubes, graphene, and others. Here stable dispersions of uniform high-aspect-ratio aramid nanofibers (ANFs) with diameters between 3 and 30 nm and up to 10 μm in length were successfully obtained. Unlike the traditional approaches based on polymerization of monomers, they are made by controlled dissolution of standard macroscale form of the aramid polymer, i.e. well known Kevlar threads, and revealed distinct morphological features similar to carbon nanotubes. ANFs are successfully processed into films using layer-by-layer (LBL) assembly as one of the potential methods of preparation of composites from ANFs. The resultant films are transparent and highly temperature resilient. They also display enhanced mechanical characteristics making ANF films highly desirable as protective coatings, ultrastrong membranes, as well as building blocks of other high performance materials in place of or in combination with carbon nanotubes.

Understanding and exploiting the remarkable optical and electronic properties of phosphorene require mass production methods that avoid chemical degradation. Although solution-based strategies have been developed for scalable exfoliation of black phosphorus, these techniques have thus far used anhydrous organic solvents in an effort to minimize exposure to known oxidants, but at the cost of limited exfoliation yield and flake size distribution. Here, we present an alternative phosphorene production method based on surfactant-assisted exfoliation and postprocessing of black phosphorus in deoxygenated water. From comprehensive microscopic and spectroscopic analysis, this approach is shown to yield phosphorene dispersions that are stable, highly concentrated, and comparable to micromechanically exfoliated phosphorene in structure and chemistry. Due to the high exfoliation efficiency of this process, the resulting phosphorene flakes are thinner than anhydrous organic solvent dispersions, thus allowing the observation of layer-dependent photoluminescence down to the monolayer limit. Furthermore, to demonstrate preservation of electronic properties following solution processing, the aqueous-exfoliated phosphorene flakes are used in field-effect transistors with high drive currents and current modulation ratios. Overall, this method enables the isolation and mass production of few-layer phosphorene, which will accelerate ongoing efforts to realize a diverse range of phosphorenebased applications.black phosphorus | deoxygenated water | liquid phase exfoliation | photoluminescence | field-effect transistor F ew-layer phosphorene (FL-P) isolated by micromechanical exfoliation has been widely studied both fundamentally and in applications such as high-performance electronic and optoelectronic devices (1-11). Although micromechanical exfoliation provides individual, high-quality FL-P flakes, this technique lacks scalability and is not amenable to large-area applications. Conventional approaches for mass production of 2D nanomaterials involve chemical vapor deposition (CVD) and liquid phase exfoliation (LPE). Whereas CVD growth of black phosphorus (BP) thin films is hindered by challenges with molecular precursors and extreme growth conditions (12), LPE of BP has been demonstrated and used for the large-scale deposition of thin films akin to the approaches for other 2D nanomaterials (13-17). Specifically, stable BP dispersions have been produced by LPE using high-boiling-point solvents including N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethyl sulfoxide, and N-cyclohexyl-2-pyrrolidone (18-21). With these anhydrous organic solvents, chemical degradation from ambient O 2 and water (11) are avoided, but the exfoliation yield and flake size distribution are suboptimal, especially compared with the results that have been achieved with other 2D nanomaterials using stabilizing surfactants in aqueous solutions (16). Furthermore, organic solvents have limited compatibility with methods such as ultracentrifugation for structu...

Recent developments in liquid-phase processing of carbon nanomaterials have established graphene as a promising candidate for printed electronics. Of great importance in the ink formulation is the stabilizer, which has to provide excellent dispersion stability and tunability in the liquid state, and also decompose into chemical moieties that promote high electrical conductivity and robust mechanical and environmental stability. Here we demonstrate the promise of nitrocellulose as a synergistic polymer stabilizer for graphene inks. Graphene processed with nitrocellulose is formulated into inks with viscosities ranging over 4 orders of magnitude for compatibility with a wide range of deposition methods. Following thermal treatment, the graphene/nitrocellulose films offer high electrical conductivity of ∼40 000 S/m, along with mechanical flexibility. Moreover, in contrast to state-of-the-art graphene inks based on ethyl cellulose, the nitrocellulose residue offers superior mechanical and environmental stability as assessed by a suite of stress tests, including the Scotch tape test, a water sonication test, and an 85/85 damp heat test. By exploring the fundamental chemistry underlying these macroscopic benefits, we provide insight into binder selection for functional nanomaterial inks while producing a high-performance graphene ink with strong potential for printed and flexible electronics.