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Abstract: Advances in the production of two-dimensional (2D) materials such as graphene and MoS2 during the past two decades have spurred the search for other van der Waals materials with distinct functional properties. However, reducing the dimensionality of bulk van der Waals materials can lead to structural rearrangement and chemical degradation, especially in the presence of air. These challenges have slowed the progress of the discovery and analysis of chemically diverse 2D materials. Here, we provide a case study on the shear exfoliation of a class of wide band gap van der Waals materials termed II–VI layered hybrids (II–VI LHs) and show how reducing their dimension influences their structural and chemical stabilities. ZnSe(butylamine) and ZnSe(octylamine) are exfoliated, yielding shear-thinned material whose resistance toward degradation via oxidation is studied in depth by a variety of macro- and microscopic characterization techniques. Mechanical energy input, solvent–ligand interaction, and exposure to ambient conditions all play important roles in the stability of these materials. Our findings suggest that moderately coordinating alkylamine layers stabilize 2D materials that would otherwise degrade during exfoliation and exposure to air.

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Abstract: Confining electric fields to a nanoscale region is challenging yet crucial for applications such as high resolution probing of electrical properties of materials and electric-field manipulation of nanoparticles. State-of-the-art techniques involving atomic force microscopy typically have a lateral resolution limit of tens of nanometers due to limitations in the probe geometry and stray electric fields that extend over space. Engineering the probes is the most direct approach to improving this resolution limit. However, current methods to fabricate high-resolution probes, which can effectively confine the electric fields laterally involve expensive and sophisticated probe manipulation, which has limited the use of this approach. Here, we demonstrate that nanoscale phase switching of configurable thin films on probes can result in high-resolution electrical probes. These configurable coatings can be both germanium-antimony-tellurium (GST) as well as amorphous-carbon, materials known to undergo electric field-induced non-volatile, yet reversible switching. By forming a localized conductive filament through phase transition, we demonstrate a spatial resolution of electrical field beyond the geometrical limitations of commercial platinum probes (i.e. an improvement of ~48%). We then utilize these confined electric fields to manipulate nanoparticles with single nanoparticle precision via dielectrophoresis. Our results advance the field of nanomanufacturing and metrology with direct applications for pick and place assembly at the nanoscale.

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Abstract: GaSe and InSe are important members of a class of 2D materials, the III-VI metal monochalcogenides, which are attracting considerable attention due to their promising electronic and optoelectronic properties. Here an investigation of point and extended atomic defects formed in mono-, bi-, and few-layer GaSe and InSe crystals is presented. Using state-of-the-art scanning transmission electron microscopy (STEM), it is observed that these materials can form both metal and selenium vacancies under the action of the electron beam. Selenium vacancies are observed to be healable; recovering the perfect lattice structure in the presence of selenium or enabling incorporation of dopant atoms in the presence of impurities. Under prolonged imaging, multiple point defects are observed to coalesce to form extended defect structures, with GaSe generally developing trigonal defects and InSe primarily forming line defects. These insights into atomic behavior could be harnessed to synthesize and tune the properties of 2D post transition metal monochalcogenide materials for optoelectronic applications.

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Abstract: Materials with highly crystalline lattice structures and low defect concentrations have classically been considered essential for high-performance optoelectronic devices. However, the emergence of high-efficiency devices based on halide perovskites is provoking researchers to rethink this traditional picture, as the heterogeneity in several properties within these materials occurs on a series of length scales. Perovskites are typically fabricated crudely through simple processing techniques, which leads to large local fluctuations in defect density, lattice structure, chemistry and bandgap that appear on short length scales (<100 nm) and across long ranges (>10 μm). Despite these variable and complex non-uniformities, perovskites maintain exceptional device efficiencies and are, as of 2018, the best-performing polycrystalline thin-film solar cell material. In this Review, we highlight the multiple layers of heterogeneity ascertained using high-spatial-resolution methods that provide access to the relevant length scales. We discuss the impact that the optoelectronic variations have on halide perovskite devices, including the prospect that it is this very disorder that leads to their remarkable power-conversion efficiencies.

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Abstract: We report on the development and verification of an enhanced computational model capable of robust predictions and yielding a single descriptor to the successful embedding of guest nanoclusters into the pores of functionalised metal–organic frameworks. Using the predictions of this model, we have been able to embed Pd nanoclusters in the pores of Br-UiO-66 and show that the embedding of Pd nanoclusters in both (OH)2-UiO-66 and (Cl)2-UiO-66 is not successful. Also, using various independent methods, we identified the strong host–guest interactions that anchor the guest nanoclusters inside the Br-UiO-66 framework which result in the surface modification of said nanoclusters. We demonstrated that the level of this surface modification is a direct function of the framework functional groups. This new approach for the rational design of nanocluster–metal–organic framework systems, and a demonstrated tool box for their characterisation, will promote the exploitation of surface modification of nanoclusters via their embedding into functionalised metal–organic framework pores.