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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: A brittle material under loading fails by the nucleation and propagation of a sharp crack. In monatomic crystals, such as silicon, the lattice geometries front to the crack-tip changes the way of propagation even with the same cleavage surface. In general, however, crystals have multiple kinds of atoms and how the deformation of each atom affects the failure is still elusive. Here, we show that local atomic distortions from the different types of atoms causes a propagation anisotropy in suspended WS2 monolayers by combining annular dark-field scanning transmission electron microscopy and empirical molecular dynamics that are validated by first-principles calculations. Conventional conditions for brittle failure such as surface energy, elasticity, and crack geometry cannot account for this anisotropy. Further simulations predict the enhancement of the strengths and fracture toughness of the materials by designing void shapes and edge structures.

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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.

Open Access

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Abstract: Electron ptychography has recently attracted considerable interest for high resolution phase-sensitive imaging. However, to date studies have been mainly limited to radiation resistant samples as the electron dose required to record a ptychographic dataset is too high for use with beam-sensitive materials. Here we report defocused electron ptychography using a fast, direct-counting detector to reconstruct the transmission function, which is in turn related to the electrostatic potential of a two-dimensional material at atomic resolution under various low dose conditions.

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Abstract: We reveal a self-limiting mechanism during the formation of a specific type of circular nanopore in monolayer WS2 that limits its diameter to sub-nm. A single W atom vacancy (triangular nanopore) is transformed into the self-limiting nanopore (SLNP) through the atomic restructuring of S atoms around the area, reducing the number of dangling bonds at the nanopore edge by shifting them further in-plane with W–W bonding instead. Bond rotations in WS2 help accommodate the electron beam induced atomic loss and ensure the stability of the SLNP. The SLNP shows significant improvement in diameter stability during electron beam irradiation compared to other triangular nanopores in WS2 that typically continue to expand in diameter during atom loss. The atomic structure of these SLNPs is studied using aberration-corrected scanning transmission electron microscopy with an in situ heating holder, revealing that the SLNPs are mostly formed at a temperature of ∼500 °C, which is a balance between thermally activated S vacancy diffusion and sufficient S vacancy density to initiate local atomic reconstruction. At higher temperatures (i.e., 1000 °C), S vacancies quickly migrate away into long line vacancies, resulting in low S vacancy density and rapidly expanding holes generated at the edges of the line vacancies. At room temperature, S vacancy migration is low and vacancy density is very high, which limits atomic reconstruction, and instead many small holes open up. These results provide insights into the factors that lead to uniform sized nanopores in the sub-nm range in transition-metal dichalcogenides.