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Current reports of thermal expansion coefficients (TEC) of two-dimensional (2D) materials show large discrepancies that span orders of magnitude. Determining the TEC of any 2D material remains difficult due to approaches involving indirect measurement of samples that are atomically thin and optically transparent. We demonstrate a methodology to address this discrepancy and directly measure TEC of nominally monolayer epitaxial WSe 2 using four-dimensional scanning transmission electron microscopy (4D-STEM). Experimentally, WSe 2 from metal-organic chemical vapor deposition (MOCVD) was heated through a temperature range of 18-564 °C using a barrel-style heating sample holder to observe temperature-induced structural changes without additional alterations or destruction of the sample. By combining 4D-STEM measurements with quantitative structural analysis, the thermal expansion coefficient of nominally monolayer polycrystalline epitaxial 2D WSe 2 was determined to be (3.5 ± 0.9) × 10 -6 K -1 and (5.7 ± 2) × 10 -5 K -1 for the in- and out-of-plane TEC, respectively, and (3.6 ± 0.2) × 10 -5 K -1 for the unit cell volume TEC, in good agreement with historically determined values for bulk crystals.

Thermoelectric materials with high electrical conductivity and low thermal conductivity (e.g., Bi 2 Te 3 ) can efficiently convert waste heat into electricity; however, in spite of favorable theoretical predictions, individual Bi 2 Te 3 nanostructures tend to perform less efficiently than bulk Bi 2 Te 3 . We report a greater-than-order-of-magnitude enhancement in the thermoelectric properties of suspended Bi 2 Te 3 nanoribbons, coated in situ to form a Bi 2 Te 3 /F 4 -TCNQ core-shell nanoribbon without oxidizing the core-shell interface. The shell serves as an oxidation barrier but also directly functions as a strong electron acceptor and p-type carrier donor, switching the majority carriers from a dominant n-type carrier concentration (∼10 21 cm -3 ) to a dominant p-type carrier concentration (∼10 20 cm -3 ). Compared to uncoated Bi 2 Te 3 nanoribbons, our Bi 2 Te 3 /F 4 -TCNQ core-shell nanoribbon demonstrates an effective chemical potential dramatically shifted toward the valence band (by 300-640 meV), robustly increased Seebeck coefficient (∼6× at 250 K), and improved thermoelectric performance (10-20× at 250 K).

Atomically thin transition metal dichalcogenides (TMDs), like MoS 2 with high carrier mobilities and tunable electron dispersions, are unique active material candidates for next generation opto-electronic devices. Previous studies on ion irradiation show great potential applications when applied to two-dimensional (2D) materials, yet have been limited to micron size exfoliated flakes or smaller. To demonstrate the scalability of this method for industrial applications, we report the application of relatively low power (50 keV) 4 He + ion irradiation towards tuning the optoelectronic properties of an epitaxially grown continuous film of MoS 2 at the wafer scale, and demonstrate that precise manipulation of atomistic defects can be achieved in TMD films using ion implanters. The effect of 4 He + ion fluence on the PL and Raman signatures of the irradiated film provides new insights into the type and concentration of defects formed in the MoS 2 lattice, which are quantified through ion beam analysis. PL and Raman spectroscopy indicate that point defects are generated without causing disruption to the underlying lattice structure of the 2D films and hence, this technique can prove to be an effective way to achieve defect-mediated control over the opto-electronic properties of MoS 2 and other 2D materials., (Creative Commons Attribution license.)

For over 25 years, transmission electron microscopy (TEM) has provided a method for the study of aerosol particles with sizes from below the optical diffraction limit to several microns, resolving the particles as well as smaller features. The wide use of this technique to study aerosol particles has contributed important insights about environmental aerosol particle samples and model atmospheric systems. TEM produces an image that is a 2D projection of aerosol particles that have been impacted onto grids and, through associated techniques and spectroscopies, can contribute additional information such as the determination of elemental composition, crystal structure, and 3D particle structures. Soot, mineral dust, and organic/inorganic particles have all been analyzed using TEM and spectroscopic techniques. TEM, however, has limitations that are important to understand when interpreting data including the ability of the electron beam to damage and thereby change the structure and shape of particles, especially in the case of particles composed of organic compounds and salts. In this paper, we concentrate on the breadth of studies that have used TEM as the primary analysis technique. Another focus is on common issues with TEM and cryogenic-TEM. Insights for new users on best practices for fragile particles, that is, particles that are easily susceptible to damage from the electron beam, with this technique are discussed. Tips for readers on interpreting and evaluating the quality and accuracy of TEM data in the literature are also provided and explained.

Nanoscale materials, when compared to their bulk components, possess unique properties. In particular, shifts in phase transitions can occur for submicrometer particles. For instance, small particles do not undergo the process of liquid-liquid phase separation (LLPS). LLPS has applications in emulsions such as Janus particles, controllable morphology to create drug-rich phases during drug delivery, and is often observed in atmospheric aqueous aerosol particles. In atmospheric particles, LLPS is tracked as a function of particle water activity, which is equivalent to the relative humidity (RH) at equilibrium. We probed three organic/inorganic aerosol systems in the range of RH over which phase separation occurs (SRH). Our findings indicate that SRH for submicrometer aerosol particles is lower than for micrometer-sized droplets. These findings show that it may be necessary to update the representation of phase transitions in aerosol particles in climate models. The vast majority of organic/inorganic aerosol particles have submicrometer diameters, and a decrease in SRH for submicrometer particles indicates that the current estimation of phase-separated aerosols may be overestimated. Furthermore, understanding the properties of LLPS at the nanoscale can provide key parameters to describe these systems and may lead to better control of phase separation in submicrometer particles.

Development of methods to measure the phase transitions and physical properties of submicron atmospheric aerosol particles is needed to better model these systems. In this paper, we present a method to flash freeze submicron particles to measure phase transitions as a function of relative humidity (RH). Particles are equilibrated at a fixed RH, vitrified in a temperature-controlled flow tube, and imaged with cryogenic transmission electron microscopy (cryo-TEM). We demonstrate the use of the technique for measuring the efflorescence relative humidity (ERH) of potassium sulfate and potassium chloride aerosol as well as the separation RH (SRH) for a multicomponent organic/inorganic system that undergoes liquid-liquid phase separation (LLPS). The location of phase transitions can shift between the micrometer and nanometer size regimes, and particles in a given population may have a range of RH over which a phase transition occurs. This technique addresses these requirements by allowing for characterization of the phase transitions for individual particles in a population on the submicron scale.

Physical properties of aerosol particles, such as liquid-liquid phase separation (LLPS), have the potential to impact the climate system. Model systems have been shown to have size-dependent LLPS in the submicron regime; however, these systems are an extreme simplification of ambient aerosol, which can include myriad organic compounds. We expand the studies of LLPS in particles consisting of ammonium sulfate and more complex organic mixtures from multiple organic compounds to α-pinene secondary organic matter (SOM). All systems display a size-dependent morphology, with small particles remaining homogeneous while large particles phase-separate. Surprisingly, three-phase particles were also observed in some of the systems in addition to a new phase state that we have termed channel morphology, which can arise upon efflorescence. The existence of size-dependent LLPS in complex organic mixtures and SOM provides evidence that this is a relevant phenomenon for ambient aerosol and should be considered when modeling atmospheric aerosol.