Liquid cell electron microscopy enables direct in situ imaging of processes in liquids and objects suspended in liquids with nanoscale resolution. However, the irradiating electrons affect the chemistry of the suspending medium, typically an aqueous solution, producing molecular and radical products such as hydrogen, oxygen, and hydrated (solvated) electrons. These may impact the imaged structures and phenomena. A good understanding of the interactions between the electrons and the irradiated medium is necessary to correctly interpret experiments, minimize artifacts, and take advantage of the irradiation. We predict the composition of water subjected to electron irradiation in the electron microscope. We reinterpret available experimental data, such as beam-induced variations in pH and colloid aggregation, in light of our predictions and show new observations of crystallization and etching as functions of dose rate, resolving conflicting reports in the scientific literature. We make our computer code available to readers. Our predictive model is useful for designing experiments that minimize unwanted beam effects, extending liquid cell microscopy to new applications, taking advantage of beam effects for nanomanufacturing such as the patterning of nanostructures, and correctly interpreting experimental observations. Additionally, our results indicate that liquid cells provide a new tool to study radiolysis effects on materials and processes.

Bubble and Pattern Formation in Liquid Induced by an Electron Beam AbstractLiquid cell electron microscopy has emerged as a powerful technique for in situ studies of nanoscale processes in liquids. An accurate understanding of the interactions between the electron beam and the liquid medium is essential to account for, suppress, and exploit beam effects. We quantify the interactions of high energy electrons with water, finding that radiolysis plays an important role, while heating is typically insignificant. For typical imaging conditions, we find that radiolysis products such as hydrogen and hydrated electrons achieve equilibrium concentrations within seconds. At sufficiently high dose-rate, the gaseous products form bubbles. We image bubble nucleation, growth, and migration. We develop a simplified reaction-diffusion model for the temporally and spatially varying concentrations of radiolysis species and predict the conditions for bubble formation by . We discuss the conditions under which hydrated electrons cause precipitation of cations from solution, and show that the electron beam can be used to "write" structures directly, such as nanowires and other complex patterns, without the need for a mask. KeywordsIn situ, electron microscopy, liquid cell, TEM, STEM, electron beam, radiation chemistry, radiolysis

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Measurements of solution-phase crystal growth provide mechanistic information that is helpful in designing and synthesizing nanostructures. Here, we examine the model system of individual Au nanocrystal formation within a defined liquid geometry during electron beam irradiation of gold chloride solution, where radiolytically formed hydrated electrons reduce Au ions to solid Au. By selecting conditions that favor the growth of well-faceted Au nanoprisms, we measure growth rates of individual crystals. The volume of each crystal increases linearly with irradiation time at a rate unaffected by its shape or proximity to neighboring crystals, implying a growth process that is controlled by the arrival of atoms from solution. Furthermore, growth requires a threshold dose rate, suggesting competition between reduction and oxidation processes in the solution. Above this threshold, the growth rate follows a power law with dose rate. To explain the observed dose rate dependence, we demonstrate that a reaction-diffusion model is required that explicitly accounts for the species H(+) and Cl(-). The model highlights the necessity of considering all species present when interpreting kinetic data obtained from beam-induced processes, and suggest conditions under which growth rates can be controlled with higher precision.

▪ Abstract  Io, innermost of Jupiter's large moons, is one of the most unusual objects in the Solar System. Tidal heating of the interior produces a global heat flux 40 times the terrestrial value, producing intense volcanic activity and a global resurfacing rate averaging perhaps 1 cm yr−1. The volcanoes may erupt mostly silicate lavas, but the uppermost surface is dominated by sulfur compounds including SO2 frost. The volcanoes and frost support a thin, patchy SO2 atmosphere with peak pressure near 10−8 bars. Self-sustaining bombardment of the surface and atmosphere by Io-derived plasma trapped in Jupiter's magnetosphere causes escape of material from Io (predominantly sulfur, oxygen, and sodium atoms, ions, and molecules) at a rate of about 103 kg s−1. The resulting Jupiter-encircling torus of ionized sulfur and oxygen dominates the Jovian magnetosphere and, together with an extended cloud of neutral sodium, is readily observable from Earth.