Temperature Dependent Nanochemistry and Growth Kinetics Using Liquid Cell Transmission Electron Microscopy.

Liquid cell transmission electron microscopy has become a powerful and increasingly accessible technique for in situ studies of nanoscale processes in liquid and solution phase. Exploring reaction mechanisms in electrochemical or crystal growth processes requires precise control over experimental conditions, with temperature being one of the most critical factors. Here we carry out a series of crystal growth experiments and simulations at different temperatures in the well-studied system of Ag nanocrystal growth driven by the changes in redox environment caused by the electron beam. Liquid cell experiments show strong changes in both morphology and growth rate with temperature. We develop a kinetic model to predict the temperature-dependent solution composition, and we discuss how the combined effect of temperature-dependent chemistry, diffusion, and the balance between nucleation and growth rates affect the morphology. We discuss how this work may provide guidance in interpreting liquid cell TEM and potentially larger-scale synthesis experiments for systems controlled by temperature.

Observations of Atmospheric Tides in the Middle and Upper Atmosphere of Mars From MAVEN and MRO.

Variability in the Martian upper atmosphere is strongly linked to the lower atmosphere and much of it can be attributed to vertical wave propagation. Atmospheric tides in particular are a well-known phenomenon in the Martian atmosphere that play a key role in the transport of energy as they propagate to higher altitudes. Previous theoretical predictions and observations suggest that tides producing wavenumber-2 and wavenumber-3 patterns are strongest in a fixed local time at high altitudes, however, the energy they carry and the region of deposition are not well characterized. Given the availability of atmospheric observations from several spacecraft at the same time, in this paper, the nature and behavior of tides are studied concurrently at several altitudes. Here, six intervals are identified focused at fixed low latitudes utilizing simultaneous observations of the middle and upper atmosphere from in situ and remote sensing instruments on different spacecraft. In the middle atmosphere, strong wavenumber-2 signatures are identified in the intervals north of the equator whereas, in the south, wavenumber-3 signatures are strongest. Wave signatures observed in the upper atmosphere seem to be dominated by a mix of wavenumbers-2 and -3. Seasonal variation is observed in the northern intervals, with very little interannual variability in all intervals considered. Estimates of energy based on dominant wavenumber amplitude suggest that most of the energy dissipates below ∼90 km. Furthermore, model sampled output captures the dominant wavenumbers observed in the middle atmosphere as well as the energy dissipation characteristics.

Spatially dependent dose rate in liquid cell transmission electron microscopy.

The use of liquid cell electron microscopy as a quantitative probe of nanomaterial structures and reactions requires an accurate understanding of how the sample is altered by the imaging electron beam. In particular, changes in the chemical environment due to beam-induced radiolysis can strongly affect processes such as solution-phase nanocrystal synthesis or electrochemical deposition. It is generally assumed that beam effects are uniform throughout the irradiated liquid. Here we show that for a liquid cell filled with water, the inevitable presence of interfaces between water and the surrounding surfaces causes a spatial variation in the energy absorbed by the water near the walls. The mechanism for this effect is that the walls act as a source of secondary and backscattered electrons which diffuse and deposit energy in the water nearby. This increased dose rate then changes the local concentrations of radiolysis species. We quantify and compare the effects for different materials used in practical liquid cells. We show that the dose rate can increase by several times within tens of nanometers of a water/Au interface, locally increasing the concentrations of species such as the hydrated electron. We discuss the implications for materials processes that are typically triggered at the solid-liquid interface.

Control of Growth Front Evolution by Bi Additives during ZnAu Electrodeposition.

The performance of many electrochemical energy storage systems can be compromised by the formation of metal dendrites during charging. Additives in the electrolyte represent a useful strategy to mitigate dendrite formation, but understanding the mechanisms involved requires knowledge of the nanoscale effects of additives during electrochemical deposition. Here we quantify the effects of an inorganic additive on the morphology of an evolving electrochemical growth front, using liquid cell electron microscopy to provide the necessary spatial and temporal resolution. We examine deposition of ZnAu on Au in the presence of Bi additive, and show that low concentrations of Bi delay but do not prevent the formation of growth front instabilities. We describe a model in which Bi segregates at the growth front and promotes the surface diffusion and relaxation of Zn, allowing better coverage of the initial Au electrode surface. A more precise knowledge of the mechanism of inorganic additive effects may help in designing electrolyte chemistry for battery and other applications where morphology control is essential.

Nanoscale evolution of interface morphology during electrodeposition.

Control of interfacial morphology in electrochemical processes is essential for applications ranging from nanomanufacturing to batteries. Here, we quantify the evolution of an electrochemical growth front, using liquid cell electron microscopy to access unexplored length and time scales. During galvanostatic deposition of copper from an acidic electrolyte, we find that the growth front initially evolves consistent with kinetic roughening theory. Subsequently, it roughens more rapidly, consistent with diffusion-limited growth physics. However, the onset of roughening is strongly delayed compared to expectations, suggesting the importance of lateral diffusion of ions. Based on these growth regimes, we discuss morphological control and demonstrate the effects of two strategies, pulse plating and the use of electrolyte additives.

Control of Electron Beam-Induced Au Nanocrystal Growth Kinetics through Solution Chemistry.

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.

Bubble and pattern formation in liquid induced by an electron beam.

Liquid 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 H2. 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.

No sodium in the vapour plumes of Enceladus.

The discovery of water vapour and ice particles erupting from Saturn's moon Enceladus fuelled speculation that an internal ocean was the source. Alternatively, the source might be ice warmed, melted or crushed by tectonic motions. Sodium chloride (that is, salt) is expected to be present in a long-lived ocean in contact with a rocky core. Here we report a ground-based spectroscopic search for atomic sodium near Enceladus that places an upper limit on the mixing ratio in the vapour plumes orders of magnitude below the expected ocean salinity. The low sodium content of escaping vapour, together with the small fraction of salt-bearing particles, argues against a situation in which a near-surface geyser is fuelled by a salty ocean through cracks in the crust. The lack of observable sodium in the vapour is consistent with a wide variety of alternative eruption sources, including a deep ocean, a freshwater reservoir, or ice. The existing data may be insufficient to distinguish between these hypotheses.