Defining the radiation chemistry during liquid cell electron microscopy to enable visualization of nanomaterial growth and degradation dynamics.

We present a critical review of methods for defining the chemical environment during liquid cell electron microscopy investigation of electron beam induced nanomaterial growth and degradation. We draw from the radiation chemistry and liquid cell electron microscopy literature to present solution chemistry and electron beam-based methods for selecting the radiolysis products formed and their relative amount during electron irradiation of liquid media in a transmission electron microscope. We outline various methods for establishing net oxidizing or net reducing reaction environments and propose solvents with minimal overall production of radicals under the electron beam. Exemplary liquid cell electron microscopy experiments in the fields of nanoparticle nucleation, growth, and degradation along with recommendations for best practices and experimental parameters are reported. We expect this review will provide researchers with a useful toolkit for designing general chemistry and materials science liquid cell electron microscopy experiments by 'directing' the effect of the electron beam to understand fundamental mechanisms of dynamic nanoscale processes as well as minimizing radiation damage to samples.

Hexatic-to-disorder transition in colloidal crystals near electrodes: rapid annealing of polycrystalline domains.

Colloids are known to form planar, hexagonal closed packed (hcp) crystals near electrodes in response to electrohydrodynamic (EHD) flow. Previous work has established that the EHD velocity increases as the applied ac frequency decreases. Here we report the existence of an order-to-disorder transition at sufficiently low frequencies, despite the increase in the attractive EHD driving force. At large frequencies (~500 Hz), spherical micron-scale particles form hcp crystals; as the frequency is decreased below ~250 Hz, however, the crystalline structure transitions to randomly closed packed (rcp). The transition is reversible and second order with respect to frequency, and independent measurements of the EHD aggregation rate confirm that the EHD driving force is indeed higher at the lower frequencies. We present evidence that the transition is instead caused by an increased particle diffusivity due to increased particle height over the electrode at lower frequencies, and we demonstrate that the hcp-rcp transition facilitates rapid annealing of polycrystalline domains.

Detection of atomic force microscopy cantilever displacement with a transmitted electron beam.

The response time of an atomic force microscopy (AFM) cantilever can be decreased by reducing cantilever size; however, the fastest AFM cantilevers are currently nearing the smallest size that can be detected with the conventional optical lever approach. Here, we demonstrate an electron beam detection scheme for measuring AFM cantilever oscillations. The oscillating AFM tip is positioned perpendicular to and in the path of a stationary focused nanometer sized electron beam. As the tip oscillates, the thickness of the material under the electron beam changes, causing a fluctuation in the number of scattered transmitted electrons that are detected. We demonstrate detection of sub-nanometer vibration amplitudes with an electron beam, providing a pathway for dynamic AFM with cantilevers that are orders of magnitude smaller and faster than the current state of the art.

Factors influencing quantitative liquid (scanning) transmission electron microscopy.

One of the experimental challenges in the study of nanomaterials in liquids in the (scanning) transmission electron microscope ((S)TEM) is gaining quantitative information. A successful experiment in the fluid stage will depend upon the ability to plan for sensitive factors such as the electron dose applied, imaging mode, acceleration voltage, beam-induced solution chemistry changes, and the specifics of solution reactivity. In this paper, we make use of a visual approach to show the extent of damage of different instrumental and experimental factors in liquid samples imaged in the (S)TEM. Previous results as well as new insights are presented to create an overview of beam-sample interactions identified for changing imaging and experimental conditions. This work establishes procedures to understand the effect of the electron beam on a solution, provides information to allow for a deliberate choice of the optimal experimental conditions to enable quantification, and identifies the experimental factors that require further analysis for achieving fully quantitative results in the liquid (S)TEM.