Direct Observations of the Rotation and Translation of Anisotropic Nanoparticles Adsorbed at a Liquid-Solid Interface

Abstract

We can learn about the interactions between nanoparticles (NPs) in solution and solid surfaces by tracking how they move. Here, we use liquid cell transmission electron microscopy (TEM) to follow directly the translation and rotation of Au nanobipyramids (NBPs) and nanorods (NRs) adsorbed onto a SiN _x surface at a rate of 300 frames per second. This study is motivated by the enduring need for a detailed description of NP motion on this common surface in liquid cell TEM. We will show that NPs move intermittently on the time scales of milliseconds. First, they rotate in two ways: (1) rotation around the center of mass and (2) pivoted rotation at the tips. These rotations also lead to different modes of translation. A NP can move through small displacements in the direction roughly parallel to its body axis (shuffling) or with larger steps via multiple tip-pivoted rotations. Analysis of the trajectories indicates that both displacements and rotation angles follow heavy-tailed power law distributions, implying anomalous diffusion. The spatial and temporal resolution afforded by our approach also revealed differences between the different NPs. The 50 nm NRs and 100 nm NBPs moved with a combination of shuffles and rotation-mediated displacements after illumination by the electron beam. With increasing electron fluence, 50 nm NRs also started to move via desorption-mediated jumps. The 70 nm NRs did not exhibit translational motion and only made small rotations. These results describe how NP dynamics evolve under the electron beam and how intermittent pinning and release at specific adsorption sites on the solid surface control NP motion at the liquid-solid interface. We also discuss the effect of SiN _x surface treatment on NP motion, demonstrating how our approach can provide broader insights into interfacial transport.

Keywords: Anisotropic nanoparticles; anomalous diffusion; liquid cell transmission electron microscopy; nanoparticles; rotational diffusion; single particle tracking.