Separating Physically Distinct Mechanisms in Complex Infrared Plasmonic Nanostructures via Machine Learning Enhanced Electron Energy Loss Spectroscopy

Abstract Electron energy loss spectroscopy (EELS) enables direct exploration of plasmonic phenomena at the nanometer level. To isolate individual plasmon modes, linear unmixing methods can be used to separate different physical mechanisms, but in larger and more complex systems the interpretability of the components becomes uncertain. Here, infrared plasmonic resonances in self‐assembled heterogeneous monolayer films of doped‐semiconductor nanoparticles are examined beyond linear unmixing techniques, and both supervised and unsupervised machine‐learning‐based analyses of hyperspectral EELS datasets are demonstrated. In the supervised approach, a human operator labels a small number of pixels in the hyperspectral dataset corresponding to features of interest which are then propagated across the entire dataset. In the unsupervised approach, non‐linear autoencoders are used to create a highly‐reduced latent‐space representation of the dataset, within which insight into the relevant physics can be gleaned from straightforward distance metrics that do not depend on operator input and bias. The advantage of these approaches is that the labeling separates physical mechanisms without altering the data, enabling robust analyses of the influence of heterogeneities in mesoscale complex systems.