Nanometric Chemical Analysis of Beam-Sensitive Materials: A Case Study of STEM-EDX on Perovskite Solar Cells

Quantitative chemical analysis on the nanoscale provides valuable information on materials and devices which can be used to guide further improvements to their performance. In particular, emerging families of technologically relevant composite materials such as organic-inorganic hybrid halide perovskites and metal-organic frameworks stand to benefit greatly from such characterization. However, these nanocomposites are also vulnerable to damage induced by analytical probes such as electron, X-ray, or neutron beams. Here the effect of electrons on a model hybrid halide perovskite is investigated, focusing on the acquisition parameters appropriate for energy-dispersive X-ray spectroscopy in a scanning transmission electron microscope (STEM-EDX). The acquisition parameters are systematically varied to examine the relationship between electron dose, data quality, and beam damage. Five metrics are outlined to assess the quality of STEM-EDX data and severity of beam damage, further validated by dark field STEM imaging. Loss of iodine through vacancy creation is found to be the primary manifestation of electron beam damage in the perovskite specimen, and iodine content is seen to decrease exponentially with electron dose. This work demonstrates data acquisition and analysis strategies that can be used for studying electron beam damage and for achieving reliable quantification for a broad range of beam-sensitive materials.