Seeing Structural Evolution of Organic Molecular Nano-crystallites Using 4D Scanning Confocal Electron Diffraction

TL;DR

The paper introduces 4D-SCED, a low-dose electron diffraction technique that enables in situ visualization of organic nanocrystals' structural evolution with high resolution, advancing the study of beam-sensitive soft materials.

Contribution

It presents a novel confocal electron diffraction method combining high angular resolution with low radiation dose, suitable for observing organic nanocrystals in real-time.

Findings

Imaging of organic nanocrystals at ~5 nm resolution.

Observation of crystal growth and orientation changes during annealing.

Detection of compositional enrichment at interfaces.

Abstract

Direct observation of organic molecular nanocrystals and their evolution using electron microscopy is extremely challenging, due to their radiation sensitivity and complex structure. Here, we introduce 4D-scanning confocal electron diffraction (4D-SCED), which enables direct in situ observation of bulk heterojunction (BHJ) thin films. 4D-SCED combines confocal electron microscopy with a pixelated detector to record focused spot-like diffraction patterns with high angular resolution, using an order of magnitude lower dose than previous methods. We apply it to study an active layer in organic solar cells, namely DRCN5T:PC$_{71}$BM BHJ thin films. Structural details of DRCN5T nano-crystallites oriented both in- and out-of-plane are imaged at ~5 nm resolution and dose budget of ~5 e$^-$/A$^2$. We use in situ annealing to observe the growth of the donor crystals, evolution of the crystal orientation, and progressive enrichment of PC$_{71}$BM at interfaces. This highly dose-efficient method opens new possibilities for studying beam sensitive soft materials.