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Low-Dose Electron Total Scattering Analysis Resolves Non-Crystalline Phase Separation in Polymer Semiconductors and

Sang T Pham^1,2, Adam F Sapnik³, Sean M Collins^2,4,5

¹Facility for Electron Microscopy, School of Metallurgy and Materials, University of Birmingham, Birmingham, UK.

|May 18, 2026

Summary

Low-dose electron diffraction reveals nanoscale phase separation in polymer blends with similar structures. This technique maps distinct amorphous phases and analyzes crystallographic texture, aiding organic electronic device analysis.

Keywords:

amorphous solid analytical electron microscopy crystallinity crystallization electron diffraction focused ion beam materials science pair distribution function polymer semiconducting polymer

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Area of Science:

Materials Science
Polymer Science
Nanotechnology

Background:

Nanoscale phase separation in polymer semiconductor blends affects device performance and longevity.
Current electron microscopy methods struggle to analyze blends with similar molecular structures.

Purpose of the Study:

To develop and apply advanced electron diffraction techniques for characterizing nanoscale phase separation in polymer blends with similar molecular structures.
To enable detailed analysis of both crystalline and amorphous phase-separated domains.

Main Methods:

Low-dose scanning electron diffraction
Crystallographic texture analysis
Angle-dependent scattering analysis coupled with intramolecular scattering intensities
Cryogenic focused ion beam milling for sample preparation

Main Results:

Successfully identified and analyzed phase-separated domains in poly(9,9-di-n-octylfluorenyl-2,7-diyl) (F8) and poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) blends.
Demonstrated phase identification and crystallographic texture analysis for semicrystalline blends.
Developed a novel method using angle-dependent scattering to map distinct amorphous phases, overcoming limitations of ePDF analysis.
Characterized a model device cross-section, visualizing non-crystalline organic multilayer interfaces.

Conclusions:

The developed electron diffraction workflows effectively decouple phase separation and crystallization processes in F8:F8BT blends.
These techniques provide insights into intermolecular π - π stacking in both crystalline and amorphous phases.
Enables direct visualization of interfaces crucial for failure analysis in organic optoelectronics.