Mapping structure and morphology of amorphous organic thin films by 4D-STEM pair distribution function analysis.

Imaging the phase distribution of amorphous or partially crystalline organic materials at the nanoscale and analyzing the local atomic structure of individual phases has been a long-time challenge. We propose a new approach for imaging the phase distribution and for analyzing the local structure of organic materials based on scanning transmission electron diffraction (4D-STEM) pair distribution function analysis (PDF). We show that electron diffraction based PDF analysis can be used to characterize the short- and medium-range order in aperiodically packed organic molecules. Moreover, we show that 4D-STEM-PDF does not only provide local structural information with a resolution of a few nanometers, but can also be used to image the phase distribution of organic composites. The distinct and thickness independent contrast of the phase image is generated by utilizing the structural difference between the different types of molecules and taking advantage of the dose efficiency due to use of the full scattering signal. Therefore, this approach is particularly interesting for imaging unstained organic or polymer composites without distinct valence states for electron energy loss spectroscopy. We explore the possibilities of this new approach using [6,6]-phenyl-C61- butyric acid methyl ester (PC61BM) and poly(3-hexylthiophene-2,5-diyl) (P3HT) as the archetypical and best-investigated semiconductor blend used in organic solar cells, compare our phase distribution with virtual dark-field analysis and validate our approach by electron energy loss spectroscopy.