Visualization of nanocrystallites in organic semiconducting blends using cryo-electron microscopy

The efficiency of an organic solar cell is highly dependent on the complex, interpenetrating morphology, and molecular order within the composite phases of the bulk heterojunction (BHJ) blend. Both these microstructural aspects are strongly influenced by the processing conditions and chemical design of donor/acceptor materials. To establish improved structure-function relationships, it is vital to visualize the local microstructural order to provide specific local information about donor/acceptor interfaces and crystalline texture in BHJ blend films. The visualization of nanocrystallites, however, is difficult due to the complex semi-crystalline structure with few characterization techniques capable of visualizing the molecular ordering of soft materials at the nanoscale. Here, it is demonstrated how cryo-electron microscopy can be utilized to visualize local nanoscale order. This method is used to understand the distribution/orientation of crystallites in a BHJ blend. Long-range (>300 nm) texturing of IEICO-4F crystallites oriented in an edge-on fashion is observed, which has not previously been observed for spin-coated materials. This approach provides a wealth of quantitative information about the texture and size of nanocrystallites, which can be utilized to understand charge generation and transport in organic film. This study guides tailoring the material design and processing conditions for high-performance organic optoelectronic devices.