Metal halide perovskites (MHPs) are frontrunners among solution-processable materials for lightweight, large-area and flexible optoelectronics. These materials, with the general chemical formula AMX3, are structurally complex, undergoing multiple polymorph transitions...

Optoelectronic properties of anisotropic crystals vary with direction requiring that the orientation of molecular organic semiconductor crystals is controlled in optoelectronic device active layers to achieve optimal performance. Here, a generalizable strategy to introduce periodic variations in the out‐of‐plane orientations of 5,11‐bis(triisopropylsilylethynyl)anthradithiophene (TIPS ADT) crystals is presented. TIPS ADT crystallized from the melt in the presence of 16 wt.% polyethylene (PE) forms banded spherulites of crystalline fibrils that twist in concert about the radial growth direction. These spherulites exhibit band‐dependent light absorption, photoluminescence, and Raman scattering depending on the local orientation of crystals. Mueller matrix imaging reveals strong circular extinction (CE), with TIPS ADT banded spherulites exhibiting domains of positive or negative CE signal depending on the crystal twisting sense. Furthermore, orientation‐dependent enhancement in charge injection and extraction in films of twisted TIPS ADT crystals compared to films of straight crystals is visualized in local conductive atomic force microscopy maps. This enhancement leads to 3.3‐ and 6.2‐times larger photocurrents and external quantum efficiencies, respectively, in photodetectors comprising twisted crystals than those comprising straight crystals.

This tutorial review highlights the role of nanoconfinement in selecting for orientations and polymorphs of organic semiconductor crystals that are optimized for optoelectronic processes, including charge transport and light emission.

Nanoconfining scaffolds can be used to orient and shape organic semiconductor crystals during solution-phase crystallization depending on the scaffold geometry and the native crystal growth habit.