Morphological Evolution of Tetrachlorinated Perylene Bisimides with Lengthy Alkyl Substituent Polycrystalline Thin Films during Reversible Phase Transitions

[Image: see text] The phase behavior and related morphological evolution of thin films of lengthy alkyl substituted core-tetrachlorinated perylene bisimide (C18-4ClPBI), a large π-conjugated molecule, have been studied. It is found that the C18-4ClPBI can exist in two different crystalline phases depending on temperature, which transform reversibly in heating and cooling processes. The X-ray diffraction results demonstrate that the two crystalline forms of C18-4ClPBI exhibit a similar packing geometry but with different unit cell dimensions. It is confirmed that the low-temperature phase is packed more compactly than its high-temperature counterpart. During high-temperature to low-temperature crystalline phase transition, nonbirefringent protrusions were observed, which disassembled in the reverse crystalline phase transition process during heating. The exact formation mechanism of the protrusions is not clear at the moment. Nevertheless, their influence on the transfer characteristics of the polycrystalline C18-4ClPBI thin film has been clearly illustrated.