One- and Two-Photon Polymerization of Solvent- and Filler-Free Aromatic Organic Precursors: Toward 3D-Printed Semiconducting Microstructures

Over the past decades, a great deal of attention has been dedicated toward developing semiconductive polymers (SP), which are now considered as a critical class of photoactive and electroactive materials. However, the processing of many SPs involves the use of solvents, leading to the fabrication of samples with limited shapes, mostly flat 2D thin films. To develop 3D-shaped materials with potential semiconducting properties, this work tackles the development of solvent- and filler-free resins for the fabrication via additive manufacturing of microscale organic semiconductors. Two molecular liquids based on electron-rich carbazole and triarylamine units are used to formulate photoresists. The successful reactivity of the formulations was investigated, both at the macroscopic scale (one-photon polymerization through UV curing) and at the microscopic scale (two-photon polymerization (2PP) via direct laser writing), with Fourier transform infrared spectroscopy (FT-IR) and Raman spectroscopy. Subsequently, the thermal properties of the macroscopic samples were investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Optimization of the printing parameters for 2PP led to the elaboration of 3D micrometer-scale samples whose morphology was assessed by scanning electron microscopy (SEM). Finally, electrical measurements revealed a semiconducting behavior as the samples were found to conduct current after p-doping with iodine.