A high-performance organic field-effect transistor based on platinum(II) porphyrin: peripheral substituents on porphyrin ligand significantly affect film structure and charge mobility

Organic field‐effect transistors incorporating planar π‐conjugated metal‐free macrocycles and their metal derivatives are fabricated by vacuum deposition. The crystal structures of [H2(OX)] (H2OX=etioporphyrin‐I), [Cu(OX)], [Pt(OX)], and [Pt(TBP)] (H2TBP=tetra‐(n‐butyl)porphyrin) as determined by single crystal X‐ray diffraction (XRD), reveal the absence of occluded solvent molecules. The field‐effect transistors (FETs) made from thin films of all these metal‐free macrocycles and their metal derivatives show a p‐type semiconductor behavior with a charge mobility (μ) ranging from 10−6 to 10−1 cm2 V−1 s−1. Annealing the as‐deposited Pt(OX) film leads to the formation of a polycrystalline film that exhibits excellent overall charge transport properties with a charge mobility of up to 3.2×10−1 cm2 V−1 s−1, which is the best value reported for a metalloporphyrin. Compared with their metal derivatives, the field‐effect transistors made from thin films of metal‐free macrocycles (except tetra‐(n‐propyl)porphycene) have significantly lower μ values (3.0×10−6–3.7×10−5 cm2 V−1 s−1)