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 pi-conjugated metal-free macrocycles and their metal derivatives are fabricated by vacuum deposition. The crystal structures of [H-2(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 (U) ranging from 10(-6) to 10(-1) cm(2)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 x 10(-1) cm(2)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 mu values (3.0 x 10(-6)-3.7 x 10(-5) cm(2)V(-1)s(-1)).