Abstract

AbstractHigh‐quality polycrystalline polyacenes (PLAs) of anthracene (AN), tetracene (TN), and pentacene (PN) doped with potassium in the 1:1 and 1:2 stoichiometries are prepared and their physical properties are systematically studied by magnetic measurements. The magnetic susceptibilities as a function of temperature for Kx(PLAs) are interpreted in the framework of a band‐filling model. Clear evidence for the occurrence of charge transfer from K to the organic semiconductors is provided. K1(AN) prepared by a solid‐state diffusion process exhibits a pronounced magnetic hump at 140 K, which is associated with antiferromagnetic interactions ascribed to the on‐site Coulomb repulsion in a Mott insulating state, whereas both K1(TN) and K1(PN) show a conventional Curie–Weiss behavior at low temperatures. We successfully demonstrate the tuning of the electronic states of PLA‐type semiconductors in bulk. Comments are given about the possibility of metallic states in potassium‐doped PLAs, which have recently been reported for other polycyclic aromatic hydrocarbons.

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