Charge Transport through Superexchange in Phenothiazine–7,7,8,8-Tetracyanoquinodimethane (PTZ–TCNQ) Cocrystal Microribbon FETs Grown Using Evaporative Alignment

Abstract

Charge transfer (CT) cocrystals, molecular crystals composed of electron donating and accepting species, are being developed for applications in optoelectronics. Here we present optical and electronic characterization of the CT cocrystal phenothiazine–tetracyanoquinodimethane (PTZ–TCNQ). This material has a broad NIR absorption peak with an optical band edge less than 0.6 eV. We used density functional theory calculations to identify the origin of the low energy CT states and changes in the Raman spectra. We also demonstrate the fabrication of long, ribbon-like oriented cocrystals using an evaporative alignment method. Cocrystals grown on Si substrates were fabricated into organic field effect transistors. Despite theoretical predictions of ambipolarity, only electron conduction was observed, with mobilities on the order of 10–4 cm2 V–1 s–1. Measurements of the temperature dependence of the mobility indicated a superexchange mediated hopping mechanism for charge transport, with a characteristic energy scale of 0.19 eV.