Cross-linkable random copolymers as dielectrics for low-voltage organic field-effect transistors

A large number of cross-linkable dielectrics with good dielectric properties have been reported; however, all of them suffer from disadvantages like uncontrolled pre-crosslinking, necessity of high process temperatures and the need for an additional cross-linking compound. In this contribution, two new poly(methyl methacrylate) polymers are introduced which can be cross-linked due to the attached benzyl azide (N-3) monomer units making the addition of hardeners or initiators obsolete. The synthesis of the copolymers as well as their successful characterization and usage as gate dielectrics for organic field-effect transistors is demonstrated. The investigated polymers have been labeled PAZ 12 and PAZ 14 according to their azide content in mol%. The additional building blocks of the polymers are methyl methacrylate for PAZ 12 and methyl methacrylate and styrene monomer units in about an equal ratio for PAZ 14. Spin-coated thin films were cross-linked by a thermal treatment at 110 degrees C followed by an UV exposure at a wavelength of 254 nm yielding insoluble, smooth and electrically dense polymeric networks. Optimal cross-linking parameters were obtained using infrared spectroscopy to follow the N-3 vibrational mode. Its disappearance confirms a complete cross-linking reaction, and thus fully reacted azide groups facilitate the analytics. The dielectric properties of the cross-linked thin films have been studied by impedance spectroscopy. The application of double layer dielectrics results in lower dielectric losses and lower leakage currents in the subsequently produced pentacene-based field-effect transistors. These devices operate at voltages below -6 V and show hysteresis-free current-voltage characteristics with hole mobilities up to 0.16 cm(2) V-1 s(-1). PAZ 12 appears to be superior to PAZ 14 due to a lower total layer thickness of down to 92 nm still providing good insulation in the transistor presumably related to a lower free volume that arises in the cross-linked network of the two-component containing copolymer PAZ 12.