Electrical properties of functionalized nanowire field effect transistors

The utilization of functional organic materials holds great promise for applications in electronic devices. Semiconducting organic molecules are frequently used as channel material in field effect transistors, due to the ease by which they can be assembled as such components, and the ease with which their properties can be specifically tailored. An extension of the use of organic materials in field effect transistors with the potential to substantially improve the performance of such devices is investigated in this thesis. It is the miniaturization of the functional parts of these devices, including their conductive channel or the gate dielectric, down to nanoscopic dimensions, which is important for their integration into complex device architectures. The materials under consideration offer advantages over conventional field effect transistor channels, including improved processibility, high mobility and electrical stability. The first part of the thesis is dedicated to the fabrication and electrochemical functionalization of nanoscopic field effect transistors comprising individual semiconducting single-walled carbon nanotubes. The combination of an ultra-thin gate dielectric based on an organic self-assembled monolayer is used for the fabrication of high-performance field effect transistors that show large on-state transconductance, as well as a large on/off ratio of 107, negligible hysteresis in the drain current, and a subthreshold swing that approaches the room temperature limit of 60 mV/decade. Two different types of self-assembled monolayers are used. The first, a silane-based self-assembled monolayer, is utilized to build field effect transistors in a global back gate geometry. This layout is useful for demonstrating the benefits of the use of a self-assembled monolayer for nanotube field effect transistors. Secondly, a gate dielectric incorporating a self-assembled monolayer composed of an alkane phosphonic-acid is exploited for the fabrication of high-performance field effect transistors with patterned aluminum gate electrodes. This geometry allows for the fabrication of more than one gate electrode per substrate and thus for the realization of logic circuits with all field effect transistors located on the same substrate. The technological relevance of nanotube field-effect transistors is proven by showing that nanotube field effect transistors can be cycled for more than 104 times between their on and off state and stored in ambient air for more than 200 days without degradation of their electrical performance. The electrochemical functionalization of individual single-walled carbon nanotubes with the organic coordination magnet Prussian Blue is investigated in the second part of this thesis. While this modification leaves metallic tubes unaffected, semiconducting SWCNTs become strongly p-doped during the electrochemical process. The temperature-dependent electrical behavior of Prussian Blue-functionalized semiconducting tubes can be understood by the freeze-out of the transfer of holes from the Prussian Blue below 150 K. In the third part of this thesis, novel core-cyanated perylene carboxylic diimides end-functionalized with substituents of varying flourine content and geometry are utilized as active material in air-stable n-channel thin film field- effect transistors. The relation between the thin-film structure and the air stability of the charge carrier mobility is investigated. Contrary to previous reports, it is found that the air stability is not related to the redox potential of the molecules. In addition, one of the compounds is used for the fabrication of field-effect transistors with a nanoribbon channel. These nanoribbons self-assemble from the solution phase, and, owing to their high crystalline order, field-effect transistors with mobilities of up to 0.2 cm2/Vs in air could be realized. The air stability of their mobility is found to be superior to that of thin-film transistors based on the same compound. Since the investigated perylene derivatives offer the possibility of fabricating thin-film as well as nanobelt field-effect transistors, they represent a valuable model system for the investigation of the relation between the crystalline order, mobility, stability and the performance of organic n-channel field-effect transistors. The last part is dedicated to a novel method for the fabrication of nanoscale polymer wires of diameters as small as 25 nm that offer potential as channel material for nanofiber field-effect transistors. These fibers emerge from a polymer solution during a standard spin-coating process. The fiber formation relies upon the Raleigh-Taylor instability of the spin-coated liquid film that arises due to a competition of the centrifugal force and the Laplace force induced by the surface curvature.