Spin-dependent transport phenomena in organic semiconductors

Thin-film organic semiconductors transport can have an anomalously high sensitivity to low magnetic fields. Such a response is unexpected considering that thermal fluctuation energies are greater than the energy associated with the intrinsic spin of charge carriers at a modest magnetic field of 100 Oe by a factor of more than 104 at room temperature and is still greater by 102 even at liquid helium temperatures. Nevertheless, we report experimental characterization of (1) spin-dependent injection, detection and transport of spin-polarized current through organic semiconductors and (2) the influence of a magnetic field on the spin dynamics of recombination-limited transport. The first focus of this work was accomplished by fabricating basic spin-valve devices consisting of two magnetic layers spatially separated by a nonmagnetic organic semiconductor. The spin-valve effect is a change in electrical resistance due to the magnetizations of the magnetic layers changing from parallel to antiparallel alignment, or vice versa. The conductivities of the metallic contacts and that of the semiconductor differed by many orders of magnitude, which inhibited the injection of a spin-polarized current from the magnet into the nonmagnet. We successfully overcame the problem of conductivity mismatch by inserting ultra-thin tunnel barriers at the metal/semiconductor interfaces which aided in yielding a &sim20% spin-valve effect at liquid helium temperatures and the effect persisted up to 150 K. We built on this achievement by constructing spin valves where one of the metallic contacts was replaced by the organic-based magnetic semiconductor vanadium tetracyanoethylene (V[TCNE]2). At 10 K these devices produced the switching behavior of the spin-valve effect. The second focus of this work was the bulk magnetoresistance (MR) of small molecule, oligomer and polymer organic semiconductors in thin-film structures. At room temperature the resistance can change up to 8% at 100 Oe and 15% at 1000 Oe. Depending on parameters such as temperature, layer thickness, or applied voltage, the resistance of these materials may increase or decrease as a function of field. A model for this phenomenon, termed magnetoresistance by the interconversion of singlets and triplets (MIST), is developed to account for this anomalous behavior. This model predicts that increasing the spin-orbit coupling in the organic semiconductor should decrease the magnitude of the MR. In an experiment where the small molecule Alq3 was doped with phosphorescent sensitizers, to increase the spin-orbit coupling, the MR was observed to decrease by an order of magnitude or more, depending on the doping. In addition to low-magnetic-field effects, we show the experimental observation of high-field MR in devices with and without magnetic contacts. To the best of our knowledge, we are the first to report (1) a tunnel-barrier-assisted spin-valve effect into an organic semiconductor using partially polarized metallic magnetic electrodes and (2) an experimental characterization of the central impact of the hyperfine interaction and spin-orbit coupling on MR in organic semiconductors.