Negative Spin Valve effects in manganite/organic based devices

We report detailed investigations of hybrid organic-inorganic vertical spin valves. Spin polarized injection in tris(8-hydroxyquinoline) aluminum (Alq3) organic semiconductor (OS) was performed using La0.7Sr0.3MnO3 manganite as the bottom electrode and Co as the top electrode. While manganite was directly connected to the organic semiconductor layer, a thin tunnel barrier was placed between the OS and the Co electrode. A clear negative spin valve effect - low resistance for antiparallel electrodes configuration - was observed below 210 K in various devices using two different tunnel barriers: LiF and Al2O3. The magnetoresistance effect was found to be strongly asymmetric with respect to the bias voltage. Photoelectron Spectroscopy (PES) investigation of the interface between manganite and Alq3 revealed a strong interface dipole, which leads to a better matching of the metal Fermi level with Alq3 LUMO (1.1 eV) rather than with HOMO level (1.7 eV). This unequivocally indicates that the current in these devices is dominated by the electron channel, and not by holes as previously suggested. The knowledge of the energy diagram at the bottom interface allowed us to work out a semi- quantitative model explaining both negative spin valve effect and strong voltage asymmetry. This model involves a sharp energy selection of the moving charges by the very narrow LUMO level of the organic material leading to peculiar resonant effects.