Organic analogues of diluted magnetic semiconductors: bridging quantum chemistry to condensed matter physics

Abstract

The selective coupling between polarized photons and electronic states in materials enables polarization-resolved spectroscopy studies of exchange interactions, spin dynamics, and collective magnetic behavior of conduction electrons in semiconductors. Here we report on Magnetic Circular Dichroism (MCD) studies of magnetic properties of electrons in crystalline thin films of small molecule organic semiconductors. Specifically, the focus was on the magnetic exchange interaction properties of d-shell ions (Cu2+, Co2+ and Mn2+) metal phthalocyanine (Pc) thin films that one may think of as organic analogues of diluted magnetic semiconductors (DMS). These films were deposited in-house using a recently developed pen-writing method that results in crystalline films with macroscopic long range ordering and improved electronic properties, ideally suited for spectroscopy techniques. Our experiments reveal that, in analogy to DMS, the extended π-orbitals of the Pc molecule mediate the spin exchange between highly localized d-like unpaired spins. We established that exchange mechanisms involve different electronic states in each species and/or hybridization between d-like orbitals and certain delocalized π-orbitals. Unprecedented 25T MCD and PL conducted in the unique 25T Split Florida HELIX magnet at the National High Magnetic Field Laboratory (NHMFL) will prove useful in probing these exchange interactions.