The spin-Dicke effect in OLED magnetoresistance

Abstract

Pairs of charge-carrier spins in organic semiconductors constitute four-level systems that can be driven electromagnetically 1 . Given appropriate conditions for ultrastrong coupling 2 -weak local hyperfine fields B hyp , large magnetic resonant driving fields B 1 and low static fields B 0 that define Zeeman splittingthe spin-Dicke e ect, a collective transition of spin states, has been predicted 3 . This parameter range is challenging to probe by electron paramagnetic resonance spectroscopy because thermal magnetic polarization is negligible. It is accessed through spin-dependent conductivity that is controlled by electron-hole pairs of singlet and triplet spin-permutation symmetry without the need of thermal spin polarization 4 . Signatures of collective behaviour of carrier spins are revealed in the steady-state magnetoresistance of organic light-emitting diodes (OLEDs), rather than through radiative transitions. For intermediate B 1 , the a.c.-Zeeman e ect appears. For large B 1 , a collective spin-ensemble state arises, inverting the current change under resonance and removing power broadening, thereby o ering a unique window to ambient macroscopic quantum coherence.Macroscopic phase coherence is a hallmark of many exotic states of matter such as superconductivity, ferromagnetism or BoseEinstein condensation. Such coherence may also emerge between two-level systems, where it is mediated by electromagnetic fields, as described by the Dicke effect in collisional narrowing 5 and superradiance 6 . Collective behaviour may already arise within a pair of interacting two-level systems 7 , an observation that can potentially be extended to the prototypical two-level system of an electron spin. For pairs of charge-carrier spins in organic semiconductors, with driving fields B 1 exceeding the hydrogen-induced random local hyperfine field 1 B hyp and approaching the magnitude of the static magnetic field B 0 , a collective macroscopic spin phase has been predicted to emerge 3 . Under these conditions, when the spin-Rabi splitting becomes comparable to the Zeeman splitting, the electromagnetic field links individually resonant spin pairs together, forming a spin-Dicke state analogous to that in the dipolar Dicke effect [5][6][7] . These macroscopic effects are observable through measurements of electronic recombination rates, which depend on spin-permutation symmetry of the pair 8 .We monitor the electron-hole recombination current in an OLED, where positive and negative charges are injected into a thin film of an organic semiconductor from opposite electrodes. As the charges drift through the material, they can capture each other on intermolecular length scales owing to weak dielectric screening. These weakly coupled intermolecular electron-hole pairs 9 can ultimately recombine on individual molecules to form a molecular excited state, or exciton, which gives rise to electroluminescence. The subsequent discussion focuses on carrier pairs and not on excitons, which have spin S = 0 or 1. Because the carriers possess spi...

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