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...

Separating the influence of hyperfine from spin-orbit interactions in spin-dependent carrier recombination and dissociation processes necessitates magnetic resonance spectroscopy over a wide range of frequencies.We have designed compact and versatile coplanar waveguide resonators for continuous-wave electrically detected magnetic resonance, and tested these on organic light-emitting diodes. By exploiting both the fundamental and higher-harmonic modes of the resonators we cover almost five octaves in resonance frequency within a single setup. The measurements with a common π-conjugated polymer as the active material reveal small but non-negligible effects of spin-orbit interactions, which give rise to a broadening of the magnetic resonance spectrum with increasing frequency. a)

We measure electrically detected magnetic resonance (EDMR) on organic light-emitting diodes (OLEDs) made of the polymer poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) at room temperature and high magnetic fields, where spectral broadening of the resonance due to spin-orbit coupling (SOC) exceeds that due to the local hyperfine fields. Density-functionaltheory calculations on an open-shell model of the material reveal g-tensors of charge-carrier spins in the lowest unoccupied (electron) and highest occupied (hole) molecular orbitals. These tensors are used for simulations of magnetic resonance line-shapes. Besides providing the first quantification and direct observation of SOC effects on charge-carrier states in these weakly SO-coupled hydrocarbons, this procedure demonstrates that spin-related phenomena in these materials are fundamentally monomolecular in nature.

Organic light-emitting diodes (OLEDs) make highly sensitive probes to test magnetic resonance phenomena under unconventional conditions since spin precession controls singlet-triplet transitions of electron-hole pairs, which in turn give rise to distinct recombination currents in conductivity. Electron paramagnetic resonance can therefore be detected in the absence of spin polarization. We exploit this characteristic to explore the exotic regime of ultrastrong light-matter coupling, where the Rabi frequency of a charge carrier spin is of the order of the transition frequency of the two-level system. To reach this domain, we have to lower the Zeeman splitting of the spin states, defined by the static magnetic field B, and raise the strength of the oscillatory driving field of the resonance, B. This is achieved by shrinking the OLED and bringing the source of resonant radio frequency (RF) radiation as close as possible to the organic semiconductor in a monolithic device structure, which incorporates an OLED fabricated directly on top of an RF microwire within one monolithic thin-film device structure. With an RF driving power in the milliwatt range applied to the microwire, the regime of bleaching and inversion of the magnetic resonance signal is reached due to the onset of the spin-Dicke effect. In this example of ultrastrong light-matter coupling, the individual resonant spin transitions of electron-hole pairs become indistinguishable with respect to the driving field, and superradiance of the magnetic dipole transitions sets in.

The magneto-electronic field effects in organic semiconductors at high magnetic fields are described by field-dependent mixing between singlet and triplet states of weakly bound charge carrier pairs due to small differences in their Landé g-factors that arise from the weak spin-orbit coupling in the material. In this work, we corroborate theoretical models for the high-field magnetoresistance of organic semiconductors, in particular of diodes made of the conducting polymer poly(3,4ethylenedioxythiophene):poly(styrene-sulfonate) (PEDOT:PSS) at low temperatures, by conducting magnetoresistance measurements along with multi-frequency continuous-wave electrically detected magnetic resonance experiments. The measurements were performed on identical devices under similar conditions in order to independently assess the magnetic field-dependent spin-mixing mechanism, the socalled Δ mechanism, which originates from differences in the charge-carrier g-factors induced by spinorbit coupling.

We have studied the role of spin-dependent processes on conductivity in polyfluorene (PFO) thin films by conducting continuous wave (c.w.) electrically detected magnetic resonance (EDMR) spectroscopy at temperatures between 10 K and 293 K using microwave frequencies between about 100 MHz and 20 GHz as well as pulsed EDMR at X-band (10 GHz). Variable frequency EDMR allows us to establish the role of spin-orbit coupling in spin-dependent processes whereas pulsed EDMR allows for the observation of coherent spin motion effects. We used PFO for this study in order to allow for the investigation of the effects of microscopic morphological ordering since this material can adopt two distinct intrachain morphologies: an amorphous (glassy) phase, in which monomer units are twisted with respect to each other, and an ordered (β) phase, where all monomers lie within one plane. In thin films of organic light-emitting diodes (OLEDs) the appearance of a particular phase can be controlled by deposition parameters and solvent vapor annealing, and is verified by electroluminescence spectroscopy. Under bipolar charge carrier 2 injection conditions we conducted multi-frequency c.w. EDMR, electrically detected Rabi spinbeat experiments, Hahn-echo and inversion-recovery measurements. Coherent echo spectroscopy reveals electrically detected electron spin-echo envelope modulation (ESEEM) due to the coupling of the carrier spins to nearby nuclei spins. Our results demonstrate that while conformational disorder can influence the observed EDMR signals, including the sign of the current changes on resonance as well as the magnitudes of local hyperfine fields and charge carrier spin-orbit interactions, it does not qualitatively affect the nature of spin-dependent transitions in this material. In both morphologies, we observe the presence of at least two different spin-dependent recombination processes. At 293 K and 10 K, polaron-pair recombination through weakly spin-spin coupled intermediate charge carrier pair states is dominant, while at low temperatures, additional signatures of spin-dependent charge transport through the interaction of polarons with triplet excitons are seen in the half-field resonance of a triplet spin-1 species. This additional contribution arises since triplet lifetimes are increased at lower temperatures. We tentatively conclude that spectral broadening induced by hyperfine coupling is slightly weaker in the more ordered β-phase than in the glassy-phase, since protons are more evenly spaced, whereas broadening effects due to spin-orbit coupling, which impacts the distribution of g-factors, appears to be somewhat more significant in the β-phase. PACS

Replacing all protons on a polymer by deuterium has a dramatic impact on spin-dependent properties of the material in devices.

Conjugated polymers are anisotropic in shape and with regard to electronic properties. Little is known as to how electronic anisotropy impacts the underlying characteristics of the electron spin, such as the coupling to orbital magnetic moments. Using multifrequency electrically detected magnetic resonance spectroscopy extending over 12 octaves in frequency, we explore the effect of spin-orbit coupling by examining the pronounced broadening of resonance spectra with increasing magnetic field. Whereas in three commonly used materials, the high-field spectra show asymmetric broadening, as would be expected from anisotropic g-strain effects associated with the molecular structure, in the conducting polymer poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) the spectra broaden isotropically, providing a direct measure of the microscopic distribution in g-factors. This observation implies that effective charge-carrier g-tensors are isotropic, which likely originates from motional narrowing in this high-mobility material.