Organic semiconductors offer a unique environment to probe the hyperfine coupling of electronic spins to a nuclear spin bath. We explore the interaction of spins in electron-hole pairs in the presence of inhomogeneous hyperfine fields by monitoring the modulation of the current through an organic light emitting diode under coherent spin-resonant excitation. At weak driving fields, only one of the two spins in the pair precesses. As the driving field exceeds the difference in local hyperfine field experienced by electron and hole, both spins precess, leading to pronounced spin beating in the transient Rabi flopping of the current. We use this effect to measure the magnitude and spatial variation in hyperfine field on the scale of single carrier pairs, as required for evaluating models of organic magnetoresistance, improving organic spintronics devices, and illuminating spin decoherence mechanisms.

Exploration of spin currents in organic semiconductors (OSECs) induced by resonant microwave absorption in ferromagnetic substrates is appealing for potential spintronics applications. Owing to the inherently weak spin-orbit coupling (SOC) of OSECs, their inverse spin Hall effect (ISHE) response is very subtle; limited by the microwave power applicable under continuous-wave (cw) excitation. Here we introduce a novel approach for generating significant ISHE signals in OSECs using pulsed ferromagnetic resonance, where the ISHE is two to three orders of magnitude larger compared to cw excitation. This strong ISHE enables us to investigate a variety of OSECs ranging from π-conjugated polymers with strong SOC that contain intrachain platinum atoms, to weak SOC polymers, to C60 films, where the SOC is predominantly caused by the curvature of the molecule's surface. The pulsed-ISHE technique offers a robust route for efficient injection and detection schemes of spin currents at room temperature, and paves the way for spin orbitronics in plastic materials.

The effects of external magnetic fields on the electrical conductivity of organic semiconductors have been attributed to hyperfine coupling of the spins of the charge carriers and hydrogen nuclei. We studied this coupling directly by implementation of pulsed electrically detected nuclear magnetic resonance spectroscopy in organic light-emitting diodes (OLEDs). The data revealed a fingerprint of the isotope (protium or deuterium) involved in the coherent spin precession observed in spin-echo envelope modulation. Furthermore, resonant control of the electric current by nuclear spin orientation was achieved with radiofrequency pulses in a double-resonance scheme, implying current control on energy scales one-millionth the magnitude of the thermal energy.

Pulsed electrically detected magnetic resonance offers a unique avenue to distinguish between polaronpair (PP) and triplet-exciton polaron (TEP) spin-dependent recombination, which control the conductivity and magnetoresistivity of organic semiconductors. Which of these two fundamental processes dominates depends on carrier balance: by injecting surplus electrons we show that both processes simultaneously impact the device conductivity. The two mechanisms are distinguished by the presence of a half-field resonance, indicative of TEP interactions, and transient spin beating, the signature of PPs. Coherent spin Rabi flopping in the half-field (triplet) channel is observed, demonstrating that the triplet exciton has an ensemble phase coherence time of at least 60 ns, offering insight into the effect of carrier correlations on spin dephasing.

Weakly coupled electron spin pairs that experience weak spin–orbit interaction can control electronic transitions in molecular and solid-state systems. Known to determine radical pair reactions, they have been invoked to explain phenomena ranging from avian magnetoreception to spin-dependent charge-carrier recombination and transport. Spin pairs exhibit persistent spin coherence, allowing minute magnetic fields to perturb spin precession and thus recombination rates and photoreaction yields, giving rise to a range of magneto-optoelectronic effects in devices. Little is known, however, about interparticle magnetic interactions within such pairs. Here we present pulsed electrically detected electron spin resonance experiments on poly(styrene-sulfonate)-doped poly(3,4-ethylenedioxythiophene) (PEDOT:PSS) devices, which show how interparticle spin–spin interactions (magnetic-dipolar and spin-exchange) between charge-carrier spin pairs can be probed through the detuning of spin-Rabi oscillations. The deviation from uncoupled precession frequencies quantifies both the exchange (<30 neV) and dipolar (23.5±1.5 neV) interaction energies responsible for the pair's zero-field splitting, implying quantum mechanical entanglement of charge-carrier spins over distances of 2.1±0.1 nm.

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Carbon‐based materials have an intrinsically weak spin–orbit coupling which imposes spin selection rules on many electronic transitions. The spin degree of freedom of electrons and nuclei can therefore play a crucial role in the electronic and optical properties of these materials. Spin‐selection rules can be studied via magnetic resonance techniques such as electron–spin resonance and optically detected magnetic resonance as well as electrically detected magnetic resonance (EDMR). The latter has progressed in recent years to a degree where the observation of coherent spin motion via current detection has become possible, providing experimental access to many new insights into the role that paramagnetic centers play for conductivity and photoconductivity. While mostly applied to inorganic semiconductor materials such as silicon, this new, often called pulsed‐(p) EDMR spectroscopy, has much potential for organic (carbon‐based) semiconductors. In this study, progress on the development of pEDMR spectroscopy on carbon‐based materials is reviewed. Insights into materials properties that can be gained from pEDMR experiments are explained and limitations are discussed. Experimental data on radiative polaron‐pair recombination in poly[2‐methoxy‐5‐(20‐ethyl‐hexyloxy)‐1,4‐phenylene vinylene] (MEH‐PPV) organic light emitting diodes (OLEDs) are shown, revealing that under operating conditions the driving current of the device can be modulated by spin‐Rabi nutation of the polaron spin within the charge carrier pairs. From this experimental data it becomes clear that for polaron pairs, the precursor states during exciton formation, exchange interaction is not the predominant influence on the observed pEDMR spectra.

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