Harnessing the spin degree of freedom in semiconductors is generally a challenging, yet rewarding task. In recent years, the large effect of a small magnetic field on the current in organic semiconductors has puzzled the young field of organic spintronics. Although the microscopic interaction mechanisms between spin-carrying particles in organic materials are well understood nowadays, there is no consensus as to which pairs of spin-carrying particles are actually influencing the current in such a drastic manner. Here we demonstrate that the spin-based particle reactions can be tuned in a blend of organic materials, and microscopic mechanisms are identified using magnetoresistance lineshapes and voltage dependencies as fingerprints. We find that different mechanisms can dominate, depending on the exact materials choice, morphology and operating conditions. Our improved understanding will contribute to the future control of magnetic field effects in organic semiconductors.
The large effect of a small magnetic field on the current, magnetoconductance (MC), in organic semiconductors-so-called organic magnetoresistance-has puzzled the field of organic spintronics during the last decade. Although the microscopic mechanisms regarding spin mixing are well understood by now, it is still unknown which pairs of spin carrying particles are influencing the current in such a drastic manner. Here, a model for the MC is presented based on the spin selective formation of metastable trions from triplet exciton-polaron pairs. Additionally, the magnetic-field and voltage dependence of the MC are experimentally investigated in materials showing large effects. Using a combination of analytical and numerical calculations, it is shown that the MC is perfectly described by a process in which trions are created at polaron trap sites.
Triplet exciton (TE) formation pathways have systematically been investigated in prototype bulk heterojunction (BHJ) SY-PPV:PCBM, SY-PPV:PC70BM, and SY-PPV:ICBA solar cell devices of varying compositions using complementary optoelectrical and electrically detected magnetic resonance (EDMR) spectroscopies. In this investigation it is shown that EDMR spectroscopy allows the unambiguous demonstration of fullerene triplet production in BHJ polymer:fullerene solar cells. EDMR triplet detection under selective photoexcitation of each blend component and of the interfacial charge transfer (CT) state unravels that low lying fullerene TEs are produced by direct intersystem crossing from singlet excitons (SEs). The direct CT-TE recombination pathway, although energetically feasible, is kinetically suppressed in these devices. However, high energy CT states in the CT manifold can contribute to the population of the fullerene triplet state via a direct CT-SE conversion. This undesirable energetic alignment could be one of the causes for the severe reduction in photocurrent observed when the open circuit voltage of polymer:fullerene solar cells is pushed to or beyond 1.0 V.
Large negative magnetoconductance (MC) of ∼12% is observed in electrochemically doped polymer light-emitting diodes at sub-band-gap bias voltages (V bias ). Simultaneously, a positive magnetoefficiency (Mη) of 9% is observed at V bias = 2 V. At higher bias voltages, both the MC and Mη diminish while a negative magnetoelectroluminescence (MEL) appears. The negative MEL effect is rationalized by triplet-triplet annihilation that leads to delayed fluorescence, whereas the positive Mη effect is related to competition between spin mixing and exciton formation leading to an enhanced singlet:triplet ratio at nonzero magnetic field. The resultant reduction in triplet exciton density is argued to reduce detrapping of polarons in the recombination zone at low-bias voltages, explaining the observed negative MC. Regarding organic magnetoresistance, this study provides experimental data to verify existing models describing magnetic field effects in organic semiconductors, which contribute to better understanding hereof. Furthermore, we present indications of strong magnetic field effects related to interactions between trapped carriers and excitons, which specifically can be studied in electrochemically doped organic light-emitting diodes (OLEDs). Regarding light-emitting electrochemical cells (LECs), this work shows that delayed fluorescence from triplet-triplet annihilation substantially contributes to the electroluminescence and the device efficiency.
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