The efficiency of light-emitting diodes (LEDs) made from organic semiconductors is determined by the fraction of injected electrons and holes that recombine to form emissive spin-singlet states rather than non-emissive spin-triplet states. If the process by which these states form is spin-independent, the maximum efficiency of organic LEDs will be limited to 25 per cent. But recent reports have indicated fractions of emissive singlet states ranging from 22 to 63 per cent, and the reason for this variation remains unclear. Here we determine the absolute fraction of singlet states generated in a platinum-containing conjugated polymer and its corresponding monomer. The spin-orbit coupling introduced by the platinum atom allows triplet-state emission, so optically and electrically generated luminescence from both singlet and triplet states can be compared directly. We find an average singlet generation fraction of 22 +/- 1 per cent for the monomer, but 57 +/- 4 per cent for the polymer. This suggests that recombination is spin-independent for the monomer, but that a spin-dependent process, favouring singlet formation, is effective in the polymer. We suggest that this process is a consequence of the exchange interaction, which will operate on overlapping electron and hole wavefunctions on the same polymer chain at their capture radius.

We report detailed studies of optoelectronic and charge transport properties at the organic-organic semiconductor interfaces formed between polymer chains (interchain) and within a polymer chain (intrachain). These interfaces are fabricated using poly(9,9-di-n-octylfluorene-alt-N-(4-butylphenyl)diphenylamine) (TFB [f8-tfb]) (electron-donor) and poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT [f8-bt]) (electron-acceptor) conjugated polymers, by blending them together or by covalently attaching them via a main polymer backbone (copolymer). For optoelectronic properties, when a bulky and twisted tfb molecule is incorporated into a rigid F8BT conjugated backbone, it disturbs the conjugation of F8BT polymer, leading to a blue-shift in the lowest absorption transition. However, by acting as an effective electron donor, it assists the formation of an intrachain singlet exciton that has a strong charge-transfer character, leading to a red-shifted and longer-lived emission than that of F8BT. An extremely efficient and fast energy transfer from tfb donor to bt acceptor is observed in the copolymer (<1 ps) compared to transfer from TFB to F8BT in the blend (tens of ps). This efficient energy transfer in the copolymer is found to be associated with its low fluorescence efficiency (40-45% vs 60-65% for blend) because of the migration of radiative singlet excitons to low-energy states such as triplet and exciplex states that are nonemissive or weakly emissive. The presence of molecular-scale tfb-f8-bt interfaces in the copolymer, however, does not hinder an efficient transport of charge carriers at high drive voltages. Instead, it provides a better balance of charge carriers inside the device, which leads to slower decay of the device efficiency and thus more stable light-emitting diodes with increasing voltage than the blend devices. These distinctive optoelectronic and charge transport properties observed at different organic-organic semiconductor interfaces will provide useful input for the design rules of conjugated polymers required for improved molecular electronics.

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