Search

The luminescence and electroluminescence of an ethyne-linked zinc(ii) porphyrin pentamer have been investigated, by testing blends in two different conjugated polymer matrices, at a range of concentrations. The best results were obtained for blends with the conjugated polymer PIDT-2TPD, at a porphyrin loading of 1 wt%. This host matrix was selected because the excellent overlap between its emission spectrum and the low-energy region of the absorption spectrum of the porphyrin oligomer leads to efficient energy transfer. Thin films of this blend exhibit intense fluorescence in the near-infrared (NIR), with a peak emission wavelength of 886 nm and a photoluminescent quantum yield (PLQY) of 27% in the solid state. Light-emitting diodes (LEDs) fabricated with this blend as the emissive layer achieve average external quantum efficiencies (EQE) of 2.0% with peak emission at 830 nm and a turn-on voltage of 1.6 V. This performance is remarkable for a singlet NIR-emitter; 93% of the photons are emitted in the NIR ( λ > 700 nm), indicating that conjugated porphyrin oligomers are promising emitters for non-toxic NIR OLEDs., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The energy gap law (E G -law) and aggregation quenching are the main limitations to overcome in the design of near-infrared (NIR) organic emitters. Here, we achieve unprecedented results by synergistically addressing both of these limitations. First, we propose porphyrin oligomers with increasing length to attenuate the effects of the E G -law by suppressing the non-radiative rate growth, and to increase the radiative rate via enhancement of the oscillator strength. Second, we design side chains to suppress aggregation quenching. We find that the logarithmic rate of variation in the non-radiative rate vs. E G is suppressed by an order of magnitude with respect to previous studies, and we complement this breakthrough by demonstrating organic light-emitting diodes with an average external quantum efficiency of ~1.1%, which is very promising for a heavy-metal-free 850 nm emitter. We also present a novel quantitative model of the internal quantum efficiency for active layers supporting triplet-to-singlet conversion. These results provide a general strategy for designing high-luminance NIR emitters.

We present the synthesis and characterization of a series of encapsulated diketopyrrolopyrrole red-emitting conjugated polymers. The novel materials display extremely high fluorescence quantum yields in both solution (>70%) and thin film (>20%). Both the absorption and emission spectra show clearer, more defined features compared to their naked counterparts demonstrating the suppression of inter and intramolecular aggregation. We find that the encapsulation results in decreased energetic disorder and a dramatic increase in backbone colinearity as evidenced by scanning tunnelling microscopy. This study paves the way for diketopyrrolopyrrole to be used in emissive solid state applications and demonstrates a novel method to reduce structural disorder in conjugated polymers.

The presence of energetically low-lying triplet states is a hallmark of organic semiconductors. Even though they present a wealth of interesting photophysical properties, these optically dark states significantly limit optoelectronic device performance. Recent advances in emissive charge-transfer molecules have pioneered routes to reduce the energy gap between triplets and "bright" singlets, allowing thermal population exchange between them and eliminating a significant loss channel in devices. In conjugated polymers, this gap has proved resistant to modification. Here, we introduce a general approach to reduce the singlet-triplet energy gap in fully conjugated polymers, using a donor-orthogonal acceptor motif to spatially separate electron and hole wave functions. This new generation of conjugated polymers allows for a greatly reduced exchange energy, enhancing triplet formation and enabling thermally activated delayed fluorescence. We find that the mechanisms of both processes are driven by excited-state mixing between π-π*and charge-transfer states, affording new insight into reverse intersystem crossing.