Metal–organic framework nanosheets for enhanced performance of organic photovoltaic cells

Metal–organic framework nanosheets (MONs) are an emerging class of two-dimensional materials whose diverse and readily tunable structures make them ideal for use in optoelectronic applications. Here, liquid exfoliation is used to synthesize ultrathin zinc-porphyrin based MONs with electronic and optical properties ideally suited for incorporation into a polythiophene–fullerene (P3HT–PCBM) organic solar cell. Remarkably, the addition of MONs to the photoactive layer of a photovoltaic device results in a power conversion efficiency of 5.2%, almost twice that for reference devices without nanosheets with a simultaneous improvement of Jsc, Voc and FF. Our analysis indicates that the complimentary electronic, optical and structural properties of the MONs allows them to act as a surface to template the crystallization of P3HT leading to a doubling of the absorbance, a tenfold increase in hole mobility and reduced grain size. These results demonstrate the potential of MONs as a tunable class of two-dimensional materials for enhancing the performance of a broad range of organic solar cells and other electronic devices

Singlet fission is incoherent in pristine orthorhombic single crystals of rubrene: no evidence of triplet-pair emission

Singlet fission (SF) and its inverse, triplet–triplet annihilation (TTA), are promising strategies for enhancing photovoltaic efficiencies. However, detailed descriptions of the processes of SF/TTA are not fully understood, even in the most well-studied systems. Reports of the photophysics of crystalline rubrene, for example, are often inconsistent. Here we attempt to resolve these inconsistencies using time-resolved photoluminescence and transient absorption spectroscopy of ‘pristine’ rubrene orthorhombic single crystals. We find the reported time-resolved photoluminescence behaviour that hinted at triplet-pair emission is found only at specific sites on the crystals and likely arises from surface defects. Using transient absorption spectroscopy of the same crystals, we also observe no evidence of instantaneous generation of triplet-pair population with ∼100 fs excitation, independent of excitation wavelength (532 nm, 495 nm) or excitation angle. Our results suggest that SF occurs incoherently on a relatively slow (picosecond) timescale in rubrene single crystals, as expected from the original theoretical calculations. We conclude that the sub-100 fs formation of triplet pairs in crystalline rubrene films is likely to be due to static disorder

Radiative pumping in a strongly coupled microcavity filled with a neat molecular film showing excimer emission

Strong light-matter interactions have attracted much attention as a means to control the physical/chemical properties of organic semiconducting materials with light-matter hybrids called polaritons. To unveil the processes under strong coupling, studies on the dynamics of polaritons are of particular importance. While highly condensed molecular materials with large dipole density are ideal to achieve strong coupling, the emission properties of such films often become a mixture of monomeric and excimeric components, making the role of excimers unclear. Here, we use amorphous neat films of a new bis(phenylethynyl anthracene) derivative showing only excimer emission and investigate the excited-state dynamics of a series of strongly coupled microcavities, with each cavity being characterised by a different exciton–photon detuning. A time-resolved photoluminescence study shows that the excimer radiatively pumps the lower polariton in the relaxation process and the decay profile reflects the density of states. The delayed emission derived from triplet–triplet annihilation is not sensitive to the cavity environment, possibly due to the rapid excimer formation. Our results highlight the importance of controlling intermolecular interactions towards rational design of organic exciton–polariton devices, whose performance depends on efficient polariton relaxation pathways

Emissive spin-0 triplet-pairs are a direct product of triplet–triplet annihilation in pentacene single crystals and anthradithiophene films

Singlet fission and triplet–triplet annihilation represent two highly promising ways of increasing the efficiency of photovoltaic devices. Both processes are believed to be mediated by a biexcitonic triplet-pair state, 1(TT). Recently however, there has been debate over the role of 1(TT) in triplet–triplet annihilation. Here we use intensity-dependent, low-temperature photoluminescence measurements, combined with kinetic modelling, to show that distinct 1(TT) emission arises directly from triplet–triplet annihilation in high-quality pentacene single crystals and anthradithiophene (diF-TES-ADT) thin films. This work demonstrates that a real, emissive triplet-pair state acts as an intermediate in both singlet fission and triplet–triplet annihilation and that this is true for both endo- and exothermic singlet fission materials

In optimized rubrene-based nanoparticle blends for photon upconversion, singlet energy collection outcompetes triplet-pair separation, not singlet fission

The conversion of near-infrared photons to visible light through triplet–triplet annihilation upconversion offers an enticing strategy for significantly boosting the efficiency of conventional solar cell technology. Rubrene is widely employed as the acceptor molecule for realising such upconversion, yet in the solid state, the reverse process of singlet fission is believed to hinder efficient upconversion. Consequently, rubrene is sometimes doped at low concentration (0.5 mol%) with the singlet energy collector tetraphenyldibenzoperiflanthene (DBP) which harvests singlet energy via Förster transfer. Although singlet fission is a multi-step process involving various intermediate triplet-pair states, the interplay between it, triplet recombination and singlet energy collection has not been studied in detail to date. Here we use both transient absorption and time-resolved fluorescence spectroscopy to investigate the dynamics of both singlet and triplet species in rubrene-based nanoparticle films. Strikingly, we find that energy transfer from rubrene to DBP does not outcompete the formation of triplet-pairs through singlet fission, despite the fact that DBP doping increases the photoluminescence quantum yield of the nanoparticle films from 3% to 61%. We rationalise this surprising result in the context of the well-known effects of triplet fusion and triplet-quenching defects on the photoluminescence yield of crystalline rubrene