Non-fullerene acceptors have revolutionised organic photovoltaics. However, greater fundamental understanding is needed of the crucial relationships between molecular structure and photophysical mechanisms. Herein, a combination of spectroscopic, morphology, and device characterization techniques are used to explore these relationships for a high-performing non-fullerene acceptor, anti-PDFC. It focuses on transient absorption spectroscopy across multiple timescales and ultrafast time-resolved vibrational spectroscopy to acquire the "holy grail" of simultaneous structural and dynamic information for anti-PDFC and its blend with the well-known conjugated polymer PM6. Most significantly, it is observed that the singlet exciton of anti-PDFC is localised on the perylene diimide central core of the molecule, but the radical anion is primarily localised on the fluorinated indene malonitrile terminal units (which are common to many state-of-the-art non-fullerene acceptors, including the Y6 family). This electron transfer from the central core to the termini of an adjacent molecule is facilitated by a close interaction between the termini and the central core, as evidenced by single crystal diffraction data and excited state calculations. Finally, the very efficient charge extraction measured for PM6:anti-PDFC photovoltaic devices may be correlated with this anion localization, enabling effective charge transport channels and thus enhancing device performance.

Non-fullerene acceptors are paving the way toward high-efficiency organic photovoltaics. In the quest to both understand the origins of these high efficiencies and to push them ever higher, the interactions between the different excited states that contribute to device function ineeds to be understood. In this work, the presence and behavior of bimodal polarons are investigated in high-performing conjugated polymer PM6 and its blends with non-fullerene acceptor ITIC-4F and fullerene acceptor PC60BM. Transient absorption spectroscopy is used to gain insight into the blends' polarons as a function of blend ratio. Two types of polymer polaron are identified in the PM6:fullerene blends: bound polarons located in pure polymer domains and "interfacial" polarons located in mixed domains. In contrast, the PM6 polarons observed in PM6:ITIC-4F blends show very different behavior, most notably an almost complete lack of the bound polarons. This loss is attributed to efficient singlet energy transfer from donor to acceptor prior to charge photogeneration taking place. This energy transfer suppresses the formation of bound polaron pairs that rapidly decay back to the ground state, thereby providing another pathway that enables high efficiencies in non-fullerene acceptor-based organic photovoltaics.

Bismuth based coordination complexes are advantageous over other metal complexes, as Bismuth is the heaviest non-toxic element with high spin orbit coupling and potential optoelectronics applications. Herein, four Bismuth halide-based coordination complexes [Bi2Cl6(phen-thio)2] (1), [Bi2Br6(phen-thio)2] (2), [Bi2I6(phen-thio)2] (3), and [Bi2I6(phen-Me)2] (4) were synthesized, characterized and subjected to detailed photophysical studies. The complexes were characterized by single crystal X-ray diffraction, powder X-ray diffraction and NMR studies. Spectroscopic analysis of 1-4 in solutions of different polarities were performed to understand the role of organic and inorganic components in determining the ground and excited state properties of the complexes. The photophysical properties of the complexes were characterized by ground state absorption, steady state photoluminescence, microsecond time-resolved photoluminescence and absorption spectroscopy. Periodic Density Functional Theory (DFT) calculations were performed on the solid state structures to understand the role of organic and inorganic part of the complexes. The studies showed that changing the ancillary ligand from chlorine (Cl), bromine (Br) to iodine (I) bathochromically shifts the absorption band along with enhancing the absorption coefficient. Also, changing the halides (Cl, Br to I) affect the photoluminescent quantum yields of the ligand centered (LC) emissive state without markedly affecting the lifetimes. The combined results confirmed that ground state properties are strongly influenced by the inorganic part and the lower energy excited state is LC. This study paves the way to design novel bismuth coordination complexes for optoelectronic applications by rigorously choosing the ligands and bismuth salt.

Organic photovoltaics are remarkably close to reaching a landmark power conversion efficiency of 20%. Given the current urgent concerns regarding climate change, research into renewable energy solutions is crucially important. In this perspective article, we highlight several key aspects of organic photovoltaics, ranging from fundamental understanding to implementation, that need to be addressed to ensure the success of this promising technology. We cover the intriguing ability of some acceptors to undergo efficient charge photogeneration in the absence of an energetic driving force and the effects of the resulting state hybridization. We explore one of the primary loss mechanisms of organic photovoltaics-non-radiative voltage losses-and the influence of the energy gap law. Triplet states are becoming increasingly relevant owing to their presence in even the most efficient non-fullerene blends, and we assess their role as both a loss mechanism and a potential strategy to enhance efficiency. Finally, two ways in which the implementation of organic photovoltaics can be simplified are addressed. The standard bulk heterojunction architecture could be superseded by either single material photovoltaics or sequentially deposited heterojunctions, and the attributes of both are considered. While several important challenges still lie ahead for organic photovoltaics, their future is, indeed, bright.

Narrow bandgap conjugated polymers are a heavily studied class of organic semiconductors, but their excited states usually have a very short lifetime, limiting their scope for applications. One approach to overcome the short lifetime is to populate long-lived triplet states for which relaxation to the ground state is forbidden. However, the triplet lifetime of narrow bandgap polymer films is typically limited to a few microseconds. Here, we investigated the effect of film morphology on triplet dynamics in red-emitting conjugated polymers based on the classic benzodithiophene monomer unit with the solubilizing alkyl side chains C16 and C2C6 and then used Pd porphyrin sensitization as a further strategy to change the triplet dynamics. Using transient absorption spectroscopy, we demonstrated a 0.45 ms triplet lifetime for the more crystalline nonsensitized polymer C2C6, 2-3 orders of magnitude longer than typically reported, while the amorphous C16 had only a 5 μs lifetime. The increase is partly due to delaying bimolecular electron-hole recombination in the more crystalline C2C6, where a higher energy barrier for charge recombination is expected. A triplet lifetime of 0.4 ms was also achieved by covalently incorporating 5% of Pd porphyrin into the C16 polymer, which introduced extra energy transfer steps between the polymer and porphyrin that delayed triplet dynamics and increased the polymer triplet yield by 7.9 times. This work demonstrates two synthetic approaches to generate the longest-lived triplet excited states in narrow bandgap conjugated polymers, which is of necessity in a wide range of fields that range from organic electronics to sensors and bioapplications.

Quantification of triplet state populations in non-fullerene acceptor blends has allowed us to correlate triplet and charge carrier concentrations, with important ramifications for organic photovoltaics.

The bimolecular recombination characteristics of conjugated polymer poly[(4,4'-bis(2-ethylhexyl)dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-(2,5-bis 3-tetradecylthiophen-2-yl thiazolo 5,4-d thiazole)-2,5diyl] (PDTSiTTz) blended with the fullerene series PC60BM, ICMA, ICBA, and ICTA have been investigated using microsecond and femtosecond transient absorption spectroscopy, in conjunction with electroluminescence measurements and ambient photoemission spectroscopy. The non-Langevin polymer PDTSiTTz allows an inspection of intrinsic bimolecular recombination rates uninhibited by diffusion, while the low oscillator strengths of fullerenes allow polymer features to dominate, and we compare our results to those of the well-known polymer Si-PCPDTBT. Using μs-TAS, we have shown that the trap-limited decay dynamics of the PDTSiTTz polaron becomes progressively slower across the fullerene series, while those of Si-PCPDTBT are invariant. Electroluminescence measurements showed an unusual double peak in pristine PDTSiTTz, attributed to a low energy intragap charge transfer state, likely interchain in nature. Furthermore, while the pristine PDTSiTTz showed a broad, low-intensity density of states, the ICBA and ICTA blends presented a virtually identical DOS to Si-PCPDTBT and its blends. This has been attributed to a shift from a delocalized, interchain highest occupied molecular orbital (HOMO) in the pristine material to a dithienosilole-centered HOMO in the blends, likely a result of the bulky fullerenes increasing interchain separation. This HOMO localization had a side effect of progressively shifting the polymer HOMO to shallower energies, which was correlated with the observed decrease in bimolecular recombination rate and increased "trap" depth. However, since the density of tail states remained the same, this suggests that the traditional viewpoint of "trapping" being dominated by tail states may not encompass the full picture and that the breadth of the DOS may also have a strong influence on bimolecular recombination.

The polymer PffBT4T-C9C13 (poly[(5,6-difluoro-2,1,3-benzothiadiazole-4,7-diyl)[3,3'''-bis(2-decyltetradecyl)[2,2':5',2'':5'',2'' -quaterthiophene]-5,5'''-diyl]]) produces organic solar cells of >11% efficiency with both fullerenes and non-fullerenes. We present a comprehensive morphology and spectroscopy study of this polymer and its blends, focusing on atomic force microscopy, x-ray diffraction, and transient absorption spectroscopy on microsecond timescales. Unusually, fullerene-induced ordering is observed, with the polymer/fullerene blend displaying a greater crystallinity compared to the pristine polymer. This was correlated with the appearance of bimodal polarons: fast-decaying polarons in the pristine amorphous polymer domains and trapped polarons localised in the fullerene-induced ordering (crystallline) domains. The lifetime of the trapped polaron was significantly enhanced upon thermal annealing, and the complex relationship observed between lifetime and film crystallinity suggest a contribution from trap states at the interfaces between ordered and disordered domains that lead to inhibited recombination. In contrast, blends incorporating the well-known analogue PffBT4T-2OD (with a shorter alkyl chain length) exhibit neither fullerene-induced ordering nor bimodal polarons. However, both PffBT4T-C9C13 and PffBT4T-2OD polymer blends show clear evidence of polymer triplet formation, which is the first time triplets have been identified in PffBT4T-based blends. In this study, we remark upon the complex relationship between morphology and the photophysics. This relationship will open the door to the synthesis of new molecules to control the blend morphology and thus optimise organic photovoltaic performance.