Recent efforts in the field of organic photodetectors (OPD) have been focused on extending broadband detection into the near-infrared (NIR) region. Here, two blends of an ultralow bandgap push-pull polymer TQ-T combined with state-of-the-art non-fullerene acceptors, IEICO-4F and Y6, are compared to obtain OPDs for sensing in the NIR beyond 1100 nm, which is the cut off for benchmark Si photodiodes. It is observed that the TQ-T:IEICO-4F device has a superior IR responsivity (0.03 AW -1 at 1200 nm and -2 V bias) and can detect infrared light up to 1800 nm, while the TQ-T:Y6 blend shows a lower responsivity of 0.01 AW -1 . Device physics analyses are tied with spectroscopic and morphological studies to link the superior performance of TQ-T:IEICO-4F OPD to its faster charge separation as well as more favorable donor-acceptor domains mixing. In the polymer blend with Y6, the formation of large agglomerates that exceed the exciton diffusion length, which leads to high charge recombination, is observed. An application of these devices as biometric sensors for real-time heart rate monitoring via photoplethysmography, utilizing infrared light, is demonstrated.

Non-fullerene acceptors (NFAs) for organic solar cells (OSCs) have significantly developed over the past five years with continuous improvements in efficiency now over 18%. However, a key challenge still remains in order to fully realize their commercialization potential: the need to extend device lifetime and to control degradation mechanisms. Herein, we investigate the effect of two different molecular engineering routes on the widely utilized ITIC NFA, to tune its optoelectronic properties and interactions with the donor polymer in photoactive blends. Heavier selenium (Se) atoms substitute sulfur (S) atoms in the NFA core in either outer or inner positions, and methyl chains are attached to the end groups. By investigating the effects of these structural modifications on the long-term operational stability of bulk-heterojunction OSC devices, we identify outer selenation as a powerful strategy to significantly increase device lifetime compared to ITIC. Combining outer selenation and methylation results in an impressive 95% of the initial OSC efficiency being retained after 450 h under operating conditions, with an exceptionally long projected half-lifetime of 5600 h compared to 400 h for ITIC. We find that the heavier and larger Se atoms at outer-core positions rigidify the molecular structure to form highly crystalline films with low conformational energetic disorder. It further enhances charge delocalization over the molecule, promoting strong intermolecular interactions among acceptor molecules. Upon methylation, this strong intermolecular interaction stabilizes acceptor domains in blends to be resilient to light-induced morphological changes, thereby leading to superior device stability. Our results highlight the crucial role of NFA molecular structure for OSC operational stability and provide important NFA design rules via heteroatom position and end-group control.

Despite many advances toward improving the stability of organic photovoltaic devices, environmental degradation under ambient conditions remains a challenging obstacle for future application. Particularly conventional systems employing fullerene derivatives are prone to oxidize under illumination, limiting their applicability. Here, the environmental stability of the small molecule donor DRCN5T together with the fullerene acceptor PC 70 BM is reported. It is found that this system exhibits exceptional device stability, mainly due to almost constant short-circuit current. By employing ultrafast femtosecond transient absorption spectroscopy, this remarkable stability is attributed to two separate mechanisms: 1) DRCN5T exhibits high intrinsic resistance toward external factors, showing no signs of deterioration.2) The highly sensitive PC 70 BM is stabilized against degradation by the presence of DRCN5T through ultrafast, long-range energy transfer to the donor, rapidly quenching the fullerene excited states which are otherwise precursors for chemical oxidation. It is proposed that this photoprotective mechanism be utilized to improve the device stability of other systems, including nonfullerene acceptors and ternary blends.

In contemporary organic solar cell (OSC) research, small A-D-A molecules comprising electron donor (D) and acceptor (A) units are increasingly used as a means to control the optoelectronic properties of photovoltaic blends. Slight structural variations to these A-D-A molecules can result in profound changes to the performance of the OSCs. Herein, we study two A-D-A molecules, BTCN-O and BTCN-M, which are identical in structure apart from a subtle difference in the position of alkyl chains, which force the molecules to adopt different equilibrium conformations. These steric effects cause the respective molecules to work better as an electron donor and acceptor when blended with benchmark acceptor and donor materials (PC71BM and PBDB-T). We study the photophysics of these “D:A” blends and devices using a combination of steady-state and time-resolved spectroscopic techniques. Time-resolved photoluminescence reveals the impact of the molecular conformation on the quenching of the A-D-A emission when BTCN-O and BTCN-M are blended with PBDB-T or PC71BM. Ultrafast broadband transient absorption spectroscopy demonstrates that the dynamics of charge separation are essentially identical when comparing BTCN-M and BTCN-O based blends, but the recombination dynamics are quite dissimilar. This suggests that the device performance is ultimately determined by the morphology of the blends imposed by the A-D-A conformation. This notion is supported by X-ray scattering measurements on the “D:A” films, electroluminescence data, and pump–push-photocurrent spectroscopy on the “D:A” devices. Our findings provide insight into the remarkable structure–function relationship in A-D-A molecules and emphasize the need for careful morphological and energetic considerations when designing high-performance OSCs.

An understanding of the initial photoexcited states of DNA is essential to unravelling deleterious photoinduced chemical reactions and the intrinsic ultrafast photoprotection of the genetic code for all life.In our combined experimental and theoretical study, we have elucidated the primary non-radiative relaxation dynamics of a model nucleotide of guanine and thymine (2 0 -deoxyguanosine 3 0 -monophosphate 5 0 -thymidine, d(GpT)) in buffered aqueous solution. Experimentally, we unequivocally demonstrate that the Franck-Condon excited states of d(GpT) are significantly delocalised across both nucleobases, and mediate d(G + pT À ) exciplex product formation on an ultrafast (o350 fs) timescale. Theoretical studies show that the nature of the vertical excited states is very dependent on the specific geometry of the dinucleotide, and dictate the degree of delocalised, charge-transfer or localised character. Our mechanism for prompt exciplex formation involves a rapid change in electronic structure and includes a diabatic surface crossing very close to the Franck-Condon region mediating fast d(G + pT À ) formation. Exciplexes are quickly converted back to neutral ground state molecules on a B10 ps timescale with a high quantum yield, ensuring the photostability of the nucleotide sequence.