Di‐n‐alkyl substituted polyfluorenes with alkyl chain lengths of 6, 7, 8, 9, and 10 carbon atoms (PF6, PF7, PF8, PF9, and PF10) are studied in dilute solution in MCH using optical spectroscopy. Beta‐phase is formed upon cooling in solutions (∼ 7 µg mL−1) of PF7, PF8, and PF9 only, which is observed as an equilibrium absorption peak at ∼ 437 nm and strong changes in the emission spectra. Beta‐phase is formed upon thermal cycling to low temperature in solutions (∼7 µg mL−1) of PF7, PF8, and PF9, which is observed as an equilibrium absorption peak at ∼ 437 nm and strong changes in the emission spectra. Beta phase is found to occur more favorably in PF8 than in PF7 or PF9, which is attributed to a balance between two factors. The first is the dimer/aggregate formation efficiency, which is poorer for longer (more disordered) alkyl chain lengths, and the second is the Van der Waals bond energy available to overcome the steric repulsion and planarize the conjugated backbone, which is insufficient in the PF6 with a shorter alkyl chain. Beta phase formation is shown to be a result of aggregation, not a precursor to it. A tentative value of the energy required to planarize the fluorene backbone of (15.6 ± 2.5) kJ mol−1 monomer is suggested. Excitation spectra of PF6, PF7, PF8, and PF9 in extremely dilute (∼ 10 ng mL−1) solution show that beta phase can form reversibly in dilute solutions of PF7, PF8 and PF9, which is believed to be a result of chain collapse or well dispersed aggregates being present in solution from dilution of more concentrated solutions. PF7, PF8, and PF9 also form beta phase in thermally cycled solid films spin‐cast from MCH. However, in the films the PF7 formed a larger fraction of beta phase than the PF9, in contrast to the case in solutions, because it is less likely that the close‐packed chains in the solid state will allow the formation of planarized chains with the longer PF9 side chains.

One of the key issues concerning the development of efficient polymer solar cell technology is the lack of viable materials which absorb in the near‐infrared (NIR) region. This could be resolved by up‐converting energy from the NIR into visible using triplet fusion (TF) with an additional layer that is fabricated separately from the solar cell and deposited on top. Theoretically a maximum upconversion (UC) via TF efficiency of 50% could be obtained. Here, it is demonstrated that in a film of commercially available poly(para‐phenylene vinylene) copolymer “super yellow” (SY) doped with 4% palladium(meso‐tetraphenyl‐tetrabenzoporphyrin) (PdTPBP) sensitizer, an UC efficiency of 6% can be achieved. By using femtosecond and nanosecond spectroscopies it is shown that the main UC efficiency loss mechanism is due to triplet quenching in PdTPBP aggregates. The PdTPBP intersystem crossing rate constant is determined to be 1.8 × 1011 s−1 and the triplet energy transfer rate constant from PdTPBP to SY to be 109 s−1. Quenching in PdTPBP aggregates can account for a triplet concentration loss in the range of 76‐99%. As such, preventing sensitizer aggregation in NIR‐to‐visible upconverting films is crucial and may lead to substantial increase of UC efficiencies in films.

The formation of self-organized structures in poly(9,9-di-n-alkylfluorene)s ∼1 vol % methylcyclohexane (MCH) and deuterated MCH solutions was studied at room temperature using neutron and x-ray scattering (with the overall q range of 0.000 58-4.29Å−1 ) and optical spectroscopy. The number of side chain carbons (N ) ranged from 6 to 10. The phase behavior was rationalized in terms of polymer overlap, cross-link density, and blending rules. For N = 6−9, the system contains isotropic areas and lyotropic areas where sheetlike assemblies (lateral size of >400Å) and free polymer chains form ribbonlike agglomerates (characteristic dimension of >1500Å) leading to a gel-like appearance of the solutions. The ribbons are largely packed together with surface fractal characteristics for N = 6−7 but become open networklike structures with mass fractal characteristics for N = 8−9, until the system goes through a transition to an isotropic phase of overlapping rodlike polymers for N = 10. The polymer order within sheets varies allowing classification for loose membranes and ordered sheets, including the so-called β phase. The polymers within the ordered sheets have restricted motion for N = 6−7 but more freedom to vibrate for N = 8−9. The nodes in the ribbon network are suggested to contain ordered sheets cross-linking the ribbons together, while the nodes in the isotropic phase appear as weak density fluctuations cross-linking individual chains together. The tendencies for macrophase separation and the formation of non beta sheets decrease while the proportion of free chains increases with increasing N. The fraction of β phase varies nonlinearly, reaching its maximum at N = 8.

In this paper, we investigate excited state dynamics in amorphous rubrene vacuum sublimed films. We report the direct observation of singlet fission in amorphous rubrene films. We have determined the fission rate to be >2.5 × 10 12 s −1 . Simultaneously, we observe strong polaron pair absorption and propose that polaron pair formation could be competing with singlet fission. Another possible conclusion from our experiments could be that two triplets from singlet fission might arise via polaron pairs. In either case, polaron pairs play an important role in singlet fission in an amorphous rubrene film. We also observe that triplets created by singlet fission fuse to regenerate a singlet, giving delayed fluorescence (DF) scaling linearly with initial laser energy (i.e., one singlet gives two triplets and two triplets give back one singlet). This is a strong evidence of S n 1 → 2T 1 . We did not observe substantial temperature dependence of DF decay curve shape, indicating that triplet migration in amorphous rubrene films is not hopping limited and that triplets undergo fusion before their migration.

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We present small-angle neutron scattering (SANS) and optical absorption studies of random poly [9,9-bis(2-ethylhexyl)fluorene]-co-(9,9-dioctylfluorene) (PF2/6-F8) mixed with deuterated methylcyclohexane (MCH-d 14 ) at room temperature. The polymers studied have identical main chains and the same number of side chain carbons, but they differ in terms of side chain branching such that the fraction of F8 repeat units with linear octyl side chains was 50, 90 or 95%. Poly[9,9-bis(2-ethylhexyl)fluorene] (PF2/6) and poly(9,9-dioctylfluorene) (PF8) homopolymers were studied for comparison. On the scale of 100 nm or less, the data imply that PF2/6 and PF2/6-F8 (50:50) appear as separated stiff chains (the diameter of the order of 1 nm). PF8 and PF2/6-F8 (10:90 and 5:95) aggregate into stiff sheetlike aggregates (the lateral size of tens of nanometers, the thickness of about 2 nm). This aggregation tendency is an inverse function of side chain branching. On scales over 100 nm, the locally dissolved polymers overlap and form macroscopically isotropic network. In contrast, the polymer sheets form cross-linked ribbonlike agglomerates. This tendency, too, varies with the degree of side chain branching. The extent of β-phase follows the existence of sheetlike structures increasing sharply with increasing F8 content.

Random copolymers of poly(9,9-di-n-octylfluorene) (PF8) incorporating 0, 8, 12, 15, and 20% dibenzothiophene (DBT), and copolymers with 2, 5, 8, 12, and 15% dibenzothiophene-S,S-dioxide (S-unit) were synthesised. Absorption and emission spectra of thin films indicate that the DBT system shows a linear decrease of toluene vapour induced β phase with increasing DBT content to a 20% cutoff, whilst in the S-unit copolymers the β phase is present up to 12% co-monomer content, and at 15% the characteristic absorption peak is absent or masked. These results demonstrate the limits, in thin films, at which the β phase can be formed in widely used PF8 copolymer systems for device applications and clearly show that it is practical to use copolymers having electron or hole transport units in the polyfluorene backbone and still be able to form efficient β phase emission sites.