Poly(9,9‐dioctylfluorene) (PFO) is a widely studied blue‐emitting conjugated polymer, the optoelectronic properties of which are strongly affected by the presence of a well‐defined chain‐extended “β‐phase” conformational isomer. In this study, optical and Raman spectroscopy are used to systematically investigate the properties of PFO thin films featuring a varied fraction of β‐phase chain segments. Results show that the photoluminescence quantum efficiency (PLQE) of PFO films is highly sensitive to both the β‐phase fraction and the method by which it was induced. Notably, a PLQE of ∼69% is measured for PFO films possessing a ∼6% β‐phase fraction induced by immersion in solvent/nonsolvent mixtures; this value is substantially higher than the average PLQE of ∼55% recorded for other β‐phase films. Furthermore, a linear relationship is observed between the intensity ratios of selected Raman peaks and the β‐phase fraction determined by commonly used absorption calibrations, suggesting that Raman spectroscopy can be used as an alternative means to quantify the β‐phase fraction. As a specific example, spatial Raman mapping is used to image a mm‐scale β‐phase stripe patterned in a glassy PFO film, with the extracted β‐phase fraction showing excellent agreement with the results of optical spectroscopy. © 2016 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 1995–2006

Imidazolium ionic side-group-containing fluorene-based conjugated polyelectrolytes (CPEs) with different π-conjugated structures, poly[(9,9-bis(8'-(3"-methyl-1"-imidazolium)octyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] dibromide (F8im-Br) and poly [(9,9-bis(8'-(3"-methyl-are synthesized and utilized as an electron injection layer (EIL) in green-emitting F8BT polymer light-emitting diodes (PLEDs). Both CPE EIL devices significantly outperform Ca cathode devices; 17.9 cd A -1 (at 3.8 V) and 16.6 lm W -1 (at 3.0 V) for F8imBT-Br devices, 11.1 cd A -1 (at 4.2 V) and 9.1 lm W -1 (at 3.4 V) for F8im-Br devices, and 7.2 cd A -1 (at 3.6 V) and 7.0 lm W -1 (at 3.0 V) for Ca devices. Importantly, unlike the F8im-Br EIL devices, F8imBT-Br PLEDs exhibit much faster electroluminescence turn-on times (< 10 μs) despite both EILs possessing the same tethered imidazolium and mobile bromide ions. The F8imBT-Br devices represent, to the best of our knowledge, the highest efficiency in thin (70 nm) single-layer F8BT PLEDs in conventional device architecture with the fastest EL response time using CPE EIL with mobile ions. Our results clearly indicate the importance of an additional factor of EIL materials, specifically the conjugated backbone structure, to determine the device efficiency and response times.3

We report a novel approach to achieve deep-blue, high-efficiency, and long-lived solution-processed polymer light-emitting diodes (PLEDs) via a simple molecular level conformation change of an emissive conjugated polymer. We introduce rigid β-phase segments into a 95% fluorene-5% arylamine copolymer emissive layer. The arylamine moieties at low density act as efficient exciton formation sites in PLEDs, whereas the conformational change alters the nature of the dominant luminescence from a broad, charge transfer like emission to a significantly blue-shifted and highly vibronically structured excitonic emission. As a consequence, we observe a significant improvement in the Commission International de L'Eclairage ( x, y) coordinates from (0.149, 0.175) to (0.145, 0.123) while maintaining high efficiency and improved stability. We achieve a peak luminous efficiency, η = 3.60 cd/A, and a luminous power efficiency, η = 2.44 lm/W, values that represent state-of-the-art performance for single copolymer deep-blue PLEDs. These values are 5-fold better than for otherwise-equivalent, β-phase poly(9,9-dioctylfluorene) PLEDs (0.70 cd/A and 0.38 lm/W). This report represents the first demonstration of the use of molecular conformation as a simple but effective method to control the optoelectronic properties of a fluorene copolymer; previous examples have been confined to homopolymers.

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