Electrodes with low work functions are required to efficiently inject electrons into semiconductor devices. However, when the work function drops below about 4 electronvolts, the electrode suffers oxidation in air, which prevents its fabrication in ambient conditions. Here we show that multivalent anions such as oxalate, carbonate and sulfite can act as powerful latent electron donors when dispersed as small ion clusters in a matrix, while retaining their ability to be processed in solution in ambient conditions. The anions in these clusters can even n-dope the semiconductor core of π-conjugated polyelectrolytes that have low electron affinities, through a ground-state doping mechanism that is further amplified by a hole-sensitized or photosensitized mechanism in the device. A theoretical analysis of donor levels of these anions reveals that they are favourably upshifted from ionic lattices by a decrease in the Coulomb stabilization of small ion clusters, and by irreversibility effects. We attain an ultralow effective work function of 2.4 electronvolts with the polyfluorene core. We realize high-performance, solution-processed, white-light-emitting diodes and organic solar cells using polymer electron injection layers with these universal anion donors, demonstrating a general approach to chemically designed and ambient-processed Ohmic electron contacts for semiconductor devices.

ABSTRACTPolytriarylamine copolymers can be prepared by Suzuki‐Miyaura cross‐coupling reactions of bis N‐methyliminodiacetic acid (MIDA) boronate ester substituted arylamines with dibromo arenes. The roles of solvent composition, temperature, reaction time, and co‐monomer structure were examined and (co)polymers prepared containing 9, 9‐dioctylfluorene (F8), 4‐sec‐butyl or 4‐octylphenyl diphenyl amine (TFB), and N, N′‐bis(4‐octylphenyl)‐N, N′‐diphenyl phenylenediamine (PTB) units, using a Pd(OAc)2/2‐dicyclohexylphosphino‐2′,6′‐dimethoxybiphenyl (SPhos) catalyst system. The performance of a di‐functionalized MIDA boronate ester monomer was compared with that of an equivalent pinacol boronate ester. Higher molar mass polymers were produced from reactions starting with a difunctionalized pinacol boronate ester monomer than the equivalent difunctionalized MIDA boronate ester monomer in biphase solvent mixtures (toluene/dioxane/water). Matrix‐assisted laser desorption/ionization mass spectroscopic analysis revealed that polymeric structures rich in residues associated with the starting MIDA monomer were present, suggesting that homo‐coupling of the boronate ester must be occurring to the detriment of cross‐coupling in the step‐growth polymerization. However, when comparable reactions of the two boronate monomers with a dibromo fluorene monomer were completed in a single phase solvent mixture (dioxane + water), high molar mass polymers with relatively narrow distribution ranges were obtained after only 4 h of reaction. © 2017 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2798–2806

Post-polymerization modification of the donor-acceptor polymer, poly(9,9-dioctylfluorene-alt-benzothiadiazole), PF8-BT, by electrophilic C-H borylation is a simple method to introduce controllable quantities of near-infrared (near-IR) emitting chromophore units into the backbone of a conjugated polymer. The highly stable borylated unit possesses a significantly lower LUMO energy than the pristine polymer resulting in a reduction in the band gap of the polymer by up to 0.63 eV and a red shift in emission of more than 150 nm. Extensively borylated polymers absorb strongly in the deep red/near-IR and are highly emissive in the near-IR region of the spectrum in solution and solid state. Photoluminescence quantum yield (PLQY) values are extremely high in the solid state for materials with emission maxima ≥ 700 nm with PLQY values of 44% at 700 nm and 11% at 757 nm for PF8-BT with different borylation levels. This high brightness enables efficient solution processed near-IR emitting OLEDs to be fabricated and highly emissive borylated polymer loaded conjugated polymer nanoparticles (CPNPs) to be prepared. The latter are bright, photostable, low toxicity bioimaging agents that in phantom mouse studies show higher signal to background ratios for emission at 820 nm than the ubiquitous near-IR emissive bioimaging agent indocyanine green. This methodology represents a general approach for the post-polymerization functionalization of donor-acceptor polymers to reduce the band gap as confirmed by the C-H borylation of poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(3-hexylthien-5-yl)-2,1,3-benzothiadiazole]-2c,2cc-diyl) (PF8TBT) resulting in a red shift in emission of >150 nm, thereby shifting the emission maximum to 810 nm.

A method to print two materials of different functionality during the same printing step is presented. In printed electronics, devices are built layer by layer and conventionally only one type of material is deposited in one pass. Here, the challenges involving printing of two emissive materials to form polymer light-emitting diodes (PLEDs) that emit light of different wavelengths without any significant changes in the device characteristics are described. The surface-energy-patterning technique is utilized to print materials in regions of interest. This technique proves beneficial in reducing the amount of ink used during blade coating and improving the reproducibility of printed films. A variety of colors (green, red, and near-infrared) are demonstrated and characterized. This is the first known attempt to print multiple materials by blade coating. These devices are further used in conjunction with a commercially available photodiode to perform blood oxygenation measurements on the wrist, where common accessories are worn. Prior to actual application, the threshold conditions for each color are discussed, in order to acquire a stable and reproducible photoplethysmogram (PPG) signal. Finally, based on the conditions, PPG and oxygenation measurements are successfully performed on the wrist with green and red PLEDs.

Abstract Stille, Suzuki–Miyaura and Negishi cross‐coupling reactions of bromine‐functionalised borylated precursors enable the facile, high yielding, synthesis of borylated donor–acceptor materials that contain electron‐rich aromatic units and/or extended effective conjugation lengths. These materials have large Stokes shifts, low LUMO energies, small band‐gaps and significant fluorescence emission >700 nm in solution and when dispersed in a host polymer.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Electrophilic borylation using BCl3and benzothiadiazole to direct the C–H functionalisation of an adjacent aromatic unit produces fused boracyclic materials with minimally changed HOMO energies but significantly reduced LUMO energies.

Through understanding of the device and photo‐physics we have developed a fluorescent and phosphorescent hybrid materials set and device architecture for stable white Polymer OLED (P‐OLED) lighting devices yielding 25 lm/W efficiency. We show that this technology can be transferred to solution processed ITO‐free lighting panels realizing 32 lm/W efficiency with out‐coupling film.

A device structure that enables the combination of phosphorescent green and fluorescent blue emitters in a solution processed polymer organic light-emitting diode device has been developed. Results demonstrate that it is possible to tune the color of emission by appropriate formulation of the polymers that are used. This enabled the development of a warm white device that had CIE coordinates of (0.462, 0.426), and an external quantum efficiency (EQE) of 13.1%. This EQE was limited by the efficiencies of the emitters used rather than through any internal quenching, and thus the device structure offers potential for further development. (C) 2011 Society of Photo-Optical Instrumentation Engineers (SPIE). [DOI: 10.1117/1.3569108]