Fluorescent Nanoparticles Based on Self‐Assembled π‐Conjugated Systems

π‐Conjugated molecules are interesting components to prepare fluorescent nanoparticles. From the use of polymer chains that form small aggregates in water to the self‐assembly of small chromophoric segments into highly ordered structures, the preparation of these materials allows to develop systems with applications as sensors or biolabels. The potential functionalization of the nanoparticles can lead to specific probing. This progress report describes the recent advances in the preparation of such emittive organic nanoparticles.     

Desktop‐Stereolithography 3D‐Printing of a Poly(dimethylsiloxane)‐Based Material with Sylgard‐184 Properties

The advantageous physiochemical properties of poly(dimethylsiloxane) (PDMS) have made it an extremely useful material for prototyping in various technological, scientific, and clinical areas. However, PDMS molding is a manual procedure and requires tedious assembly steps, especially for 3D designs, thereby limiting its access and usability. On the other hand, automated digital manufacturing processes such as stereolithography (SL) enable true 3D design and fabrication. Here the formulation, characterization, and SL application of a 3D‐printable PDMS resin (3DP‐PDMS) based on commercially available PDMS‐methacrylate macromers, a high‐efficiency photoinitiator and a high‐absorbance photosensitizer, is reported. Using a desktop SL‐printer, optically transparent submillimeter structures and microfluidic channels are demonstrated. An optimized blend of PDMS‐methacrylate macromers is also used to SL‐print structures with mechanical properties similar to conventional thermally cured PDMS (Sylgard‐184). Furthermore, it is shown that SL‐printed 3DP‐PDMS substrates can be rendered suitable for mammalian cell culture. The 3DP‐PDMS resin enables assembly‐free, automated, digital manufacturing of PDMS, which should facilitate the prototyping of devices for microfluidics, organ‐on‐chip platforms, soft robotics, flexible electronics, and sensors, among others.     

A Self‐Organized Poly(vinylpyrrolidone)‐Based Cathode Interlayer in Inverted Fullerene‐Free Organic Solar Cells

Herein, poly(vinylpyrrolidone) (PVP) is used as the cathode interlayer (CIL) through the self‐organization method in inverted organic solar cells (OSCs). By coating a solution of PVP and active layer materials onto a glass/indium tin oxide (ITO) substrate, the PVP can segregate to the near ITO side due to its high surface energy and strong intermolecular interaction with the ITO electrode. The power conversion efficiency (PCE) of the obtained OSC device reaches 13.3%, much higher than that of the control device with a PCE of only 10.1%. The improvement results from the increased exciton dissociation efficiency and the depressed trap‐assisted recombination, which can be attributed to the reduced work function of the cathode by the self‐organized PVP. Additionally, the molecular weight of the PVP has almost no influence on the device performance, and the PVP‐modified device presents superior stability. This method can also be applied in other highly efficient fullerene‐free OSCs, and with a fine selection of the active layer, a high PCE of 14.0% is obtained. Overall, this work demonstrates the great potential of the PVP‐based CIL in inverted OSCs fabricated via the self‐organization method.     

Optical Bandgaps of π‐Conjugated Organic Materials at the Polymer Limit: Experiment and Theory

In this Review, the extreme care that must be taken when predicting the optical properties of conjugated polymers via the oligomer approach, and when comparing theoretical and experimental data, is illustrated. In the first part, conceptual strategies for the correct determination of optical transitions from experimental spectra and relevant extrapolation procedures at the polymer limit are introduced. The impact of conformational, substitution, solvent, and solid‐state effects on the optical properties is discussed in light of experimental data reported for molecular backbones based on phenylene, phenylenevinylene, and thiophene repeat units. A comparison is then made between experimental results and those provided by standard quantum‐chemical methods, to assess their reliability.     

Photoinduced Self‐Assembled Nanostructures and Permanent Polaron Formation in Regioregular Poly(3‐hexylthiophene)

Solution processing of conjugated polymers into ordered self‐assembled precursors has attracted great interest in the past years owing to the ability to manipulate their structural and physical properties. Regioregular poly(3‐hexylthiophene) (P3HT) has become the benchmark polymer in this scenario, where ordered lamellar structures significantly improve carrier mobility of the thin films due to increased crystallinity, extended intrachain conjugation, and ordered interchain π‐stacking. Here, a new photoinduced approach is presented for the generation of highly ordered P3HT aggregate structures that is amenable to the use of visible light to control the aggregate formation. Strong intra‐ and interchain interactions in the solution precursors allow for permanent formation of localized and delocalized polarons that are stable for months. Spin‐coated thin films are found to preserve, in part, the morphological and physical properties of the aggregated P3HT solution precursors with high degree of crystallinity and short π‐stack interchain distances.     

π‐Conjugated Polymers Incorporating a Novel Planar Quinoid Building Block with Extended Delocalization and High Charge Carrier Mobility

Two novel conjugated polymers incorporating quinoidal thiophene are successfully synthesized. By combining 1D nuclear magnetic resonance (NMR) and 2D nuclear Overhauser effect spectroscopy analyses, the isomeric form of the major quinoid monomer is clearly identified as the asymmetric Z, E‐configuration. The quinoidal polymers are synthesized via Stille polymerization with thiophene or bithiophene. Both quinoidal polymers exhibit the low band gap of 1.45 eV and amphoteric redox behavior, indicating extended conjugation owing to the quinoidal backbone. These quinoidal polymers show ambipolar behaviors with high charge carrier mobilities when applied in organic field‐effect transistors. In addition, the radial alignment of polymer chains achieved by off‐center spin‐coating leads to further improvement of device performance, with poly(quinoidal thiophene–bithiophene) exhibiting a high hole mobility of 8.09 cm² V^?1 s^?1, which is the highest value among the quinoidal polymers up to now. Microstructural alteration via thermal annealing or off‐center spin‐coating is found to beneficially affect charge transport. The enhancement of crystallinity with strong π–π interactions and the nanofibrillar structure arising from planar well‐delocalized quinoid units is considered to be responsible for the high charge carrier mobility.