Elastic-Plastic Fully π-Conjugated Polymer with Excellent Energy Dissipation Capacity for Ultra-Deep-Blue Flexible Polymer Light-Emitting Diodes with CIEy = 0.04.

Emerging intrinsically flexible fully π-conjugated polymers (FπCPs) are a promising functional material for flexible optoelectronics, attributed to their potential interchain interpenetration and entanglement. However, the challenge remains in obtaining elastic-plastic FπCPs with intrinsic robust optoelectronic property and excellent long-term and cycling deformation stability simultaneously for applications in deep-blue flexible polymer light-emitting diodes (PLEDs). This study, demonstrates a series of elastic-plastic FπCPs (P1-P4) with an excellent energy dissipation capacity via side-chain internal plasticization for the ultra-deep-blue flexible PLEDs. First, the freestanding P1 film exhibited a maximum fracture strain of 34.6%. More interestingly, the elastic behavior is observed with a low strain (≤10%), and the stretched film with a high deformation (>10%) attributed to plastic processing revealed the robust capacity to realize energy absorption and release. The elastic-plastic P1 film exhibits outstanding ultra-deep-blue emission, with an efficiency of 56.38%. Subsequently, efficient PLEDs are fabricated with an ultra-deep-blue emission of CIE (0.16, 0.04) and a maximum external quantum efficiency of 1.73%. Finally, stable and efficient ultra-deep-blue electroluminescence are obtained from PLEDs based on stretchable films with different strains and cycling deformations, suggesting excellent elastic-plastic behavior and deformation stability for flexible electronics.

Triphenylamine Spirofunctionalized Light-Emitting Conjugated Polymer with an Ultradeep-Blue Narrowband Emission for Large-Area Printed Display.

Emerging printed large-area polymer light-emitting diodes (PLEDs) are essential for manufacturing flat-panel displays and solid lighting devices. However, it is challenging to obtain large-area and stable ultradeep-blue PLEDs because of the lack of light-emitting conjugated polymers (LCPs) with robust deep-blue emissions, excellent morphological stabilities, and high charging abilities. Here, a novel unsymmetrically substituted polydiarylfluorene (POPSAF) is obtained with stable narrowband emission for large-area printed displays via triphenylamine (TPA) spirofunctionalization of LCPs. POPSAF films show narrowband and stable ultradeep-blue emission with a full width at half maximum (FWHM) of 36 nm, associated with their intrachain excitonic behavior without obvious polaron formation. Compared to controlled poly[4-(octyloxy)-9,9-diphenylfluoren-2,7-diyl]-co-[5-(octyloxy)-9,9-diphenylfluoren-2,7-diyl] (PODPF), excellent charge transport is observed in the POPSAF films because of the intrinsic hole transport ability of the TPA units. Large-area PLEDs are fabricated via blade-coating with an emission area of 9 cm2, which exhibit uniform ultradeep-blue emission with an FWHM of 36 nm and corresponding Commission internationale de l'éclairage (CIE) coordinates of (0.155, 0.072). These findings are attributed to the synergistic effects of robust emission, stable morphology, and printing capacity. Finally, preliminary printed passive matrix (PM) PLED displays with 20 × 20 pixels monochromes are fabricated, confirmed the effectiveness of spirofunctionalization in optoelectronics.

Intrinsically Stretchable and Efficient Fully Π-Conjugated Polymer via Internal Plasticization for Flexible Deep-Blue Polymer Light-Emitting Diodes with CIEy = 0.08.

Intrinsically stretchable polymeric semiconductors are essential to flexible polymer light-emitting diodes (PLEDs) owing to their excellent strain tolerance capacity under long-time deformation operation. Obtaining intrinsic stretchability, robust emission properties, and excellent charge-transport behavior simultaneously from fully π-conjugated polymers (FCPs) is difficult, particularly for applications in deep-blue PLEDs. Herein, an internal plasticization strategy is proposed to introduce a phenyl-ester plasticizer into polyfluorenes (PF-MC4, PF-MC6, and PF-MC8) for narrowband deep-blue flexible PLEDs. Compared with controlled poly[4-(octyloxy)-9,9-diphenylfluoren-2,7-diyl]-co-[5-(octyloxy)-9,9-diphenylfluoren-2,7-diyl] (PODPFs) (2.5%), the freestanding PF-MC8 thin film shows a fracture strain of >25%. The three stretchable films exhibit stable and efficient deep-blue emission (PLQY > 50%) because of the encapsulation of π-conjugated backbone via pendant phenyl-ester plasticizers. The PF-MC8-based PLEDs show deep-blue emission, which corresponds to CIE and EQE values of (0.16, 0.10) and 1.06%, respectively. Finally, the narrowband deep-blue electroluminescence (FWHM of ≈25 nm; CIE coordinates: (0.15, 0.08)) and performance of the transferred PLEDs based on the PF-MC8 stretchable film are independent of the tensile ratio (up to 45%); however, they show a maximum brightness of 1976 cd m-2 at a ratio of 35%. Therefore, internal plasticization is a promising approach for designing intrinsically stretchable FCPs for flexible electronics.

Large-Area Blade-Coated Deep-Blue Polymer Light-Emitting Diodes with a Narrowband and Uniform Emission.

Large-area polymer light-emitting diodes (PLEDs) manufactured by printing are required for flat-panel lighting and displays. Nevertheless, it remains challenging to fabricate large-area and stable deep-blue PLEDs with narrowband emission due to the difficulties in precisely tuning film uniformity and obtaining single-exciton emission. Herein, efficient and stable large-area deep-blue PLEDs with narrowband emission are prepared from encapsulated polydiarylfluorene. Encapsulated polydiarylfluorenes presented an efficient and stable deep-blue emission (peak: 439 nm; full width at half maximum (FWHM): 39 nm) in the solid state due to their single-chain emission behavior without inter-backbone chain aggregation. Large-area uniform blade-coated films (16 cm2 ) are also fabricated with excellent smoothness and morphology. Benefitting from efficient emission and excellent printed capacity, the blade-coated PLEDs with a device area of 9 mm2 realized uniform deep-blue emission (FWHM: 38 nm; CIE: 0.153, 0.067), with a corresponding maximum external quantum efficiency and the brightness comparable to those of devices based on spin-coated films. Finally, considering the essential role of deep-blue LEDs, a preliminary patterned PLED array with a pixel size of 800 × 1000 µm2 and a monochrome display is fabricated, highlighting potential full-color display applications.

Photoexcitation dynamics and energy engineering in supramolecular doping of organic conjugated molecules.

Doping and blending strategies are crucial means to precisely control the excited states and energy level in conjugated molecular systems. However, effective models and platforms are rarely proposed to systematically explore the effects of the formation of trapped doped centers on heterogeneous structures, energy level and ultrafast photophysical process. Herein, for deeply understanding the impact of molecular doping in film energy levels and photoexcitation dynamics, we set a supramolecular N-B coordination composed by the conjugated molecules of pyridine functionalized diarylfluorene (host material), named as ODPF-Phpy and ODPF-(Phpy)2, and the molecule of tris(perfluorophenyl)borane (BCF) (guest material). The generation of the molecular-level coordination bond increased the binding energy of N atoms and tuned the band-gap, leading to a new fluorescent emission center with longer excitation wavelength and emission wavelength. The intermolecular Förster resonance energy transfer (FRET) in blending films make it present inconsistent fluorescent behaviors compared to that in solution. The charge transfer (CT) state of N-B coordinated compounds and the changed dielectric constant of blending films resulted in a large PL spectra red-shift with the increased dopant ratio, causing a wide-tunable fluorescent color. The excited state behaviors of two compounds in blending system was further investigated by the transient absorption (TA) spectroscopy. Finally, we found supramolecular coordination blending can effectively improve the films' photoluminescence quantum yield (PLQY) and conductivity. We believe this exploration in the internal coordination mechanisms would deepen the insights about doped semiconductors and is helpful in developing novel high-efficient fluorescent systems.

Improving the Intrinsic Stretchability of Fully Conjugated Polymer for Deep-Blue Polymer Light-Emitting Diodes with a Narrow Band Emission: Benefits of Self-Toughness Effect.

It is challenging to construct the intrinsically stretchable active layer of rigid conjugated polymers (CPs) toward flexible deep-blue light-emitting diodes (FLEDs). Inspired by the self-toughness effect, sacrificial hydrogen bonding (H-bonding) and a cross-linked network synergistically enabled polydiarylfluorene (PFs-NH) films to present efficient deep-blue emission and excellent intrinsic stretchability. In particular, a cross-linked network structure presenting viscoelasticity behaviors, which was successfully inherited into postprocessed films with interchain interpenetration and a crystallinity domain and behaved as energy absorption and dissipation centers, was induced by the interchain H-bonding interaction in toluene (Tol) precursor solutions where the storage moduli (G') gradually exceeded the loss moduli (G″). Subsequently, intrinsic stretchable films with a tensile rate of 30% were prepared from Tol solutions, different from the brittle films from polar solvents. Eventually, narrow band, deep-blue PLEDs showed a maximum EQE of 1.28% and a full width half-maximum (fwhm) of 28 nm. Therefore, the self-toughness effect induced by hierarchical structures will be feasible to obtain high-performance FLEDs.

Unveiling the Effects of Interchain Hydrogen Bonds on Solution Gelation and Mechanical Properties of Diarylfluorene-Based Semiconductor Polymers.

The intrinsically rigid and limited strain of most conjugated polymers has encouraged us to optimize the extensible properties of conjugated polymers. Herein, learning from the hydrogen bonds in glucose, which were facilitated to the toughness enhancement of cellulose, we introduced interchain hydrogen bonds to polydiarylfluorene by amide-containing side chains. Through tuning the copolymerization ratio, we systematically investigated their influence on the hierarchical condensed structures, rheology behavior, tensile performances, and optoelectronic properties of conjugated polymers. Compared to the reference copolymers with a low ratio of amide units, copolymers with 30% and 40% amide units present a feature of the shear-thinning process that resembled the non-Newtonian fluid, which was enabled by the interchain dynamic hydrogen bonds. Besides, we developed a practical and universal method for measuring the intrinsic mechanical properties of conjugated polymers. We demonstrated the significant impact of hydrogen bonds in solution gelation, material crystallization, and thin film stretchability. Impressively, the breaking elongation for P4 was even up to ~30%, which confirmed the partially enhanced film ductility and toughness due to the increased amide groups. Furthermore, polymer light-emitting devices (PLEDs) based on these copolymers presented comparable performances and stable electroluminescence (EL). Thin films of these copolymers also exhibited random laser emission with the threshold as low as 0.52 µJ/cm2, suggesting the wide prospective application in the field of flexible optoelectronic devices.

Hierarchical Uniform Supramolecular Conjugated Spherulites with Suppression of Defect Emission.

Easily processed, well-defined, and hierarchical uniform artificial architectures with intrinsic strong crystalline emission properties are necessary for a range of light-emitting optoelectronic devices. Herein, we designed and prepared ordered supramolecular spherulites, comprising planar conformational molecules as primary structures and multiple hydrogen bonds as physical cross-links. Compared with serious aggregation-induced fluorescence quenching (up to 70%), these highly ordered architectures exhibited unique and robust crystalline emission with a high PLQY of 55%, which was much higher than those of other terfluorenes. The primary reasons for the high PLQY are the uniform exciton energetic landscape created in the planar conformation and the highly ordered molecular packing in spherulite. Meanwhile, minimal residual defect (green-band) emissions are effectively suppressed in our oriented crystalline framework, whereas the strong and stable blue light radiations are promoted. These findings may confirm that supramolecular ordered artificial architectures may offer higher control and tunability for optoelectronic applications.

Ultrastable Supramolecular Self-Encapsulated Wide-Bandgap Conjugated Polymers for Large-Area and Flexible Electroluminescent Devices.

Controlling chain behavior through smart molecular design provides the potential to develop ultrastable and efficient deep-blue light-emitting conjugated polymers (LCPs). Herein, a novel supramolecular self-encapsulation strategy is proposed to construct a robust ultrastable conjugated polydiarylfluorene (PHDPF-Cz) via precisely preventing excitons from interchain cross-transfer/coupling and contamination from external trace H2 O/O2 . PHDPF-Cz consists of a mainchain backbone where the diphenyl groups localize at the 9-position as steric bulk moieties, and carbazole (Cz) units localize at the 4-position as supramolecular π-stacked synthon with the dual functionalities of self-assembly capability and hole-transport facility. The synergistic effect of the steric bulk groups and π-stacked carbazoles affords PHDPF-Cz as an ultrastable property, including spectral, morphological stability, and storage stability. In addition, PHDPF-Cz spin-coated gelation films also show thickness-insensitive deep-blue emission with respect to the reference polymers, which are suitable to construct solution-processed large-scale optoelectronic devices with higher reproducibility. High-quality and uniform deep-blue emission is observed in large-area solution-processed films. The electroluminescence shows high-quality deep-blue intrachain emission with a CIE (0.16, 0.12) and a very narrow full width at half-maximum of 32 nm. Finally, large-area and flexible polymer light-emitting devices with a single-molecular excitonic behavior are also fabricated. The supramolecular self-encapsulation design provides an effective strategy to construct ultrastable LCPs for optoelectronic applications.

Photophysical and Fluorescence Anisotropic Behavior of Polyfluorene ß-Conformation Films.

We demonstrate a systematic visualization of the unique photophysical and fluorescence anisotropic properties of polyfluorene coplanar conformation (ß-conformation) using time-resolved scanning confocal fluorescence imaging (FLIM) and fluorescence anisotropy imaging microscopy (FAIM) measurements. We observe inhomogeneous morphologies and fluorescence decay profiles at various micrometer-sized regions within all types of polyfluorene ß-conformational spin-coated films. Poly(9,9-dioctylfluorene-2,7-diyl) (PFO) and poly[4-(octyloxy)-9,9-diphenylfluoren-2,7-diyl]-co-[5-(octyloxy)-9,9-diphenylfluoren-2,7-diyl] (PODPF) ß-domains both have shorter lifetime than those of the glassy conformation for the longer effective conjugated length and rigid chain structures. Besides, ß-conformational regions have larger fluorescence anisotropy for the low molecular rotational motion and high chain orientation, while the low anisotropy in glassy conformational regions shows more rotational freedom of the chain and efficient energy migration from amorphous regions to ß-conformation as a whole. Finally, ultrastable ASE threshold in the PODPF ß-conformational films also confirms its potential application in organic lasers. In this regard, FLIM and FAIM measurements provide an effective platform to explore the fundamental photophysical process of conformational transitions in conjugated polymer.

Steric-Hindrance-Functionalized Polydiarylfluorenes: Conformational Behavior, Stabilized Blue Electroluminescence, and Efficient Amplified Spontaneous Emission.

Control of the hierarchical molecular organization of polydiarylfluorenes by synthetic strategies is significant for optimizing photophysical properties as well as the performance of light-emitting devices. Herein, for the suppression of molecular aggregation and enhancement of luminescence efficiency, a series of steric units were introduced into polydiarylfluorenes by copolymerization, with the aim of integrating the advantages of the steric-hindrance effect and of the ß-phase. Optical and Raman spectroscopies revealed a ß-phase conformation for a polymer copolymerized with spiro[fluorene-9,9'-xanthene] (SFX), with photoluminescence (PL) peaks at 454, 482, and 517 nm. Moreover, the morphological stability and electroluminescence (EL) stability were also improved without compromising the performance of the polymer light-emitting diodes (PLEDs). Furthermore, three steric-hindrance-functionalized copolymers showed significantly decreased thresholds for amplified spontaneous emission (EthASE) and enhanced stability following thermal annealing treatment. These results indicate that steric-hindrance functionalization is a superior approach to improve the overall stability and optoelectronic properties for blue-light-emitting π-conjugated polymers.