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  1. Abstract

    Fiber-based electronics enabling lightweight and mechanically flexible/stretchable functions are desirable for numerous e-textile/e-skin optoelectronic applications. These wearable devices require low-cost manufacturing, high reliability, multifunctionality and long-term stability. Here, we report the preparation of representative classes of 3D-inorganic nanofiber network (FN) films by a blow-spinning technique, including semiconducting indium-gallium-zinc oxide (IGZO) and copper oxide, as well as conducting indium-tin oxide and copper metal. Specifically, thin-film transistors based on IGZO FN exhibit negligible performance degradation after one thousand bending cycles and exceptional room-temperature gas sensing performance. Owing to their great stretchability, these metal oxide FNs can be laminated/embedded on/into elastomers, yielding multifunctional single-sensing resistors as well as fully monolithically integrated e-skin devices. These can detect and differentiate multiple stimuli including analytes, light, strain, pressure, temperature, humidity, body movement, and respiratory functions. All of these FN-based devices exhibit excellent sensitivity, response time, and detection limits, making them promising candidates for versatile wearable electronics.

     
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  2. The rational creation of two-component conjugated polymer systems with high levels of phase purity in each component is challenging but crucial for realizing printed soft-matter electronics. Here, we report a mixed-flow microfluidic printing (MFMP) approach for two-componentπ-polymer systems that significantly elevates phase purity in bulk-heterojunction solar cells and thin-film transistors. MFMP integrates laminar and extensional flows using a specially microstructured shear blade, designed with fluid flow simulation tools to tune the flow patterns and induce shear, stretch, and pushout effects. This optimizes polymer conformation and semiconducting blend order as assessed by atomic force microscopy (AFM), transmission electron microscopy (TEM), grazing incidence wide-angle X-ray scattering (GIWAXS), resonant soft X-ray scattering (R-SoXS), photovoltaic response, and field effect mobility. For printed all-polymer (poly[(5,6-difluoro-2-octyl-2H-benzotriazole-4,7-diyl)-2,5-thiophenediyl[4,8-bis[5-(2-hexyldecyl)-2-thienyl]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl]-2,5-thiophenediyl]) [J51]:(poly{[N,N′-bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)}) [N2200]) solar cells, this approach enhances short-circuit currents and fill factors, with power conversion efficiency increasing from 5.20% for conventional blade coating to 7.80% for MFMP. Moreover, the performance of mixed polymer ambipolar [poly(3-hexylthiophene-2,5-diyl) (P3HT):N2200] and semiconducting:insulating polymer unipolar (N2200:polystyrene) transistors is similarly enhanced, underscoring versatility for two-componentπ-polymer systems. Mixed-flow designs offer modalities for achieving high-performance organic optoelectronics via innovative printing methodologies.

     
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  3. The field-effect electron mobility of aqueous solution-processed indium gallium oxide (IGO) thin-film transistors (TFTs) is significantly enhanced by polyvinyl alcohol (PVA) addition to the precursor solution, a >70-fold increase to 7.9 cm2/Vs. To understand the origin of this remarkable phenomenon, microstructure, electronic structure, and charge transport of IGO:PVA film are investigated by a battery of experimental and theoretical techniques, including In K-edge and Ga K-edge extended X-ray absorption fine structure (EXAFS); resonant soft X-ray scattering (R-SoXS); ultraviolet photoelectron spectroscopy (UPS); Fourier transform-infrared (FT-IR) spectroscopy; time-of-flight secondary-ion mass spectrometry (ToF-SIMS); composition-/processing-dependent TFT properties; high-resolution solid-state1H,71Ga, and115In NMR spectroscopy; and discrete Fourier transform (DFT) analysis with ab initio molecular dynamics (MD) liquid-quench simulations. The71Ga{1H} rotational-echo double-resonance (REDOR) NMR and other data indicate that PVA achieves optimal H doping with a Ga···H distance of ∼3.4 Å and conversion from six- to four-coordinate Ga, which together suppress deep trap defect localization. This reduces metal-oxide polyhedral distortion, thereby increasing the electron mobility. Hydroxyl polymer doping thus offers a pathway for efficient H doping in green solvent-processed metal oxide films and the promise of high-performance, ultra-stable metal oxide semiconductor electronics with simple binary compositions.

     
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  4. Metal oxide (MO) semiconductor thin films prepared from solution typically require multiple hours of thermal annealing to achieve optimal lattice densification, efficient charge transport, and stable device operation, presenting a major barrier to roll-to-roll manufacturing. Here, we report a highly efficient, cofuel-assisted scalable combustion blade-coating (CBC) process for MO film growth, which involves introducing both a fluorinated fuel and a preannealing step to remove deleterious organic contaminants and promote complete combustion. Ultrafast reaction and metal–oxygen–metal (M-O-M) lattice condensation then occur within 10–60 s at 200–350 °C for representative MO semiconductor [indium oxide (In2O3), indium-zinc oxide (IZO), indium-gallium-zinc oxide (IGZO)] and dielectric [aluminum oxide (Al2O3)] films. Thus, wafer-scale CBC fabrication of IGZO-Al2O3thin-film transistors (TFTs) (60-s annealing) with field-effect mobilities as high as ∼25 cm2V−1s−1and negligible threshold voltage deterioration in a demanding 4,000-s bias stress test are realized. Combined with polymer dielectrics, the CBC-derived IGZO TFTs on polyimide substrates exhibit high flexibility when bent to a 3-mm radius, with performance bending stability over 1,000 cycles.

     
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  5. Abstract

    Considerable progress in materials development and device integration for mechanically bendable and stretchable optoelectronics will broaden the application of “Internet‐of‐Things” concepts to a myriad of new applications. When addressing the needs associated with the human body, such as the detection of mechanical functions, monitoring of health parameters, and integration with human tissues, optoelectronic devices, interconnects/circuits enabling their functions, and the core passive components from which the whole system is built must sustain different degrees of mechanical stresses. Herein, the basic characteristics and performance of several of these devices are reported, particularly focusing on the conducting element constituting them. Among these devices, strain sensors of different types, energy storage elements, and power/energy storage and generators are included. Specifically, the advances during the past 3 years are reported, wherein mechanically flexible conducting elements are fabricated from (0D, 1D, and 2D) conducting nanomaterials from metals (e.g., Au nanoparticles, Ag flakes, Cu nanowires), carbon nanotubes/nanofibers, 2D conductors (e.g., graphene, MoS2), metal oxides (e.g., Zn nanorods), and conducting polymers (e.g., poly(3,4‐ethylenedioxythiophene):poly(4‐styrene sulfonate), polyaniline) in combination with passive fibrotic and elastomeric materials enabling, after integration, the so‐called electronic skins and electronic textiles.

     
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  6. Abstract

    In principal, the direct copolymerization of ethylene with polar comonomers should be the most efficient means to introduce functional groups into conventional polyolefins but remains a formidable challenge. Despite the tremendous advances in group 4‐centered catalysis for olefin polymerization, successful examples of ethylene + polar monomer copolymerization are rare, especially without Lewis acidic masking reagents. Here we report that certain group 4 catalysts are very effective for ethylene + CH2=CH(CH2)nNR2copolymerizations with activities up to 3400 Kg copolymer mol−1‐Zr h‐1 atm‐1, and with comonomer enchainment up to 5.5 mol % in the absence of masking reagents. Group 4 catalyst‐amino‐olefin structure–activity‐selectivity relationships reflect the preference of olefin activation over free amine coordination, which is supported by mechanistic experiments and DFT analysis. These results illuminate poorly understood facets of d0metal‐catalyzed polar olefin monomer copolymerization processes.

     
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