Effect of SWNT Defects on the Electron Transfer Properties in P3HT/SWNT Hybrid Materials

Poly(3‐hexylthiophene) (P3HT) hybrids with single‐walled carbon nanotubes (SWNTs) were prepared using a series of SWNTs with various defect contents on their surfaces. The hybrids were synthesized by exploiting the π–π interaction between P3HT and the SWNTs, resulting in efficient dispersion of the carbon nanotubes in the P3HT solution. UV‐visible and photoluminescence (PL) spectra showed that the carbon nanotubes quench the PL of P3HT in the hybrids, indicating that electron transfer occurs from photo‐excited P3HT to the SWNTs. This electron transfer from P3HT to carbon nanotubes was disrupted by the presence of defects on the SWNT surfaces. However, the PL lifetime of P3HT in the hybrids was found to be the same as that of pure P3HT in solution, indicating the formation of a ground‐state non‐fluorescent complex of P3HT/SWNTs.     

Synthesis,Morphology, and Properties of Poly(3‐hexylthiophene)‐block‐Poly(vinylphenyl oxadiazole) Donor–Acceptor Rod–Coil Block Copolymers and Their Memory Device Applications

Novel donor–acceptor rod–coil diblock copolymers of regioregular poly(3‐hexylthiophene) ( P3HT )‐block‐poly(2‐phenyl‐5‐(4‐vinylphenyl)‐1,3,4‐oxadiaz‐ole) ( POXD ) are successfully synthesized by the combination of a modified Grignard metathesis reaction ( GRIM ) and atom transfer radical polymerization ( ATRP ). The effects of the block ratios of the P3HT donor and POXD pendant acceptor blocks on the morphology, field effect transistor mobility, and memory device characteristics are explored. The TEM, SAXS, WAXS, and AFM results suggest that the coil block fraction significantly affects the chain packing of the P3HT block and depresses its crystallinity. The optical absorption spectra indicate that the intramolecular charge transfer between the main chain P3HT donor and the side chain POXD acceptor is relatively weak and the level of order of P3HT chains is reduced by the incorporation of the POXD acceptor. The field effect transistor (FET) hole mobility of the system exhibits a similar trend on the optical properties, which are also decreased with the reduced ordered P3HT crystallinity. The low‐lying highest occupied molecular orbital (HOMO) energy level (–6.08 eV) of POXD is employed as charge trap for the electrical switching memory devices. P3HT‐ b ‐POXD exhibits a non‐volatile bistable memory or insulator behavior depending on the P3HT / POXD block ratio and the resulting morphology. The ITO/ P3HT₄₄ ‐b‐ POXD₁₈ /Al memory device shows a non‐volatile switching characteristic with negative differential resistance (NDR) effect due to the charge trapped POXD block. These experimental results provide the new strategies for the design of donor‐acceptor rod‐coil block copolymers for controlling morphology and physical properties as well as advanced memory device applications.     

Self Encapsulated Poly(3‐hexylthiophene)‐poly(fluorinated alkyl methacrylate) Rod‐Coil Block Copolymers with High Field Effect Mobilities on Bare SiO2

Conjugated rod‐coil block copolymers provide an interesting route towards enhancing the properties of the conjugated block due to self‐assembly and the interplay of rod‐rod and rod‐coil interactions. Here, we demonstrate the ability of an attached semi‐fluorinated block to significantly improve upon the charge carrier properties of regioregular poly(3‐hexyl thiophene) (rr‐P3HT) materials on bare SiO₂. The thin film hole mobilities on bare SiO₂ dielectric surfaces of poly (3‐hexyl thiophene)‐block‐polyfluoromethacrylates (P3HT‐b‐PFMAs) can approach up to 0.12 cm² V^?1 s^?1 with only 33 wt% of the P3HT block incorporated in the copolymer, as compared to rr‐P3HT alone which typically has mobilities averaging 0.03 cm² V^?1 s^?1. To our knowledge, this is the highest mobility reported in literature for block copolymers containing a P3HT. More importantly, these high hole mobilities are achieved without multistep OTS treatments, argon protection, or post‐annealing conditions. Grazing incidence wide‐angle x‐ray scattering (GIWAX) data revealed that in the P3HT‐b‐PFMA copolymers, the P3HT rod block self‐assembles into highly ordered lamellar structures, similar to that of the rr‐P3HT homopolymer. Grazing incidence small‐angle x‐ray scattering (GISAXS) data revealed that lamellar structures are only observed in perpendicular direction with short PFMA blocks, while lamellae in both perpendicular and parallel directions are observed in polymers with longer PFMA blocks. AFM, GIWAXS, and contact angle measurements also indicate that PFMA block assembles at the polymer thin film surface and forms an encapsulation layer. The high charge carrier mobilities and the hydrophobic surface of the block copolymer films clearly demonstrates the influence of the coil block segment on device performance by balancing the crystallization and microphase separation in the bulk morphological structure.     

Super‐Fast Switching of Twisted Nematic Liquid Crystals on 2D Single Wall Carbon Nanotube Networks

We have developed a high performance liquid crystal (LC) alignment layer of ultra‐thin single wall carbon nanotubes (SWNTs) and a conjugated block copolymer nanocomposite that is solution‐processible for conventional twisted nematic (TN) LC cells. The alignment layer is based on the non‐destructive solution dispersion of nanotubes with a poly(styrene‐b‐ paraphenylene) (PS‐b‐PPP) copolymer and subsequent spin coating, followed by conventional rubbing without a post‐annealing process. Topographically grooved nanocomposite films with two dimensionally (2D) networked SWNTs embedded in a block copolymer matrix were created using a rubbing process in which bundles of SWNTs on the composite surface were effectively removed. The LCs were well aligned with a stable pre‐tilt angle of approximately 2° on our extremely transparent nanocomposite, which gave rise to superfast switching of the TN LC molecules that was approximately 3.8 ms, or four times faster than that on a commercial polyimide layer. Furthermore, the TN LCD cells containing our SWNT nanocomposite alignment layers exhibited low power operation at an effective switching voltage amplitude of approximately 1.3 V without capacitance hysteresis.     

Donor–Acceptor Poly(3‐hexylthiophene)‐block‐Pendent Poly(isoindigo) with Dual Roles of Charge Transporting and Storage Layer for High‐Performance Transistor‐Type Memory Applications

Field‐effect transistor memories usually require one additional charge storage layer between the gate contact and organic semiconductor channel. To avoid such complication, new donor–acceptor rod–coil diblock copolymers (P3HT₄₄‐b‐Piso_n) of poly(3‐hexylthiophene) (P3HT)‐block‐poly(pendent isoindigo) (Piso) are designed, which exhibit high performance transistor memory characteristics without additional charge storage layer. The P3HT and Piso blocks are acted as the charge transporting and storage elements, respectively. The prepared P3HT₄₄‐b‐Piso_n can be self‐assembled into fibrillar‐like nanostructures after the thermal annealing process, confirmed by atomic force microscopy and grazing‐incidence X‐ray diffraction. The lowest‐unoccupied molecular orbital levels of the studied polymers are significantly lowered as the block length of Piso increases, leading to a stronger electron affinity as well as charge storage capability. The field‐effect transistors (FETs) fabricated from P3HT₄₄‐b‐Piso_n possess p‐type mobilities up to 4.56 × 10^?2 cm² V^?1 s^?1, similar to that of the regioregular P3HT. More interestingly, the FET memory devices fabricated from P3HT₄₄‐b‐Piso_n exhibit a memory window ranging from 26 to 79 V by manipulating the block length of Piso, and showed stable long‐term data endurance. The results suggest that the FET characteristics and data storage capability can be effectively tuned simultaneously through donor/acceptor ratio and thin film morphology in the block copolymer system.     

Hierarchical Assembly of Complex Block Copolymer Nanoparticles into Multicompartment Superstructures through Tunable Interparticle Associations

A challenging aim in both materials physics and chemistry is the construction of complex and functional superstructures from designed nanoscale building units. Block copolymer nanoparticles with morphological variety and compositional complexity have been made with solution‐based assembly. However, routine ability to build hierarchical superstructures by inter‐nanoparticle association is not yet possible. A hierarchical assembly strategy of organizing pre‐formed spherical block copolymer nanoparticles into superstructures, including linear, circular, and close‐packed arrays, via tunable interparticle interactions is presented. Solution‐state mixtures are made of two amphiphilic diblock copolymers, poly(acrylic acid)‐block‐poly(methyl methacrylate) (PAA‐b‐PMMA) and poly(acrylic acid)‐block‐polybutadiene (PAA‐b‐PB) with additional crown ether functionalities grafted onto 40 mol% of the AA repeat units on the PAA‐b‐PMMA diblock copolymer. Through kinetic control of the solution assembly process in aqueous/N,N‐dimethylformamide (DMF) mixtures (4:1 water:DMF), spherical nanoparticles with compositional complexity confined in both the core and shell are obtained. Benefiting from host‐guest chemistry, interparticle association is triggered and tuned by the addition of di‐functional organoamines due to amine‐crown ether complexation. The resultant multiparticle superstructures contain well‐defined multicompartments within individual, constituent nanoparticles due to the local separation of unlike PB and PMMA hydrophobic blocks within the cores of the individual particles. Through competitive complexation with potassium ions, the superstructures are disassembled into individual multicomparment nanoparticles.     

Nanoporous Ultra‐Low‐Dielectric‐Constant Fluoropolymer Films via Selective UV Decomposition of Poly(pentafluorostyrene)‐block‐Poly(methyl methacrylate) Copolymers Prepared Using Atom Transfer Radical Polymerization

Block copolymers of poly(pentafluorostyrene) (PFS) and poly(methyl methacrylate) (PMMA) (PFS‐b‐PMMA) have been synthesized using atom transfer radical polymerization (ATRP). Then, nanoporous fluoropolymer films have been prepared via selective UV decomposition of the PMMA blocks in the PFS‐b‐PMMA copolymer films. The chemical composition and structure of the PFS homopolymers and copolymers have been characterized using nuclear magnetic resonance (NMR) spectroscopy, thermogravimetric analysis (TGA), X‐ray photoelectron spectroscopy (XPS), time‐of‐flight secondary‐ion mass spectrometry (ToF‐SIMS), and molecular‐weight measurements. The cross‐sectional and surface morphologies of the PFS‐b‐PMMA copolymer films before and after selective UV decomposition of the PMMA blocks have been studied using field‐emission scanning electron microscopy (FESEM). The nanoporous fluoropolymer films with pore sizes in the range 30–50 nm and porosity in the range 15–40 % have been obtained from the PFS‐b‐PMMA copolymers of different PMMA content. Dielectric constants approaching 1.8 have been achieved in the nanoporous fluoropolymer films which contain almost completely decomposed PMMA blocks.     

Intramolecular Donor–Acceptor Regioregular Poly(3‐hexylthiophene)s Presenting Octylphenanthrenyl‐Imidazole Moieties Exhibit Enhanced Charge Transfer for Heterojunction Solar Cell Applications

Intramolecular donor–acceptor structures prepared by covalently binding conjugated octylphenanthrenyl‐imidazole moieties onto the side chains of regioregular poly(3‐hexylthiophene)s exhibit lowered bandgaps and enhanced electron transfer compared to the parent polymer, e.g., conjugation of 90 mol% octylphenanthrenyl‐imidazole moieties onto poly(3‐hexylthiophene) chains reduces the optical bandgap from 1.91 to 1.80 eV, and the electron transfer probability is at least twice as high as that of pure poly(3‐hexylthiophene) when blended with [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester. The lowered bandgap and the fast charge transfer both contribute to much higher external quantum efficiencies, thus much higher short‐circuit current densities for copolymers presenting octylphenanthrenyl‐imidazole moieties, relative to those of pure poly(3‐hexylthiophene)s. The short‐circuit current density of a device prepared from a copolymer presenting 90 mol% octylphenanthrenyl‐imidazole moieties is 13.7 mA · cm^?2 which is an increase of 65% compared to the 8.3 mA · cm^?2 observable for a device containing pure poly(3‐hexylthiophene). The maximum power conversion efficiency of this particular copolymer is 3.45% which suggest that such copolymers are promising polymeric photovoltaic materials.     

Thermogelling,ABC Triblock Copolymer Platform for Resorbable Hydrogels with Tunable,Degradation‐Mediated Drug Release

Clinical application of injectable, thermoresponsive hydrogels is hindered by lack of degradability and controlled drug release. To overcome these challenges, a family of thermoresponsive, ABC triblock polymer‐based hydrogels has been engineered to degrade and release drug cargo through either oxidative or hydrolytic/enzymatic mechanisms dictated by the “A” block composition. Three ABC triblock copolymers are synthesized with varying “A” blocks, including oxidation‐sensitive poly(propylene sulfide), slow hydrolytically/enzymatically degradable poly(ε‐caprolactone), and fast hydrolytically/enzymatically degradable poly(d ,l ‐lactide‐co‐glycolide), forming the respective formulations PPS₁₃₅‐b‐PDMA₁₅₂‐b‐PNIPAAM₂₂₅ (PDN), PCL₈₅‐b‐PDMA₁₅₀‐b‐PNIPAAM₁₅₀ (CDN), and PLGA₆₀‐b‐PDMA₁₄₈‐b‐PNIPAAM₁₅₂ (LGDN). For all three polymers, hydrophilic poly(N,N‐dimethylacrylamide) and thermally responsive poly(N‐isopropylacrylamide) comprise the “B” and “C” blocks, respectively. These copolymers form micelles in aqueous solutions at ambient temperature that can be preloaded with small molecule drugs. These solutions quickly transition into hydrogels upon heating to 37 °C, forming a supra‐assembly of physically crosslinked, drug‐loaded micelles. PDN hydrogels are selectively degraded under oxidative conditions while CDN and LGDN hydrogels are inert to oxidation but show differential rates of hydrolytic/enzymatic decomposition. All three hydrogels are cytocompatible in vitro and in vivo, and drug‐loaded hydrogels demonstrate differential release kinetics in vivo corresponding with their specific degradation mechanism. These collective data highlight the potential cell and drug delivery use of this tunable class of ABC triblock polymer thermogels.     

pH‐Responsive Flower‐Type Micelles Formed by a Biotinylated Poly(2‐vinylpyridine)‐block‐poly(ethylene oxide)‐block‐poly(ε‐caprolactone) Triblock Copolymer

In the present work, a method is proposed to assemble pH‐responsive, flower‐like micelles that can expose a targeting unit at their periphery upon a decrease in pH. The micelles are composed of a novel biotinylated triblock copolymer of poly(εε‐caprolactone)‐block‐poly(ethylene oxide)‐block‐poly(2‐vinylpyridine) (PCL‐b‐PEO‐b‐P2VP) and the non‐biotinylated analogue. The block copolymers are synthesized by sequential anionic and ring‐opening polymerization. The pH‐dependent micellization behaviour in aqueous solution of the triblock copolymers developed is studied using dynamic light scattering, zeta potential, transmission electron microscopy (TEM), and fluorimetric measurements. The shielding of the biotin at neutral pH and their availability at the micelle surface upon protonation is established by TEM and surface plasmon resonance with avidin and streptavidin‐coated gold surfaces. The preliminary stealthy behavior of these pH‐responsive micelles is examined using the complement activation (CH50) test.     

Microphase‐Separated Donor–Acceptor Diblock Copolymers: Influence of HOMO Energy Levels and Morphology on Polymer Solar Cells

The synthesis of novel semiconducting donor–acceptor (D–A) diblock copolymers by means of nitroxide‐mediated polymerization (NMP) is reported. The copolymers contain functional moieties for hole transport, electron transport, and light absorption. The first block, representing the donor, is made up of either substituted triphenylamines (poly(bis(4‐methoxyphenyl)‐4′‐vinylphenylamine), PvDMTPA) or substituted tetraphenylbenzidines (poly(N,N′‐bis(4‐methoxyphenyl)‐N‐phenyl‐N′‐4‐vinylphenyl‐(1,1′‐biphenyl)‐4,4′‐diamine), PvDMTPD). The second block consists of perylene diimide side groups attached to a polyacrylate backbone (PPerAcr) via a flexible spacer. This block is responsible for absorption in the visible range and for electron‐transport properties. The electrochemical properties of these fully functionalized diblock copolymers, PvDMTPA‐b‐PPerAcr and PvDMTPD‐b‐PPerAcr, are investigated by cyclic voltammetry (CV), and their morphology is investigated by transmission electron microscopy (TEM). All diblock copolymers exhibit microphase‐separated domains in the form of either wire‐ or wormlike structures made of perylene diimide embedded in a hole‐conductor matrix. In single‐active‐layer organic solar cells, PvDMTPD‐b‐PPerAcr reveals a fourfold improvement in power conversion efficiency (η = 0.26 %, short‐circuit current (I_SC) 1.21 mA cm^–2), and PvDMTPA‐b‐PPerAcr a fivefold increased efficiency (η = 0.32 %, I_SC = 1.14 mA cm^–2) compared with its unsubstituted analogue PvTPA‐b‐PPerAcr (η = 0.065 %, I_SC = 0.23 mA cm^–2).     

Intrinsic Surface Dipoles Control the Energy Levels of Conjugated Polymers

Conjugated polymers are an important class of materials for organic electronics applications. There, the relative alignment of the electronic energy levels at ubiquitous organic/(in)organic interfaces is known to crucially impact device performance. On the prototypical example of poly(3‐hexylthiophene) and a fluorinated derivative, the energies of the ionization and affinity levels of π‐conjugated polymers are revealed to critically depend on the orientation of the polymer backbones with respect to such interfaces. Based on extensive first‐principles calculations, an intuitive electrostatic model is developed that quantitatively traces these observations back to intrinsic intramolecular surface dipoles arising from the π‐electron system and intramolecular polar bonds. The results shed new light on the working principles of organic electronic devices and suggest novel strategies for materials design.     

Photoconductivity of a Low‐Bandgap Conjugated Polymer

The photoconductive properties of a novel low‐bandgap conjugated polymer, poly[2,6‐(4,4‐bis‐(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b′]dithiophene)‐alt‐4,7‐(2,1,3‐benzothiadiazole)], PCPDTBT, with an optical energy gap of E_g ～ 1.5 eV, have been studied. The results of photoluminescence and photoconductivity measurements indicate efficient electron transfer from PCPDTBT to PCBM ([6,6]‐phenyl‐C61 butyric acid methyl ester, a fullerene derivative), where PCPDTBT acts as the electron donor and PCBM as the electron acceptor. Electron‐transfer facilitates charge separation and results in prolonged carrier lifetime, as observed by fast (t > 100 ps) transient photoconductivity measurements. The photoresponsivities of PCPDTBT and PCPDTBT:PCBM are comparable to those of poly(3‐hexylthiophene), P3HT, and P3HT:PCBM, respectively. Moreover, the spectral sensitivity of PCPDTBT:PCBM extends significantly deeper into the infrared, to 900 nm, than that of P3HT. The potential of PCPDTBT as a material for high‐efficiency polymer solar cells is discussed.     

Amorphous Carbon Nanotubes with Tunable Properties via Template Wetting

Amorphous carbon nanotubes have been prepared by casting thin films of polyacrylonitrile (PAN) and polystyrene‐block‐polyacrylonitrile (PS‐b‐PAN) within a porous anodic aluminum oxide (AAO) membrane followed by pyrolysis. Raman and wide‐ angle X‐ray diffraction (WAXD) measurements indicate that the carbon nanotubes are of low crystallinity. The thickness of the carbon nanotube walls is controlled by either changing the concentration of the precursor solution or by using multiple casting and pyrolysis steps. When diblock copolymers of PS‐b‐PAN are used, it is found that nanopores are created within the nanotube walls after pyrolysis. The carbon nanotubes can be used to create carbon coated nanorods of polystyrene‐block‐polybutadiene (PS‐b‐PBD).     

Highly Tunable Nanostructures in a Doubly pH-Responsive Pentablock Terpolymer in Solution and in Thin Films

Multiblock copolymers with charged blocks are complex systems that show great potential for enhancing the structural control of block copolymers. A pentablock terpolymer PMMA-b-PDMAEMA-b-P2VP-b-PDMAEMA-b-PMMA is investigated. It contains two types of midblocks, which are weak cationic polyelectrolytes, namely poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(2-vinylpyridine) (P2VP). Furthermore, these are end-capped with short hydrophobic poly(methyl methacrylate) (PMMA) blocks in dilute aqueous solution and thin films. The self-assembly behavior depends on the degrees of ionization α of the P2VP and PDMAEMA blocks, which are altered in a wide range by varying the pH value. High degrees of ionization of both blocks prevent structure formation, whereas microphase-separated nanostructures form for a partially charged and uncharged state. While in solutions, the nanostructure formation is governed by the dependence of the P2VP block solubility of the and the flexibility of the PDMAEMA blocks on α, in thin films, the dependence of the segregation strength on α is key. Furthermore, the solution state plays a crucial role in the film formation during spin-coating. Overall, both the mixing behavior of the 3 types of blocks and the block sequence, governing the bridging behavior, result in strong variations of the nanostructures and their repeat distances.     

Self‐Healing Materials via Reversible Crosslinking of Poly(ethylene oxide)‐Block‐Poly(furfuryl glycidyl ether) (PEO‐b‐PFGE) Block Copolymer Films

The application of well‐defined poly(furfuryl glycidyl ether) (PFGE) homopolymers and poly(ethylene oxide)‐b‐poly(furfuryl glycidyl ether) (PEO‐b‐PFGE) block copolymers synthesized by living anionic polymerization as self‐healing materials is demonstrated. This is achieved by thermo‐reversible network formation via (retro) Diels‐Alder chemistry between the furan groups in the side‐chain of the PFGE segments and a bifunctional maleimide crosslinker within drop‐cast polymer films. The process is studied in detail by differential scanning calorimetry (DSC), depth‐sensing indentation, and profilometry. It is shown that such materials are capable of healing complex scratch patterns, also multiple times. Furthermore, microphase separation within PEO‐b‐PFGE block copolymer films is indicated by small angle X‐ray scattering (lamellar morphology with a domain spacing of approximately 19 nm), differential scanning calorimetry, and contact angle measurements.     

Blood‐Inert Surfaces via Ion‐Pair Anchoring of Zwitterionic Copolymer Brushes in Human Whole Blood

A strategy to create blood‐inert surfaces in human whole blood via ion‐pair anchoring of zwitterionic copolymer brushesand a systematic study of how well‐defined chain lengths and well‐controlled surface packing densities of zwitterionic polymers affect blood compatibility are reported. Well‐defined diblock copolymers, poly(11‐mercaptoundecyl sulfonic acid)‐block‐poly(sulfobetaine methacrylate) (PSA‐b‐PSBMA) with varying zwitterionic PSBMA or negatively charged PSA lengths, are synthesized via atom‐transfer radical polymerization (ATRP). PSA‐b‐PSBMA is grafted onto a surface covered with polycation brushes as a mimic polar/hydrophilic biomaterial surface via ion‐pair anchoring at a range of copolymer concentrations. Protein adsorption from single‐protein solutions, 100% blood serum, and 100% blood plasma onto the surfaces covered with PSA‐b‐PSBMA brushes is evaluated using a surface plasmon resonance sensor. Copolymer brushes containing a high amount of zwitterionic SBMA units are further challenged with human whole blood. Low protein‐fouling surfaces with >90% reduction with respect to uncoated surfaces are achieved with longer PSA blocks and higher concentrations of PSA‐b‐PSBMA copolymers using the ion‐pair anchoring approach. This work provides a platform to achieve the control of various surface parameters and a practical method to create blood‐inert surfaces in whole blood by grafting ionic‐zwitterionic copolymers to charged biomaterials via charge pairing.     

Over 13% Efficient Single-Component Organic Solar Cells Enabled by Adjusting the Conjugated-Length of Intermediate PBDB-T Block

Batch-to-batch variation widely exists in conjugated donor-acceptor (D-A) block copolymer materials and plays a crucial role in photovoltaic performance of organic solar cells (OSCs). To investigate the influence of conjugated-length of the intermediate block on the performance of single-component OSC (SCOSCs), herein, four batches of conjugated block copolymers (CBCs, PB-b-PY-1, PB-b-PY-2, PB-b-PY-3, and PB-b-PY-4) are synthesized, which possess different D/A block lengths. As the conjugation length of intermediate D-block increases, the lamellar packing order of these CBCs shows a monotonically increasing trend, leading to stronger absorption spectra in the visible region, efficient charge transfer, and suppressed carrier recombination loss. Consequently, the PB-b-PY-4 device yields a higher efficiency of 13.28% than those of other CBCs. This study demonstrates the effectiveness of the conjugated length of intermediate D-blocks in designing high-performance conjugated D-A block copolymers, which paves the way toward developing high-performance SCOSCs.     

Ultrafast Responsive Non‐Volatile Flash Photomemory via Spatially Addressable Perovskite/Block Copolymer Composite Film

The exotic photophysical properties of organic–inorganic hybrid perovskite with long exciton lifetimes and small binding energy have appeared as promising front‐runners for next‐generation non‐volatile flash photomemory. However, the long photo‐programming time of photomemory limits its application on light‐fidelity (Li‐Fi), which requires high storage capacity and short programming times. Herein, the spatially addressable perovskite in polystyrene‐block‐poly(ethylene oxide) (PS‐b‐PEO)/perovskite composite film as an photoactive floating gate is demonstrated to elucidate the effect of morphology on the photo‐responsive characteristics of photomemory. The chelation between lead ion and PEO segment promotes the anti‐solvent functionalities of the perovskite/PS‐b‐PEO composite film, thus allowing the solution‐processable poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) to act as the active channel. Through manipulating the interfacial area between perovskite and P3HT, fast photo‐induced charge transfer rate of 0.056 ns^?1, high charge transfer efficiency of 89%, ON/OFF current ratio of 10⁴, and extremely low programming time of 5 ms can be achieved. This solution‐processable and fast photo‐programmable non‐volatile flash photomemory can trigger the practical application on Li‐Fi.     

Simple and Efficient Generation of White Light Emission From Organophosphorus Building Blocks

This paper describes a structure–property study using two dithieno[3,2‐b;2′,3′‐d]phosphole building blocks for the generation of white light emission and the incorporation of these units in a single polystyrene material. The emission of one of the light‐emitting organophosphorus building blocks can efficiently be switched from orange to green by simple protonation of the amino functional groups that are part of the π‐conjugated scaffold. The resulting three components (blue, green, and orange) exhibit photophysical properties that allow for an efficient fluorescence resonance energy transfer (FRET) in the mixture/polymer and provide intense white fluorescence upon excitation of the blue component; the fluorescence is close to pure white in solution and similar to the emission of an incandescent light bulb in the thin film. The results nicely illustrate the intriguing features that can be obtained by exclusively using organophosphorus‐based organic electronic materials.