Yellow and Red Electrophosphors Based on Linkage Isomers of Phenylisoquinolinyliridium Complexes: Distinct Differences in Photophysical and Electroluminescence Properties

We report the synthesis and organic light‐emitting devices (OLEDs) made from a series of 1‐phenyl‐ and 3‐phenylisoquinolinyliridium complexes in which the phenyl group is linked to the C1 and C3 carbons of isoquinoline, respectively. These linkage isomers show distinct differences in their photophysical and electroluminescence (EL) properties, including the magnitude of phosphorescent lifetimes and photoluminescence (PL) and EL emission wavelengths, as well as the phenomenon of triplet–triplet (T–T) annihilation. Complexes of these two families show a strong absorption band in the region 440–490 nm assignable to spin‐forbidden ³MLCT (metal–ligand charge‐transfer) bands. The extinction coefficients of these bands are similar to those of spin‐allowed ¹MLCT bands, indicative of an anomalously strong spin–orbital coupling. Upon excitation, 1‐phenylisoquinolinyliridium complexes exhibit a single phosphorescent emission band in the red region (595–631 nm). All of these red phosphors show outstanding EL performance with negligible T–T annihilation because of short phosphorescent lifetimes (1.04–2.46 μs in CH₂Cl₂) and good emission quantum yields. One representative, [Ir(5‐f‐1piq)₂(acac)] (acac = acetylacetonate) ( 3 ) (5‐f‐1piqH = 5‐fluoro‐1‐phenylisoquinoline), is not only the brightest at low voltages (1883 cd m^–2 at 7.1 V; 8320 cd m^–2 at 9.0 V) but also shows a η_ext value of. 6.50 % at high current (J = 400 mA cm^–2). The maximum brightness is 38 218 cd m^–2 (x = 0.68, y = 0.31) with the full width at half maximum (FWHM) only 50 nm at 8 V. In contrast, 3‐phenylisoquinolinyliridium complexes show phosphorescent emissions in the yellow region (534–562 nm) but with a long phosphorescent lifetime (3.90–15.6 μs in CH₂Cl₂)_. Most of these yellow phosphors suffer T–T annihilation in the EL performance. The exception is [Ir(3‐piq)₂(acac)] ( 5 ) (3‐piqH = 3‐phenylisoquinoline), which has a relatively short lifetime 3.90 μs in CH₂Cl₂. Complex 5 achieves an external efficiency (η_ext) value of 5.27 % at J = 20 mA cm^–2 and maintains a η_ext value of 3.58 at J = 400 mA cm^–2 with a maximum brightness of 65 448 cd m^–2 (x = 0.49, y = 0.51).     

Thin Films of Insoluble Poly(Oligothienylene vinylenes) Prepared by Chemical Vapor Deposition Polymerization

A series of poly(oligothienylene vinylenes) (PT_mVs, m = 2–4) with a varying number of consecutively bound thienylene rings are successfully prepared in thin films by chemical vapor deposition polymerization (CVDP) using the corresponding bis(halomethyl)thiophenes as starting materials. The chemical and electronic structures are studied spectroscopically and also by cyclic voltammetry. Top‐gate field‐effect transistors are fabricated by two consecutive CVDP cycles of PT_mV and poly(p‐xylylene) followed by the deposition of a Au gate electrode. In the case of a PT₃V active layer, a field‐effect mobility value of 0.5 × 10^–4 cm² V^–1 s^–1 is obtained.     

Multiferroic Polymer Laminate Composites Exhibiting High Magnetoelectric Response Induced by Hydrogen‐Bonding Interactions

The coupling of the magnetic, electric, and elastic properties in multiferroics creates new collective phenomena and enables next‐generation device paradigms. In this work, the hydrogen bonding interaction between hydrate salts and ferroelectric polymers is exploited in the development of high‐performance magnetoelectric (ME) polymer laminate composites. The microstructures and crystallite structures of the Al(NO₃)₃·9H₂O doped poly(vinylidene fluoride‐co‐hexafluoropropylene), P(VDF‐HFP), are carefully studied. The effect of hydrogen bonding interaction on the polarization ordering of the ferroelectric polymers is investigated by 2D wide‐angle X‐ray diffraction, polarized Fourier transform infrared spectra, and dielectric spectra at varied frequencies and temperatures. It is found that hydrogen bond not only promotes the formation of the polar crystallite phase but also improves the polarization ordering in the ferroelectric polymer, which subsequently increases the remnant polarization of the polymers as verified in the polarization‐electric field loop measurements. These entail marked improvement in the ME voltage coefficients (α_ME) of the resulting polymer laminate composites based on ferromagnetic Metglas relative to analogous composites. The composite exhibits a state‐of‐the‐art α_ME value of 20 V cm^‐1 Oe under a dc magnetic field of ≈4 Oe and a colossal α_ME of 320 V cm^‐1 Oe at a frequency of 68 kHz.     

Air‐Operable,High‐Mobility Organic Transistors with Semifluorinated Side Chains and Unsubstituted Naphthalenetetracarboxylic Diimide Cores: High Mobility and Environmental and Bias Stress Stability from the Perfluorooctylpropyl Side Chain

N,N′‐bis(3‐(perfluoroctyl)propyl)‐1,4,5,8‐naphthalenetetracarboxylic acid diimide (8–3‐NTCDI) was newly synthesized, as were related fluorooctylalkyl‐NTCDIs and alkyl‐NTCDIs. The 8–3‐NTCDI‐based organic thin‐film transistor (OTFT) on an octadecyltrimethoxysilane (OTS)‐treated Si/SiO₂ substrate shows apparent electron mobility approaching 0.7 cm² V^‐1s^‐1 in air. The fluorooctylethyl‐NTCDI (8–2‐NTCDI) and fluorooctylbutyl‐NTCDI (8–4‐NTCDI) had significantly inferior properties even though their chemical structures are only slightly different, and nonfluorinated decyl and undecyl NTCDIs did not operate predictably in air. From atomic force microscopy, the 8–3‐NTCDI active layer deposited with the substrate at 120 °C forms a polycrystalline film with grain sizes >4μm. Mobilities were stable in air for one week. After 100 days in air, the average mobility of three OTFTs decreased from 0.62 to 0.12 cm² V^‐1s^‐1, but stabilized thereafter. The threshold voltage (V_T) increased by 15 V in air, but only by 3 V under nitrogen, after one week. On/off ratios were stable in air throughout. We also investigated transistor stability to gate bias stress. The transistor on hexamethlydisilazane (HMDS) is more stable than that on OTS with mobility comparable to amorphous Si TFTs. V_T shifts caused by ON (30 V) and OFF (–20 V) gate bias stress for the HMDS samples for 1 hour were 1.79 V and 1.27 V under N₂, respectively, and relaxation times of 10⁶ and 10⁷ s were obtained using the stretched exponential model. These performances are promising for use in transparent display backplanes.     

Highly Ordered Mesoporous Silicon Carbide Ceramics with Large Surface Areas and High Stability

Highly ordered mesoporous silicon carbide ceramics have been successfully synthesized with yields higher than 75 % via a one‐step nanocasting process using commercial polycarbosilane (PCS) as a precursor and mesoporous silica as hard templates. Mesoporous SiC nanowires in two‐dimensional (2D) hexagonal arrays (p6m) can be easily replicated from a mesoporous silica SBA‐15 template. Small‐angle X‐ray diffraction (XRD) patterns and transmission electron microscopy (TEM) images show that the SiC nanowires have long‐range regularity over large areas because of the interwire pillar connections. A three‐dimensional (3D) bicontinuous cubic mesoporous SiC structure (Ia3d) can be fabricated using mesoporous silica KIT‐6 as the mother template. The structure shows higher thermal stability than the 2D hexagonal mesoporous SiC, mostly because of the 3D network connections. The major constituent of the products is SiC, with 12 % excess carbon and 14 % oxygen measured by elemental analysis. The obtained mesoporous SiC ceramics are amorphous below 1200 °C and are mainly composed of randomly oriented β‐SiC crystallites after treatment at 1400 °C. N₂‐sorption isotherms reveal that these ordered mesoporous SiC ceramics have high Brunauer–Emmett–Teller (BET) specific surface areas (up to 720 m² g^–1), large pore volumes (～ 0.8 cm³ g^–1), and narrow pore‐size distributions (mean values of 2.0–3.7 nm), even upon calcination at temperatures as high as 1400 °C. The rough surface and high order of the nanowire arrays result from the strong interconnections of the SiC products and are the main reasons for such high surface areas. XRD, N₂‐sorption, and TEM measurements show that the mesoporous SiC ceramics have ultrahigh stability even after re‐treatment at 1400 °C under a N₂ atmosphere. Compared with 2D hexagonal SiC nanowire arrays, 3D cubic mesoporous SiC shows superior thermal stability, as well as higher surface areas (590 m² g^–1) and larger pore volumes (～ 0.71 cm³ g^–1).     

Triple‐Shape Polymeric Composites (TSPCs)

In this paper, the fabrication and characterization of triple‐shape polymeric composites (TSPCs) that, unlike traditional shape memory polymers (SMPs), are capable of fixing two temporary shapes and recovering sequentially from the first temporary shape (shape 1) to the second temporary shape (shape 2), and eventually to the permanent shape (shape 3) upon heating, are reported. This is technically achieved by incorporating non‐woven thermoplastic fibers (average diameter ～760 nm) of a low‐T_m semicrystalline polymer into a T_g‐based SMP matrix. The resulting composites display two well‐separated transitions, one from the glass transition of the matrix and the other from the melting of the fibers, which are subsequently used for the fixing/recovery of two temporary shapes. Three thermomechanical programming processes with different shape fixing protocols are proposed and explored. The intrinsic versatility of this composite approach enables an unprecedented large degree of design flexibility for functional triple‐shape polymers and systems.     

Fabrication of Reversibly Crosslinkable, 3‐Dimensionally Conformal Polymeric Microstructures

Multifaceted porous materials were prepared through careful design of star polymer functionality and properties. Functionalized core crosslinked star (CCS) polymers with a low glass transition temperature (T_g) based on poly(methyl acrylate) were prepared having a multitude of hydroxyl groups at the chain ends. Modification of these chain ends with 9‐anthracene carbonyl chloride introduces the ability to reversibly photocrosslink these systems after the star polymers were self‐assembled by the breath figure technique to create porous, micro‐structured films. The properties of the low T_g CCS polymer allow for the formation of porous films on non‐planar substrates without cracking and photo‐crosslinking allows the creation of stabilized honeycomb films while also permitting a secondary level of patterning on the film, using photo‐lithographic techniques. These multifaceted porous polymer films represent a new generation of well‐defined, 3D microstructures.     

High‐Strain Shape‐Memory Polymers

Shape‐memory polymers (SMPs) are self‐adjusting, smart materials in which shape changes can be accurately controlled at specific, tailored temperatures. In this study, the glass transition temperature (T_g) is adjusted between 28 and 55 °C through synthesis of copolymers of methyl acrylate (MA), methyl methacrylate (MMA), and isobornyl acrylate (IBoA). Acrylate compositions with both crosslinker densities and photoinitiator concentrations optimized at fractions of a mole percent demonstrate fully recoverable strains at 807% for a T_g of 28 °C, at 663% for a T_g of 37 °C, and at 553% for a T_g of 55 °C. A new compound, 4,4′‐di(acryloyloxy)benzil (referred to hereafter as Xini) in which both polymerizable and initiating functionalities are incorporated in the same molecule, was synthesized and polymerized into acrylate shape‐memory polymers, which were thermomechanically characterized yielding fully recoverable strains above 500%. The materials synthesized in this work were compared to an industry standard thermoplastic SMP, Mitsubishi's MM5510, which showed failure strains of similar magnitude, but without full shape recovery: residual strain after a single shape‐memory cycle caused large‐scale disfiguration. The materials in this study are intended to enable future applications where both recoverable high‐strain capacity and the ability to accurately and independently position T_g are required.     

Fully Printed Organic Electrochemical Transistors from Green Solvents

To achieve the full potential of scalable and cost‐effective organic electronic devices, developments are being made in both academic and industry environments to move toward continuous solution‐processing techniques that make use of safe and environmentally benign “green” solvents. In this work, the first example of a transistor device that is fully solution processed using only green solvents is demonstrated. This achievement is enabled through a novel multistage cleavable side chain process that provides aqueous solubility for semiconducting conjugated polymers, paired with aqueous inkjet printing of PEDOT:PSS electrodes, and a solution deposited ion gel electrolyte as the dielectric layer. The resulting organic electrochemical transistor devices operate in accumulation mode and reach maximum transconductance values of 1.1 mS at a gate voltage of ? 1 V. Normalizing the transconductance value to the channel dimensions yields g_m/W = 2200 S m^?1 (µC* = 22 F cm^?1 V^?1 s^?1), making these devices suitable for a range of applications requiring small signal amplification such as transistors, biosensors, and ion pumps. This new material design and device process paves the way toward scalable, safe, and efficient production of organic electronic devices.     

Linear and Nonlinear Optical Properties of Ag Nanowire Polarizing Glass

An R₂O–B₂O₃–SiO₂ (R = Li, Na, K) polarizing glass containing Ag nanorods is prepared by thermal elongation–reduction technology. The transverse and longitudinal plasmon absorption peaks of the embedded Ag nanorods are near 460 and 720 nm, respectively. When the polarization of the laser is parallel to the long axis of the Ag nanorods, the nonlinear absorption coefficient β = 0.82 cm GW^–1 and the nonlinear refractive index n₂ = –1.5 × 10^–4 cm² GW^–1. When the polarization of light is perpendicular to the long axis of the Ag nanorods β = 0.12 cm GW^–1 and n₂ = –7.2 × 10^–5 cm² GW^–1 and the appropriate one‐ and two‐photon figures of merit (FOM), W = 1.6 and T = 0.16, respectively, are obtained, which satisfies the demand, W > 1 and T < 1, for applications in all optical switching, where W is a one‐photon FOM, and T is a two‐photon FOM.     

Strong,Tailored, Biocompatible Shape‐Memory Polymer Networks

Shape‐memory polymers are a class of smart materials that have recently been used in intelligent biomedical devices and industrial applications for their ability to change shape under a predetermined stimulus. In this study, photopolymerized thermoset shape‐memory networks with tailored thermomechanics are evaluated to link polymer structure to recovery behavior. Methyl methacrylate (MMA) and poly(ethylene glycol) dimethacrylate (PEGDMA) are copolymerized to create networks with independently adjusted glass transition temperatures (T_g) and rubbery modulus values ranging from 56 to 92 °C and 9.3 to 23.0 MPa, respectively. Free‐strain recovery under isothermal and transient temperature conditions is highly influenced by the T_g of the networks, while the rubbery moduli of the networks has a negligible effect on this response. The magnitude of stress generation of fixed‐strain recovery correlates with network rubbery moduli, while fixed‐strain recovery under isothermal conditions shows a complex evolution for varying T_g. The results are intended to help aid in future shape‐memory device design and the MMA‐co‐PEGDMA network is presented as a possible high strength shape‐memory biomaterial.     

Effect of Spacer Length of Siloxane‐Terminated Side Chains on Charge Transport in Isoindigo‐Based Polymer Semiconductor Thin Films

A series of isoindigo‐based conjugated polymers (PII2F‐C_mSi, m = 3–11) with alkyl siloxane‐terminated side chains are prepared, in which the branching point is systematically “moved away” from the conjugated backbone by one carbon atom. To investigate the structure–property relationship, the polymer thin film is subsequently tested in top‐contact field‐effect transistors, and further characterized by both grazing incidence X‐ray diffraction and atomic force microscopy. Hole mobilities over 1 cm² V^?1 s^?1 is exhibited for all soluble PII2F‐C_mSi (m = 5–11) polymers, which is 10 times higher than the reference polymer with same polymer backbone. PII2F‐C₉Si shows the highest mobility of 4.8 cm² V^?1 s^?1, even though PII2F‐C₁₁Si exhibits the smallest π–π stacking distance at 3.379 Å. In specific, when the branching point is at, or beyond, the third carbon atoms, the contribution to charge transport arising from π–π stacking distance shortening becomes less significant. Other factors, such as thin‐film microstructure, crystallinity, domain size, become more important in affecting the resulting device's charge transport.     

Effect of Temperature and Illumination on the Electrical Characteristics of Polymer–Fullerene Bulk‐Heterojunction Solar Cells

The current–voltage characteristics of ITO/PEDOT:PSS/OC₁C₁₀‐PPV:PCBM/Al solar cells were measured in the temperature range 125–320 K under variable illumination, between 0.03 and 100 mW cm^–2 (white light), with the aim of determining the efficiency‐limiting mechanism(s) in these devices, and the temperature and/or illumination range(s) in which these devices demonstrate optimal performance. (ITO: indium tin oxide; PEDOT:PSS: poly(styrene sulfonate)‐doped poly(ethylene dioxythiophene); OC₁C₁₀‐PPV: poly[2‐methoxy‐5‐(3,7‐dimethyl octyloxy)‐1,4‐phenylene vinylene]; PCBM: phenyl‐C₆₁ butyric acid methyl ester.) The short‐circuit current density and the fill factor grow monotonically with temperature until 320 K. This is indicative of a thermally activated transport of photogenerated charge carriers, influenced by recombination with shallow traps. A gradual increase of the open‐circuit voltage to 0.91 V was observed upon cooling the devices down to 125 K. This fits the picture in which the open‐circuit voltage is not limited by the work‐function difference of electrode materials used. The overall effect of temperature on solar‐cell parameters results in a positive temperature coefficient of the power conversion efficiency, which is 1.9 % at T = 320 K and 100 mW cm^–2 (2.5 % at 0.7 mW cm^–2). The almost‐linear variation of the short‐circuit current density with light intensity confirms that the internal recombination losses are predominantly of monomolecular type under short‐circuit conditions. We present evidence that the efficiency of this type of solar cell is limited by a light‐dependent shunt resistance. Furthermore, the electronic transport properties of the absorber materials, e.g., low effective charge‐carrier mobility with a strong temperature dependence, limit the photogenerated current due to a high series resistance, therefore the active layer thickness must be kept low, which results in low absorption for this particular composite absorber.     

Pt Nanoparticles Sensitized Ordered Mesoporous WO3 Semiconductor: Gas Sensing Performance and Mechanism Study

In this study, a straightforward coassembly strategy is demonstrated to synthesize Pt sensitized mesoporous WO₃ with crystalline framework through the simultaneous coassembly of amphiphilic poly(ethylene oxide)‐b‐polystyrene, hydrophobic platinum precursors, and hydrophilic tungsten precursors. The obtained WO₃/Pt nanocomposites possess large pore size (≈13 nm), high surface area (128 m² g^?1), large pore volume (0.32 cm³ g^?1), and Pt nanoparticles (≈4 nm) in situ homogeneously distributed in mesopores, and they exhibit excellent catalytic sensing response to CO of low concentration at low working temperature with good sensitivity, ultrashort response‐recovery time (16 s/1 s), and high selectivity. In‐depth study reveals that besides the contribution from the fast diffusion of gaseous molecules and rich interfaces in mesoporous WO₃/Pt nanocomposites, the partially oxidized Pt nanoparticles that chemically and electronically sensitize the crystalline WO₃ matrix, dramatically enhance the sensitivity and selectivity.     

Characterization and Field‐Emission Properties of Needle‐like Zinc Oxide Nanowires Grown Vertically on Conductive Zinc Oxide Films

Needle‐like ZnO nanowires with high density are grown uniformly and vertically over an entire Ga‐doped conductive ZnO film at 550 °C. The nanowires are grown preferentially in the c‐axis direction. The X‐ray diffraction (XRD) θ‐scan curve shows a full width at half maximum (FWHM) value of 2°. This indicates that the c‐axes of the nanorods are along the normal direction of the substrate surface. The investigation using high‐resolution transmission electron microscopy (HRTEM) confirmed that each nanowire is a single crystal. A room‐temperature photoluminescence (PL) spectrum of the wires consists of a strong and sharp UV emission band at 380 nm and a weak and broad green–yellow band. It reveals a low concentration of oxygen vacancies in the ZnO nanowires and their high optical quality. Field electron emission from the wires was also investigated. The turn‐on field for the ZnO nanowires was found to be about 18 V μm^–1 at a current density of 0.01 μA cm^–2. The emission current density from the ZnO nanowires reached 0.1 mA cm^–2 at a bias field of 24 V μm^–1.     

Toward the Prediction and Control of Glass Transition Temperature for Donor–Acceptor Polymers

Semiconducting donor–acceptor (D–A) polymers have attracted considerable attention toward the application of organic electronic and optoelectronic devices. However, a rational design rule for making semiconducting polymers with desired thermal and mechanical properties is currently lacking, which greatly limits the development of new polymers for advanced applications. Here, polydiketopyrrolopyrrole (PDPP)‐based D–A polymers with varied alkyl side‐chain lengths and backbone moieties are systematically designed, followed by investigating their thermal and thin film mechanical responses. The experimental results show a reduction in both elastic modulus and glass transition temperature (T_g) with increasing side‐chain length, which is further verified through coarse‐grained molecular dynamics simulations. Informed from experimental results, a mass‐per‐flexible bond model is developed to capture such observation through a linear correlation between T_g and polymer chain flexibility. Using this model, a wide range of backbone T_g over 80 °C and elastic modulus over 400 MPa can be predicted for PDPP‐based polymers. This study highlights the important role of side‐chain structure in influencing the thermomechanical performance of conjugated polymers, and provides an effective strategy to design and predict T_g and elastic modulus of future new D–A polymers.     

Diphenylmethanofullerenes: New and Efficient Acceptors in Bulk‐Heterojunction Solar Cells

A novel fullerene derivative, 1,1‐bis(4,4′‐dodecyloxyphenyl)‐(5,6) C₆₁, diphenylmethanofullerene (DPM‐12), has been investigated as a possible electron acceptor in photovoltaic devices, in combination with two different conjugated polymers poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐para‐phenylene vinylene] (OC₁C₁₀‐PPV) and poly[3‐hexyl thiophene‐2,5‐diyl] (P3HT). High open‐circuit voltages, V_OC = 0.92 and 0.65 V, have been measured for OC₁C₁₀‐PPV:DPM‐12‐ and P3HT:DPM‐12‐based devices, respectively. In both cases, V_OC is 100 mV above the values measured on devices using another routinely used fullerene acceptor, [6,6]‐phenyl‐C₆₁ butyric acid methyl ester (PCBM). This is somewhat unexpected when taking into account the identical redox potentials of both acceptor materials at room temperature. The temperature‐dependent V_OC reveals, however, the same effective bandgap (HOMO_Polymer–LUMO_Fullerene; HOMO = highest occupied molecular orbital, LUMO = lowest unoccupied molecular orbital) of 1.15 and 0.9 eV for OC₁C₁₀‐PPV and P3HT, respectively, independent of the acceptor used. The higher V_OC at room temperature is explained by different ideality factors in the dark‐diode characteristics. Under white‐light illumination (80 mW cm^–2), photocurrent densities of 1.3 and 4.7 mA cm^–2 have been obtained in the OC₁C₁₀‐PPV:DPM‐12‐ and P3HT:DPM‐12‐based devices, respectively. Temperature‐dependent current density versus voltage characteristics reveal a thermally activated (shallow trap recombination limited) photocurrent in the case of OC₁C₁₀‐PPV:DPM‐12, and a nearly temperature‐independent current density in P3HT:DPM‐12. The latter clearly indicates that charge carriers traverse the active layer without significant recombination, which is due to the higher hole‐mobility–lifetime product in P3HT. At the same time, the field‐effect electron mobility in pure DPM‐12 has been found to be μ_e = 2 × 10^–4 cm² V^–1 s^–1, that is, forty‐times lower than the one measured in PCBM (μ_e = 8 × 10^–3 cm² V^–1 s^–1).     

The Effect of Polymer Optoelectronic Properties on the Performance of Multilayer Hybrid Polymer/TiO2 Solar Cells

We report a study of the effects of polymer optoelectronic properties on the performance of photovoltaic devices consisting of nanocrystalline TiO₂ and a conjugated polymer. Three different poly(2‐methoxy‐5‐(2′‐ethylhexoxy)‐1,4‐phenylenevinylene) (MEH‐PPV)‐based polymers and a fluorene–bithiophene copolymer are compared. We use photoluminescence quenching, time‐of‐flight mobility measurements, and optical spectroscopy to characterize the exciton‐transport, charge‐transport, and light‐harvesting properties, respectively, of the polymers, and correlate these material properties with photovoltaic‐device performance. We find that photocurrent is primarily limited by the photogeneration rate and by the quality of the interfaces, rather than by hole transport in the polymer. We have also studied the photovoltaic performance of these TiO₂/polymer devices as a function of the fabrication route and device design. Including a dip‐coating step before spin‐coating the polymer leads to excellent polymer penetration into highly structured TiO₂ networks, as was confirmed through transient optical measurements of the photoinduced charge‐transfer yield and recombination kinetics. Device performance is further improved for all material combinations studied, by introducing a layer of poly(ethylene dioxythiophene) (PEDOT) doped with poly(styrene sulfonic acid) (PSS) under the top contact. Optimized devices incorporating the additional dip‐coated and PEDOT:PSS layers produced a short‐circuit current density of about 1 mA cm^–2, a fill factor of 0.50, and an open‐circuit voltage of 0.86 V under simulated AM 1.5 illumination (100 mW cm^–2, 1 sun). The corresponding power conversion efficiency under 1 sun was ≥ 0.4 %.     

High‐Performance [001]c‐Textured PNN‐PZT Relaxor Ferroelectric Ceramics for Electromechanical Coupling Devices

[001]_C‐Textured 0.55Pb(Ni_1/3Nb_2/3)O₃–0.15PbZrO₃–0.3PbTiO₃ (PNN‐PZT) ceramics are prepared by the templated grain‐growth method using BaTiO₃ (BT) platelet templates. Samples with different template contents are fabricated and compared in terms of texture fraction, microstructure, and piezoelectric, ferroelectric and dielectric properties. High piezoelectric performance (d₃₃ = 1210 pC N^?1, d₃₃* = 1773 pm V^?1 at 5 kV cm^?1) and high figure of merit g₃₃?d₃₃ (21.92 × 10^?12 m² N^?1) are achieved in the [001]_C‐textured PNN‐PZT ceramic with 2 vol% BaTiO₃ template, for which the texture fraction is 82%. In addition, domain structures of textured PNN‐PZT ceramics are observed and analyzed, which provide clues to the origin of the giant piezoelectric and electromechanical coupling properties of PNN‐PZT ceramics.     

Highly Efficient Electrocatalysts for Oxygen Reduction Reaction Based on 1D Ternary Doped Porous Carbons Derived from Carbon Nanotube Directed Conjugated Microporous Polymers

One‐dimensional (1D) porous materials have shown great potential for gas storage and separation, sensing, energy storage, and conversion. However, the controlled approach for preparation of 1D porous materials, especially porous organic materials, still remains a great challenge due to the poor dispersibility and solution processability of the porous materials. Here, carbon nanotube (CNT) templated 1D conjugated microporous polymers (CMPs) are prepared using a layer‐by‐layer method. As‐prepared CMPs possess high specific surface areas of up to 623 m² g^?1 and exhibit strong electronic interactions between p‐type CMPs and n‐type CNTs. The CMPs are used as precursors to produce heteroatom‐doped 1D porous carbons through direct pyrolysis. As‐produced ternary heteroatom‐doped (B/N/S) 1D porous carbons possess high specific surface areas of up to 750 m² g^?1, hierarchical porous structures, and excellent electrochemical‐catalytic performance for oxygen reduction reaction. Both of the diffusion‐limited current density (4.4 mA cm^?2) and electron transfer number (n = 3.8) for three‐layered 1D porous carbons are superior to those for random 1D porous carbon. These results demonstrate that layered and core–shell type 1D CMPs and related heteroatom‐doped 1D porous carbons can be rationally designed and controlled prepared for high performance energy‐related applications.