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1.
Despite the excellent work function adjustability of conjugated polyelectrolytes (CPEs), which induce a vacuum level shift via the formation of permanent dipoles at the CPE/metal electrode interface, the exact mechanism of electron injection through the CPE electron transport layer (ETL) remains unclear. In particular, understanding the ionic motion within the CPE ETLs when overcoming the sizable injection barrier is a significant challenge. Because the ionic functionality of CPEs is a key component for such functions, a rigorous analysis using highly controlled ion density (ID) in CPEs is crucial for understanding the underlying mechanism. Here, by introducing a new series of CPEs with various numbers of ionic functionalities, energy level tuning at such an interface can be determined directly by adjusting the ID in the CPEs. More importantly, these series CPEs indicate that two different mechanisms must be invoked according to the CPE thickness. The formation of permanent interfacial dipoles is critical with respect to electron injection through CPE ETL (≤ 10 nm, quantum mechanical tunneling limit), whereas electron injection through thick CPE ETL (20–30 nm) is dominated by the reorientation of the ionic side chains under a given electric field.  相似文献   

2.
Elucidating the interrelation between the molecular structure and charge transport properties in conjugated polymer thin films is an essential issue in developing the design principle of high‐performance polymer materials for application in organic electronics. In particular, the backbone planarity is suggested to be a key element that governs the transport performance, especially in recently developed donor–acceptor (D–A)‐type copolymers exhibiting high mobility, whereas the direct evaluation of the intrinsic transport performance, usually realized only within the small crystalline domains, is difficult by using conventional macroscopic measurements. Here, it is demonstrated that a D–A type copolymer, PDPPF‐DTT, which consists of furan‐flanked diketopyrrolopyrrole (DPP) and dithienothiophene (DTT) units in the conjugated backbone, exhibits a highly efficient charge transport performance within the crystalline domains with a remarkably low activation energy of less than 8 meV, based on microscopic measurements using field‐induced electron spin resonance spectroscopy. This high transport performance is primarily caused by the high backbone planarity realized by introducing furan‐flanked DPP and fused dithienothiophene units, which is demonstrated from the density functional theory calculations. This result provides a microscopic indication of the effectiveness of the present molecular design to produce a planar backbone and realize highly efficient charge transport performance.  相似文献   

3.
Today, there is an urgent demand to develop all solid-state lithium-ion batteries (LIBs) with a high energy density and a high degree of safety. The core technology in solid-state batteries is a solid-state electrolyte, which determines the performance of the battery. Among all the developed solid electrolytes, composite polymer electrolytes (CPEs) have been deemed as one of the most viable candidates because of their comprehensive performance. In this review, the limitations of traditional solid polymer electrolytes and the recent progress of CPEs are introduced. The effect and mechanism of inorganic fillers to the various properties of electrolytes are discussed in detail. Meanwhile, the factors affecting ionic conductivity are intensively reviewed. The recent representative CPEs with synthetic fillers and natural clay-based fillers are highlighted because of their great potential. Finally, the remaining challenges and promising prospects are outlined to provide strategies to develop novel CPEs for high-performance LIBs.  相似文献   

4.
To achieve highly efficient organic photovoltaic (OPV) devices, the interface between the photoactive layer and the electrode must be modified to afford the appropriate alignment of the energy levels and to ensure efficient charge extraction at the same time as suppressing charge recombination and accumulation. Recently, p-type conjugated polyelectrolytes (CPEs) have emerged as new hole-transporting materials that can be deposited on electrodes through simple solution processes without additional heat treatment. However, the applications of CPEs have been limited so far because the high electron richness of their conjugated backbones result in low work functions, ∼5.0 eV. Here, by inserting a donor−acceptor (D−A) building block into the CPE backbone, we successfully synthesized a new p-type CPE (PhNa-DTBT), which shows a deep work function above 5.3 eV on several electrodes including Au, Ag, and indium tin oxide. More importantly, PhNa-DTBT produces stable polarons on the polymer backbone and thus achieves a high electrical conductivity of 5.7 × 10−4 S cm−1. As a result, an OPV incorporating PhNa-DTBT as a hole-transporting layer was found to exhibit a high performance with a power conversion efficiency of 9.29%. Also, the OPV device shows improved stability in air due to the neutral characteristics of the CPE which is favorable for stabilizing neighbored active and electrode layers.  相似文献   

5.
Several new solution‐processable organic semiconductors based on dendritic oligoquinolines were synthesized and were used as electron‐transport and hole‐blocking materials to realize highly efficient blue phosphorescent organic light‐emitting diodes (PhOLEDs). Various substitutions on the quinoline rings while keeping the central meta‐linked tris(quinolin‐2‐yl)benzene gave electron transport materials that combined wide energy gap (>3.3 eV), moderate electron affinity (2.55‐2.8 eV), and deep HOMO energy level (<‐6.08 eV) with electron mobility as high as 3.3 × 10?3 cm2 V?1 s?1. Polymer‐based PhOLEDs with iridium (III) bis(4,6‐(di‐fluorophenyl)pyridinato‐N,C2′)picolinate (FIrpic) blue triplet emitter and solution‐processed oligoquinolines as the electron‐transport layers (ETLs) gave luminous efficiency of 30.5 cd A?1 at a brightness of 4130 cd m?2 with an external quantum efficiency (EQE) of 16.0%. Blue PhOLEDs incorporating solution‐deposited ETLs were over two‐fold more efficient than those containing vacuum‐deposited ETLs. Atomic force microscopy imaging shows that the solution‐deposited oligoquinoline ETLs formed vertically oriented nanopillars and rough surfaces that enable good ETL/cathode contacts, eliminating the need for cathode interfacial materials (LiF, CsF). These solution‐processed blue PhOLEDs have the highest performance observed to date in polymer‐based blue PhOLEDs.  相似文献   

6.
Flexible transparent electrodes (FTEs) play an important role in determining the performance of flexible organic solar cells (OSCs), Ag-nanowires (AgNWs) with the unique merits of high conductivity, excellent flexibility, and good thermal stability has been taken into more consideration in fabricating highly efficient FTEs. However, the pristine AgNWs film usually suffers a huge surface roughness and incompatibility with the organic absorption layer, thus always leads to a poor power conversion efficiency (PCE). Herein, we demonstrated a simple and effective way through employing poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PH1000) to modify the surface of AgNWs to prepare high-quality FTEs. Based on the PH1000 (100 nm)/AgNWs FTEs, the optimized flexible OSC with PM6:Y6 as active layer exhibits a highest PCE of 12.71%, with an open-circuit voltage (Voc) of 0.814 V, a short-circuit current (Jsc) of 22.61 mA/cm2, and a fill factor (FF) of 0.691, respectively. Which is much higher than the PCE (7.20%) of pristine AgNWs FTEs based device. The enhanced device performance was attributed to the improved morphologies both of the FTEs and the active layers, more effective charge transport and collection efficiency, as well as the decreased charge recombination properties. This work provides an efficient way to fabricate high-quality FTEs and realize efficient flexible OSCs.  相似文献   

7.
The effect of solution‐processed p‐type doping of hole‐generation layers (HGLs) and electron‐transporting layer (ETLs) are systematically investigated on the performance of solution‐processable alternating current (AC) field‐induced polymer EL (FIPEL) devices in terms of hole‐generation capability of HGLs and electron‐transporting characteristics of ETLs. A variety of p‐type doping conjugated polymers and a series of solution‐processed electron‐transporting small molecules are employed. It is found that the free hole density in p‐type doping HGLs and electron mobility of solution‐processed ETLs are directly related to the device performance, and that the hole‐transporting characteristics of ETLs also play an important role since holes need to be injected from electrode through ETLs to refill the depleted HGLs in the positive half of the AC cycle. As a result, the best FIPEL device exhibits exceptional performance: a low turn‐on voltage of 12 V, a maximum luminance of 20 500 cd m?2, a maximum current and power efficiency of 110.7 cd A?1 and 29.3 lm W?1. To the best of the authors' knowledge, this is the highest report to date among FIPEL devices driven by AC voltage.  相似文献   

8.
Considering there is growing interest in the superior charge transport in the (E)‐2‐(2‐(thiophen‐2‐yl)‐vinyl)thiophene (TVT)‐based polymer family, an essential step forward is to provide a deep and comprehensive understanding of the structure–property relationships with their polymer analogs. Herein, a carefully chosen set of DPP‐TVT‐n polymers are reported here, involving TVT and diketopyrrolopyrrole (DPP) units that are constructed in combination with varying thiophene content in the repeat units, where n is the number of thiophene spacer units. Their OFET characteristics demonstrate ambipolar behavior; in particular, with DPP‐TVT‐0 a nearly balanced hole and electron transport are observed. Interestingly, the majority of the charge‐transport properties changed from ambipolar to p‐type dominant, together with the enhanced hole mobilities, as the electron‐donating thiophene spacers are introduced. Although both the lamellar d‐spacings and π‐stacking distances of DPP‐TVT‐n decreased with as the number of thiophene spacers increased, DPP‐TVT‐1 clearly shows the highest hole mobility (up to 2.96 cm2 V?1 s?1) owing to the unique structural conformations derived from its smaller paracrystalline distortion parameter and narrower plane distribution relative to the others. These in‐depth studies should uncover the underlying structure–property relationships in a relevant class of TVT‐like semiconductors, shedding light on the future design of top‐performing semiconducting polymers.  相似文献   

9.
With the development of wearable electronics, the use of engineered functional inks with printing technologies has attracted attention owing to its potential for applications in low-cost, high-throughput, and high-performance devices. However, the improvement in conductivity and stretchability in the mass production of inks is still a challenge for practical use in wearable applications. Herein, a scalable and efficient fluid dynamics process that produces highly stretchable, conductive, and printable inks containing a high concentration of graphene is reported. The resulting inks, in which the uniform incorporation of exfoliated graphene flakes into a viscoelastic thermoplastic polyurethane is employed, facilitated the screen-printing process, resulting in high conductivity and excellent electromechanical stability. The electrochemical analysis of a stretchable sodium ion sensor based on a serpentine-structured pattern results in excellent electrochemical sensing performance even under strong fatigue tests performed by repeated stretching (300% strain) and release cycles. To demonstrate the practical use of the proposed stretchable conductor, on-body tests are carried out in real-time to monitor the sweat produced by a volunteer during simultaneous physical stretching and stationary cycling. These functional graphene inks have attractive performance and offer exciting potential for a wide range of flexible and wearable electronic applications.  相似文献   

10.
The correlation between the molecular design of a conjugated polyelectrolyte (CPE) and its aggregated structure and the emissive properties in water is systematically investigated by means of UV–vis spectrometry, fluorescence spectroscopy, and scanning/transmission electron microscopy. Five different and rationally designed CPEs having carboxylic acid side chains are synthesized. All five conjugated polyelectrolytes are seemingly completely soluble in water in visual observation. However, their quantum yields are dramatically different, changing from 0.45 to 51.4%. Morphological analysis by electron microscopy combined with fluorescence spectrophotometry reveals that the CPEs form self‐assembled aggregates at the nanoscale depending on the nature of their side chains. The feature of the self‐assembled aggregates directly determines the emissive property of the CPEs. The nature and the length of the spacer between the carboxylic acid group and the CPE backbone have a strong influence on the quantum yield of the CPEs. Our study demonstrates that bulky and hydrophilic side chains and spacers are required to achieve complete water‐solubility and high quantum yield of CPEs in water, providing an important molecular design principle to develop functional CPEs.  相似文献   

11.
Three fused-ring small-molecule electron acceptors, IDTC16-IC, IDTC16-Th, and IDTC16-4F, were designed and synthesized by introducing indacenodithiophene (IDT) as the electron-donating core and 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (IC), fluorinated IC, and a thiophene-based unit as the electron-withdrawing end group. Here, instead of the commonly used n-hexyl or n-hexylphenyl side chains, n-hexadecyl peripheral substituents were employed at the IDT core to study the influence of alkyl groups on photovoltaic performance of the nonfullerene acceptors. The introduction of flexible n-hexadecyl group endowed the three acceptors with excellent solubility in common organic solvents. All the three acceptors presented strong absorption ranging from 450 nm to 720 nm in solution with high molar extinction coefficients. As a result, the as-cast organic solar cells (OSCs) based on IDTC16-IC and the wide bandgap polymer donor PM6 exhibited a power conversion efficiency (PCE) of 5.12%. The OSCs based on PM6:IDTC16-Th and PM6:IDTC16-4F showed much better photovoltaic performance with PCEs of 8.76% and 8.55%, respectively. The PCE values were improved to 5.89%, 9.09%, and 9.42% for the PM6:IDTC16-IC, PM6:IDTC16-Th, and PM6:IDTC16-4F OSCs, respectively, with the addition of the solvent additive 1,8-diiodooctane. These findings demonstrate that the combination of alkyl chains at the fused rings and fluorination or aromatic structure change of the terminal groups leads to greatly enhanced photovoltaic performance of nonfullerene acceptors through improving the photophysical, molecular orbital, and film morphological properties.  相似文献   

12.
Although organic materials with near infrared (NIR)-II fluorescence and a photothermal effect have been widely investigated for the accurate diagnosis and treatment of tumors, optimizing the output signals of both remain challenging. Here, a strategy by “enlarging absorption reservoir” to address this issue, since an increase in photon absorption can naturally enhance output signals, is proposed. As a proof-of-concept, a large π-conjugated diketopyrrolopyrrole (DPP) unit is selected to fabricate strong light-absorbing systems. To enhance solid-state fluorescence, highly twisted alkylthiophene–benzobisthiadiazole–alkylthiophene and triphenylamine rotor are introduced to restrict the strong intermolecular π–π interactions. Moreover, the number of DPP units in molecules is engineered to optimize photophysical properties. Results show that TDADT with two DPP units possesses an exceptionally high molar absorptivity of 2.1 × 105 L mol−1 cm−1 at 808 nm, an acceptable NIR-II quantum yield of 0.1% (emission peak at 1270 nm), and a sizeable photothermal conversion efficiency of 60.4%. The excellent photophysical properties of the TDADT nanoparticles are particularly suitable for in vivo NIR-II imaging-guided cancer surgery and NIR-I photothermal therapy. The presented strategy provides a new approach of designing highly efficient NIR-II phototheranostic agents.  相似文献   

13.
Inorganic/organic composite polymer electrolytes (CPEs) with good flexibility and electrode contact have been pursued for solid−state sodium-metal batteries. However, the application of CPEs for high energy density solid−state sodium-metal batteries is still limited by the low Na+ conductivity, large thickness, and low ion transference number. Herein, an ultra-thin single-particle-layer (UTSPL) composite polymer electrolyte membrane with a thickness of ≈20 µm straddled by a sodium beta−alumina ceramic electrolyte (SBACE) is presented. A ceramic Na+-ion electrolyte that bridges or percolates across an ultra-thin and flexible polymer membrane provides: 1) the strength and flexibility from the polymer membrane, 2) excellent electrolyte/electrode interfacial contact, and 3) a percolation path for Na+-ion transfer. Owing to this novel design, the obtained UTSPL-35SBACE membrane exhibits a high Na+-ion conductivity of 0.19 mS cm−1 and a transference number of 0.91 at room temperature, contributing to long−term cycling stability of symmetric sodium cells with a small overpotential. The assembled quasi-solid-state cell with the as−prepared UTSPL-35SBACE membrane displays superior cycling performance with a discharge capacity of 105 mAh g−1 at 0.5 °C rate after 100 cycles and excellent rate performance (82 mAh g−1 at 5 °C rate) at room temperature with the potassium manganese hexacyanoferrate (KMHCF)@CNTs/CNFs cathode, where KMHCF refers to potassium manganese hexacyanoferrate.  相似文献   

14.
The high crystallinity and ability to harvest near‐infrared photons make diketopyrrolopyrrole (DPP)‐based polymers one of the most promising donors for high performing organic solar cells (OSCs). However, DPP‐based OSC devices still suffer from the trade‐off between energetic loss (Eloss) and maximum external quantum efficiency (EQEmax), which significantly hinders their potential. Thus far, the replacement of fullerenes with small molecule acceptors did not wisdom the performance development of DPP‐donor‐based solar cells due to severe charge recombination issues. In this work, efficient DPP‐based solar cells are reported using low bandgap fused ring electron acceptor, IEICO‐4F. PBDTT‐DPP:IEICO‐4F OSC devices deliver a champion power conversion efficiency of 9.66% with successful interface engineering along with low Eloss of 0.57 eV and a high EQEmax (>70%).  相似文献   

15.
Developing new polymerized small molecular acceptor (PSMA) is pivotal for improving the performance of all-polymer solar cells. On the basis of this newly developed CH-series small molecule acceptors, two PSMAs are reported herein (namely PZC16 and PZC17, respectively). To reduce the molecular torsion caused by the traditional aromatic π-bridges, non-aromatic conjugated units (ethynyl for PZC16 and vinylene for PZC17) are adopted as the linkers and their effect on the photo-physical properties as well as the device performance are systematically investigated. Both polymer acceptors exhibit co-planar molecular conformation, along with broad absorption ranges and suitable energy levels. In comparison with the PM6:PZC16 film, the PM6:PZC17 film exhibits more uniform phase separation in morphology with a distinct bi-continuous network and better crystallinity. The PM6:PZC17-binary-based devices exhibit a satisfactory PCE of 16.33%, significantly higher than 9.22% of the PZC16-based devices. Impressively, PM6:PZC17-based large area device (ca. 1 cm2) achieves an excellent PCE of 15.14%, which is among the top performance for reported all-polymer solar cells (all-PSCs).  相似文献   

16.
Fabricating high‐efficient electron transporting interfacial layers (ETLs) with isotropic features is highly desired for all‐directional electron transfer/collection from an anisotropic active layer, achieving excellent power conversion efficiency (PCEs) on nonfullerene acceptor (NFA) organic solar cells (OSCs). The complicated synthesis and cost‐consumption in exploring versatile materials arouse great interest in the development of binary‐doping interlayers without phase separation and flexible manipulation. Herein, for the first time, a novel cathode interfacial layer based on biomass‐derived demethylated kraft lignin (DMeKL) is proposed. Features of multiple phenolic‐hydroxyl (PhOH) and uniform‐distributed render DMeKL to exhibit an excellent bonding capacity with amino terminal substituted perylene diiminde (PDIN), and successfully form a high‐efficient isotropic electron transfer 3D network. Synchronously, secondary bonds completely modify conjugate‐blocked linkages of DMeKL, significantly enhance the electron transporting performance on cross‐section and vertical‐sections, and repair the contact of PDIN with active layer. The DMeKL/PDIN‐based 3D‐network exhibits well‐matched work function (WF) (–4.34 eV) with cathode (–4.30 eV) and energy level of electron acceptor (–4.11 eV). DMeKL/PDIN‐based NFAs‐OSC shows excellent short‐circuit current density (26.61 mA cm–2) and PCE (16.02%) beyond the classic PDIN‐based NFA‐OSC (25.64 mA cm–2, 15.41%), which is the highest PCEs among biomaterials interlayers. The results supply a novel method to achieve high‐efficient cathode interlayer for NFAs‐OSCs.  相似文献   

17.
SnO2 has been well investigated in many successful state‐of‐the‐art perovskite solar cells (PSCs) due to its favorable attributes such as high mobility, wide bandgap, and deep conduction band and valence band. Several independent studies show the performances of PSCs with SnO2 are higher than that with TiO2, especially in device stability. In 2015, the first planar PSCs were reported with a power conversion efficiency over 17% using a low temperature sol‐derived SnO2 nanocrystal electron transport layer (ETL). Since then, many other groups have also reported high performance PSCs based on SnO2 ETLs. SnO2 planar PSCs show currently the highest performance in planar configuration devices (21.6%) and are close to the record holder of TiO2 mesoporous PSCs, suggesting their high potential as ETLs in PSCs. The main concerns with the application of SnO2 as ETL are that it suffers from degradation in high temperature processes and that its much lower conduction band compared to perovskite may result in a voltage loss of PSCs. Here, notable achievements to date are outlined, the unique attributes of SnO2 as ETLs in PSCs are described, and the challenges facing the successful development of PSCs and approaches to the problems are discussed.  相似文献   

18.
n‐Doping electron‐transport layers (ETLs) increases their conductivity and improves electron injection into organic light‐emitting diodes (OLEDs). Because of the low electron affinity and large bandgaps of ETLs used in green and blue OLEDs, n‐doping has been notoriously more difficult for these materials. In this work, n‐doping of the polymer poly[(9,9‐dioctylfluorene‐2,7‐diyl)‐alt‐(benzo[2,1,3]thiadiazol‐4,7‐diyl)] (F8BT) is demonstrated via solution processing, using the air‐stable n‐dopant (pentamethylcyclopentadienyl)(1,3,5‐trimethylbenzene)ruthenium dimer [RuCp*Mes]2. Undoped and doped F8BT films are characterized using ultraviolet and inverse photoelectron spectroscopy. The ionization energy and electron affinity of the undoped F8BT are found to be 5.8 and 2.8 eV, respectively. Upon doping F8BT with [RuCp*Mes]2, the Fermi level shifts to within 0.25 eV of the F8BT lowest unoccupied molecular orbital, which is indicative of n‐doping. Conductivity measurements reveal a four orders of magnitude increase in the conductivity upon doping and irradiation with ultraviolet light. The [RuCp*Mes]2‐doped F8BT films are incorporated as an ETL into phosphorescent green OLEDs, and the luminance is improved by three orders of magnitude when compared to identical devices with an undoped F8BT ETL.  相似文献   

19.
In this work, we propose a facile microwave-assisted approach for annealing sol-gel derived ZnO films to serve as electron transport layers (ETLs) for inverted bulk heterojunction polymer solar cells. We have demonstrated an impressive enhancement in performance for devices based on a poly (3-hexylthiophene) (P3HT): (6,6)-phenyl-C61-butyric acid methyl ester (PC61BM) system employing the microwave-annealed ZnO (ZnO (MW)) ETLs in comparison to the cases using the conventional hotplate-annealed ZnO (ZnO (HP)) ones. The better electron transport in the device with the ZnO (MW) ETL is mainly ascribed to the preferable interfacial contact as evidenced by the morphology characteristics. Furthermore, the comprehensive analyses conducted from the light intensity dependent photocurrent and photovoltage measurements, the capacitance-voltage characteristics, and the alternating current impedance spectra suggest that the utilization of the ZnO (MW) ETLs can effectively suppress trap-assisted recombination as well as charge accumulation at the interface between P3HT: PC61BM layers and ZnO layers, which is responsible for the enhanced device performance.  相似文献   

20.
Perovskite solar cells (PSCs) are one of the most promising solar energy conversion technologies owing to their rapidly developing power conversion efficiency (PCE). Low‐temperature solution processing of the perovskite layer enables the fabrication of flexible devices. However, their application has been greatly hindered due to the lack of strategies to fabricate high‐quality electron transport layers (ETLs) at the low temperatures (≈100 °C) that most flexible plastic substrates can withstand, leading to poor performances for flexible PSCs. In this work, through combining the spin‐coating process with a hydrothermal treatment method, ligand‐free and highly crystalline SnO2 ETLs are successfully fabricated at low temperature. The flexible PSCs based on this SnO2 ETL exhibit an excellent PCE of 18.1% (certified 17.3%). The flexible PSCs maintained 85% of the initial PCE after 1000 bending cycles and over 90% of the initial PCE after being stored in ambient air for 30 days without encapsulation. The investigation reveals that hydrothermal treatment not only promotes the complete removal of organic surfactants coated onto the surface of the SnO2 nanoparticles by hot water vapor but also enhances crystallization through the high vapor pressure of water, leading to the formation of high‐quality SnO2 ETLs.  相似文献   

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