Non-conjugated polymers as thickness-insensitive electron transport materials in high-performance inverted organic solar cells

Two non-conjugated polymers PEIE-DBO and PEIE-DCO, prepared by quaternization of polyethyleneimine ethoxylate by 1,8-dibromooctane and 1,8-dichlorooctane respectively, are developed as electron transport layer(ETL) in high-performance inverted organic solar cells(OSCs), and the effects of halide ions on polymeric photoelectric performance are fully investigated. PEIE-DBO possesses higher electron mobility(3.68×10-4 cm2 V-1s-1), higher conductivity and more efficient exciton dissociation and electron extraction, attributed to its lower work function(3.94 eV) than that of PEIE-DCO, which results in better photovoltaic performance in OSCs. The inverted OSCs with PTB7-Th: PC71BM as photoactive layer and PEIE-DBO as ETL exhibit higher PCE of 10.52%, 9.45% and 9.09% at the thickness of 9, 35 and 50 nm,respectively. To our knowledge, PEIE-DBO possesses the best thickness-insensitive performance in polymeric ETLs of inverted fullerene-based OSCs. Furthermore, PEIE-DBO was used to fabricate the inverted non-fullerene OSCs(PM6:Y6) and obtained a high PCE of 15.74%, which indicates that PEIE-DBO is effective both in fullerene-based OSCs and fullerene-free OSCs.

Carbon nanotube-hyperbranched polymer core-shell nanowires with highly accessible redox-active sites for fast-charge organic lithium batteries

Organic electrode materials are promising for lithium-ion batteries(LIBs) because of their environmental friendliness and structural diversity.However,they always suffer from limited capacity,poor cycling stability,and rate performance.Herein,hexaazatrinaphthalene-based azo-linked hyperbranched polymer(HAHP) is designed and synthesized as a cathode for LIBs.However,the densely stacked morphology lowers the chance of the active sites participating in the redox reaction.To address this issue,the singlewalled carbon nanotube(SWCNT) template is used to induce the growth of nanosized HAHP on the surface of SWCNTs.The HAHP@SWCNT nanocomposites have porous structures and highly accessible active sites.Moreover,the strong π-π interaction between HAHP and highly conductive SWCNTs effectively endows the HAHP@SWCNT nanocomposites with improved cycling stability and fast charge-discharge rates.As a result,the HAHP@SWCNT nanocomposite cathode shows a high specific capacity(320.4 mA h g^(-1)at 100 mA g^(-1)),excellent cycling stability(800 cycles;290 mA h g^(-1)at 100 mA g^(-1),capacity retained 91%) and outstanding rate performance(235 mA h g^(-1)at 2000 mA g^(-1),76% capacity retention versus 50 mA g^(-1)).This work provides a strategy to combine the macromolecular structural design and micromorphology control of electrode materials for obtaining organic polymer cathodes for high-performance LIBs.

An Environment-Friendly High-Performance Aqueous Mg-Na Hybrid-Ion Battery Using an Organic Polymer Anode

Aqueous Mg ion batteries(AMIBs)show great potential in energy storage for their advantages of high capacity,abundant resource,and environmental friendliness.However,the development of AMIBs is limited due to the scarcity of suitable anode materials.In this study,a new polymer anode material(PNTAQ)with flower-like nanosheet structure is synthesized for aqueous Mg-Na hybrid-ion battery(AMNHIB).PNTAQ possess carbonyl functional groups which can be oxidized and reduced reversibly in aqueous solution containing alkaline metal ions.PNTAQ displays a discharge specific capacity of 245 mAh g^(−1)at 50 mA g^(−1)in 1 M MgCl_(2)+0.5 M NaCl electrolyte,which is much higher than that in single 1 M MgCl_(2)or 0.5 M NaCl electrolyte.Even cycling at 1000 mA g^(−1)for 1000 times,the capacity retention can still maintain at 87.2%.A full Mg-Na hybrid-ion cell is assembled by employingβ-MnO_(2)as cathode and PNTAQ as anode material,it exhibits a specific capacity of 91.6 mAh g^(−1)at 100 mA g^(−1).The polymer electrode material well maintains its framework structure during the discharge/charge cycling process of the hybrid-ion battery.

Sulfur-linked carbonyl polymer as a robust organic cathode for rapid and durable aluminum batteries

Rechargeable aluminum batteries are believed as a promising next-generation energy-storage system due to abundant low-cost Al sources and high volumetric specific capacity.The Al-storage cathodes,however,are plagued by strong electrostatic interaction between host materials and carrier ions,leading to large overpotential and undesired cycling stability as well as sluggish ion diffusion kinetics.Herein,sulfur-linked carbonyl polymer based on perylene-3,4,9,10-tetracarboxylic dianhydride(PTCDA) as the cathode materials for ABs is proposed,which demonstrates a small voltage polarization(135 mV),a reversible capacity of 110 mAh g^(-1) at 100 mA g^(-1) even after 1200 cycles,and rapid Al-storage kinetics.Compared with PTCDA,the sulfide polymer possesses higher working voltage because of its lower LUMO energy level according to theoretical calculation.The ordered carbonyl active sites in sulfide polymer contribute to the maximized material utilization and rapid ion coordination and dissociation,resulting in superior rate capability.Besides,the bridged thioether bonds endow the polysulfide with robust and flexible structure,which inhibits the dissolution of active materials and improves cycling stability.This work implies the importance of ordered arrangement of redox active moieties for organic electrode,which provides the theoretical direction for the structural design of organic materials applied in multivalent-ion batteries.

Composite bilayer films with organic compound-triggered bending properties

Organic compounds are widely used in both industry and daily life,and composite bilayer films with organic compound-triggered bending properties are promising for applications of transducers,soft robotics,and so on.Here,a universal and straightforward strategy to generate composite bilayer films with organic compoundtriggered bending properties is demonstrated.The composite bilayer films with organic compound-triggered bending properties are designed with bilayer structures,in which one layer is a porous polymeric membrane with appropriate solubility parameter that matches the value of organic solvents in order to produce prominent affinity to the solvent molecules,and the other layer is reduced graphene oxide membrane stacked on the porous polymeric membrane as an inert layer for restraining the swelling of the polymeric membrane on one side.Guided by matching the solubility parameters between solvent and polymer,a significant bending curvature of 27.3 cm-1 is obtained in acetone vapor.The results in this study will provide valuable guidance for designing and developing functional composite materials with significant organic compound-triggered bending properties.

Synthesis of a Novel Blue- light- emitting Polymer Material Bearing Coumarin Pendants

A novel blue luminescent polymer bearing coumarin pendants was prepared. Its luminescent properties were determined indicating that it had strong blue fluorescent properties and good film formation ability. This novel polymer can be used as a blue organic electroluminescent material (OELM) in organic electroluminescent devices.

Triphenyl Phosphine Oxide and Carbazole-based Polymer Host Materials for Green Phosphorescent Organic Light-emitting Diodes

Four novel polymers, poly（3,6-9-decyl-carbazole-alt-1,3-benzene） （PB13CZ）, poly（3,6-9-decyl-carbazole-alt- bis（4-phenyl） （phenyl） phosphine oxide） （PTPPO38CZ）, poly（3,6-9-decyl-carbazole-alt-2,4-phenyl（diphenyl） phosphine oxide） （PTPPO13CZ） and poly（3,6-9-decyl-carbazole-alt-bis（3-phenyl） （phenyl） phosphine oxide） （PTTPO27CZ） were synthesized, and their thermal, photophysical properties and device applications were further investigated to correlate the chemical structures with the photoelectric performance of bipolar host materials for phosphorescent organic light emitting diodes. All of them show high thermal stability as revealed by their high glass transition temperatures and thermal decomposition temperatures at 5% weight loss. These polymers have wide band gaps and relatively high triplet energy levels. As a result, the spin coating method was used to prepare the green phosphorescent organic light emitting diodes with polymers PTPPO38CZ, PTPPO13CZ and PTTPO27CZ as the typical host materials. The green device of polymer PTPPO38CZ as host material shows electroluminescent performance with maximum current efficiency of 2.16 cd.A-1, maximum external quantum efficiency of 0.7%, maximum brightness of 1475 cd.m-2 and reduced efficiency roll-off of 7.14% at 600 cd.m-2, which are much better than those of the same devices hosted by polymers PTTPO27CZ and PTPPO13CZ.

Virtual special issue:Organic and polymer materials for electronics

Welcome to this virtual special issue focusing on organic and polymer materials for electronics published in Chinese Chemical Letters since 2017. For more than a century, people have always believed that organic compounds cannot be well employed for electronic conducting. Till 2000,Heeger,MacDiarmid and Shirakawa were acknowledged by the Nobel Prize of chemistry for

Rational design of new in situ reduction of Ni(II)catalytic system for low-cost and large-scale preparation of porous aromatic frameworks

Porous aromatic framework 1(PAF-1)is an extremely representative nanoporous organic framework owing to its high stability and exceptionally high surface area.Currently,the synthesis of PAF-1 is catalyzed by the Ni(COD)2/COD/bpy system,suffering from great instability and high cost.Herein,we developed an in situ reduction of the Ni(II)catalytic system to synthesize PAF-1 in low cost and high yield.The active Ni(0)species produced from the NiCl_(2)/bpy/NaI/Mg catalyst system can effectively catalyze homocoupling of tetrakis(4-bromophenyl)methane at the room temperature to form PAF-1 with high Brunauer-Emmett-Teller(BET)-specific surface area up to 4948 m^(2) g^(−1)(Langmuir surface area,6785 m2 g−1).The possible halogen exchange and dehalogenation coupling mechanisms for this new catalytic process in PAF's synthesis are discussed in detail.The efficiency and universality of this innovative catalyst system have also been demonstrated in other PAFs'synthesis.This work provides a cheap,facile,and efficient method for scalable synthesis of PAFs and explores their application for high-pressure storage of Xe and Kr.

OBD-1(黑色)可逆热致变色微胶囊制备及其在防伪领域的应用

当今社会,假冒伪劣产品泛滥,给社会经济带来严重的负面影响。旨在研发一种灵敏度高、温变区间小、耐酸耐碱的OBD-1(黑色)可逆热致变色微胶囊,并将其应用在温变防伪涂料。选取黑色发色剂OBD-1、双酚A、十六醇为芯材料,脲醛树脂为壁材料,通过原位聚合法制备微胶囊。利用显微镜观察微胶囊的外部形貌,通过激光粒径测定仪对微胶囊粒径及粒径分布范围进行了测定,考察了微胶囊制备时的不同的制备条件对微胶囊粒径大小和样品性能的影响,并得到最佳制备比例。

A Three-Dimensional Silicon-Diacetylene Porous Organic Radical Polymer

Radical-containing porous organic polymers(POPs)have drawn great interest in various applications.However,the synthesis of radical POPs remains challenging due to the unstable nature of organic radicals.Here,a persistent and stable three-dimensional silicon-diacetylene porous organic radical polymer was synthesized via a classic Eglinton homocoupling reaction of tetraethynylsilane.The presence of carbon radicals in this material was confirmed by electron paramagnetic resonance,and its paramagnetic behavior was analyzed by a superconducting quantum interference device.This unique material has a low-lying lowest unoccupied molecular orbital(LUMO)energy level(−5.47 eV)and a small energy gap(ca.1.46 eV),which shows long-term cycling stability and excellent rate capability as an anode material for lithium-ion batteries,demonstrating potential application in energy fields.

Synthesis and properties of novel low band-gap polymers bearing squaraine units

Novel main-chain-conjugated poly(carbazol-alt-squaraine) and poly(dipyridyl-alt-squaraine) were successfully synthesized through direct polycondensation of 9-(2-ethylhexyl)carbazole-bridged or dipyridyl-bridged bispyrrole and squaric acid.The structures and properties of the polymers were characterized using ~1H NMR,FT-IR,UV-vis and cyclic voltammetry.Both polymers exhibit excellent solubility in common organic solvents and good thermal stability.Their UV-vis absorption spectra indicated the polymers have b...

Recent progress in design of conductive polymers to improve the thermoelectric performance

Organic semiconductors,especially polymer semiconductors,have attracted extensive attention as organic thermoelectric materials due to their capabilities for flexibility,low-cost fabrication,solution processability and low thermal conductivity.However,it is challenging to obtain high-performance organic thermoelectric materials because of the low intrinsic carrier concentration of organic semiconductors.The main method to control the carrier concentration of polymers is the chemical doping process by charge transfer between polymer and dopant.Therefore,the deep understanding of doping mechanisms from the point view of chemical structure has been highly desired to overcome the bottlenecks in polymeric thermoelectrics.In this contribution,we will briefly review the recently emerging progress for discovering the structure–property relationship of organic thermoelectric materials with high performance.Highlights include some achievements about doping strategies to effectively modulate the carrier concentration,the design rules of building blocks and side chains to enhance charge transport and improve the doping efficiency.Finally,we will give our viewpoints on the challenges and opportunities in the field of polymer thermoelectric materials.

PHOTOINDUCED ALIGNMENT OF OPTICALLY ACTIVE POLYMER CONTAINING A TEMPO RADICAL END GROUP

A new azobenzene side-chain polymer (TEMPO-PAZ) containing TEMPO (4-hydroxy-2, 2, 6, 6-tetramethyl-piperidinooxy) radical end group was synthesized by free radical copolymerization. Photoinduced alignment was studied onthe polymer films at room temperature with linearly polarized light of 514.5 nm, The experimental results showed that themagnetic response intensity of the TEMPO-PAZ could be easily controlled by choosing the appropriate polarized lightirradiating times, presumably due to the nitroxide radical in the TEMPO-PAZ molecular structure. For the polymerinvestigated here, the photoinduced alignment technique was introduced to increase the magnetic response intensity ofpolymer under irradiation, aiming originally at searching for a new photo-active organic magnetic multifunctional materials.On the other hand, experimental results also showed that the TEMPO-PAZ can be used as a material for optical image storage.

SYNTHESIS AND PROPERTIES OF A NEW AZOBENZENE SIDE-CHAIN POLYMER CONTAINING A TEMPO RADICAL

To allow anisotropies of optical properties in a magnetic field, nitroxide radical is introduced into the ortho-position of the phenylene ring in the side chain. A new azobenzene side-chain polymer (TEMPO-PAZ) containing TEMPO radical was synthesized. The polymer has a good solubility in organic solvents. The ESR spectrum of the polymer indicated three absorption lines characteristic of TEMPO radical. The optical phase conjugated responses (I-4) of the polymer films were investigated by degenerate four-wave mixing (DFWM). The experimental results showed that optical phase conjugated response of the TEMPO-PAZ could be easily controlled by choosing the appropriate direction of magnetic field presumably due to the nitroxide radical in the TEMPO-PAZ molecular structure. For the polymer investigated here, the nitroxide radical was introduced to increase optical phase conjugated response intensity in a magnetic field, aiming originally at searching for a new photo-active organic magnetic multifunctional materials.

Tunable wavelength filters using polymer long-period waveguide gratings based on metal-cladding directly defined technique

In this work, long-period waveguide grating-based tunable wavelength filters using organic–inorganic grafting poly（methyl methacrylate）（PMMA） materials are designed and fabricated by metal-cladding directly defined technique.The thermal stabilities and optical properties of the organic–inorganic grafting PMMA core materials are analyzed. Structures and performance parameters of the waveguide gratings and self-electrode heaters are designed and simulated. The contrast of the filter is about 15 d B and the resonant wavelength can be tuned by different electric powers applied to the metal-cladding self-electrode heaters. The temperature sensitivity is 3.5 nm/℃ and the switching time is about 1 ms. The technique is very suitable for realizing the optoelectronic integrated wavelength-division-multiplexing systems.

Recent progress in organic solar cells(PartⅠmaterial science)

During past several years,the photovoltaic performances of organic solar cells(OSCs)have achieved rapid progress with power conversion efficiencies(PCEs)over 18%,demonstrating a great practical application prospect.The development of material science including conjugated polymer donors,oligomer-like organic molecule donors,fused and nonfused ring acceptors,polymer acceptors,single-component organic solar cells and water/alcohol soluble interface materials are the key research topics in OSC field.Herein,the recent progress of these aspects is systematically summarized.Meanwhile,the current problems and future development are also discussed.

Piezoelectrically Mediated Reactions:From Catalytic Reactions to Organic Transformations

Recently,piezocatalysis has attracted considerable attention as a new type of renewable mechanical energy conversion technology,which relies on the strain induced polarization of the piezoelectric material.This new technology has been extensively applied in the applications of water splitting,water remediation,gas purification and tumor therapy.Despite the rapid development in the piezo-catalysis,the utilization of piezoelectric materials for synthetic purpose is still under exploration.Piezoelectric means to promote or-ganic reactions expand the scope of piezoelectrically mediated reactions and show successes in both organic and polymer synthesis.Herein,we provide a comprehensive review on recent progress of piezoelectrically mediated reactions,catalytic mechanisms and applications in the last few years.The limitations and future directions of this area are also discussed.We believe this review will provide new insights into the underlying mechanism of piezoelectric mediated electron transfer process and guide the design of new chemistry.

纳米TiO_(2)改性丙烯酸酯增透膜的研究

将丙烯酸酯共聚物与纳米TiO_(2)利用羟基之间的缩合反应形成有机-无机杂化材料,涂覆于聚对苯二甲酸乙二醇酯(PET)薄膜表面后,可提高基体薄膜的透光率,最高可达93.0%,性能优于共混改性材料。此外,薄膜表面接触角也在涂覆后有明显上升。经过热重分析可知,纳米TiO_(2)缩合改性后的杂化材料热分解温度高于纯共聚物和共混改性材料。

Synthesis and properties of two novel copolymers based on squaraine and fluorene units for solar cell materials

Two novel copolymers based on squaraine and fluorine units have been synthesized through palladium catalyzed Suzuki coupling reaction and Sonogashira coupling reaction,respectively.The structures and properties of the two copolymers were characterized by FT-IR.NMR,UV-vis absorbance（Abs）,gel permeation chromatography（GPC）,thermal gravimetric analysis （TGA）,differential scanning calorimetry（DSC） and cyclic voltammetry（CV）.The solution absorption spectrums of P_1 and P_2 show two distinct absorption bands,one locates at 300-500 nm and the other at 600-800 nm.The absorption spectrums of P_1 and P_2 in films are broadened obviously and the spectral responses are extended up to 900 nm.Thermal gravimetric analysis demonstrates that the polymers are stable.Cyclic voltammetry experiment shows that the band gaps of the copolymers are 1.65 eV and 1.67 eV. respectively,suggesting their potential for applications as solar cells materials.