Achieving Synergistic Improvement in Dielectric and Energy Storage Properties of All-Organic Poly(Methyl Methacrylate)-Based Copolymers Via Establishing Charge Traps

How to achieve synergistic improvement of permittivity(ε_(r))and breakdown strength(E_(b))is a huge challenge for polymer dielectrics.Here,for the first time,theπ-conjugated comonomer(MHT)can simultaneously promote theε_(r)and E_(b)of linear poly(methyl methacrylate)(PMMA)copolymers.The PMMA-based random copolymer films(P(MMA-co-MHT)),block copolymer films(PMMA-b-PMHT),and PMMA-based blend films were prepared to investigate the effects of sequential structure,phase separation structure,and modification method on dielectric and energy storage properties of PMMA-based dielectric films.As a result,the random copolymer P(MMA-coMHT)can achieve a maximumε_(r)of 5.8 at 1 kHz owing to the enhanced orientation polarization and electron polarization.Because electron injection and charge transfer are limited by the strong electrostatic attraction ofπ-conjugated benzophenanthrene group analyzed by the density functional theory(DFT),the discharge energy density value of P(MMA-co-PMHT)containing 1 mol%MHT units with the efficiency of 80%reaches15.00 J cm^(-3)at 872 MV m^(-1),which is 165%higher than that of pure PMMA.This study provides a simple and effective way to fabricate the high performance of polymer dielectrics via copolymerization with the monomer of P-type semi-conductive polymer.

Regioisomeric Polymer Semiconductors Based on Cyano-Functionalized Dialkoxybithiophenes:Structure-Property Relationship and Photovoltaic Performance

Cyano substitution is vital to the molecular design of polymer semiconductors toward highly efficient organic solar cells.However,how regioselectivity impacts relevant optoelectronic properties in cyano-substituted bithiophene systems remain poorly understood.Three regioisomeric cyano-functionalized dialkoxybithiophenes BT_(HH),BT_(HT),and BT_(TT) with headto-head,head-to-tail,and tail-to-tail linkage,respectively,were synthesized and characterized in this work.The resulting polymer semiconductors(PBDTBTs)based on these building blocks were prepared accordingly.The regiochemistry and property relationships of PBDTBTs were investigated in detail.The BTHH moiety has a higher torsional barrier than the analogs BT_(HT) and BT_(TT),and the regiochemistry of dialkoxybithiophenes leads to fine modulation in the optoelectronic properties of these polymers,such as optical absorption,band gap,and energy levels of frontier molecular orbitals.Organic field-effect transistors based on PBDTBT_(HH) had higher hole mobility(4.4×10^(-3) cm^(2)/(V·s))than those(ca.10^(-4) cm^(2)/(V·s))of the other two polymer analogs.Significantly different short-circuit current densities and fill factors were obtained in polymer solar cells using PBDTBTs as the electron donors.Such difference was probed in greater detail by performing space-charge-limited current mobility,thin-film morphology,and transient photocurrent/photovoltage characterizations.The findings highlight that the BTHH unit is a promising building block for the construction of polymer donors for highperformance organic photovoltaic cells.

n-Type acceptor-acceptor polymer semiconductors

Polymer semiconductors have aroused interests from both academic and industry due to their wide applications in electronic devices,such as organic thin-film transistors(OT-FTs)[1],polymer solar cells(PSCs)[2−6],organic thermoelectrics(OTEs)[7−11],and perovskite solar cells(PVSCs)[12−14].To date,great efforts have been devoted to developing p-type poly-mer semiconductors,while the development of n-type poly-mers lags far behind.In fact,n-type polymers are essential for organic electronic devices.

Acceptor-acceptor-type conjugated polymer semiconductors

The rapid development of electronic devices such as organic field-effect transistors(OFETs)and solar cells makes the research and development of electronic transport materials imminent.The acceptor-acceptortype(AàA-type)conjugated n-type polymer semiconductors have caught much attention due to the outstanding advantages on excellent electron-accepting capabilities,the precise adjustment of energy levels and the mass production at low fabrication cost.This article systematically reviews the polymerization methods of AàA-type polymers and the recent advancements applied in OFETs and polymer solar cells(PSCs).The analyses of the synthesis and the relationship between device performances and polymer molecular structures may provide a constructive guidance for the further development of highperformance n-type polymer materials.

Layered coordination polymer with two-dimensional covalent bismuth-organic networks:Semiconductor and lithium ion storage

Single crystals of a bismuth-based coordination polymer(CP)with carboxyl-thiol ligands,[Bi(C_(8)H_(2)O_(4)S_(2))(C2H8N)]n(Bi-DSBDC-DMA,DMBDC=2,5-disulfur-1,4-dicarboxylate,DMA=dimethylamine),have been successfully synthesized.X-ray diffraction analysis reveals that Bi-DSBDC-DMA possesses a layered structure,with two-dimensional(2D)Bi-DSBDC networks alternating with layers composed of dimethylamine ions.This material demonstrates semiconducting properties,featuring an optical bandgap of 2.2 eV and an electrical conductivity of 2×10^(-8) S/cm.Furthermore,electrodes based on this material exhibit a capacity of 250 mAh/g after 200 cycles for lithium-ion storage.

A New Layer W/Cu/S Polymer with Heterobimetallic Nodes and Tridentate Trithiocyanuric Acid

Solvothermal reaction of [WS4]2-with CuCN and trithiocyanuric acid（L1） in orga-nic solvents gave rise to a new W/Cu/S polymer with a 2D anionic network,namely [Et4N]2[WS4Cu3（C3N3S3H1.5）2]（1）.The anionic layer of 1 is constructed by the T-shaped {WS4Cu3} subunits as nodes and L1 as linkers and features a（4,4） topology.Both 1 and its isomorphous compound [Et4N]2[MoS4Cu3（C3N3S3H1.5）2]（2） have been fully characterized by X-ray crystal analysis,IR and microanalyses.Compounds 1 and 2 show optical transitions with band gaps of 2.17 and 1.84 eV,respectively.

Structure design for high performance n-type polymer thermoelectric materials

Organic thermoelectric(OTE)materials have been regarded as a potential candidate to harvest waste heat from complex,low temperature surfaces of objects and convert it into electricity.Recently,n-type conjugated polymers as organic thermoelectric materials have aroused intensive research in order to improve their performance to match up with their ptype counterpart.In this review,we discuss aspects that affect the performance of n-type OTEs,and further focus on the effect of planarity of backbone on the doping efficiency and eventually the TE performance.We then summarize strategies such as implementing rigid n-type polymer backbone or modifying conventional polymer building blocks for more planar conformation.In the outlook part,we conclude forementioned devotions and point out new possibility that may promote the future development of this field.

Photoswitchable semiconducting polymer dots with photosensitizer molecule and photochromic molecule loading for photodynamic cancer therapy

Photodynamic therapy(PDT)is a new and rapidly developing treatment modality for dinical cancer therapy.Semiconductor polymer dots(Pdots)doped with photosensitizers have been successfully applied to PDT,and have made progress in the field of tumor therapy.However,the problems of severe photosensitivity and limited tisue penetration depth are needed to be solved during the implementation process of PDT.Here we developed the Pdots doped with photosensitizer molecule Chlorin e6(Ce6)and photochromic molecule 1,2-bis(2,4-dimethy1-5 phenyl-3-thiophene)-3,3,4,5-hexafuoro-1-cyclopentene(BTE)to construct a photoswitchable nanoplatform for PDT.The Ce6-BTE-doped Pdots were in the green region,and the tissue penetration depth was increased compared with most Pdots in the blue region.The reversible conversion of BTE under different light irradiation was utilized to regulate the photodynamic effect and solve the problem of photosensitivity.The prepared Ce6-BTE-doped Pdots had small size,excellent optical property,efficient ROS generation and good photoswitchable ability.The cellular uptake,cytotoxicity,and photodynamic effect of the Pdots were detected in human colon tumor cells.The experiments in vitro indicated that Ce6-BTE-doped Pdots could exert excellent photodynamic effect in ON state and reduce photosensitivity in OFF state.These results demonstrated that this nanoplatform holds the potential to be used in clinical PDT.

半导体发光聚合物设计与制备实验虚拟仿真系统开发及应用

半导体发光聚合物被广泛应用于有机电致发光器件和生物荧光成像探针等领域,发光聚合物的制备条件苛刻、成本相对较高,实验操作对于本科生难度较大。开发虚拟仿真系统对实验室场景、实验设备、测试仪器和操作环节等进行仿真,能降低实验风险和实验成本。仿真系统对实验的重点和难点设置独立操作环节,有利于学生进行重点训练。仿真系统中设置了聚合物结构调控,增强学生对聚合物结构与发光性能构效关系的理解。该仿真实验有助于提升学生的动手和创新能力,有效培养学生自主设计开发新型发光聚合物和解决复杂工程问题的能力。

Intrinsically stretchable polymer semiconductor based electronic skin for multiple perceptions of force,temperature,and visible light

As a stretchable seamless device,electronic skin(E-skin)has drawn enormous interest due to its skin-like sensing capability.Besides the basic perception of force and temperature,multiple perception that is beyond existing functions of human skin is becoming an important direction for E-skin developments.However,the present E-skins for multiple perceptions mainly rely on different sensing materials and heterogeneous integration,resulting in a complex device structure.Additionally,their stretchability is usually achieved by the complicated microstructure design of rigid materials.Here,we report an intrinsically stretchable polymer semiconductor based E-skin with a simple structure for multiple perceptions of force,temperature,and visible light.The E-skin is on the basis of poly(3-hexylthiophene)(P3HT)nanofibers percolated polydimethylsiloxane(PDMS)composite polymer semiconductor,which is fabricated by a facile solution method.The E-skin shows reliable sensing capabilities when it is used to perceive strain,pressure,temperature,and visible light.Based on the E-skin,an intelligent robotic hand sensing and controlling system is further demonstrated.Compared with conventional E-skins for multiple perceptions,this E-skin only has a simple monolayer sensing membrane without the need of combining different sensing materials,heterogeneous integration,and complicated microstructure design.Such a strategy of utilizing intrinsically stretchable polymer semiconductor to create simple structured E-skin for multiple perceptions will promote the development of E-skins in a broad application scenario,such as artificial robotic skins,virtual reality,intelligent gloves,and biointegrated electronics.

基于荧光淬灭传感技术检测三硝基甲苯的研究

目前针对常见爆炸物三硝基甲苯(TNT)的检测越来越受到重视。本研究采用低成本的芴基发绿光共轭聚合物(FGEP)研制荧光淬灭传感器用于检测TNT。实验研究了FGEP在不同溶液浓度下形成的不同厚度薄膜对TNT淬灭的效率,实验结果表明浓度为0.5 mg/mL (厚度为19.50 nm)的样品薄膜在TNT蒸气中淬灭效率最大达到71.71%,基于此淬灭效率最高的样品薄膜的研究发现:该薄膜对TNT的响应具有良好的可逆性;激发光强度为16.5mW时,荧光淬灭效率最佳;最后开展了样品在TNT作用下与光漂白作用下的实验研究。研究结果为后续实现一种低成本、易于制备、可重复性高且有利于工程化的爆炸物传感器提供了一定基础。

Diketopyrrolopyrrole-based Conjugated Polymers as Representative Semiconductors for High-Performance Organic Thin-Film Transistors and Circuits

Since the first report of diketopyrrolopyrrole(DPP)-based conjugated polymers for organic thin-film transistors(OTFTs),these polymers have attracted great attention as representative semiconductors in high-performance OTFTs.Through unremitting efforts in molecular-structure regulation and device optimization,significant mobilities exceeding 10 cm2·V–1·s–1 have been achieved in OTFTs,greatly promoting the applied development of organic circuits.In this review,we summarize our progress in molecular design,synthesis and solution-processing of DPP-based conjugated polymers for OTFT devices and circuits,focusing on the roles of design strategies,synthesis methods and processing techniques.Furthermore,the remaining issues and future outlook in the field are briefly discussed.

高稳定性Mn:ZnO/Mn2O_(3)纳米复合光催化剂的制备及光催化特性

采用修饰的高分子网络凝胶法成功制备了Mn2O_(3)复合Mn掺杂ZnO纳米复合光催化剂(Mn:ZnO/Mn2O_(3)),并基于模拟太阳光照射下罗丹明B(RhB)及亚甲基蓝(MB)染料的光降解研究了催化剂光催化降解有机染料的特性。X射线衍射,扫描电子显微镜及BET比表面积测试结果显示,微量(0.1 mol%)Mn掺杂再复合微量(0.2 mol%)Mn2O_(3)后,Mn:ZnO/Mn2O_(3)的颗粒尺寸减小且分散性提高,有效比表面积增大。紫外-可见光吸收光谱表明,相对于纯ZnO,Mn:ZnO/Mn2O_(3)在可见光区域的光吸收能力明显提高。光致发光光谱表明微量Mn掺杂和微量Mn2O_(3)复合促进了光生电子-空穴对的分离。结合X射线光电子能谱,发现可见光吸收能力和光生电子-空穴对分离率的提高源于催化剂表面氧空位的增加以及Mn:ZnO和Mn2O_(3)之间形成的Ⅱ型异质结结构。因此,Mn:ZnO/Mn2O_(3)对RhB的降解展现出稳定且优越的光催化活性。然而,由于Mn2O_(3)的带隙(Eg≈1.4 eV)过窄,其价带位置高于羟基自由基(·OH)的氧化还原电位,因此光生空穴的氧化电势过低,无法生成氧化能力更强的·OH,这导致Mn2O_(3)复合ZnO光催化剂(ZnO/Mn2O_(3))对RhB和MB的光降解效率降低。此外,Mn:ZnO/Mn2O_(3)对RhB和MB展现出选择性光降解行为,即对容易降解的MB的光降解效率明显降低。这种选择性光催化特性归因于光催化反应过程中活性物种之间的差异性以及催化剂零电荷点和初始染料溶液的pH值之间的关系。

界面材料PFN-Br的光放大性质及其在电泵浦有机激光中的应用潜力

系统研究了水/醇溶性共轭聚电解质Poly[(9,9-bis(3′-((N,N-dimethyl)-N-ethylammonium)-propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)]dibromide(PFN-Br)的光放大性质,发现其具有较小的放大自发辐射(ASE)阈值(~11μJ/cm^(2))和ASE截止厚度(<50 nm),是一种高效的蓝光(~456 nm)增益介质.利用其对于有机溶剂的良好耐性,如甲苯等,分别在石英和ITO玻璃基底上制备了PFN-Br/F8BT以及PFN-Br/MEH-PPV双层器件.经过研究发现,PFN-Br界面层不会明显增加系统损耗并影响上层F8BT的光增益.然而,在ITO玻璃基底上,通过引入PFN-Br界面层,减少了ITO电极对MEH-PPV增益介质损耗,显著地降低了其ASE阈值(相比于没有PFN-Br界面降低约60%).这些发现说明了PFN-Br本身具备良好的增益性能,同时也是成熟的载流子传输界面功能材料,在有机激光领域应用前景十分广泛.

用于降解印染废水中有机污染物的光催化剂的研究进展

纺织工业印染废水的大量排放是造成水体污染物增多的主要因素之一,对人体健康和生态环境的良性循环造成严重威胁。目前,采用的物理吸附法、化学氧化法以及生物分解法等废水处理技术成本高昂、治污不彻底且容易产生二次污染,加快研发经济高效的处理技术对降低水资源消耗、保护环境意义重大。光催化降解法是催化剂受光辐照后在反应体系中产生活性自由基,自由基进一步与有机污染物反应,使其完全降解。由于该方法经济高效,不易造成二次污染,符合绿色环保的发展要求,已成为污染物降解的研究热点。本文主要综述了近10年光催化技术在降解有机污染物领域的具体方法与研究进展,指出无机半导体、金属有机框架和有机小分子材料作为光催化剂存在的弊端,而多孔共轭聚合物兼具优异的光催化降解和吸附性能,具有很好的发展前景。

g-C_(3)N_(4)纳米片的改性及光催化降解应用

石墨相氮化碳纳米片(2D g-C_(3)N_(4))属于非金属聚合物半导体,具有成本低、无毒、对环境友好、能吸收可见光等优点,但也存在一定的缺陷。介绍了2D g-C_(3)N_(4)的基本结构和光催化机理,重点分析了2D g-C_(3)N_(4)的改性方法,包括金属掺杂、非金属掺杂、TypeⅡ型异质结、Z型异质结、S型异质结,以及助催化剂修饰等,并分析了它们在光催化降解方面的应用,展望了2D g-C_(3)N_(4)的发展方向。

Bioassay of Carcinoembryonic Antigens by Organic Field-effect Transistors Based on D-A Type Conjugated Polymer

Biosensors based on organic field-effect transistors(OFETs)are one of the most promising electronic devices for emerging bioanalytical applications.The selection of organic semiconductors(OSCs)is essential to improve the sensitivity and reliability of this kind of biosensors.Given the good field effect performance and tunable structures of D-A type conjugated polymers,here,we design two D-A type copolymers[P(BDT-co-DPP2T-ThC_(2))and P(BDT-co-DPP2T-Th)],which are applied as the OSC layers.With carcinoembryonic antigen antibody(anti-CEA)adsorbed onto the OSC layers as the recognition sites,OFETs based biosensors for CEA detection are developed.The experimental findings support that the attachment of ester side groups onto the polymer backbone[as for P(BDT-co-DPP2T-ThC_(2))]is favorable for improved solubility and filming properties of the polymer.The introduction of ester side groups affects molecular stacking and enhances intermolecular forces.The resultant devices show high charge mobility and antibody adsorption ability,both of which are critical for sensitive and facile detection of CEA biomarkers.The reliable determination of CEA down to the picomolar level is determined.It is expected that this kind of biosensors fabricated by D-A type conducting polymers will open new avenues toward the early diagnosis,real-time monitoring and treatment of future cancer diseases.

Tetramethylammonium Iodide Additive for Enhancing the Charge Carrier Mobilities of Diketopyrrolopyrrole-Based Conju-gated Polymer in Ambipolar Organic Field-Effect Transistors

Diketopyrrolopyrrole(DPP)is one of the most promising building blocks for constructing polymer semiconductors with high charge-carrier mobilities in organic field-effect transistors(OFETs).In this study,a novel DPP-based conjugated polymer,PDPPy-BDD,was designed and synthesized.The ambipolar field-effect transistor characteristics were realized with the average hole and electron mobilities of 3.5×10^(-3)and 3.07×10^(-2)cm^(2)V^(-1)s^(-1),respectively.Both the hole and electron mobilities could be successfully en-hanced by using a tetramethylammonium iodide(NMe4l)additive.Such an enhancement was attributed to the formation of stronger interchainπ-πstackings,the weakening of the face-on packing orientation in the thin film state,and the higher channel conductivi-ties in the OFETs.

High-Mobility Ambipolar Benzodifurandione-Based Copolymers with Regular Donor–Acceptor Dyads Synthesized via Aldol Polycondensation

In this study,a family of three benzodifurandione-baseddonor–acceptor(D–A)copolymers,namelypoly[3,7-bis((E)-1-(4-octadecyldocosyl)-2-oxo-6-yl-indolin-3-ylidene)-3,7-dihydrobenzo[1,2-b:4,5-b′]difuran-2,6-dionealt-(E)-1,2-di(2,2′-bithiophen-5-yl)ethene](PBDO-DTE),poly[3,7-bis((E)-7-fluoro-1-(4-octadecyldocosyl)-2-oxo-6-yl-indolin-3-ylidene)-3,7-dihydrobenzo[1,2-b:4,5-b′]difuran-2,6-dione-alt-(E)-1,2-di(2,2′-bithiophen-5-yl)ethene](PFBDO-DTE),and poly[(3E,7E)-3,7-bis(1-(4-octadecyldocosyl)-2-oxo-6-yl-1,2-dihydro-3Hpyrrolo[2,3-b]pyridin-3-ylidene)-3,7-dihydrobenzo[1,2-b:4,5-b′]difuran-2,6-dione-alt-(E)-1,2-di(2,2′-bithiophen-5-yl)ethene](PNBDO-DTE),was designed and synthesized by employing aldol polycondensation reactions between benzodifurandione and bisindolin-2-ones in high yields.Further incorporation of fluorine or sp2-hybridized nitrogen atoms on the bisindolin-2-one unit induced S…F or S…N nonbonding interactions-locked polymeric conjugated backbones for PFBDO-DTE and PNBDO-DTE,respectively.Ultraviolet photoelectron spectroscopy and inverse photoemission spectroscopy measurements revealed that the two copolymers have lower frontier molecular orbitals than that of PBDO-DTE.Atomic force microscopy and two-dimensional grazing-incidence wide-angle X-ray scattering investigations indicated the PNBDO-DTE copolymer could form more ordered molecular aggregation in the solid state than PBDO-DTE and PFBDO-DTE copolymers.We fabricated thin film transistors based on these copolymers on plastic polyethylene terephthalate substrates,and they all showed ambipolar charge transport characteristics.Among them,the PNBDO-DTE-based devices afforded optimal charge transport characteristics with high hole and electron mobilities of 5.16 and 1.33cm^(2)V^(−1)s^(−1),respectively.Our study highlights that aldol polycondensation would be an extremely useful protocol in constructing high-performance polymer semiconductors.

导电聚合物基氨肼类气体传感器的研究现状

氨肼类气体是一种肝毒性气体,对人体生命健康具有危害作用,故在工业生产和工程实际等应用场景中实现实时监测非常重要。近年来,出现了众多类型的氨肼类气体的气敏材料,其传感器也得到了迅速发展。本文综述了导电聚合物复合敏感材料对氨气和低浓度肼气的传感响应的研究现状,并探讨了氨肼类气体传感器下一步发展趋势。