Electrosynthesis and charge-transport properties of poly(3′,4′-ethylenedioxy-2,2′:5′,2′′-terthiophene)

Polythiophene containing 3,4-ethylenedioxythiophene (EDOT), poly(3′,4′-ethylenedioxy-2,2′:5′,2′′-terthiophene), was synthesized by electrochemical oxidation of the corresponding monomer, 3′,4′-ethylenedioxy-2,2′:5′,2′′-terthiophene, in acetonitrile. The resulting polymer was soluble in DMSO and THF, and was characterized by ¹H NMR and mass spectroscopies, and GPC. The electrical conductivity of the oxidized polymer film was found to be comparable to those for polythiophene and poly(methylthiophene) despite of its short π-conjugation length.     

Correlation of viscoelastic properties with solvation of regioregular poly(3-decylthiophene) films

Viscoelastic properties of regioregular poly(3-decylthiophene) films cast on gold electrodes and exposed to acetonitrile/LiClO4 solution were studied using high-frequency acoustic impedance. Values of shear moduli, G = G' + jG', were determined under conditions of potentiodynamic and potentiostatic electrochemical control, as functions of potential (0.0 < E/V < 0.8), temperature (5 < T/ degrees C < 70), and angular frequency (omega = 2pi f; 10 < f/MHz < 110). The effect of potential was small, of temperature was significant, and of frequency was dominant. The principle of time-temperature equivalence was used to construct master relaxation curves. Application of activation, Williams-Landel-Ferry, and Rouse-Zimm models shows the material to be quite different from other thiophene-based conducting polymers, namely, poly(3,4-ethylenedioxythiophene) and regioregular poly(3-hexylthiophene). Detailed exploration of the data reveals novel insights into the compositional origins--notably with regard to solvation--of the shear modulus behavior.     

山梨醇掺杂对PEDOT:PSS薄膜结构与性能的影响

为改善聚乙撑二氧噻吩:聚(对苯乙烯磺酸)根阴离子(PEDOT:PSS)薄膜的光学及电学性能,采用共混-旋涂法在石英玻片上制备出山梨醇掺杂的PEDOT:PSS透明导电膜.利用X射线衍射仪(XRD),傅立叶变换拉曼光谱(FT-RM),原子力显微镜(AFM),场发射扫描电子显微镜(FE-SEM),紫外-可见吸收光谱(UV-Vis)及四点探针法对薄膜的微结构与性能进行了研究.XRD结果显示山梨醇的掺杂未改变薄膜的聚集态结构;FT-RM表明PEDOT的主要特征峰发生红移,主链结构发生苯-醌转变,分子间作用力增大,导致薄膜表面粗糙度增大,横截面出现索状条纹;薄膜透光率在600～900nm略有升高,导电性能有较大提高,最佳掺杂浓度下,薄膜电导率可达到105S/cm.     

Surface characterization of polythiophene:fullerene blends on different electrodes using near edge X-ray absorption fine structure

We study the top surface composition of blends of the conjugated polymer regioregular poly-3-hexylthiophene (P3HT) with the fullerene (6,6)-phenyl-C(61)-butyric acid methyl ester (PCBM), an important model system for organic photovoltaics (OPVs), using near-edge X-ray absorption fine structure spectroscopy (NEXAFS). We compare the ratio of P3HT to PCBM near the air/film interface that results from preparing blend films on two sets of substrates: (1) poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) coated indium tin oxide (ITO) as is commonly used in conventional OPV structures and (2) ZnO substrates that are either unmodified or modified with a C(60)-like self-assembled monolayer, similar to those that have been recently reported in inverted OPV structures. We find that the top surface (the film/air interface) is enriched in P3HT compared to the bulk, regardless of substrate or annealing conditions, indicating that changes in device performance due to substrate modification treatments should be attributed to the buried substrate/film interface and the bulk of the film rather than the exposed film/air interface.     

新型聚2,4-二乙烯基3-十二烷基噻吩-1,3,4-噁二唑交替共聚物的合成、表征及性能研究

采用Heck偶合法首次合成了新型的含有空穴传输单元3-十二烷基噻吩和电子传输单元1,3,4-噁二唑的低带隙能的聚2,4-二乙烯基-3-十二烷基噻吩-1,3,4-噁二唑共轭聚合物(P3DDTV-OXD).并且通过1H-NMR、FT-IR、凝胶色谱(GPC)、UV-vis光谱、荧光光谱(PL)、循环伏安(CV)法对所合成的共聚物进行了分析表征.与规整的聚3-十二烷基噻吩均聚物(P3DDT)相比,共聚物的UV最大吸收波长和Pl最大发射波长明显蓝移,具有强烈的蓝色荧光,且电子亲和势较高,同时拥有空穴和电子传输能力,实现了电荷在分子内的双向传输.     

Hybrid organic on inorganic semiconductor heterojunction

Hybrid organic on inorganic semiconductor heterojunctions with a sandwich structure have been fabricated and studied using conjugated polymers. The inorganic semiconductor was n-type silicon substrate. The conjugated polymers used include poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) containing polyhedral oligomeric silsesquioxanes (MEH-PPV POSS), regioregular poly(3-hexylthiophene) (RR-P3HT) and poly(3,4-ethylenedioxythiophene) (PEDOT). Current density–voltage and capacitance–voltage measurements were performed. All of the devices displayed a rectifying characteristic. Among these devices, the first ever reported PEDOT doped with BF₃ on n-Si heterojunction devices showed the best performance with a rectification ratio around 5.7 × 10⁵ at ± 2 V and an ideality factor of 2.3. The results showed better device performance with decreased potential barrier height at the organic–inorganic interface. Results also suggested that smaller energy level offset between the HOMO of the conjugated polymer and the work function of anode metal will improve device performance.     

Fourier transform photocurrent spectroscopy applied to a broad variety of electronically active thin films (silicon, carbon, organics)

Steady state and low frequency photocurrent spectroscopies have proved as a valuable tool for investigation of many different semiconductors, used for example as an absorber in photovoltaic solar cells or in the large area sensors. Fourier transform photocurrent spectroscopy (FTPS), described here, exhibits advantages as a high sensitivity (we demonstrate dynamical range up to 9 orders of magnitude of the optical absorption coefficient, connected with the absorption process leading to free carriers; or sensitivity for dopant detection better than 1 part-per-billion), fast acquisition of data (it can be of the order of seconds) or high resolution (under more lengthy acquisition of data). Results on amorphous silicon, microcrystalline silicon, diamond layers, nanocrystalline diamond and very thin organic films, as poly(2-methoxy-5-(3′,7′-dimethyl-octyloxy))-p-phenylene-vinylene (MDMO-PPV), regioregular poly(3-hexylthiophene (P3HT) and their blends with (6,6)-phenyl-C61-butyric-acid (PCBM) are reported, together with the results measured on various thin film silicon or polymer solar cells.     

Control of self organization in conjugated polymer fibers

We propose new strategy to facilitate the fabrication of conjugated polymer fiber with higher oriented structures, which focused on electrospinning of a blend solution of regioregular poly(3-hexylthiophene) (rr-P3HT) and poly(vinyl pyrrolidone) (PVP). SEM observation revealed that the blend system forms homogeneous composite nanofibers. This system exhibits the specific feature of strong interchain contribution of P3HT from UV-vis absorption, fluorescence spectroscopic, XRD, and photoelectron spectrometric (for HOMO levels) investigations. We also demonstrate the removal of the PVP component from the P3HT/PVP composite fibers through the selective extraction and such strong interchain stacking of pristine P3HT fiber mat can be remarkably maintained.     

合成方法对聚(3-己基噻吩)立构规整度的影响

采用化学氧化法、格式反应法、GRIM (Grignard Metathesis Method)法和超声辅助GRIM法、合成了不同立构规整度的聚3-己基噻吩(P3HT).用GPC、紫外-可见光谱、红外光谱(FT-IR)和核磁共振谱(1 H-NMR)对P3HT的分子结构和立构规整度进行了表征.结果表明,GRIM法合成的P3...     

Electrochemical and spectroscopic characteristics of copolymers electrochemically synthesized from 3-(4-fluorophenyl)thiophene and 3,4-ethylenedioxythiophene

The copolymerization of 3-(4-fluorophenyl)thiophene (FPT) and 3,4-ethylenedioxythiophene (EDOT) was successfully achieved electrochemically in acetonitrile containing 0.1 M tetrabutylammonium tetrafluoroborate as supporting electrolyte by direct anodic oxidation of the monomer mixtures on platinum or stainless steel electrodes. As-formed copolymer own both the advantages of poly(3-(4-fluorophenyl)thiophene) (PFPT) and poly(3,4-ethylenedioxythiophene) (PEDOT), such as good electrochemical behaviors, high conductivity and excellent ambient stability. The structure and morphology of the copolymer were investigated by UV-vis, infrared spectroscopy, thermal analysis and scanning electron microscopy (SEM), respectively.     

Composition and annealing effects in polythiophene/fullerene solar cells

We have fabricated organic solar cells with blends of regioregular poly(3-hexylthiophene) (P3HT) and 1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6)C₆₁ (PCBM) as electron donor and electron acceptor, respectively. Blend composition and device annealing effects were investigated with optical absorption and photoluminescence spectroscopy, atomic force microscopy, photocurrent spectroscopy, and current-voltage characteristic measurements on devices under monochromatic or air mass (AM) 1.5 simulated solar light illumination. The highest efficiency was achieved for the 1:1 (P3HT:PCBM) weight ratio composition. The good performance is attributed to an optimized morphology that enables close intermolecular packing of P3HT chains. Inferior performance for the 1:2 composition is attributed to poorer intermolecular packing with increased PCBM content, while phase segregation on a sub-micron scale was observed for the 1:4 composition. The power conversion efficiency (AM 1.5) was doubled by the thermal annealing of devices at 140^∘C to reach a value of 1.4%.     

Investigation of P3HT/n-Si heterojunction using surface photovoltage spectroscopy

Surface photovoltage spectroscopy (SPS) was used to investigate the interactions of the interface between regioregular poly(3-hexylthiophene) (P3HT) and n-type single crystalline silicon. The SPS responses of silicon and the P3HT/n-Si heterojunction caused by band to band transition of silicon are 30 mV and 160 mV respectively. The band-bending in the silicon side of the P3HT/n-Si structure is larger than that of bare n-Si. The density of the interface states of the P3HT/n-Si heterojunction increased significantly after the deposition of P3HT. Based on the contact potential difference (CPD) transient results, charge transport and separation processes are fast in the silicon substrate and slow in the P3HT layer respectively.     

Electrochemical copolymerization of indole and 3,4-ethylenedioxythiophene

The copolymerization of indole and 3,4-ethylenedioxythiophene (EDOT) was achieved electrochemically in acetonitrile containing lithium perchlorate as supporting electrolyte by direct anodic oxidation of the monomer mixtures on platinum and stainless steel electrodes. As-formed copolymers own both the advantages of polyindole (PIn) and poly (3,4-ethylenedioxythiophene) (PEDOT), i.e., good thermal stability, good electrochemical behavior, high conductivity and excellent ambient stability. The structure and morphology of the copolymer were investigated by UV-vis, infrared spectroscopy, thermal analysis and scanning electron microscopy (SEM), respectively.     

Biodegradable polyester hybrid nanocomposites containing titanium dioxide network and poly(ε-caprolactone): Synthesis and characterization

In this paper, biodegradable poly(ε-caprolactone)/titanium dioxide hybrid film materials were prepared via in situ sol-gel process with tetrabutyl titanate (TBT) as inorganic precursor in the presence of poly(ε-caprolactone) and were characterized by means of Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electronic microscopy (SEM), X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The hybrids displayed microphase-separated structure on the nanometer scale. The studies of crystallization and melting behaviors of the hybrid films indicate that TiO₂ inorganic components have a considerable influence on behavior of crystallization of poly(ε-caprolactone) in hybrid materials.     

Poly(acrylonitrile-co-itaconic acid)–poly(3,4-ethylenedioxythiophene) and poly(3-methoxythiophene) nanoparticles and nanofibres

This work aimed to produce poly(acrylonitrile-co-itaconic acid) (P(AN-co-IA)) nanocomposites with poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3-methoxythiophene) (PMOT). An anionic surfactant sodium dodecyl benzene sulphonate was used in emulsion polymerization for nanocomposite production. Incorporations of PEDOT and PMOT on the nanoparticles were characterized by scanning electron microscopy (SEM), atomic force microscopy, Fourier transform infrared-attenuated total reflectance spectroscopy and ultra-violet spectroscopy. These nanoparticles were blended with PAN and the blends were electrospun to produce P(AN-co-IA)–polythiophene-derivative-based nanofibres, and the obtained nanofibres were characterized by SEM and energy dispersive spectroscopy. In addition, electrochemical impedance studies conducted on nanofibres showed that PEDOT and PMOT in matrix polymer P(AN-co-IA) exhibited capacitive behaviour comparable to that of ITO–PET. Their capacitive behaviour changed with the amount of electroactive polymer.     

导电聚3,4-乙撑二氧噻吩的制备及性能

以水为溶剂,分别选用对甲苯磺酸钠、高氯酸锂、硫酸钠为支持电解质,用电化学法合成聚3,4-乙撑二氧噻吩(PEDOT)膜。采用线性扫描伏安法(LSV)确定了合适的聚合电位;采用循环伏安法(CV)、电化学交流阻抗谱(EIS)研究了PEDOT膜的电化学行为。结果表明,掺杂阴离子种类对膜的循环伏安特性、EIS曲线等有很大的影响;此外研究了掺杂不同阴离子的PEDOT膜对电极的粘接性能,发现粘接性能也与阴离子种类有关。     

以聚醚胺为单体的超支化聚酰亚胺的制备与表征

以聚醚胺(T-403)、4,4′-二氨基二苯醚(ODA)和3,3′,4,4′-二苯甲酮二酐(BTDA)为单体,采用A2+B3法通过热亚胺化和化学亚胺化得到一系列超支化聚酰亚胺(HBPIs)。通过红外光谱测试(FT-IR)、热重分析测试(TGA)、溶解性测试和X射线衍射分析(XRD)对聚合物进行了结构表征和性能测试。FT-IR表明生成了预期的聚合物;TGA表明合成的超支化共聚PI随着共聚体系中芳香二胺的比例增大,其在N2中5%和10%的热失重温度也随之升高;溶解性测试表明合成的超支化聚酰胺酸具有较好的溶解性,化学亚胺化合成的HBPI溶解性良好;X射线衍射分析(XRD)表明聚合物的结晶度较低。     

Novel regioregular polythiophenes containing side-chain porphyrin groups for polymeric photovoltaic cells

The paper presents a new strategy for the preparation of porphyrin-functionalized head-to-tail regioregular thiophene copolymers using a simple and effective post polymerization functionalization (PPF) procedure based on the synthesis of a regioregular and soluble polythiophene precursor followed by subsequent reaction with a suitably functionalized porphyrin derivative. Thus, thiophene copolymers poly[3-(6-bromohexyl)thiophene-co-(3-[5-(4-phenoxy)-10,15,20-triphenylporphyrinyl] hexylthiophene)]s at different porphyrin chromophore contents were prepared, obtaining, in all cases, very soluble and easily filmable derivatives. Their thermal, optical and electrochemical properties were determined and their performances as the active layer in bulk heterojunction solar cells tested.     

Methanofullerene elongated nanostructure formation for enhanced organic solar cells

Using transmission electron microscopy (TEM) and Z-contrast imaging we have demonstrated elongated nanostructure formation of fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) within an organic host through annealing. The annealing provides an enhanced mobility of the PCBM molecules and, with good initial dispersion, allows for the formation of exaggerated grain growth within the polymer host. We have assembled these nanostructures within the regioregular conjugated polymer poly(3-hexylthiophene) (P3HT). This PCBM elongated nanostructure formation maybe responsible for the very high efficiencies observed, at very low loadings of PCBM (1:0.6, polymer to PCBM), in annealed photovoltaics. Moreover, our high resolution TEM and electron energy loss spectroscopy studies clearly show that the PCBM crystals remain crystalline and are unaffected by the 200-keV electron beam.     

反向胶束法制备PEDOT纳米粒子气体敏感性的研究

通过用紫外-可见-近红外光谱、X射线光电子能谱及透射电镜等手段对采用反向胶束合成法,以二乙基磺基琥珀酸钠(AOT)形成的反胶束为模板制备出的导电聚合物聚3,4乙烯二氧噻吩(PEDOT)纳米粒子对HCl气体敏感性进行研究。沉积有纳米粒子的QCM器件对2.0×10-5气体响应时间为20s,具有较好的响应恢复特性,能够有效探测低浓度(5×10-6)气体,气敏特性明显优于普通PEDOT粒子。