纳微米聚（3，4-二氧乙基噻吩）导电高分子的合成及其性能研究

在导电高分子家族中，聚（3，4-二氧乙基噻吩）（PEDOT）由于具有高的电导率、环境稳定性、透明性以及良好的成膜性等优异性能而广泛地应用于有机电致发光器件、太阳能电池、防静电、电致变色器件、传感器等领域．本论文研究了绝缘高分子聚乙二醇（PEG）和乙二醇、一缩二乙二醇等有机极性溶剂提高PEDOT／PSS（聚苯乙烯磺酸钠）电导率的机理，并通过改变稳定剂、掺杂剂等因素制备了具有不同结构和性能的PEDOT胶体颗粒以及PEDOT／PMMA（聚甲基丙烯酸酯）复合微球，取得了以下主要的创新性结果。     

金纳米颗粒掺杂导电聚合物对有机-硅杂化光伏电池性能的影响研究

本研究将金纳米颗粒掺入聚3, 4-乙烯二氧噻吩:聚苯乙烯磺酸（PEDOT:PSS）薄膜中,制备了有机-硅杂化光伏电池。与纯PEDOT:PSS-硅电池相比,掺入金纳米颗粒制备的杂化光伏电池的光电转化效率（PCE）提高了23%,达到12.85%。电池的电流密度-电压曲线（J-V）、外量子效率（EQE）和电容-电压曲线（C-V）测试结果表明,掺入金纳米颗粒后电池性能提高的主要原因在于电池的光学性能和电学性能得到了改善：在金纳米颗粒的等离子共振区域,电池对光的反射性能降低;金纳米颗粒还能提高PEDOT:PSS薄膜的导电率、增加该电池的内建电场,因此极大减少了电荷在传输过程中的损失,提高了电池中电荷的传输和收集效率。     

PEDOT:PSS导电自支撑薄膜的合成与制备

以3,4-乙烯二氧噻吩（EDOT）为原料，聚对苯乙烯磺酸钠（PSS-Na）为分散剂和掺杂剂，通过化学氧化合成法在水体系中聚合制备了聚(3,4-乙烯二氧噻吩):聚苯乙烯磺酸（PEDOT:PSS）悬浮液，通过真空抽滤的方法制备了PEDOT:PSS自支撑柔性导电薄膜。通过FTIR、UV-Vis对聚合产物结构进行了表征与确认，通过四探针电导率测试、SEM、拉伸断裂强度测试对PEDOT:PSS薄膜的导电性、微观形貌与力学性能进行了表征。结果表明，成功制备了PEDOT:PSS目标产物，在氧化剂与单体物质的量之比为0.875时达到最佳电导率（19.19 S/cm）。自支撑薄膜厚度约18 μm，在25 ℃，40%~60%相对湿度范围内拉伸断裂强度达到45~60 MPa，具有良好的导电性与机械性能。     

金颗粒掺杂对有机-硅光伏电池性能的影响

将金纳米颗粒(Au NPs)掺入导电聚合物聚3,4-乙烯二氧噻吩∶聚苯乙烯磺酸(PEDOT∶PSS)薄膜中,制备了有机-硅杂化光伏电池。利用TEM和SEM对Au NPs及其掺杂的有机膜进行了表征。考察了金纳米颗粒对有机-硅杂化光伏电池光学和电学性能的影响。电池的电流密度-电压曲线(J-V)、外量子效率(EQE)和电容-电压曲线(C-V)测试结果表明,Au NPs的引入提高了电池的光电性能,与纯PEDOT∶PSS-硅电池相比,掺入金纳米颗粒制备的杂化光伏电池的光电转化效率(PCE)提高了24%,达到12.87%;在金纳米颗粒的等离子共振区域,电池对光的反射性能降低;当V(金纳米颗粒)∶V(PEDOT∶PSS)=0.15∶1.0时,膜的导电率由560 S/cm增加到860S/cm、PEDOT∶PSS-硅光伏电池的内建电场(Vbi)由0.68 V增加到0.78 V,金纳米颗粒与PEDOT∶PSS共同作用,极大地减少了电荷在传输过程中的损失,提高了电池中电荷的传输和收集效率。     

基于二甲氧基乙醇处理聚3,4-乙烯二氧噻吩/聚苯乙烯磺酸盐做透明电极在有机太阳能电池中的应用

聚3,4-乙烯二氧噻吩/聚苯乙烯磺酸盐（PEDOT:PSS）具有优异的光电性能,目前研究者尝试用PEDOT:PSS材料来取代常用透明电极氧化铟锡（ITO）,由于未经处理过的PEDOT:PSS电导率极低,目前急需寻找到新的方法来提高PEDOT:PSS的电导率。本文使用了热（130℃）二甲氧基乙醇多次处理PEDOT:PSS薄膜,结果表明随着处理次数的增加,PEDOT:PSS薄膜电阻逐渐减小。采用了原子力扫描电镜（AFM）和X射线衍射（XRD）等表征手段,发现热二甲氧基乙醇溶剂处理能有效的去除PSS,从而提升了薄膜的电导率。经过热二甲氧基乙醇溶剂处理六次后的品质因素（FoM）高达51.61,并将热二甲氧基乙醇处理六次后的PEDOT:PSS薄膜作为无ITO有机太阳能电池的透明电极,光电转化效率为2.05%,达到了ITO电极的83.67%。     

导电聚（3，4-二氧乙基噻吩）／无机纳米复合材料研究

本论文围绕制备导电聚合物PEDOT（聚3，4-二氧乙基噻吩）与无机氧化物及金属纳米复合材料的研究，探索了不同复合材料所表现的独特的电学、光学和结构等方面性质，并建立了一种无模板制备有机／无机一维纳微米结构复合材料的一步合成新方法，制备了具有core-shell结构的PEDOT／PSS-ZnO，PEDOT／PSS-Au复合纳米线，取得了以下创新性结果．     

PEDOT:PSS薄膜导电性能优化的研究进展

聚（3,4-乙撑二氧噻吩）:聚苯乙烯磺酸盐（PEDOT:PSS）具有高导电性、高柔韧性、出色的稳定性、易于成膜和成本低等优点,被认为是最有价值的导电聚合物之一,它在储能转换和电子系统中有着广阔的应用前景。然而,原始的PEDOT:PSS薄膜的电导率较低（<1 S/cm）,阻碍了要求其高导电性的实际应用,于是人们提出了各种方法来提高PEDOT:PSS薄膜的电导率。本文综述了优化PEDOT:PSS薄膜电导率的新进展,并介绍了掺杂处理、后处理等提高PEDOT:PSS薄膜电导率的方法。     

NIPAM改性PEDOT:PSS导电聚合物的制备及在电致变色器件中的应用

以柔性疏水小分子N-异丙基丙烯酰胺（NIPAM）对聚苯乙烯磺酸盐（PSS）进行共聚改性，制备了一系列聚[(苯乙烯磺酸盐)-共-异丙基丙烯酰胺][P(SS-co-NIPAM)]，并以其为模板采用氧化聚合法与3,4-乙烯二氧噻吩（EDOT）制备了导电聚合物PEDOT:P(SS-co-NIPAM)。与PEDOT:PSS薄膜相比，NIPAM摩尔分数（以对苯乙烯磺酸钠物质的量为基准，下同）为15%时，PEDOT:P(SS-co-NIPAM)薄膜平均透光率保持在80%左右，水接触角从18.5°增至39.0°，疏水性提高，并且弯曲1000次后方阻变化量为5.71 kΩ/sq，远小于PEDOT:PSS薄膜（10.60 kΩ/sq）。以NIPAM摩尔分数为15%的PEDOT:P(SS-co-NIPAM)薄膜作为离子储存层的电致变色器件的光学对比度（ΔT）为9.83%，循环800次后ΔT仍达到9.55%，衰减量为0.28%，衰减量与PEDOT:PSS器件相当，说明NIPAM共聚改性能改善PEDOT:PSS导电聚合物的柔韧性和疏水性，以其作为离子储存层的器件可维持优异的电致变色性能。     

PEDOT:PSS导电性能优化方法的研究进展

导电高分子材料聚(3,4-乙撑二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)因其稳定性好、电导率高、溶液加工性好等优点而受到人们的广泛关注。PEDOT:PSS的电导率经化学或物理的方法处理后会有较大改变。对提高PEDOT:PSS材料电导率的方法进行了综述,通过掺杂(有机溶剂、无机纳米粒子、酸处理)、与碳材料复合等方法可以提高PEDOT:PSS的电导率,并对其以后的发展进行了展望。     

以低分子量聚乙烯基苯磺酸钠为模板的聚3,4-二氧乙烯噻吩水分散体的制备及性能

通过RAFT聚合,制备了低分子量的聚乙烯基苯磺酸钠（PSS）;其次以低分子量的聚乙烯基苯磺酸钠为模板制备了聚3,4-二氧乙烯噻吩（PEDOT）：聚乙烯基苯磺酸钠（PSS）水分散体,研究了作为模板的聚乙烯基苯磺酸钠的不同分子量对PEDOT：PSS水分散体结构和性能的影响。结果显示：通过核磁氢谱（¹H NMR）表征,证明成功制备了分子量为3900,4900,9600和18300的聚乙烯基苯磺酸钠。用荧光探针法发现低分子量PSS在水中能形成胶束,临界胶束浓度在10^-6g·ml^-1左右。用四探针表面电阻测试发现,低分子量PSS为模板可明显提高PEDOT薄膜的导电性,最大提高了近3倍。用紫外可见分光光度计（UV）研究发现,以低分子量PSS为模板使PEDOT的透明性有一定的下降,这主要是由于RAFT试剂部分和PEDOT：PSS的相分离造成的。热稳定性的测试表明,低分子量PSS为模板对PEDOT的热稳定性没有明显的影响。     

In situ-prepared composite materials of PEDOT: PSS buffer layer-metal nanoparticles and their application to organic solar cells

We report an enhancement in the efficiency of organic solar cells via the incorporation of gold (Au) or silver (Ag) nanoparticles (NPs) in the hole-transporting buffer layer of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), which was formed on an indium tin oxide (ITO) surface by the spin-coating of PEDOT:PSS-Au or Ag NPs composite solution. The composite solution was synthesized by a simple in situ preparation method which involved the reduction of chloroauric acid (HAuCl₄) or silver nitrate (AgNO₃) with sodium borohydride (NaBH₄) solution in the presence of aqueous PEDOT:PSS media. The NPs were well dispersed in the PEDOT:PSS media and showed a characteristic absorption peak due to the surface plasmon resonance effect. Organic solar cells with the structure of ITO/PEDOT:PSS-Au, Ag NPs/poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM)/LiF/Al exhibited an 8% improvement in their power conversion efficiency mainly due to the enlarged surface roughness of the PEDOT:PSS, which lead to an improvement in the charge collection and ultimately improvements in the short-circuit current density and fill factor.     

Effect of silver decorated graphene oxide on the PEDOT:PSS-matrix composite films

Silver decorated graphene oxide (GO) was added in poly(3,4-ethylenedioxythiopphene): poly(styrene sulfonate) (PEDOT:PSS) matrix to fabricate composite films, aiming for an improved electrical conductivity. Silver particles were deposited on GO surfaces by reaction with Tollens’ reagent. The composite films reinforced by silver decorated GO showed a sheet resistance of 744 Ω/sq. with 88.9% transparency, which outperformed PEDOT:PSS matrix and GO/PEDOT:PSS composite films. The deposited silver particles were consisted of elementary silver and positively charged silver. The GO surfaces were negatively charged. The distinction of positive domain and negative domain on silver decorated GO surfaces promoted the phase separation of conductive PEDOT molecules and insulting PSS molecules, which contributed to the increase of the electrical conductivity of the composite films. Moreover, the deposition of elementary silver introduced extra electron pathways in the composite films.     

A novel hierarchical Pt- and FTO-free counter electrode for dye-sensitized solar cell

A novel hierarchical Pt- and FTO-free counter electrode (CE) for the dye-sensitized solar cell (DSSC) was prepared by spin coating the mixture of TiO₂ nanoparticles and poly(3,4-ethylenedioxy-thiophene):poly(styrenesulfonate) (PEDOT:PSS) solution onto the glass substrate. Compared with traditional Pt/FTO CE, the cost of the new CE is dramatically reduced by the application of bilayer TiO₂-PEDOT:PSS/PEDOT:PSS film and the glass substrate. The sheet resistance of this composite film is 35 Ω sq⁻¹ and is low enough to be used as an electrode. The surface morphologies of TiO₂-PEDOT:PSS layer and modified PEDOT:PSS layer were characterized by scanning electron microscope, which shows that the former had larger surface areas than the latter. Electrochemical impedance spectra and Tafel polarization curves prove that the catalytic activity of TiO₂-PEDOT:PSS/PEDOT:PSS/glass CE is higher than that of PEDOT:PSS/FTO CE and is similar to Pt/FTO CE''s. This new fabricated device with TiO₂-PEDOT:PSS/PEDOT:PSS/glass CE achieves a high power conversion efficiency (PCE) of 4.67%, reaching 91.39% of DSSC with Pt/FTO CE (5.11%).     

Flexible and Highly Conductive AgNWs/PEDOT:PSS Functionalized Aramid Nonwoven Fabric for High-Performance Electromagnetic Interference Shielding and Joule Heating

High-performance multifunctional textiles are highly demanded for human health-related applications. In this work, a highly conductive nonwoven fabric is fabricated by coating silver nanowires (AgNWs)/poly(3,4-ethyl enedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) on a poly(m-phenylene isophthalamide) (PMIA) nonwoven fabric through a multistep dip coating process. The as-prepared PMIA/AgNWs/PEDOT:PSS composite nonwoven fabric shows an electrical resistance as low as 0.92 ± 0.06 Ω sq⁻¹ with good flexibility. The incorporation of the PEDOT:PSS coating layer improves the adhesion between AgNWs and PMIA nonwoven fabric, and also enhances the thermal stability of the composite nonwoven fabric. Electromagnetic interference (EMI) shielding and Joule heating performances of the PMIA/AgNWs/PEDOT:PSS composite nonwoven fabric are also investigated. The results show that the average EMI shielding effectiveness (SE) of the single-layer nonwoven fabric in X-band is as high as 56.6 dB and retains a satisfactory level of SE after being washed, bended, and treated with acid/alkali solution and various organic solvents. The composite nonwoven fabric also exhibits low voltage-driven Joule heating performance with reliable heating stability and repeatability. It can be envisaged that the multifunctional PMIA/AgNWs/PEDOT:PSS nonwoven fabric with reliable stability and chemical robustness can be used in EMI shielding devices and personal thermal management products.     

Transparent,conductive polymer blend coatings from latex-based dispersions

Flexible, transparent and conductive polymer blend coatings were prepared from aqueous dispersions of poly(3,4-ethylenedixoythiophene)/poly(styrenesulfonate) [PEDOT/PSS] gel particles (∼80 nm) and latex (∼300 nm). The stable dispersions were deposited as wet coatings onto poly(ethylene terephthalate) substrates and dried at 80 °C. Microstructure studies using tapping mode atomic force microscopy (TMAFM) indicate that a network-like microstructure formed during drying at 0.03 volume fraction PEDOT/PSS loading. In this network-like structure, the PEDOT/PSS phase was forced into the boundary regions between latex. In addition, migration of the PEDOT/PSS particles towards coating surface is likely during drying of the aqueous dispersions. The addition of a small amount of dimethyl sulfoxide (DMSO) in dispersions altered the distribution of the PEDOT/PSS phase. As PEDOT/PSS concentration increases to 0.15 volume fraction, the coating surface is dominated by the PEDOT/PSS phase. The effect of DMSO on microstructure becomes less apparent as PEDOT/PSS concentration increases. The conductivity of the polymer blend coatings increases in a percolation-like fashion with a threshold of ∼0.02 volume fraction PEDOT/PSS. The addition of DMSO in dispersions enhanced the coating conductivity beyond the threshold by more than two orders of magnitude. The highest conductivity, ∼3 S/cm, occurs at 0.20 volume fraction PEDOT/PSS concentration. The polymer blend coatings have good transparency with only a weak dependence of transparency on wavelength due to the small refractive index difference between filler and matrix.     

Chemical cross-linking of conducting poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) using poly(ethylene oxide) (PEO)

Hybrid films of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) were prepared with different molecular weights of poly(ethylene oxide) (PEO). The cross-linking reaction between PEO and PEDOT:PSS was performed at high temperature and confirmed by using differential scanning calorimeter (DSC), contact angle measurement, and solid-state ¹H NMR. The effect of chemical reaction on the conductivity and morphology of these hybrid films was studied by using 4-point probe and atomic force microscope (AFM), respectively. As-spun PEO/PEDOT:PSS films have lower electric conductivity due to the addition of nonconductive PEO, and exhibits no molecular weight dependence on conductivity. After chemical cross-linking reaction at high temperature, only PEDOT:PSS films with lowest molecular weight PEO additives show enhanced conductivity with increasing reaction time. AFM result indicates that the heat-treated PEO/PEDOT:PSS hybrid films show grain-like morphology compared to ethylene glycol treated PEDOT:PSS films which shows continuous PEDOT domain. In the present work we demonstrate that the cross-linking reaction can be used to improve the wet stability of PEDOT:PSS nanofiber, showing good water resistance and excellent dimensional stability.     

聚合物顶发射发光二极管的研究

采用铬(Cr)作为聚合物顶发射发光二极管阳极,得到了一种高效的顶发射发光器件结构。在使用铬作为器件阳极时,首先使用磁控溅射方法使其沉积在玻璃衬底表面,然后使用不同厚度PEDOT:PSS薄膜提高阳极表面的平整度,并得出当PEDOT:PSS厚度为60nm时器件具有最高效率。本实验采用聚合物P-PPV(poly[2-(4-3’,7’-dimethyloctyloxy)-phenyl]-p-pheny-lenevinylene))作为发光层。器件阴极结构为钡/银(Ba/Ag),通过不同厚度阴极的器件对比,得出阴极最适合的结构为Ba(4nm)/Ag(15nm)。此时,该结构的器件最大效率达4.41cd/A,最大效率时亮度达到738cd/m2。     

Conjugated polymer mediated synthesis of nanoparticle clusters and core/shell nanoparticles

Two water soluble conjugated polymers, poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) and ammonium ion stabilized poly(phenylene vinylene) (P2), are found to be able to reduce noble metal ions to zero-valent metals via a direct chemical deposition technique. Au nanoparticle clusters can be obtained through reduction of Au³⁺ ions by PEDOT:PSS and the electronic coupling between them can be controlled by HAuCl₄ concentration. Core/shell Ag/polymer nanostructures are prepared from reduction of Ag⁺ ions by P2, which have a ppb detection limit for 4-MBA using surface-enhanced Raman spectroscopy (SERS). This conjugated polymer mediated synthesis of metal nanoparticles may open a new avenue for fabricating nanomaterials and nanocomposites with tunable optical properties that are dominated by their structure and electronic coupling between nanoparticles.     

Effects of pentacene-doped PEDOT:PSS as a hole-conducting layer on the performance characteristics of polymer photovoltaic cells

We have investigated the effect of pentacene-doped poly(3,4-ethylenedioxythiophene:poly(4-styrenesulfonate) [PEDOT:PSS] films as a hole-conducting layer on the performance of polymer photovoltaic cells. By increasing the amount of pentacene and the annealing temperature of pentacene-doped PEDOT:PSS layer, the changes of performance characteristics were evaluated. Pentacene-doped PEDOT:PSS thin films were prepared by dissolving pentacene in 1-methyl-2-pyrrolidinone solvent and mixing with PEDOT:PSS. As the amount of pentacene in the PEDOT:PSS solution was increased, UV-visible transmittance also increased dramatically. By increasing the amount of pentacene in PEDOT:PSS films, dramatic decreases in both the work function and surface resistance were observed. However, the work function and surface resistance began to sharply increase above the doping amount of pentacene at 7.7 and 9.9 mg, respectively. As the annealing temperature was increased, the surface roughness of pentacene-doped PEDOT:PSS films also increased, leading to the formation of PEDOT:PSS aggregates. The films of pentacene-doped PEDOT:PSS were characterized by AFM, SEM, UV-visible transmittance, surface analyzer, surface resistance, and photovoltaic response analysis.