【作者】 徐建华；

【导师】 杨邦朝；

【作者基本信息】 电子科技大学 ， 微电子学与固体电子学， 2008， 博士

【摘要】 有机固体电解电容器具有高频大容量、低等效串联电阻、高可靠等特点,可广泛应用于计算机、雷达、导弹、超音速飞机、自动控制装置等电子线路中,并满足当前电子电路日益高频化的要求。该类电容器广阔的应用前景和潜在的巨大商业价值引起了企业和研究者的关注。目前高频低ESR固体电解电容器的研究主要集中于高性能电极材料的制备以及电容器制备工艺两个方面。本论文针对有机固体钽电解电容器开展了从原料到材料到电极到电容器的系统而深入的研究工作,主要有:高得率导电聚合物单体的合成研究、高电导率高稳定性聚合物电极薄膜的制备研究、片式有机固体钽电解电容器被膜工艺及相关机理研究、高频低ESR有机固体钽电解电容器的制备与性能研究、有机固体钽电解电容器失效机理及可靠性研究、有机固体钽电解电容器产业化可行性研究。论文的主要研究内容及创新点归纳如下:1.提出采用导电聚合物聚乙烯二氧噻吩作为片式固体电容器的阴极材料,独特的化学原位聚合工艺使电容器的等效串联电阻由300mΩ降低至40mΩ,电容器的频率使用范围由10KHz提高至100KHz。（授权专利03105908.2）。2.在乙撑二氧噻吩单体材料合成中,使用比表面积大、催化活性高的复合铜粉为催化剂,使用反应物可溶而产物不溶促使平衡向正方向移动的质子型极性化合物为溶剂,使反应温度降低50℃、反应时间缩短6小时,而产率提高近25%（专利申请号200610055264.X）3.鉴于PEDT的的阳离子自由基聚合机理,聚合反应速度快,反应难以控制的难点,在聚合物电极薄膜制备过程中采用独特的氧化剂、溶剂体系和聚合改良剂,使聚合物薄膜的电导率高且可在10～100S/cm间调控（授权专利ZL03105755.1）。4.在聚合物阴极电容器制备过程中采用表面活性处理和薄膜吸附技术提高电容器静电容量引出率,使容量引出率由35%提高至95%（授权专利ZL03105907.4）。5.首次采用在线掺杂原位沉积的PEDT电极薄膜,可在修补金属氧化层缺陷的同时大幅提高聚合物薄膜的电导率,降低电容器ESR,同时还可简化被膜工艺。（授权专利03105908.2）6.首次通过在活化剂处理后的芯子表面沉积有机硅烷类偶联剂,制备硅烷类偶联剂-PEDT界面复合材料作为中间隔离层材料,研究结果表明中间隔离技术可显著提高电容器的耐压能力,在相同容量和外形尺寸的情况下,使用中间隔离技术后的产品工作电压可提高一倍以上。7.发现了在平坦与多孔表面沉积聚合物薄膜的电导率变化规律,提出并建立了受限空间内导电聚合物薄膜生长机理及模型,为在多孔阳极表面沉积聚合物薄膜奠定了理论基础（论文:在钽电解电容器多孔阳极体表面化学原位被覆聚乙烯二氧噻吩（PEDT）薄膜研究″）。8.研制出的PEDT有机固体钽电解电容器的工作电压为2～16V,容量范围在10～220μF,研制的产品除漏电流外,电容器的工作电压、容量、损耗和频率特性、温度特性等参数均优于MnO₂电容器,并达到美国KEMET公司聚吡咯产品目录公布的性能水平,目前该研究技术成果已在相关企业开始初步实现生产化。更多还原

【Abstract】 As a novel kind of energy storage component, organic solid electrolyte capacitor （OSEC） has lots of merits such as with high energy density, high power density, long life time and broad temperature range for practical application et al. OSECs have already been applied in fields such as computer, radar, missile, supersonic airplane, automatic control system. Due to the wide application field and huge commercial value, more and more attention is being paid on the research of OSECs. Currently, studies on OSECs are mainly focused on the preparation of high performance electrode materials and device. In this dissertation, we systematically studied on the preparation of high performance device involving in material, electrode, and capacitor, which includes the synthesis of high yield conductive polymer monomer, the preparation high conductive and stable polymer electrode thin films, the processing, fabrication , and mechanism of thin film for slice OSEC, the fabrication and property of high frequency low ESR OSEC, the disable mechanism and reliability of OSEC, and the feasibility of large scale production for OSEC. The main results are as following.1. Synthetic method and processing for novel monomer to synthesize conductive poly（3,4-ethylene dioxythiophene） （PEDT） polymer as a cathode material fro sliced solid capacitor was optimized. The results show that using this novel in situ chemical polymerization technique equivalent series-wound resistance decreased from 300 mΩto 40 mΩ. The frequency range increased from 10 KHZ to 100 KHZ. The capacitor and its fabrication method were patented via No. 03105908.2.2. During the synthesis of PEDT monomer, using porous copper as a de-carboxylic agent, reaction temperature reduces 50℃, and reaction time decreases 6 hr. On the other hand, final target yield increases from 25% using proton type solvent which is soluble for reactant but insoluble for product, and the product can be easily purified by separation funnel and distillation to attain high grade. Moreover, solvent can be recycled as well as environmental friendly. This result is applied patent through appl. No. 200610055264.X.3. As the reaction of PEDT polymerization involves in cationic free polymeric mechanism, which the reaction rate is very fast and uneasily controlled, in this work a novel method for using unique oxidant, solvent system, and polymerization improver was applied. As a result, the conductivity of polymer film can be modified from 10 to 100 S/cm, which was patented via No. ZL03105755.1.4. Using surfactant active processing and thin film absorption technique, the eduction yield of capacitance increased from 35% to 95% （Patent No. ZL03105907.4）.5. Using in situ doping into in situ deposition PEDT electrode, the defect in metal oxide was remedied, and the conductivity of polymer film was greatly improved. At the same time, film processing procedure was simplified. This work was patented through No. 03105908.2.6. It is first time to deposit silane coupling agent on surfactant polished the core surface of OSEC and fabricate silane coupling agent-PEDT interfacial material as internal separator. It was found that as internal separation technique is significantly helpful to improve the pressure endurance capability of the OSECs, e.g., in the case of identical volume and exterior size, the working pressure of product using internal separation technique has been doubled.7. The variation rule of OSEC conductivity of polymer films deposited on flat and porous surface was found, and thin film formation mechanism and model in limited space was established, which paved base stone for polymer thin film deposition on porous surface.8. The working pressure of the obtained PEDT OSEC is 2-16 V, and the capacitance ranges from 10 to 20μF. The parameter of working pressure , capacitance, wasting, frequency and temperature characteristic is much better than those of MnO₂ capacitor, which is comparable to the device performance listed in USA KEMET Co. product catalogue. At the present stage, large scale production is being attempted in relevant enterprise using the result and technique achieved in this work.In summary, a novel series of capacitors based on PEDT conductive polymer were systematically studied, and high performance device was achieved. It can be anticipated that more novel kind of capacitors using other different organic electronic materials can be exploited with the pioneering study in this work.更多还原