印制电子技术是一种基于印刷原理的简单快速的电子制造技术。随着电子产品向高密度、轻薄化、对环境友好等方面的发展，印制电子技术得到迅速发展，导电油墨的研究也受到广泛关注。其中铜导电油墨因其优异的导电性以及低成本，成为目前研究的热点。本论文围绕铜导电油墨展开，为了解决铜油墨中纳米颗粒易氧化的问题，研制了新型的制备工艺简单、烧结温度低且导电性能优良的铜油墨，并对烧结机理和改善导电性进行了研究。主要内容如下： 1.首次选用铜含量高、成本低的氢氧化铜作为前体，克服了氢氧化铜加热分解为氧化铜、不能自还原的问题，利用3-二甲基氨基-1，2-丙二醇(DMAPD)，研制了氢氧化铜-DMAPD自还原配合物体系，DMAPD可以将氢氧化铜部分还原为金属铜。研究表明，在该体系中加入少量甲酸，可以将氢氧化铜全部转化为金属铜。在对该体系进行深入分析的基础上，提出了甲酸循环催化的机理：少量甲酸能够与部分氢氧化铜反应生成Cu(OH)(HCOO)， Cu(OH)(HCOO)在DMAPD的存在下能够低温还原生成金属铜，同时生成的HCOOH与余下Cu(OH)₂反应，参与下一个还原过程。该循环催化过程能够有效还原氢氧化铜，并大幅度降低还原温度。通过调节自还原体系的材料配比，在160-200℃烧结得到导电性能良好、均匀致密的铜膜，在200℃氮气氛中烧结30min铜膜的体电阻率为139±24μΩ·㎝。 2.将氢氧化铜自还原复合体系与铜微米颗粒混合，制备了新型的混合油墨体系，既克服了纳米油墨易氧化、易团聚的问题，又解决了有机分解油墨铜固含量低、结构疏松、强度较差的问题。首先将氢氧化铜与DMAPD混合，再加入一定量的甲酸混合均匀后，加入一定比例的铜粉混合，形成铜-氢氧化铜配合物复合体系。该体系中的氢氧化铜复合物包覆在铜颗粒表面，防止铜颗粒团聚及氧化；氢氧化铜复合物体系在加热时能分解为小颗粒，促进铜颗粒在较低温度下烧结；同时该体系中含有铜颗粒，大大提升了体系的铜固含量，避免了烧结时疏松多孔的问题。通过优化体系的材料配比，得到了颗粒致密、导电性优良的铜膜。200℃氮气氛中烧结30min铜膜的体电阻率为34±5 μΩ·㎝，比氢氧化铜自还原复合体系的电阻大大降低。 3.研发了一种工艺简单、能够在空气中低温快速烧结的微米铜-甲酸-DMAPD油墨，利用甲酸对铜颗粒表面的活化作用与DMAPD抗氧化作用的协同效应，克服了微米颗粒烧结温度高以及空气中烧结易氧化、导电性差的问题。采用市售的易于制得的铜微米颗粒，将未经任何处理的铜粉与甲酸混合，甲酸与表面的氧化层反应生成可自还原的甲酸铜，同时，铜颗粒表面能够吸附甲酸，并被甲酸活化；DMAPD与活化的铜颗粒表面以及甲酸铜配位；加热时，活化的表层铜原子移动速度快，迅速熔融烧结，铜-胺配合物在较低温度分解成纳米颗粒，可迅速聚结合并，促进微米颗粒在较低温度下烧结；DMAPD可以保护铜颗粒在空气中烧结不被氧化，最终实现微米颗粒在空气氛中的低温快速烧结。该体系在热台上空气氛围中，200℃以下加热不超过一分钟，铜微米颗粒即发生烧结，极大的简化了工艺与流程。通过调节不同组分的配比，得到了54±2μΩ·㎝的体电阻率，为目前空气中烧结铜颗粒的最优报道。 关键词：导电油墨，低温烧结，空气烧结，自还原，抗氧化，氢氧化铜 中图类分号：TG14

 The printed electronic technology is a simple and rapid electronic manufacturing technology based on the printing principle. With the development of electronic products to high density, light and environment-friendly, the electronic printing electronic technology has developed rapidly, and the research of conductive inks has been widely concerned. The copper conductive ink has become the hotspot of research because of its excellent conductivity and low cost. In order to solve the problem of easy oxidation of nano-particles in copper ink, new kinds of copper ink which have the advantages of simple preparation process, low sintering temperature and excellent conductive performance, and studied the sintering mechanism were developed in this research. The main contents are as follows: 1.Copper hydroxide was firstly used as a copper precursor, and Cu(OH)₂-DMAPD self-reduction complex system was developed by using the reductive property of 3-dimethylamino-1,2-propanediol(DMAPD).DMAPD could reduce the copper hydroxide partially.Subsequently,a small amount of formic acid was added in the system to catalyze the reduction of copper hydroxide, and the reduction temperature of cupric hydroxide was greatly reduced. The catalytic mechanism of formic acid was studied by analytical test, and the uniform and dense conductive copper film was obtained. Finally, copper films with good conductivity were obtained at 160-200℃ sintering temperatures. 2.A new mixed ink was prepared by mixing the copper hydroxide self- decomposition complex with micron copper particles. The copper hydroxide complex was coated on the surface of copper particles to prevent agglomeration and oxidation of copper particles. The copper hydroxide complex can decomposed into small particles during heating process to promote the sintering of copper particles at lower temperature. This mixed ink contained copper particles, which improved the copper solid content, avoiding the problem of porous porosity in the sintered films. The role of formic acid in the system was analyzed by characterization, and the conductive films with compact and excellent conductive properties were obtained. 3.A convenient fabrication process for conductive copper films with a simple heat treatment on hotplate in air was successfully developed. The ink was prepared by mixing copper micron particles with formic acid and DMAPD. The copper oxide on the surface of untreated copper micron particles reacted with formic acid, and the copper micron particles could be activated by the chemisorbed formic acid and sinter at low temperatures. DMAPD could protect copper from oxidation when sintered in air, and could promote the decomposition of copper formate by forming copper-amine complex.A resistivity of 54±2μΩ·㎝ was obtained after sintered at 200℃ for 50s. Keywords: Conductive inks,low-temperature sintering, air sintering, self reduction, anti-oxidation, copper hydroxide Chinese library classification: TG14