光敏聚酰亚胺抗蚀剂的研究

光敏聚酰亚胺是近20年来随着微电子工业的发展而迅速崛起的一类新型高分子材料,它广泛应用于微电子领域,在航空航天等尖端工业中也有着重要用途.预亚胺化可溶性负性光敏聚酰亚胺光致抗蚀剂在简化光刻工艺,增强耐热性,提高图形留膜率等方面具有诱人的前景[1～2].     

光敏聚酰亚胺光刻胶研究进展

近年来,光敏聚酰亚胺(PSPI)在先进封装、微机电系统和有机发光二极管(OLED)显示等新兴领域的需求牵引下得到了快速发展。在基础研究、应用研究以及产业化方面,PSPI的进展都引起了广泛关注。光敏聚酰亚胺作为一种实用的可自图案化薄膜材料显示出越来越突出的重要性。本文综述了近年来正性、负性光敏聚酰亚胺的结构设计、光化学反应及其感光性能等方面的研究进展,简要介绍了在集成电路、微机电系统以及OLED显示等方面的应用需求,最后对光敏聚酰亚胺在研究和应用中存在的问题及其前景进行了展望。     

光敏聚酰亚胺合成方法及应用的最新进展

从负性、正性和化学增幅三个方面阐述了光敏聚酰亚胺（ＰＳＰＩ）几十年来的研究和发展现状，并做了一定深度的讨论。     

光敏性聚酰亚胺的合成及其在液晶光致取向中的运用

通过羟基聚酰亚胺与肉桂酸的接枝反应合成了具有光敏性的聚酰亚胺,并且通过红外,核磁确定了光敏性聚酰亚胺的结构,将合成的聚酰亚胺作为液晶取向层用在液晶显示器件中,证明其有良好的热稳定性。     

光敏聚酰亚胺的最新进展

综述光敏聚酰亚胺作为感光高分子的最新进展，着重叙述了有机硅改性光敏聚酰亚胺，自增感光敏聚酰亚胺和含氟光敏聚酰亚胺的制备方法和性能研究。     

含氟聚酰亚胺及其在微电子工业中的研究进展Ⅱ含氟聚酰亚胺在微电子工业中的应用

综述了近年来国内外在含氟聚酰亚胺(PI)研究及应用领域中的最新进展情况。主要从现代微电子工业对相关材料的性能要求、标准型聚酰亚胺材料所面临的挑战以及新型含氟聚酰亚胺在微电子工业中的应用等几个方面进行了详细的综述。重点阐述了中国科学院化学研究所305组近几年在这方面的研究进展情况。并指出为了推动我国微电子工业的发展，研制开发低成本、高技术含量的含氟聚酰亚胺材料具有十分重要的现实意义．     

化学法制备低介电常数聚酰亚胺的研究进展

随着微电子工业的快速发展,为了提高大规模集成电路中芯片间的传输速度以满足高集成化的要求,需要层间绝缘材料具有较低的介电常数。聚酰亚胺已被广泛用于大规模集成电路的层间绝缘材料,降低其介电常数的研究在近年来受到了广泛关注。当采用化学方法降低介电常数时,调控聚酰亚胺的分子结构是基础;在聚酰亚胺中构建多孔结构则是进一步降低介电常数的有效手段。本文从调控分子结构和构建多孔结构的角度出发,综述了化学法制备低介电常数聚酰亚胺的研究进展,并对低介电常数聚酰亚胺的研究前景进行了展望。     

耐高温聚酰亚胺泡沫材料

聚酰亚胺泡沫具有低介电、隔热、吸声、高比强度以及高经济效益等诸多优点,因而近些年来在航空、航天、船舶航舰、能源与环境保护等领域有着广泛的应用。聚酰亚胺泡沫按照泡孔结构分为软质开孔泡沫和硬质闭孔泡沫两大类,其通常是由芳香族二酐与芳香族二胺通过缩聚反应制备得到分子量可控的聚酯铵盐,再将其作为前驱体经过热发泡制备得到最终的聚酰亚胺泡沫。前驱体的化学结构对最终的聚酰亚胺泡沫的机械性能和热性能都有非常显著的影响,同时前驱体的分子量也会对泡沫的密度、机械性能和热性能有非常显著的影响。聚酰亚胺泡沫的研究进展,特别是其化学结构、性能和应用都会在本文中逐一阐述。     

新的离子型光敏聚酰亚胺

新的离子型光敏聚酰亚胺侯豪情李悦生丁孟贤＊（中国科学院长春应用化学研究所，中国科学院－中国石化总公司高分子化学联合开放实验室长春１３００２２）关键词光敏聚酰亚胺，制备，光刻胶１９９７－０７－１７收稿，１９９７－１２－１８修回吉林省重点科技发展项目离子...     

苯乙炔基封端聚酰亚胺材料研究进展

在过去二十年中，芳香族聚酰亚胺材料得到越来越广泛的应用，其中苯乙炔基封端的聚酰亚胺材料因其优异的性能成为目前耐高温聚合物材料研究的热点。本文综述了苯乙炔基封端聚酰亚胺材料的研究现状与发展趋势，着重对材料的化学结构设计与制备方法、以及化学结构与性能之间的关系进行介绍。     

New Photosensitive High Temperature Polymers for Electronic Applications

A new photosensitive high temperature polymer stable up to 500%deg;C with high photosensitivity and high resolution has been developed. The trend toward a high degree of integration in solid-state technology requires the use of new high temperature photosensitive insulating materials. Toray's Photoneece system provides such versatile polyimide pattern-generation techniques, containing a unique photosensitive polyimide precursor which can be spun or coated on the substrate. The resultant relief of photosensitive polyimide precursor, after exposure to UV light with a mask, development, and cure processing, is transformed into a cyclized aromatic polyimide. The new system has higher photosensitivity and resolution and eliminates three steps in the conventional pattern-making process for integrated circuits, resulting in a significant cost reduction. The characterization of pattern generation, the conversion to polyimide patterns, and the properties of both Photoneece and the patterns are discussed.     

PHOTOSENSITIVE POLYIMIDES

The polyimides are known for their practical usage as passivation or insulation in the microelectronics industry. They have excellent properties such as chemical and mechanical resistance, good insulation and planarizability. Photosensitive polyimides have significantly enhances the development in microelectronics devices, since they offer the simplification of polyimide layer pattern generation by eliminating the need for a photoresist. The present review comprises the examples as model as more tractable, soluble in organic solvent and easily processable polyimides without the loss of thermal stability. Present review article deals with the synthesis, characterization and applications of photosensitive polyimides which has been cited in the literature for the past two decades.     

Recent advances in photosensitive polyimides

The state of the art of photosensitive polyimides is reviewed with respect to the incorporation of photosensitivity into both polyimide precursors and soluble polyimides, for patterning in positive and negative modes. This paper emphasizes, in particular, the discussion of the performance of commercially available photosensitive polyimides with respect to their applications in electronics. The decisive properties, especially the patterning performance, and in the case of precursors the curing conditions, required to obtain full imidization, thermomechanical and electrical properties, solvent resistance and water uptake, as well as planarization of the commercially available materials, are compared with each other. An outlook presents the future demands on photosensitive polyimides.     

Self-Supporting Polymer Films for MEMS Applications

Summary: The fabrication of a self supporting novolac-based photoresist layer is demonstrated. A technology is presented using a sacrificial layer of PMMA and a carrier layer of photosensitive PI. The solely use of polymers for the creation of a self-supporting structure is distinguished by simple processing and relatively low cost materials. Additionally the mechanical stability of the self-supporting layer is under consideration. Finally the cross-linking process of the novolac-based photoresist by curing is discussed using FTIR, DSC and TGA measurements.     

Preparation and properties of conductive silver/photosensitive polyimide nanocomposites

A new electrically conductive photoresist has been developed. It is based on the dispersion of silver nanoflakes in a negative‐tone photosensitive polyimide (PSPI) precursor. 2‐Mercaptopropionic acid was used as the surfactant to modify the silver nanoflake surface for the dispersion of silver nanoflakes in the polymer. The silver/PSPI nanocomposites showed electrical conductivity at a low silver content of 10 wt %. The electrical conductivity of the silver/PSPI nanocomposites ranged from 10 to 10⁴ S/cm, which was dependent on the silver weight fraction in the resist formulation. Patterns with a resolution of 30 μm were obtained from the silver/PSPI nanocomposites. The silver/PSPI nanocomposites had excellent thermal properties. Their glass transition temperatures were above 360 °C and thermal decomposition temperatures were over 420 °C. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1575–1583, 2009     

可紫外光固化聚酰亚胺的设计制备及性能研究

以含酚羟基的2,2-双(3-氨基-4-羟基苯基)六氟丙烷(6FAP)作为接枝光敏单元的载体,以刚性苯并咪唑单元赋予材料良好的力学性能,设计合成了一种具有紫外光固化能力的可溶性聚酰亚胺.系统探究了光源距离、光源电流通量、光引发剂种类和含量、活性稀释剂种类等对固化成型过程的影响,确定了光固化聚酰亚胺的组成配方及工艺条件(光源距离为10 cm、电流通量为100%、双(2,4,6-三甲基苯甲酰基)-苯基氧化膦(Irgacure 819)含量为3 wt%、活性稀释剂1-乙烯基-2-吡咯烷酮(NVP)为20 wt%),并对光固化薄膜的基本性能进行了分析.光固化薄膜的拉伸强度达到123 MPa,固化树脂在5%(Td5)和10%(Td10)热失重时的温度分别为410和487℃,且具有较低的润湿性和吸水性.研究结果可为开发新型光敏性聚酰亚胺提供研究基础.     

一种可以正负互用的水型化学增幅抗蚀剂的研究

研究了一种由甲酚醛树脂、六甲氧基甲基三聚氰胺(HMMM)、六氟磷酸根二苯碘盐和光敏剂组成的水型紫外化学增幅抗蚀剂,发现二苯基碘盐不仅可以作为光敏产酸物,而且可以作为阻溶剂.用碘盐作为光敏产酸物,光解产生的酸可以在中烘时催化甲酚醛树脂与HMMM的交联反应;用氢氧化钠-乙醇水溶液显影可以得到负性光刻图形;采用碘盐作为阻溶剂,可阻止非曝光区的胶膜溶解在显影液中,用稀的氢氧化钠水溶液显影可以得到正性光刻图形.通过优化后的光刻工艺条件,采用不同的显影液和光刻工艺流程,实现了同一光致抗蚀剂的正负性反转,并分别得到负性和正性光刻图形.     

Photosensitive polyimides for applications in electrical and optical interconnection technology

The application of photosensitive polyimides in electrical and optical interconnection technology is discussed. Critical properties of two photosensitive polyimide formulations with significantly different structural chemistries have been compared. Polyamic ester based formulations such as Selectilux® HTR3 show significant distortions in the photopatterned features upon high-temperature baking, which can be ascribed to anisotropic shrinkage. A BTDA-alkylated diamine based preimidized formulation (Probimide®), on the other hand, shows a more uniform shrinkage of the photopatterned features. HTR3 films interacts strongly with metals such as copper, which adversely affect the photopatternability of these materials. Planarization behavior in multiple layer structures has also been investigated. We explored the viability of these materials for applications in optical interconnection. Probimide® materials exhibit low scattering losses and appear to be promising candidates for the development of a MCM-compatible optical interconnection technology. We also describe here a novel technique for optical recording of refractive index patterns in Probimide® films.     

Synthesis of New Functional Silicon-Based Condensation Polymers

A new class of photosensitive aromatic polymers containing disilane units was successfully synthesized from new disilane-based monomers such as 1,2-bis(diethylamino)tetramethyldisilane and 1,2-bis(p-aminophenyl)tetrarnethyldisilane. The disilane-contain-ing aramids and polyimides had glass transition temperatures above 190°C, and all the polymers were thermally stable up to 300°C in air. The polymers were photosensitive; their molecular weight decreased rapidly upon ultraviolet light irradiation. The photosensitive polymers, especially the soluble polyimides having diphenyl sulfone units, were potential candidates for positive working photoresist materials. New highly branched polysiloxane star-burst polymers were synthesized by a siloxane synthetic reaction starting from tris[(phenyldimethylsiloxy)dimethylsiloxy]methylsilane and bis[(phenyldimethylsiloxy)methylsiloxy]dimethylsilanol as the initial core (G0-Ph) and the building block, respectively. Thus, the first generation polymer G1-Ph, second generation polymer G2-Ph, and third generation polymer G3-Ph had 6, 12, and 24 phenylsilyl groups in their exterior layers. The formation of the siloxane-based starburst polymers were confirmed by means of ¹H-, ¹³C-, and ²⁹Si-NMR spectroscopy. These polysiloxane starburst polymers were suggested to have spherical structure. Some functionalized starburst polymers were further synthesized by the introduction of functional groups in their exterior layers. New silica-polyimide hybrid materials were prepared by the sol-gel process through the hydrolysis-condensation reactions of tetraethoxysilane in the presence of the polyamic acid (polyimide precursor) in dimethylacetamide, followed by heating at 270°C. The hybrid system having silica content up to 70 wt% had good quality films. The spherical silica particles were dispersed homogeneously in the polyimide matrix. With increasing silica content, the glass transition temperature and decomposition temperature, as well as the modulus of the hybrid films, increased, while the coefficient of thermal expansion decreased.