负性光敏聚酰亚胺材料研究进展

芳香族聚酰亚胺具有优异的绝缘性、热稳定性、介电性能、机械性能以及化学稳定性,可在微电子工业中用作绝缘和保护材料。负性光敏聚酰亚胺具有芳香族聚酰亚胺的优点,同时也具有感光性,使得微电子加工过程中减少对光刻胶的依赖,简化图案形成的工艺,有力促进了生产效率。本文综述了负性光敏聚酰亚胺的发展,重点介绍聚酰亚胺光刻胶体系的原理及近期研究进展,并对负性光敏聚酰亚胺的发展给予展望。     

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...     

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。     

新型光敏聚酰亚胺/SiO2杂化材料的制备与性能研究

通过溶胶－凝胶法制备了一种新型的光敏聚酰亚胺／二氧化硅杂化材料。研究表明当ＳｉＯ２的含量≤１０ｗｔ％时杂化材料除了保持光敏聚酰亚胺原有的感光性能外其热稳定性能、力学性能以及与基底的粘附性能均有明显地提高,同时材料的热膨胀系数也显著地降低。     

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].     

主链含有机硅结构单元的光敏聚酰亚胺的研究

提出了一类主链上含有机硅结构单元的光敏聚酰亚胺（ＰＳＰＩ）。其合成过程是首先制备聚酰胺酸预聚体，接着在二环己基碳二酰亚胺存在下，使之转变为聚硅氧酰亚胺，然后引入光敏基团。通过ＩＲ、ＤＳＣ、元素分析、ＵＶ、介电分析方法对聚酰亚胺的结构、感光特性、热性能、电性能、粘附性、吸湿性能等进行了表征。对结构与性能之间的关系进行了初步探讨。     

3,3'-二氨基查尔酮的合成

3;3'-二氨基查尔酮的合成;光敏性二胺;查尔酮;聚酰亚胺;合成     

高灵敏度的酯型光敏聚酰亚胺

通过液－固逐步溶解缩聚的方法,合成了几种有较高分子量的光敏聚酰胺酸酯,并对它们的光刻性能进行了研究和讨论。其中,米赤酮或双叠氮对以联苯二酐间苯二胺残在为主的链结构的光敏ＰＩ前体的感光性能有最大的影响,由这种ＰＩ前体配制的光敏聚酰亚胺光刻胶具有最高的灵敏度。     

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.     

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.     

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.     

Polyimides for electronics applications

A variety of options exists for lithographically defining polyimides for microelectronics applications. The two investigated here, photosensitive polyimide and wet etching of low-stress polyimides, offer lower cost, higher throughput solutions compared with dry etch processes. Via sizes of less than 25 μm and film thicknesses of greater than 14 μm are difficult to process using these techniques: however, for applications such as interlayer dielectrics for high-density packaging or solder masks for flip chip die attachment, these limitations may not be insurmountable. Photosensitive polyimide can be patterned with fewer steps, but the overall quality of the film in terms of surface planarity and residual stress is not as good as wet etching of conventional polyimide.     

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.     

Preparation and application of photosensitive copolymers for PDP barrier ribs formed by photolithography

In this work, the photosensitive paste was prepared. It was comprised of inorganic particles and a photosensitive organic component. The inorganic particles included glass, ceramics, and metals. The organic component should contain at least the following photosensitive materials: photosensitive monomers, photoreactive copolymer and photopolymerization initiators. The photoreactive copolymer played a role of an adhesive in the photosensitive paste. Meanwhile in the development stage, the carboxyl groups of the copolymer reacted with the alkalescent developer. Following this, the unexposed part must be removed and an excellent pattern can be formed. A series of three-component acrylic copolymers (MAA/St/MMA) were designed, and then synthesized via free radical polymerization. Subsequently glycidyl methacrylate (GMA) was employed to modify the prepared copolymers through ring-opening reactions between the carboxyl groups and the epoxide groups. Eventually the photosensitive copolymers were obtained and used to form the barrier ribs of PDPs. The chemical structure, glass transition temperature, acid value and molecular weight of photosensitive copolymers had different effects on the structure and pattern of PDP barrier ribs. Through analyzing effects of different polymer performance parameters on the patterns of barrier ribs, the optimal photosensitive copolymer was acquired.     

A mechanism for the electron beam lithography of solvent-soluble photosensitive polyimides

Solvent-soluble and intrinsically photosensitive polyimides were prepared, and their electron beam reaction was investigated. Negative tone patterns were formed by the electron beam irradiation of PI(BTDA/DEDPM) and PI(BEDA/DEDPM). The mechanism for the pattern formation of PI(BTDA/DEDPM) was determined from transient absorption measurements, changes in the molecular weights, and IR spectrum measurements to be crosslinking via hydrogen abstraction by the triplet excited state benzophenone moiety. For the case of PI(BEDA/DEDPM), the pattern was formed by insolubilization due to chemical change in the polymer. These reactions are found to be so inhomogeneous that insolubilization of the polymer occurs at an early stage of gelation.     

Polyimides with alicyclic diamines. II. Hydrogen abstraction and photocrosslinking reactions of benzophenone-type polyimides

Photosensitive polyimides with alicyclic diamines and benzophenone moiety were prepared by reactions of 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) with diamines in aprotic solvents, followed by thermal or chemical imidizations. Among them the polyimide from BTDA and bis(4-amino-3-methylcyclohexyl) methane (DMDHM) can be dissolved in several organic solvents such as dichloromethane, tetrachloroethane, and N-methyl-2-pyrrolidone (NMP). In order to compare properties of the polyimides with alicyclic diamines with those of corresponding aromatic polyimides, the UV absorption spectra and fluorescence spectra of these polyimides and their model compounds were investigated. No occurrence of charge transfer at photoexcited states was ascertained for the polyimides with alicyclic diamines. The hydrogen abstraction and crosslinking during photoirradiation have been studied to learn the influence of the elimination of charge transfer process in these photosensitive polyimides. The quantum yield of hydrogen abstraction for the model compound of alicyclic polyimides is 0.56 in THF measured with HPLC. The quantum yield for the photocrosslinking reaction of the solvent-soluble polyimide with alicyclic diamine, PI(BTDA/DMDHM), was determined to be 0.004 in air from gel permeation chromatography (GPC) measurement, which is four times higher than that for photosensitive polyimides with aromatic diamines. © 1994 John Wiley & Sons, Inc.     

Preparation and properties of new photosensitive polyimides from bis(4-aminophenyl)tetramethyldisilane and various aromatic tetracarboxylic dianhydrides

New photosensitive polymides containing photosensitive disilane unit were synthesised from 1,2-bis(4-aminophenyl)tetramethyldisilane and various aromatic tetracarboxylic dianhydrides by the usual two-step procedure that includes ring-opening polyaddition to yield the precursor polyamic acids, followed by cyclodehydration giving the respective polyimides. The polymaic acids had inherent viscosities between 0.63 and 0.85 dL/g depending on the tetracarboxylic dianhydride used. Excepting the polyimide obtained from pyromellitic dianhydride, all other polyimides were soluble in N-methyl-2-pyrrolidone, m-cresol, and pyridine. While the polyimide containing diphenyl sulfone unit was amorphous, the other polyimides were semi-crystalline polymers based on their x-ray diffractograms. The polyimides had glass transition temperatures between 235 and 304°C. They were thermally stable up to 380°C in both air and nitrogen atmospheres. All the polyamic acids showed a drastic decrease in the inherent viscosity upon UV light irradiation, implying the inherent photosensitivity of the polymers containing the disilane moiety.     

Synthesis and characterization of photosensitive polyimides

All aromatic polyimides bearing diarylsulfide linkages in the main chain were prepared either by condensation of a sulfur containing dianhydride with an aromatic diamine or the condensation of a sulfur containing aromatic diamine with a dianhydride. Phenylation with diphenyl iodonium salts was then used to convert the diarylsulfide groups to triarylsulfonium salts. The resulting photosensitive polyimides were shown to undergo main chain cleavage during photolysis using UV irradiation. These new polyimides are candidates for positive working, high temperature photoresist materials.