新型阻溶促溶酚树脂用于热敏CTP版的性能研究

使酚树脂与乙烯基醚发生反应,合成出一种新型醚化物,作为新型阻溶促溶剂.将它与产酸剂、背景染料、红外染料、成膜树脂、其它助剂及有机溶剂作为热敏CTP组合物.研究了该热敏CTP组合物的化学性能和热敏成像性能,发现在热敏CTP组合物中适量的新型阻溶促溶剂能够使热敏CTP版的热敏性、显影性、抗碱性及耐异丙醇性都得到了较大的改善.     

酸酐改性PVA树脂用于阴图PS版成膜树脂的性能研究

聚乙烯醇(PVA)首先与丁醛进行缩醛反应,再与酸酐进行酯化反应合成了酸酐改性PVA树脂.将此树脂与进口重氮树脂、染料和有机溶剂以一定比例混合形成了阴图PS版感光胶.本文研究了B/P以及酸酐改性PVA树脂的分子量、缩醛度、酯化度等因素对阴图PS版成像性能的影响.结果表明酸酐改性PVA树脂对阴图PS版的显影性能,亲油墨性和耐磨性都起关键作用,对阴图PS版的感度和保存稳定性也有一定影响.因此其分子量、酯化度和缩醛度的确定,必须综合考虑各项性能之间的平衡.缩醛度为60-80 mol%,酯化度10-15mol%,羟基5-25 mol%,分子量约为4-8万,B/P为4-4.5时,制得的阴图PS版的感度、显影性、着墨性和耐磨性都较好.     

光/热成像用活性醚化物阻溶/促溶剂的分子设计

本文提供了低分子量酚类化合物与乙烯基烷基醚合成醚化率百分之百的高酸解活性醚化物(以下简称活性醚化物)的一般合成方法,并对其合成条件的优选进行了讨论.建立了原料酚类化合物与成像性能密切相关的参数,如羟当量,临界碱水不可溶羟当量,临界碱水可溶羟当量,表征原料酚类化合物阻溶、促溶能力比的M_P/A值,按照成像要求所设定的碱水易溶、碱水可溶、碱水微溶、碱水不溶(难溶)的AS_TW参数.测定或推算出活性醚化物的平均醚当量、与分子量相关的校正醚当量、活性醚化物的M_E/A_E值以及M_E/A_E值与M_P/A值的比值(即DL值)等多项参数.围绕上述参数的建立,提出了一些经验计算公式,根据所建立的参数值以及多年来从事光/热成像实验的实践,提出了光/热成像用活性醚化物分子设计的有关规则.     

水溶性负性光致抗蚀剂的研制

以自制丙烯酰胺-双丙酮丙烯酰胺共聚物和聚乙烯吡咯烷酮(PVP)为成膜基体物质,芳香族叠氮化合物为感光剂,研制出水溶性负性光致抗蚀剂配方.通过正交试验确定了最优配方.即共聚物中AM与DAAM质量比为1:1;P(AM-DAAM)与PVP质量比为1:2;感光剂用量为占成膜基体物质质量的1/6;偶联剂用量占成膜基体物质质量的1/60;表面活性剂G-18用量占成膜基体物质质量的1/40.在该配方下配制的光致抗蚀剂达到商品规格要求.通过与国外同类商品的比较得出自制光致抗蚀剂具有同国外商品相当的感光性能.     

免处理型CTP版材研究进展

根据1999-2002年公开的专利,评述了这几年间免处理CTP版材研制开发的内容:1)水处理型;2)附加型;3)形态变化性;4)相变化型.免处理版材被认为是今后CTP版材,尤其是热敏CTP版材发展的方向.但免处理版材若想在实际中推广应用,还有许多问题需待研究解决.     

一种高感度深紫外正性化学增幅型抗蚀剂的制备

聚对羟基苯乙烯和环己基乙烯基醚反应得到缩醛保护的聚合物.该聚合物易溶于常见的有机溶剂,具有较好的热稳定性,在248 nm处透明性良好.该聚合物可与聚对羟基苯乙烯-甲基丙烯酸金刚烷基酯及二砜光产酸剂等组成一种三组分正性化学增幅型深紫外光致抗蚀剂,初步研究了该抗蚀剂的感光成像性能.采用KrF激光（248 nm）曝光,在较低的后烘温度下,显影得到分辨率为180 nm的线条图形.显影后的留膜率在99%以上.在光致抗蚀剂体系中引入对羟基苯乙烯-金刚烷基甲基丙烯酸酯共聚物,可提高光刻胶材料的玻璃化转变温度,有利于其实际应用.     

成膜树脂对重氮萘醌体系正性光致抗蚀材料性能的影响

多数的重氮萘醌体系正性光致抗蚀材料(以下简称抗蚀材料)都是用线性酚醛树脂作为成膜组分,用重氮萘醌的酯化产物作为感光性组分的光分解型感光材料.这种材料以其高反差的成像性能广泛地应用于电子、印刷及精密加工等各个领域中.常用的光致抗蚀剂及平版印刷的PS版材大多用的是这种材料.也像其他的各种银盐体系或非银盐体系的感光材料一样,抗蚀材料的各种成像性能或物理性能之间同样存在着相互影响、相互制约的关系.     

纳米氮化硅在提高PS版耐磨性中的应用研究

测试了纳米氮化硅可以使阳图PS版耐磨性提高30%,对感光度和分辨率没有影响.将<20nm氮化硅(0.0%—2.0%质量分数)超声波分散在混合溶剂中,再依次投入成膜树脂和光敏剂配制成感光胶,经离心涂布在(砂目Ra=0.65)铝版基上干燥后,晒版,显影,磨版.由反射密度的损失量评定印版耐磨性,由扫描电镜观察氮化硅纳米粒子在版面的状态.氮化硅质量分数为0.15%时耐印效果最好,大于2.0%时由SEM观察到团聚现象,印刷力下降.     

含碘鎓盐光产酸剂和增感染料的化学增幅型i-线正性光致抗蚀剂

4,4’-二甲苯基三氟甲磺酸碘鎓盐可以被染料增感,在365 nm光照时分解产酸.尽管产生的酸与染料的胺基发生作用,依然能在后烘过程中催化缩醛聚合物酸敏基团的分解,但需要稍高的后烘温度和稍长的后烘时间.基于此,本文将酚醛树脂、缩醛聚合物、碘鎓盐产酸剂和染料组成了一种新型的化学增幅型i-线正性光致抗蚀剂材料,在曝光量为10...     

几类醚化物的水溶性、碱水溶解性和酸解活性

本文对几类典型醚类化合物的水溶性、碱水(5%的Na₂SiO₃·9H₂O)溶解性和酸解活性进行了初步研究,查阅了这些醚类化合物的水溶性,并测定了其碱水溶解性、临界碱水不可溶醚当量以及在微量酸存在条件下的酸解活性,研究结果表明,对一般醚类化合物而言,当醚键中不含p-π共轭时其临界水不溶醚当量为116,临界碱水不溶醚当量为102;当醚键中含p-π共轭时其临界水不溶醚当量在56-100之间,临界碱水不溶醚当量在56-72之间,这些数据对光/热成像用活性醚化物阻溶/促溶剂的分子设计以及碱显影成像制版具有重大的指导意义。     

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.     

Novel vinyl ether functionalized fluorene polymers for active incorporation into common photoresist matrices

A novel vinyl ether functionalized fluorene monomer was prepared to produce a series of fluorene-based polymers with different emitter units to cover emission in the visible spectrum whilst retaining the same main absorption profile. The vinyl ether functionality allows for active incorporation of the light emitting polymers into standard vinyl ether and glycidyl ether photoresist materials. This enables photopatterning of light emitting structures for application in UV down-conversion, waveguiding and for lasing media.     

Thermal and acid-catalyzed reaction of bifunctional vinyl ether urethane in nonionic and ionic polymer matrices

A bifunctional vinyl ether urethane derivative (BVU) was synthesized and characterzed. Photoresist systems consisting of BVU and a photoacid generator (PAG) along with various matrix polymers were prepared and the photoresist characteristics were evaluated. In the presence of BVU and a PAG, poly(methylmethacrylate-co-acrylic acid) and poly(methylmethacrylate) exhibited positive and negative tone behavior, respectively, where as poly(p-hydroxystyrene) showed both positive and negative working properties depending on the prebake temperature of the system. The depandence of the photoresist behaviors on these matrix polymers was studied. The mechanism of the thermal and photochemical reactions was revealed.     

New synthetic route for photosensitive poly(benzoxazole)

A new positive working photosensitive poly(benzoxazole) (PBO) precursor based on poly(o‐hydroxyazomethine) ( 3 ) and 1‐{1,1‐bis[4‐(2‐diazo‐1‐(2H)naphthalenone‐5‐sulfonyloxy)phenyl]ethyl}‐4‐{1‐[4‐(2‐diazo‐1(2H)naphthalenone‐5‐sulfonyloxy)phenyl]methylethyl}benzene (S‐DNQ) as a photosensitive compound was developed. 3 was prepared by the condensation of 2,2‐bis(3‐amino‐4‐hydroxyphenyl)hexafluoropropane with isophthalaldehyde in 1‐methyl‐2‐pyrrolidinone/toluene under azeotropic conditions. The photosensitive PBO precursor containing 30 wt % S‐DNQ showed a sensitivity of 120 mJ cm^?2 and a contrast of 2.2 when it was exposed to 436‐nm light and developed with a 2.38 wt % aqueous tetramethylammonium hydroxide solution at room temperature. A fine positive image featuring 10‐μm line and space patterns was observed on the film of the photoresist exposed to 200 mJ cm^?2 ultraviolet light at 436 nm by the contact mode. The positive image was successfully converted into the PBO pattern by a thermal treatment. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3399–3405, 2002     

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。     

二苯基碘鎓盐引发乙烯基醚热聚合研究

合成了一种液态聚氨酯乙烯基醚预聚物 (PUE)并对其进行了表征 .研究发现二苯基碘六氟磷酸盐(PI810 )能够引发PUE和三缩乙二醇二乙烯基醚 (DVE 3)进行阳离子热聚合 ,热聚合温度远低于PI810的纯态热分解温度 ,且聚合转化率较高 .热聚合的机理初步认为是电子转移机理 .研究了乙烯基醚化合物、环氧树脂、二苯基碘六氟磷酸盐混合体系的热聚合 .     

甲酚醛树脂—HMMM负性水型化学增幅抗蚀剂的研究

本文利用二苯碘 盐为光敏产酸物,吩噻嗪为敏化剂,配制了一种甲酚醛树脂——六甲氧基甲基三聚氰胺(HMMM)负性水型紫外化学增抗蚀剂,并研究了光敏产酸物和增感剂对体系光敏性的影响及体系中存在的拉平效应,通过优化后的光刻工艺条件得到了分辨率为1.24μm的光刻图形。     

Novel synthesis of photocrosslinkable polymers

A new preparative route to photocrosslinkable polymers in which the polymers are produced directly from the polymerization of vinyl monomers having photocrosslinkable groups has been investigated. The photosensitive resins thus produced have higher sensitivity and resolution than conventional photosensitive resins. The monomers were synthesized from the esterification of vinylphenols or vinyl β-chloroethyl ether with cinnamic acid, β-styrylacrylic acid, and their homologs, and from the etherification of vinyl β-chloroethyl ether with hydroxychalcones. Homopolymerizations of these monomers and their copolymerizations with other comonomers were investigated with the use of both radical and ionic initiators. It is shown that radical polymerization of the monomers gave soluble polymers only at low conversion. Anionic initiators did not initiate polymerization. Cationic polymerization imparted soluble polymers in high yield, except for the monomers bearing cyano groups, which generally gave insoluble polymers. Infrared and NMR spectroscopic investigation of the cationically obtained soluble polymers and comparative investigation by cationic polymerization of model compounds indicated that polymerization of the monomers proceeds through the vinyl double bond without affecting the photosensitive unsaturated bond. Thus, linear photocrosslinkable polymers with an intact photoreactive group may be produced by cationic polymerization. In general, these polymers have uniform structure and modifiable physical properties depending on the monomer used. The polymer thus obtained from β-vinyloxyethyl cinnamate has been shown to have excellent properties for use as a photo-resist.