【作者】 刘建国；

【导师】 郑家燊； 李平；

【作者基本信息】 华中科技大学 ， 材料学， 2007， 博士

【摘要】 光刻胶是完成微电子制造光刻工艺的关键性基础材料,它决定着微电子技术的发展水平。光刻胶通常由成膜树脂、感光剂、溶剂和一些添加剂组成。在光刻胶的研制方面,我国与国外相比,还有比较大的差距。本文采用新的方法,合成出了一系列光刻胶成膜树脂的单体,包括:N-苯基甲基丙烯酰胺、N-(p-羟基苯基)甲基丙烯酰胺、N-(p-乙酰氧基苯基)甲基丙烯酰胺、对特丁氧酰氧基苯乙烯(PTBOCS)、N-羟基-5-降冰片烯-2,3-二甲酰亚胺甲基丙烯酸酯和N-羟基-3,6-内氧桥-4-环己烯二甲酰亚胺甲基丙烯酸酯;并对它们进行了FT-IR和1H NMR表征。制备了两种常用的248nm深紫外光刻胶用光致酸发生剂(PAG)对甲基苯磺酸三苯基硫鎓盐和N-羟基邻苯二甲酰亚胺对甲基苯磺酸酯,对它们进行了FT-IR和1H NMR表征,测试了它们的热性能、紫外光吸收性能和溶解性能。结果表明它们适合作深紫外光刻胶的PAG。通过自由基聚合的方法,采用苯乙烯和前面制备的单体合成了三种聚合物:聚苯乙烯共N-(p-羟基苯基)马来酰亚胺,聚N-(p-羟基苯基)甲基丙烯酰胺共N-苯基马来酰亚胺和聚N-苯基甲基丙烯酰胺共N-(p-羟基苯基)马来酰亚胺。测试了它们的相关性能。结果表明它们的玻璃化温度Tg均在250℃以上,具有良好的耐高温性能、溶解性能、成膜性能和亲水性,可以用作耐高温紫外正型光刻胶的成膜树脂。利用前面已经合成的单体PTBOCS和N-羟基-3,6-内氧桥-4-环己烯二甲酰亚胺甲基丙烯酸酯,制备了新的聚合物聚PTBOCS共N-羟基-3,6-内氧桥-4-环己烯二甲酰亚胺甲基丙烯酸酯,对它进行了FT-IR表征,测试了它的热性能和紫外吸收性能;结果表明,该聚合物具有良好的耐热性能(Tg=175℃)、248nm深紫外光透光性能、溶解性能和成膜性能,并且与基体有良好的结合力,适合作248nm深紫外光刻胶的成膜树脂。而另外一种新的聚合物聚PTBOCS共N-羟基-5-降冰片烯-2,3-二甲酰亚胺甲基丙烯酸酯因其溶解性不好,不适合作光刻胶的成膜树脂。首次将聚N-(p-羟基苯基)甲基丙烯酰胺共N-苯基马来酰亚胺和聚N-苯基甲基丙烯酰胺共N-(p-羟基苯基)马来酰亚胺用作耐高温的紫外正型光刻胶的成膜树脂;通过与感光剂重氮奈醌磺酰氯(DNS)和阻溶剂二苯甲酮复配,较详细地探讨了聚N-(p-羟基苯基)甲基丙烯酰胺共N-苯基马来酰亚胺—DNS系紫外正型光刻胶的配方组成和与之配套的光刻工艺条件,表明它的成像反差γ=3.001,它的等离子蚀刻速率可以与线形酚醛树脂—重氮萘醌(DNQ)系紫外光刻胶的相比,它的分辨率可以达到1μm左右。开发了一种新的248nm深紫外单层光刻胶体系,成膜树脂采用聚PTBOCS共N-羟基-3,6-内氧桥-4-环己烯二甲酰亚胺甲基丙烯酸酯,PAG采用对甲基苯磺酸三苯基硫鎓盐,阻溶剂为(4,4’-二特丁氧酰氧基)二苯基丙烷,溶剂采用1:1(v/v)的乙二醇单甲醚乙酸酯(EGMEA)和乳酸乙酯(EL)的混合液,显影液为2.38%(w/w)氢氧化四甲基铵(TMAH)溶液。探讨了该系光刻胶的配方组成和与之配套的光刻工艺条件,结果表明这是一种环境稳定的化学增幅型深紫外光刻胶。它的抗蚀刻能力与线性酚醛树脂—DNQ系光刻胶的基本相同,初步的光刻实验表明,它的分辨率至少在0.5μm左右,它的感光灵敏度为22mJ/cm2。分别探讨了耐高温紫外正型光刻胶聚N-(p-羟基苯基)甲基丙烯酰胺共N-苯基马来酰亚胺—DNS系和248nm深紫外光刻胶聚PTBOCS共N-羟基-3,6-内氧桥-4-环己烯二甲酰亚胺甲基丙烯酸酯—对甲基苯磺酸三苯基硫鎓盐体系的显影成像机理。更多还原

【Abstract】 Photoresist is a key and foundmental material for the photolithographic technique in the microelectronics manufacturing system. It defines the development level of microelectronics technique. As a rule, photoresist is composed of matrix resin, photosensitizer (photoactive compound), solvent and other additives. At the present time, the research and development of photoresist in China is much behind the internationally leading level.By using novel methods, a series of monomers for the matrix resins of photoresist were synthesized, including N-phenyl-methacrylamide, N-(p-hydroxyphenyl) methacrylamide, N-(p-acetoxyphenyl)methacrylamide, p-tert-butoxycarbonyloxystyrene (PTBOCS), N-hydroxy-5-norbornene-2,3-dicarboximidomethacrylate and N-hydroxy-3,6- endo-oxo-4-cyclohexene-dicarboximidomethacrylate. Their FT-IR and 1H NMR spectra were measured for characterization.Two common photoacid generators(PAGs) triphenylsulfonoum tosylate and N-hydroxyphthalimidotosylate were prepared. They were characterized by FT-IR and 1H NMR, and tested by thermal property, UV absorbance and solubility. It showed that they could be used as the PAGs of deep-UV photoresist.Three copolymers were obtained from the solution free radical copolymerization of the above monomers and comonomer styrene, i.e. poly-styrene-co-N-(p-hydroxy phenyl)maleimide, poly-N-(p-hydroxyphenyl)methacrylamide-co-N-phenylmaleimide and poly-N-phenylmethacrylamide-co-N-(p-hydroxyphenyl)maleimide. The investigations of their properties showed that all of them had high glass transition temperatures(Tg>250℃), good solubilities, film forming characteristics and hydrophilicities, so they could be used as the matrix resins of high thermostability UV positive photoresist.A new copolymer poly-PTBOCS-co-N-hydroxy-5-norbornene-2,3-dicarboximido methacrylate was prepared from the above monomers PTBOCS and N-hydroxy-5- norbornene-2,3-dicarboximidomethacrylate. Its FT-IR spectrum, thermal property and UV transmittance were determined. A conclusion could be drawn that it had excellent solubility, film forming characteristic, thermostability(Tg=175℃),UV transmittance in 248nm wavelength and adhesiveness to the wafer substrates, so it could be a good matrix resin of deep-UV photoresist. But another new polymer poly-PTBOCS-co- N-hydroxy-5-norbornene-2,3-dicarboximidomethacrylate had poor solubility in organic solvent, so it was unfit for the matrix resin of deep-UV photoresist.For the first time, poly-N-(p-hydroxyphenyl)methacrylamide-co-N-phenyl maleimide and poly-N-penylmethacrylamide-co-N-(p-hydroxyphenyl)maleimide were used as the matrix resins of the high thermostability UV positive photoresist. The optimal formulation and photolithographic processing conditions of a new UV positive photoresist, which was a mixture of poly-N-(p-hydroxyphenyl)methacrylamide-co-N–phenylmaleimide, diazonaphthoquinone sulfochloride(DNS), benzophenone and solvent, were studied in detail. It was found that its imaging contrast was 3.001, its resolution was up to about 1μm and its plasma etching resistance was comparable to that of the novolak-diazonaphthoquinone(DNQ) system UV photoresist.A new single-layer 248nm deep-UV photoresist system was developed, whose matrix resin was the above poly-PTBOCS-co-N-hydroxy-3,6-endo-oxo-4-cyclohexene- dicarboximidomethacrylate, PAG was triphenylsulfonium tosylate, dissolution inhibitor was (4,4’-di-tert-butoxycarbonyloxy)diphenylpropane, solvent was 1:1(v/v) ethylene glycol monomethyl ether acetate(EGMEA) and ethyl lactate(EL), and developer was 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution. Its optimal formulation and photolithographic processing conditions were explored. It showed that it was an environmentally stable chemically amplified photoresist(ESCAP), and it had the resolution of no less than 0.5μm, the plasma etching resistance comparable to that of the novolak-DNQ system photoresist, and the sensitivity of 22mJ/cm2.The development imaging mechanisms were simply explored for the high thermostability UV positive photoresist of poly-N-(p-hydroxyphenyl)methacrylamide -co-N-phenylmaleimid-DNS system and the 248nm deep-UV photoresist of poly-PTBOCS-co-N-hydroxy-3,6-endo-oxo-4-cyclohexene-dicarboximidomethacrylate-triphenylsulfonium tosylate system.更多还原