光刻胶灰化工艺与深亚微米线条的制作

随着器件尺寸的缩小，细线条的制作成为很关键的工艺，普通光学光刻已接近其分辨率的极限，而电子束光刻和Ｘ射线光刻技术复杂、费用昂贵。本文对光刻胶灰化工艺进行了分析和研究，并应用此工艺进行了深亚微米线条的制作，在普通光学光刻机上制作出宽度小于０．２５μｍ细线条。我们已将此工艺成功地应用在深亚微米ＭＯＳＦＥＴ的制作中。     

Synthesis and characterization of novel copolymers with the trimethylsilyl group for deep‐UV photoresists

N‐(4‐Acetoxyphenyl) maleimide (APMI) and three kinds of comonomers bearing a trimethylsilyl group were copolymerized at 60°C in the presence of azobisisobutyronitrile (AIBN) as an initiator in 1,4‐dioxane to obtain the three IP, IIP, and IIIP copolymers. These copolymers were removed from the acetoxy group in a transesterification process into new IVP, VP, and VIP copolymers with a pendant hydroxyl group. Two modified processes were adopted to prepare photoresists using these copolymers. The first process involved mixing the dissolution inhibitor, o‐nitrobenzyl cholate, with the new copolymers. Second, o‐nitrobenzyl cholate was introduced into the copolymers using 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) in dimethylformamide (DMF). The cyclic maleimide structure is responsible for the high thermal stability of these copolymers. After irradiation using deep–UV light and development with aqueous Na₂CO₃ (0.01 wt %), the developed patterns showed positive images and exhibited good adhesion to the silicon wafer without using any adhesion promoter. The resolution of these resists was at least 0.8 μm and an oxygen‐plasma etching rate was 1/5.3 to that of hard‐baked HPR‐204. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2791–2798, 2002; DOI 10.1002/app.10255     

193nm光刻胶的研制

从主体树脂的结构设计、单体的合成工艺、主体树脂的合成工艺、光致产酸剂的评价、配方研究等多个方面论述了193nm光刻胶的研制工艺，合成出了多种适用的单体及多种结构的主体树脂，进行了大量的配方研究，筛选出了最佳配方．研制出的样品经美国SEMATECH实验室应用评价其最佳分辨率为0．1μm，最小曝光量为26mJ／cm^2，不但具有优异的分辨率和光敏性，而且还具有良好的粘附性和抗干法腐蚀性．     

Development of high‐definition aqueous polyvinylpyrrolidone photoresists for cathode ray tubes

Aqueous photoresists that are capable of higher resolutions than are currently employed by the cathode ray tube (CRT) industry were developed by combining photoactivators, which activate at shorter UV wavelengths with polyvinylpyrrolidone (PVP). Two photoactivators were synthesized: 4,4′‐diazido‐2,2′‐biphenyl disodium disulfonate (DABP), which has a maximum absorbance at 264 nm, and 4,4′‐diazido‐2,2′‐biphenylethane disodium disulfonate (DABPE), which has a maximum absorbance at 258 nm. The PVP/DABP and PVP/DABPE photoresists successfully imaged a pattern with resolution as small as 4.4 μm with photoactivator concentrations greater than 20% of the PVP concentration. Addition of silane and emulgen greatly improved the performance of the photoresists with more uniform coatings of thicknesses of up to 1.4 μm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1637–1644, 2006     

A water‐developable negative photoresist based on the photocrosslinking of N‐phenylamide groups with reduced environmental impact

A water‐developable negative photoresist based on the photocrosslinking of N‐phenylamide groups was prepared by the copolymerization of 4‐styrenesulfonic acid sodium salts (SSS) with N‐phenylmethacrylamide (copolymer A) or p‐hydroxy‐N‐phenylmethacrylamide (copolymer B), and its properties such as solubility changes, photochemical reaction, and photoresist characteristics were studied. The copolymer containing a relatively higher amount of SSS units was soluble in water. Solubility changes of the copolymers in the various buffer solutions of pH 4 ～ 11 and in water upon irradiation were observed by the measurement of insoluble fraction. The copolymers were soluble in water before irradiation, whereas they became insoluble upon irradiation with the UV light of 254 nm. The photochemical reaction of the copolymer studied by the UV and IR absorption spectroscopies indicated that a photo‐Fries rearrangement was favored for copolymer A, whereas a photocrosslinking reaction was predominate for copolymer B. Resist properties of the copolymers were studied by measurement of the normalized thickness and by development of the micropattern. Negative tone images with a resolution of 1 μm were obtained with these materials that have a sensitivity (D) of ～ 1100 mJ/cm² with an aqueous developing process.© 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1172–1180, 2002     

酸增殖源及其在化学增幅抗蚀剂体系中的应用

介绍了酸增殖机理、酸增殖源的种类、典型化合物在化学增幅抗蚀剂体系中的应用及对灵敏度的提高 ,提出在计算机直接制版版材研究中的应用     

Synthesis and characterization of a positive‐working,aqueous‐base‐developable photosensitive polyimide precursor

A positive‐working, aqueous‐base‐developable photosensitive polyimide precursor based on poly(amic ester)‐bearing phenolic hydroxyl groups and a diazonaphthoquinone photosensitive compound was developed. The poly(amic ester) was prepared from a direct polymerization of 2,2′‐bis‐(3‐amino‐4‐hydroxyphenyl)hexafluoropropane and bis(n‐butyl)ester of pyromellitic acid in the presence of phenylphosphonic dichloride as an activator. Subsequently, the thermal imidization of the poly(amic ester) precursor at 300°C produced the corresponding polyimide. The inherent viscosity of the precursor polymer was 0.23 dL/g. The cyclized polyimide showed a glass‐transition temperature at 356°C and a 5% weight loss at 474°C in nitrogen. The structures of the precursor polymer and the fully cyclized polymer were characterized by Fourier transform infrared spectroscopy and ¹H‐NMR. The photosensitive polyimide precursor containing 25 wt % diazonaphthoquinone photoactive compound showed a sensitivity of 150 mJ/cm² and a contrast of 1.65 in a 3 μm film with 1.25 wt % tetramethylammonium hydroxide developer. A pattern with a resolution of 10 μm was obtained from this composition. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 352–358, 2002     

Synthesis and properties of UV-curable hyperbranched polyurethane and its application in the negative-type photoresist

UV-curable hyperbranched polyurethane(UV-HBPU) containing carboxyl groups was synthesized from isophorone diisocyanate(IPDI), diethanolamine(DEOA), polyethylene glycol(PEG-400), hydroxyethyl acrylate(HEA), and 2,2-bis(hydroxymethyl) propionic acid(DMPA). The UV-HBPU was used as a negative-type photoresist for a printed circuit board(PCB). Fourier-transform infrared spectroscopy(FTIR) and proton nuclear magnetic resonance(1HNMR) spectroscopy of UV-HBPUs indicated that the synthesis was successful. Differential scanning calorimetry(DSC) and thermogravimetric analysis(TGA) showed that the thermal stability of the UV-HBPUs decreased as the HEA content increased. The polymer exhibited excellent photoresist properties, and the resolution of circuits based on this negative-type photoresist reached 10 μm.     

静电纺丝制备SU-8光刻胶纳米纤维及图案阵列

利用静电纺丝和紫外光刻技术直接制备了不同结构的SU-8光刻胶纳米纤维薄膜及图案阵列。通过光学显微镜和扫描电子显微镜表征了纳米纤维的形貌、尺寸及结构。结果表明,通过改变SU-8光刻胶的黏度可形成不同直径和形貌的纤维结构,其中用SU-8 3010和SU-8 3050光刻胶制备的纳米纤维具有最优的形貌,其平均直径分别为470 nm和610nm。利用带有长方形缺口的铝箔和同轴电纺的方法分别制备了平行趋向和空心结构的纳米纤维。通过紫外光刻过程,可将SU-8纳米纤维加工成点阵、条状等不同形貌的图案阵列或结构,有望用作细胞培养研究的功能基底材料。     

非离子型产酸剂——N-羟基邻苯二甲酰亚胺对甲苯磺酸酯的合成与性能研究

以邻苯二甲酸酐、盐酸羟胺和对甲苯磺酰氯为起始原料，合成了非离子型光致产酸剂——N-羟基邻苯二甲酰亚胺对甲苯磺酸酯，对其进行了红外、核磁共振和紫外表征，测定了其化学结构、溶解性和紫外吸收等性能．结果表明，这种非离子型产酸剂较离子型产酸剂在常用溶剂中有非常良好的溶解性，并在248nm处有好的透明性，可用于深紫外光刻工艺体系．