Synthesis and evaluation of novel acid amplifiers liberating fluoroalkanesulfonic acids
Synthesis and evaluation of novel acid amplifiers liberating fluoroalkanesulfonic acids
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释放氟代烷磺酸的新型酸放大器的合成与评价
DOI：
10.2494/photopolymer.13.215
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发表时间：
2000
影响因子：
0.8
通讯作者：
K. Ichimura
中科院分区：
文献类型：
--
作者：
Sungeun Lee;K. Arimitsu;Sang Wok Park;K. Ichimura
化学放大光致抗蚀剂（CAP）已经被广泛研究用于微图案化。[1]CAP通过酸性物质的光化学生成和随后的聚合物侧链或酸敏感溶解控制剂的酸催化脱保护而起作用。Ichimura等人提出了一种新的概念，即通过酸增殖来提高CAP的光敏性。[2]我们的努力集中在酸放大剂的开发上，包括乙酰乙酸酯、[2-3] 1，2-二醇单磺酸酯、[4-5] Jo' -磺酰氧基缩酮、[6-7]三恶烷衍生物[8]和取代的苄基磺酸酯[9]，它们由于由光生酸引发的自催化酸解反应而释放芳烃或链烷磺酸。本文报道了由1，4-环己二醇衍生的带有两个磺酸基的酸放大剂的合成和评价，以释放具有更强酸性的氟代烷磺酸。1，4-环己二醇分别以对甲苯磺酰氯、三氟甲苯磺酰氯和三氟甲磺酸酐为原料，经对甲苯磺酰化、三氟甲烷磺酰化和三氟乙烷磺酰化反应合成了三氟甲烷磺酸酯（1）和三氟乙烷磺酸酯（2），总收率分别为65%和42%。[ 10]请注意，它们在环境温度下都表现出优异的储存稳定性，并且每个分子由于酸解反应而产生两个等摩尔量的酸物质。1和2在100 °C下在均三甲苯作为内标物存在下在CDCl 3（180 mmol dm 3）溶液中的热分解之后，1H-NMR谱中次甲基峰的相对强度发生变化。在对甲苯磺酸存在下，这两种化合物的分解速度约快两到三倍。1和2在加热210 min和160 min后突然发生转化，转化率曲线呈S形，表明这些化合物发生自催化酸解，
Chemically amplified photoresists (CAP) have been extensively studied for the application to micropatterning.[1] CAP works through the photochemical generation of acidic species and the subsequent acid-catalyzed deprotection of polymer side chains or acid-sensitive dissolution controllers. A novel concept of acid proliferation to improve the photosensitivity of CAP was proposed by Ichimura et al.[2] Our efforts have been focused on the development of acid amplifiers including acetoacetates,[2-3] 1, 2-diol monosulfonates,[4-5] Jo' -sulfonyloxyketals,[6-7] trioxane derivatives[8] and substituted benzyl sulfonates,[9] which liberate areneor alkanesulfonic acids as a result of their autocatalytic acidolysic reactions initiated by photogenerated acids. We report herein the synthesis and evaluation of acid amplifiers bearing two sulfonate groups derived from 1, 4-cyclohexanediol to release fluorinated alkanesulfonic acids with stronger acidity. The novel acid amplifiers substituted with trifluorinated methanesulfonate (1) and ethanesulfonate (2) were readily synthesized in 65% and 42% overall yields by tosylation, trifluoromethaneand trifluoroethanesulfonylation of 1, 4-cyclohexanediol using tosyl chloride, tresyl chloride and triflic anhydride, respectively. [ 10] Note that they both exhibit excellent storage stability at an ambient temperature and that each molecule produces two equimolar amounts of acid species as a consequence of acidolysis reactions. Thermal decomposition of 1 and 2 in CDC13 (180mmol dm3) solutions at 100 °C in the presence of mesitylene as an internal standard were followed by changes of relative intensity of the methin peak in ' H-NMR spectra. The decomposition of both compounds occurred about two or three times faster in the presence of p-toluenesulfonic acid. The conversion of 1 and 2 took place abruptly after heating for 210 mm and 160 min with sigmoidal time conversion curves, implying that these compounds suffer from autocatalytic acidolysis to