Novel Photobase Generators Derived from Proazaphosphatrane–Aryl Borate for High-Pressure Mercury Lamp Lithography

IF 3 4区 化学 Q3 CHEMISTRY, PHYSICAL
Yuji Shibasaki, Junichi Sato
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引用次数: 0

Abstract

Herein, novel borate-type photobase generators (PBGs) that generate a proazaphosphatrane known as Verkade's base (2,8,9-triisobuthyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane (TTP)) were developed for photopatterning using a high-pressure mercury lamp. Eight PBGs were synthesized, each featuring distinct borate substituents: phenyl, p-fluorophenyl, p-tolyl, p-methoxyphenyl, m-fluoro-p-methylphenyl, 4-biphenyl, 2-naphthyl, and 6-methoxy-2-naphthyl. The relation between these substituents and their light absorption characteristics was analyzed via ultraviolet–visible spectroscopy and time-dependent density functional theory calculations. The PBG with the 6-methoxy-2-naphthylborate group (TTP–tetrakis[2-(6-methoxynaphthyl)]borate (TTP–TMNB)) demonstrated substantial light absorption near 365 nm (the i-line of the high-pressure mercury lamp), generating approximately 60 % of the corresponding TTP in deuterated tetrahydrofuran (THF) upon exposure to 650 mJ/cm2, as confirmed via 1H nuclear magnetic resonance spectroscopy. To evaluate its photolithographic potential, TTP–TMNB was mixed with epoxy resin (jER1001) and a poly(methacrylic acid)-co-poly(methyl methacrylate) copolymer (PMA1.6-co-PMMA100) in THF. The resulting mixture was spin-coated onto a silicon wafer and irradiated with the i-line through a photomask to create a negative-tone image. The sensitivity and contrast of this photopolymer system were measured to be 45 mJ/cm2 and 1.0, respectively; moreover, a clear 10-μm negative-tone resolution was achieved.

Abstract Image

用于高压汞灯光刻技术的新型原氮磷酸盐-芳基硼酸盐光基发生器
在此,我们开发了新型硼酸酯类光碱发生器(PBGs),可生成一种被称为 Verkade 碱(2,8,9-三异丁基-2,5,8,9-四氮杂-1-磷杂双环[3.3.3]十一烷 (TTP))的原氮磷烷,并使用高压汞灯进行光分光。合成了八种 PBG,每种都具有不同的硼酸酯取代基:苯基、对氟苯基、对甲苯基、对甲氧基苯基、间氟对甲基苯基、4-联苯基、2-萘基和 6-甲氧基-2-萘基。通过紫外-可见光谱和随时间变化的密度泛函理论计算,分析了这些取代基与其光吸收特性之间的关系。带有 6-甲氧基-2-萘基硼酸酯基团的 PBG(TTP-四[2-(6-甲氧基萘基)]硼酸酯(TTP-TMNB))在 365 纳米(高压汞灯的 i 线)附近表现出很强的光吸收能力,在氚代四氢呋喃(THF)中暴露于 650 mJ/cm2 时,产生约 60% 的相应 TTP,1H 核磁共振光谱证实了这一点。为了评估其光刻潜力,将 TTP-TMNB 与环氧树脂(jER1001)和聚(甲基丙烯酸)-共聚(甲基丙烯酸甲酯)共聚物(PMA1.6-co-PMMA100)在 THF 中混合。将得到的混合物旋涂在硅晶片上,然后用 i 线通过光罩照射,形成负色调图像。据测量,这种光聚合物系统的灵敏度和对比度分别为 45 mJ/cm2 和 1.0;此外,还实现了清晰的 10 微米负色调分辨率。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
ChemPhotoChem
ChemPhotoChem Chemistry-Physical and Theoretical Chemistry
CiteScore
5.80
自引率
5.40%
发文量
165
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