高感度和高留膜率光敏聚酰亚胺光刻胶的制备及性能

Preparation and Performance of Photosensitive Polyimide Photoresist with High Sensitivity and High Retention Rate

摘要

光敏聚酰亚胺（PSPI）作为微电子工业的核心材料，具有优异的热稳定性、力学性能和介电特性，但其感度（E_th）和留膜率不足是制约其光刻胶应用的关键问题，开发具有高感度、高留膜率的 PSPI 具有重要意义。以没食子酸的衍生物 3,4,5-三羟基-N-(2-羟乙基) 苯甲酰胺（GEA）和甲醇为原料，分别与二酐单体 4,4'-氧双邻苯二甲酸酐（ODPA）开环反应，再与 2,2-双 (3-氨基-4-羟基苯基) 六氟丙烷（6FAP）反应合成了高性能聚酰胺酸酯聚合物（OGMFPAE）。采用傅里叶变换红外光谱 (FT-IR)、核磁共振氢谱 (¹H-NMR)、紫外-可见吸收光谱 (UV-Vis)、凝胶渗透色谱 (GPC) 等对聚合物的结构与性能进行了表征，所合成的聚合物 OGMFPAE 在 365、405、436 nm 处展现出优异的光学透过率。此外，利用接近式曝光机测试了基于聚合物 OGMFPAE 制备的光刻胶性能。膜厚为 2 μm 的 PSPI 光刻胶具有高感度（E_th<50 mJ/cm²），显影留膜率高于 97%，固化留膜率高于 90%，光刻图案形貌良好，线条清晰，分辨率高。当膜厚为 11.5 μm时，该光刻胶仍保持良好的感光性能，显影留膜率超过 90%，固化留膜率超过 75%。该光刻胶在有机发光二极管（OLED）显示、微机电系统（MEMS）及芯片封装中展现出良好的应用前景。

Abstract

Photosensitive polyimide (PSPI), as a core material in the microelectronics industry, exhibits excellent thermal stability, mechanical properties, and dielectric characteristics. However, its insufficient photosensitivity (E _th) and retention rate are critical issues limiting its application in photoresists. Therefore, the development of polyimide photoresists with high sensitivity and high retention rate holds significant research importance. Using gallic acid derivatives, namely 3,4,5-trihydroxy-N-(2-hydroxyethyl) benzamide (GEA) and methanol as raw materials, a high-performance polyamic ester polymer (OGMFPAE) was synthesized via ring-opening reaction with the dianhydride monomer 4,4'-oxydiphthalic anhydride (ODPA), followed by polymerization with 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP). The structure and properties of the polymer were characterized using Fourier transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance spectroscopy (¹H-NMR), ultraviolet-visible absorption spectroscopy (UV-Vis), and gel permeation chromatography (GPC). The characterization results confirmed the successful synthesis of the polymer, and OGMFPAE exhibited excellent optical transmittance at 365, 405 nm, and 436 nm. Furthermore, the lithographic performance of the photoresist formulated with the OGMFPAE polymer was evaluated using a proximity exposure system. Results demonstrated that the prepared PSPI photoresist possesses high sensitivity (E _th < 50 mJ/cm²) at a film thickness of 2 μm, with a developed film retention rate exceeding 97% and a cured film retention rate greater than 90%. Even at an 11.5 µm film thickness, the photoresist maintains good photosensitivity, achieving a developed retention rate higher than 90% and a cured retention rate higher than 75%. Well-defined photolithographic patterns with clear line profiles and high resolution were obtained, indicating promising application potential in organic light-emitting diode (OLED) displays, micro-electro-mechanical systems (MEMS), and chip packaging.

关键词

没食子酸 / 光敏聚酰亚胺 / 光刻胶 / 高留膜率 / 高感度

Key words

gallic acid / photosensitive polyimide / photoresist / high retention rate / high sensitivity

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