可低温固化正性光敏聚酰亚胺的制备与性能  

Preparation and properties of low-temperature curable positive-tone photosensitive polyimide

作　　者：唐衍超 张翠红 李铭新 TANG Yanchao;ZHANG Cuihong;LI Mingxin(Pome Technology Co.,Ltd.,Liaocheng 252300,China)

机构地区：[1]波米科技有限公司,山东聊城252300

出　　处：《工程塑料应用》2024年第10期7-12,共6页Engineering Plastics Application

基　　金：山东省竞争性创新平台项目(2022CXPT036);山东省重大科技创新工程项目(2023CXGC010315)。

摘　　要：随着重新布线层半导体封装技术的发展,对可低温固化的正性光敏材料的光刻性能、力学性能、热力学性能和耐化学性能的要求越来越高。为此,笔者研制了一种可低温固化的正性光敏聚酰亚胺(p-PSPI)材料。在溶剂N-甲基吡咯烷酮(NMP)中,将4,4′-氧双邻苯二甲酸酐与2,2′-双[3-(3-氨基苯甲酰胺)-4-羟基苯基]六氟丙烷、硅二胺(SiDA)和3-氨基苯酚通过聚合反应得到聚酰胺酸,再进行羧基的酯化得到聚酰胺酸酯(PAE),将PAE与感光剂重氮萘醌化合物、酚酯型热交联剂、偶联剂KBM-1403和亚胺化催化剂2,6-二甲基哌啶溶解于γ-丁内酯中进行复配,得到可低温固化的p-PSPI胶液。对p-PSPI进行水性碱性显影性能测试,在膜厚15μm条件下,光刻分辨率能够达到10μm;经200℃低温固化后,利用傅里叶变换红外光谱仪、动态热机械分析仪、热重分析仪等分析测试,结果表明,p-PSPI的亚胺化率达到98%以上,拉伸强度为108.4 MPa,断裂伸长率为10.35%,储能模量(150℃)为2.18 GPa,5%热失重温度达到367.69℃;经耐化学性能测试,p-PSPI对有机溶剂(NMP,二甲基亚砜和丙酮)、酸碱(30%HNO3,30%H2SO4,1%HF和5%KOH)以及氧化剂(10%H2O2)具有优良的耐化学稳定性,可满足低温固化条件下半导体封装所需的工艺条件。Along with the development of rewiring layer semiconductor packaging technology,the requirements for lithography performance,mechanical properties,thermodynamic properties and chemical resistance of positive photosensitive materials that can be cured at low temperature are getting higher and higher.Therefore,a positive photosensitive polyimide material that can be cured at low temperature was developed.In the N-methylpyrrolidone(NMP)solvent,4,4′-oxydiphthalic anhydride was polymerized with 2,2′-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]hexafluoropropane,silicon diamine(SiDA)and 3-aminophenol to obtain polyamic acid,and then the carboxyl group was esterified to obtain polyamic acid ester(PAE).PAE was dissolved inγ-butyrolactone with photosensitive agent napthoquinone diazide compounds,phenolic ester type thermal crosslinking agent,coupling agent KBM-1403 and imidization catalyst 2,6-dimethylpiperidine to obtain a low temperature curable p-PSPI glue.The water-based alkaline development performance of p-PSPI was tested.Under the condition of film thickness of 15μm,the lithography resolution can reach 10μm;after curing at 200℃,the p-PSPI was characterized by Fourier transform infrared spectroscopy,dynamic thermomechanical analyzer and thermogravimetric analyzer.The results showed that the imidization rate of p-PSPI was more than 98%,the tensile strength was 108.4 MPa,the elongation at break was 10.35%,the storage modulus(150℃)was 2.18 GPa,and the 5%weight loss temperature was 367.69℃.After chemical resistance test,p-PSPI has excellent chemical resistance to organic solvents(NMP,Dimethyl sulfoxide and acetone),to acid-base(30%HNO3,30%H2SO4,1%HF and 5%KOH),and oxidant(10%H2O2).It can meet the process conditions of semiconductor packaging under low-temperature curing conditions.

关 键 词：低温固化 正性 光敏聚酰亚胺 光刻性能 力学性能 耐化学性能 

分 类 号：TQ323.7[化学工程—合成树脂塑料工业]