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DOI: https://doi.org/10.6023/A25050197

研究论文

纳米聚酰亚胺超薄膜的多级松弛与热转变★

  • Xu ,
  • Quanyin ,
  • Shi ,
  • Xinyang ,
  • Luo ,
  • Jintian ,
  • Zuo ,
  • Biao*
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  • 浙江理工大学 化学与化工学院 杭州 310018

收稿日期: 2025-05-29

  网络出版日期: 2025-07-03

基金资助

国家自然科学基金(No. 22303084, 52373025).

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Relaxation of Nanoscale Polyimide Ultrathin Films

  • 徐全印 ,
  • 石欣阳 ,
  • 罗锦添 ,
  • 左彪
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  • School of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, Hangzhou 310018, China

Received date: 2025-05-29

  Online published: 2025-07-03

Supported by

National Natural Science Foundation of China (No. 22303084, 52373025).

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摘要

聚酰亚胺(PI)薄膜因优异的耐高温性、绝缘性及化学稳定性, 广泛应用于光电器件与半导体封装领域. 纳米厚度PI薄膜的松弛行为关系到其热稳定性和尺寸稳定性等性质, 是影响PI薄膜应用的重要物理性质. 本文先用介电松弛和动态力学分析研究了PI的多级松弛行为, 明确PI的α和β松弛的温度区间;; 利用椭圆偏振光谱表征纳米级厚度PI薄膜的热膨胀和松弛行为, 探究薄膜厚度对PI分子热运动的影响. 结果表明, 当膜厚降低至100 nm以下时, 与链段运动关联的α松弛温度(Tα)随膜厚降低而减小, 而与芳环振动相关的β松弛温度(Tβ)保持不变;; 同时,薄膜的热膨胀系数随厚度减小显著增大. 本研究揭示了PI本体及超薄膜的松弛行为, 为开发高稳定、低膨胀的超薄封装材料提供了理论指导.

关键词： 聚酰亚胺; 松弛; 椭圆偏振光谱; 热膨胀; 纳米受限

本文引用格式

Xu , Quanyin , Shi , Xinyang , Luo , Jintian , Zuo , Biao* . 纳米聚酰亚胺超薄膜的多级松弛与热转变★[J]. 化学学报, 0 : 25050197 -25050197 . DOI: 10.6023/A25050197

Abstract

Polyimide (PI) films are widely used in semiconductor packaging due to their excellent properties, including low dielectric constant, high temperature resistance, and enhanced thermal and chemical stability. In recent decades, the development of modern nanotechnology has led to devices being downsized to the nanoscale, and packaging these nanodevices would require ultrathin films of PI. Understanding the thermal transition and molecular relaxation of the PI ultrathin films is essential for high-quality microelectronic packaging. Although the dynamics of bulk PI have been extensively studied using techniques such as broadband dielectric spectroscopy (BDS) and dynamic mechanical analysis (DMA), the impact of reduced film thickness on these dynamics remains unclear. In this study, we used temperature-variable spectroscopic ellipsometry to examine the thermal expansion and molecular relaxation of PI films as thin as 6 nm, and concurrently, the bulk dynamics of PI were investigated using BDS and DMA for comparison purposes. The PI films were prepared by the heat imidization of poly(amide acid) films, which were polymerized using biphenyltetracarboxylic diandhydride (BPDA) and 4, 4'-oxydianiline (ODA). In 300-nm-thick films, we observed the α-relaxation arising from the segmental cooperative rearrangement, and the β-relaxation originating from phenyl ring motion at approximately 260 °C (Tα) and 99 °C (Tβ), respectively. As the film thickness decreased below 100 nm, Tα decreased. Specifiacally, Tα decreased by 30 °C for 6-nm PI films. In contrast, Tβ remains unchanged in the ultrathin films, indicating a thickness-independent β-relaxation. Furthermore, the coefficients of thermal expansion increased remarkably with a reduction in film thickness across various temperature ranges (i.e., T < Tβ, Tβ < T < Tα, and T > Tα), indicating that ultrathin PI films are more sensitive to temperature variations than bulk samples. Such observation of the thickness-dependent thermal expansivity and Tα of ultrathin PI films provide a deep understanding of the effects of nanoconfinement on the dynamics of polymers with rigid chain backbones, which is also meaningful for designing and fabricating stable nano-devices based on ultrathin PI films.

Key words： polyimide; relaxation; ellipsometry; thermal expansion; nanoconfinement

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