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

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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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

Cite this article

徐全印 , 石欣阳 , 罗锦添 , 左彪 . Relaxation of Nanoscale Polyimide Ultrathin Films[J]. Acta Chimica Sinica, 0 : 25050197 -25050197 . DOI: 10.6023/A25050197

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