全氢聚硅氮烷-氧化硅的转化过程研究※

doi:10.6023/A21120621

摘要/Abstract

利用全氢聚硅氮烷(PHPS)转化制备的氧化硅材料在存储芯片、柔性显示封装等领域展现出较高的应用价值. 本工作系统研究了PHPS在高温加热条件下的氧化硅形成过程, 考察了转化过程中化学组成和微观结构对体积收缩、折射率和力学性能的影响. 研究结果表明: 转化温度低于180 ℃时, PHPS的转化以Si—H和Si—N的水解缩合反应为主, 转化程度较低, 形成的是氧化硅为分散相、PHPS为连续相的海岛结构; 转化温度在180~300 ℃区间内, 转化以氧化反应为主, 氧化硅相逐渐生长, 形成双连续的相结构, 且在温度高于200 ℃时发生相反转, 氧化硅相成为连续相. 转化温度在300~600 ℃区间时, 氧化硅网络骨架基本形成, 在高温的作用下进一步致密化. PHPS转化样品的体积收缩、折光指数和力学性能与其转化程度和相分布有关.

关键词: 全氢聚硅氮烷, 氧化硅, 转化过程, 微观结构, 双连续相

Perhydropolysilazane (PHPS) derived silica materials have received extensive attention due to their potential applications in fields of memory chip and flexible display encapsulation. However, the current understanding of PHPS conversion process is not deepened yet, which is unfavorable to further research. To clarify PHPS conversion process, this work systematically studied conversion mechanism from PHPS to silica, and investigated the influence of chemical composition and microstructure on volume shrinkage, refractive index and mechanical properties in the conversion process. The coating samples were prepared by hydrolysis and condensation reaction of PHPS under conversion condition of heat. Chemical composition and microstructure of the obtained samples were analyzed by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, energy dispersive spectrometer and peak table mode of atomic force microscope. It is found that, when the conversion temperature is below 180 ℃, the conversion of PHPS is dominated by the hydrolysis and condensation reaction of Si—H and Si—N bonds, and its conversion degree is low. The formed samples show sea-island structure, which is composed of a dispersed silica phase and continuous PHPS phase. When the conversion temperature is in the range of 180~300 ℃, the transformation depends on oxidation reaction. It results in growth of silica phase, formation of bi-continuous phase, phase reverse between PHPS and silica phase with the temperature above 200 ℃, and formation of continuous silica phase. When the conversion temperature is in the range of 300~600 ℃, the silica network is basically formed, and it is densified by further treatment at higher temperature. The volume shrinkage, refractive index, and mechanical properties of PHPS converted samples depend on the conversion degree and phases’ distribution.

Key words: perhydropolysilazane, silica, conversion process, microstructure, bi-continuous phase

引用此文

王丹, 郭香, 李鹏飞, 张昱临, 徐彩虹, 张宗波. 全氢聚硅氮烷-氧化硅的转化过程研究^※[J]. 化学学报, 2022, 80(6): 734-740.

Dan Wang, Xiang Guo, Pengfei Li, Yulin Zhang, Caihong Xu, Zongbo Zhang. Conversion Process of Perhydropolysilazane to Silica^※[J]. Acta Chimica Sinica, 2022, 80(6): 734-740.

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图/表 10

图1. (a)不同温度转化样品的FT-IR图; (b)样品中红外吸收峰归一化强度随温度的变化

Figure 1. (a) FT-IR spectra of samples obtained at different temperatures; (b) normalized FT-IR absorbance intensity of the samples as a function of temperature

图2. PHPS不同转化温度样品的XPS分析

Figure 2. XPS analysis of PHPS derived samples obtained at different temperatures

图3. 不同温度转化样品的AFM照片, 图片右上角的数据为粗糙度均方根值

Figure 3. AFM images of samples obtained at different temperatures. The data in the top right of the image is root mean square value of the roughness

图4. 不同温度转化样品的AFM模量图

Figure 4. AFM modulus mappings of samples obtained at different temperatures

图5. PHPS转化过程中的相演变示意图: (a) PHPS相, (b) PHPS相为连续相的海岛结构, (c)双连续相结构, (d)氧化硅相为连续相的海岛结构

Figure 5. Schematic of phase evolution from PHPS to silica: (a) PHPS phase; (b) sea-island structure with continuous PHPS phase; (c) bi-continuous structure; (d) sea-island structure with continuous silica phase

图6. 不同温度转化样品的截面EDS分析(厚度约900 nm): (a) H200和(b) H600; 样品中组成分布示意图: (c) H200和(d) H600

Figure 6. Cross-section EDS analysis of samples obtained at (a) 200 ℃and (b) 600 ℃; composition schematic of (c) H200 and (d) H600

图7. 样品厚度收缩率随温度的变化

Figure 7. Reduction rate in thickness of samples as a function of temperature

图8. 不同温度转化样品的折光指数

Figure 8. Refractive index of samples converted at different temperatures

制备方法	折光指数^a	参考文献
热氧化	1.45~1.46	^[56]
离子束溅射	1.47	^[57]
化学气相沉积	1.45~1.46	^[58]
PHPS转化法	1.447	本工作

表1. PHPS转化和其它沉积方式得到的氧化硅的折光指数对比

Table 1. Comparison between refractive index of silica prepared by PHPS conversion and other deposition methods

图9. 样品力学性能随温度的变化: (a)硬度和(b)模量

Figure 9. Mechanical properties of samples as a function of temperature: (a) hardness and (b) modulus

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