Conversion Process of Perhydropolysilazane to Silica※

doi:10.6023/A21120621

Abstract

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

Cite this article

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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Fig. & Tab. 10

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

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

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

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

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

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

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

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

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

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

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全氢聚硅氮烷-氧化硅的转化过程研究^※