原子层沉积法制备稀土氧化物表面改性多孔SiO2薄膜

doi:10.15541/jim20240433

摘要/Abstract

摘要：

宽带增透膜在透镜和太阳能电池等领域具有广泛应用, 其中多孔结构增透膜表现出巨大潜力。本工作研究了一种由原子层沉积(ALD)法制备的多孔SiO₂折射率梯度减反射膜。通过磷酸刻蚀Al₂O₃/SiO₂多层膜, 得到具有渐变孔隙率的多孔SiO₂膜, 折射率从衬底到表面逐渐降低。在320~1200 nm波长范围内, 薄膜的平均透过率达97.8%。利用稀土氧化物La₂O₃表面改性, 薄膜表面形成荷叶状疏水结构, 水接触角为100.0°, 在保持薄膜透过率的同时显著提高了疏水自清洁能力。改性薄膜在擦拭测试后未受到破坏, 表明其具有优异的表面耐久性, 而且环境适应性得到明显增强。

关键词: 多孔SiO₂, 稀土氧化物, 原子层沉积, 减反射, 自清洁

Abstract:

Broadband transparent films play a pivotal role in various applications such as lenses and solar cells, particularly porous structured transparent films exhibit significant potential. This study investigates a porous SiO₂ refractive index gradient anti-reflective film prepared by atomic layer deposition (ALD). A porous SiO₂ film with gradual porosity was obtained by phosphoric acid etching of Al₂O₃/SiO₂ multilayers with gradient Al₂O₃ ratios, achieving a gradual decrease in refractive index from the substrate to the surface. The film exhibited an average transmittance as high as 97.8% within the wavelength range from 320 nm to 1200 nm. The environmental adaptability was further enhanced by surface modification using rare earth oxide (REO) La₂O₃, resulting in formation of a lotus leaf-like structure and achieving a water contact angle of 100.0°. These data proved that the modification significantly improved hydrophobic self-cleaning capability while maintaining exceptional transparency of the film. The surface structure of the modified film remained undamaged even after undergoing wipe testing, demonstrating its excellent surface durability.

Key words: porous SiO₂, rare earth oxide, atomic layer deposition, anti-reflective, self-cleaning

中图分类号:

TB43

金剑飞, 吕林, 李莹, 闫璐, 曹韫真, 李伟. 原子层沉积法制备稀土氧化物表面改性多孔SiO₂薄膜[J]. 无机材料学报, 2025, 40(9): 1029-1036.

JIN Jianfei, LÜ Lin, LI Ying, YAN Lu, CAO Yunzhen, LI Wei. Rare Earth Oxide Surface Modification of Porous SiO₂ Film Prepared by Atomic Layer Deposition[J]. Journal of Inorganic Materials, 2025, 40(9): 1029-1036.

图/表 10

Table 1 Preparation parameters of films

Material	First reactant (pulse time)	First purge (purge time)	Second reactant (pulse time)	Second purge (purge time)	Deposition temperature/℃
Al₂O₃	TMA (0.15 s)	N₂ (1.5 s)	H₂O (0.1 s)	N₂ (1.5 s)	350
SiO₂	DIPAS (0.10 s)	N₂ (1.5 s)	O₃ (1.0 s)	N₂ (1.5 s)	350
La₂O₃	La(ⁱPrfAMD)₃ (0.10 s)	N₂(1.5 s)	Plasma-O₂ (5.0 s)	N₂ (1.5 s)	250

Fig. 1 Diagram of the film structure (a) Schematic diagram of the Al2O3/SiO2 multilayers with gradient Al2O3 ratios; (b) 3D structure of NP SiO2 film with a gradient index

Fig. 2 SEM images after acid etching of Al2O3/SiO2 multilayers with thickness ratios at (a) 2 : 2, (b) 3 : 2, (c) 4 : 2, and (d) 5 : 2

Fig. 3 FE-SEM images of cross sections and diagram of films (a-c) Acid etching for (a) 3, (b) 9 and (c) 24 h; (d) Schematic diagram of acid etching conjecture Al2O3/SiO2 layers; (e) Different thickness of SiO2 layer in Al2O3/SiO2 films after acid etching for 24 h; (f) Deposition diagram of SiO2 layers with different thicknesses Colorful figures are available on website

Fig. 4 Performance of NP SiO2 films with different Al2O3/SiO2 thickness ratios (a) Refractive index at 580 nm; (b) Transmittance curves. Colorful figures are available on website

Fig. 5 WCA test result of NP SiO2 films

Fig. 6 Morphology and performance of the film (a) 45° cross-section morphology of NP SiO2 films with La2O3 modification; (b) Transmittance curves of different samples

Fig. 7 SEM images and WCA test results (a, b) La2O3 film on SiO2 glass; (c, d) La2O3 film on NP SiO2 films; (e, f) Fogging results of (e) freeze test and (f) steam test

Fig. 8 Results of the wipe resistance test (a) NP SiO2 films; (b) La2O3-modified NP SiO2 films; (c) WCA test result of La2O3-modified NP SiO2 films after being wiped

Fig. S1 XPS spectra of La2O3 layer (a) Wide-scan spectrum; (b) La3+3d spectrum

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原子层沉积法制备稀土氧化物表面改性多孔SiO₂薄膜

Rare Earth Oxide Surface Modification of Porous SiO₂ Film Prepared by Atomic Layer Deposition

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