刻蚀机内腔体长期遭受高能等离子体腐蚀,直接影响芯片质量与设备寿命,是半导体芯片的“卡脖子”问题。高性能耐刻蚀涂层是突破半导体“卡脖子”的关键。本综述聚焦于刻蚀机内腔体耐刻蚀涂层,从涂层材料的选取和涂层的制备方法两方面入手,分别对其研究进展进行梳理。材料选取方面,将刻蚀机内腔体耐刻蚀涂层所用的主流材料分为氧化物陶瓷涂层和含氟陶瓷涂层2类,从材料的基本性能入手对几种典型材料进行分析,并总结归纳前人的实验,得出每种材料的优势与短板,在此基础上,重点阐述了综合防护性能优异的钇铝石榴石耐蚀涂层的特性。涂层制备方法方面,综述详细介绍了大气等离子喷涂、气溶胶沉积,以及微弧氧化等6种当前耐刻蚀陶瓷涂层主流制备技术的工作原理,对比分析各制备方法的优缺点,并给出了当前的适用场景。最后,本综述展望了刻蚀机内腔体耐刻蚀涂层的未来发展趋势,旨在为开发下一代高性能刻蚀机内腔体耐刻蚀陶瓷涂层提供理论参考与技术思路。
Abstract
Etch chamber components of semiconductor etchers suffer continuous synergistic damage from chemically active halogen radicals and high-energy ion bombardment during dry etching processes. Aluminum alloys, the most common substrate for chamber liners and internal fixtures, undergo severe plasma erosion under fluorine- or chlorine-containing discharge environments. Such erosion generates abundant contaminant particles that adhere to wafer surfaces and drastically reduce chip manufacturing yield, while accelerating the wear and failure of chamber components and shortening the service cycle of advanced etching equipment. The degradation of inner chamber materials has long been a core technical bottleneck restricting the localized manufacturing of Chinese semiconductor equipment. Plasma-resistant ceramic coatings act as critical barrier layers separating aluminum substrates from corrosive plasma, representing a feasible and mainstream technical route to mitigate particle pollution and extend equipment service life. This review systematically summarizes state-of-the-art research on protective ceramic coatings for inner chambers of etchers, comprehensively elaborating research progress from two core dimensions: functional coating material systems and industrial-scale fabrication technologies.
In terms of coating material systems, existing commercial and laboratory-developed anti-plasma ceramic materials are classified into oxide ceramic coatings and fluorine-containing ceramic coatings. Six representative materials, namely fused silica, alumina, yttria, yttrium aluminum garnet (YAG), yttrium fluoride and yttrium oxyfluoride, are analyzed in detail regarding their crystal structures, fundamental thermal and mechanical properties, corrosion reaction mechanisms under plasma exposure, and inherent service limitations. Fused silica (SiO2) features low raw material cost and stable chemical inertness, yet it readily forms volatile SiF4 in fluorinated plasma, restricting its application only to low-power fluorine-free etching processes. Alpha-phase alumina (α-Al2O3) possesses high hardness and mature preparation procedures, but its fluorination product AlF3 forms loose porous layers that easily spall and generate particles, resulting in limited service life in high-power fluorine-based etching chambers. Cubic yttria (Y2O3) forms compact and stable YF3 passivation films on coating surfaces under plasma irradiation, delivering superior chemical corrosion resistance compared with alumina. Nevertheless, its Mohs hardness ranges merely from 5 to 6, leading to insufficient resistance against physical sputtering induced by high-speed charged particles. Yttrium aluminum garnet (Y3Al5O12, YAG) integrates three prominent merits: exceptional hardness, low thermal expansion coefficient, and robust fluorinated passivation layers. It can simultaneously resist both chemical corrosion and physical ion bombardment, and avoids interfacial cracking and peeling under frequent thermal cycling, making it the most promising candidate material with optimal comprehensive protective performance and the primary research focus in current academia. Yttrium fluoride (YF3) and yttrium oxyfluoride (YOF) remain stable in extreme fluorinated plasma without secondary fluorination reactions, but their weak mechanical strength and narrow feasible processing windows limit their utilization to special chamber components with low ion flux.
For coating fabrication techniques, six mainstream manufacturing approaches including atmospheric plasma spraying (APS), high-velocity oxygen fuel spraying (HVOF), aerosol deposition (AD), chemical vapor deposition (CVD), anodization and micro-arc oxidation (MAO) are fully discussed with respect to deposition mechanisms, microstructure regulation rules, applicable chamber service conditions and intrinsic drawbacks. Thermal spraying technologies boast mature industrial workflows and the capability of large-area coating formation, yet interlamellar voids and structural defects cannot be completely eliminated. Aerosol deposition enables room-temperature fabrication of dense, oxidation-free coatings that meet ultra-high cleanliness requirements for advanced semiconductor nodes, whereas low deposition efficiency and uneven coverage on complex curved surfaces become major obstacles for mass production. Wet chemical methods such as anodization and micro-arc oxidation exhibit low manufacturing cost and strong substrate adhesion, but inherent microporous structures in oxide films trigger premature coating failure under long-term plasma exposure.
Two universal research challenges prevailing in this field are summarized in this work. Firstly, inconsistent plasma etching experimental parameters (including discharge power, gas mixing ratio and bias voltage) across published literature prevent quantitative horizontal comparison of plasma resistance among diverse coating materials. Secondly, there lacks a unified industrial standard for evaluating coating failure, with parallel evaluation metrics such as thickness loss, particle generation count and interfacial delamination adopted by different research groups, which hinders the industrial translation of laboratory achievements. From the perspective of independent and controllable Chinese semiconductor equipment, future research orientations are proposed accordingly: rare-earth ion doping modification on YAG ceramics to simultaneously improve chemical corrosion resistance and mechanical wear resistance, composite coating processes combining APS for large-area priming and aerosol deposition for precision finishing on complex structural features and establishment of unified Chinese testing standards for plasma-resistant coatings to narrow the technical gap between Chinese and international advanced chamber protection technologies. This review provides systematic theoretical references and practical engineering strategies for developing next-generation ceramic coatings with long service life and ultralow particle contamination for semiconductor etcher inner chambers.
关键词
刻蚀机 /
耐等离子体腐蚀涂层 /
钇铝石榴石 /
热喷涂 /
陶瓷涂层：刻蚀
Key words
etcher /
plasma corrosion-resistant coating /
yttrium aluminum garnet (YAG) /
thermal spraying /
ceramic coating: etching
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