悬浮液等离子喷涂制备Y2O3涂层及耐等离子刻蚀性

doi:10.15541/jim20230548

无机材料学报 ›› 2024, Vol. 39 ›› Issue (8): 929-936.DOI: 10.15541/jim20230548

悬浮液等离子喷涂制备Y₂O₃涂层及耐等离子刻蚀性

马文¹^,²(), 申喆¹^,², 刘琪¹^,², 高元明¹^,², 白玉¹^,², 李荣星¹^,²

1.内蒙古工业大学材料科学与工程学院, 内蒙古自治区薄膜与涂层重点实验室, 呼和浩特 010051
2.内蒙古自治区稀土新材料及功能涂层工程研究中心, 呼和浩特 010051

收稿日期:2023-11-29 修回日期:2024-02-04 出版日期:2024-08-20 网络出版日期:2024-02-22
作者简介:马文(1973-), 男, 博士, 教授. E-mail: w.ma@imut.edu.cn
基金资助:
内蒙古自然科学基金(2022MS05003);内蒙古自然科学基金(2021PT0008);内蒙古自然科学基金(JY20220041);内蒙古自治区高校创新科研团队项目(NMGIRT2319)

Preparation of Y₂O₃ Coating by Suspension Plasma Spraying and Its Resistance to Plasma Etching

MA Wen¹^,²(), SHEN Zhe¹^,², LIU Qi¹^,², GAO Yuanming¹^,², BAI Yu¹^,², LI Rongxing¹^,²

1. Inner Mongolia Key Laboratory of Thin Film and Coatings, School of Materials Science and Engineering, Inner Mongolia University of Technology, Hohhot 010051, China
2. Inner Mongolia Engineering Research Center of Rare-earth New Materials and Functional Coatings, Hohhot 010051, China

Received:2023-11-29 Revised:2024-02-04 Published:2024-08-20 Online:2024-02-22
About author:MA Wen (1973-), male, PhD, professor. E-mail: w.ma@imut.edu.cn
Supported by:
Inner Mongolia Natural Science Foundation(2022MS05003);Inner Mongolia Natural Science Foundation(2021PT0008);Inner Mongolia Natural Science Foundation(JY20220041);Inner Mongolia University Innovative Research Team Project(NMGIRT2319)

摘要/Abstract

摘要：

随着高端芯片竞争的白热化, Y₂O₃涂层作为等离子体刻蚀工艺腔的重要组成部分, 对其研究逐渐成为科研热点。利用悬浮液等离子喷涂(Suspension Plasma Spraying, SPS)在铝合金表面制备Y₂O₃涂层, 研究了不同工艺参数对涂层的物相组成、力学性能、显微形貌和介电强度等的影响; 在CF₄/Ar/O₂氟等离子体环境中对Y₂O₃涂层分别刻蚀30、60、120 min后, 分析了Y₂O₃涂层微观孔隙率对刻蚀速率的影响。最优工艺1(喷涂距离80 mm、送液速率35 mL/min、雾化气流速15 L/min、横向移枪速率700 mm/s、纵向移动步进1 mm/step)制备的Y₂O₃涂层的显微硬度为(3.78±0.36) GPa, 孔隙率为(2.35±0.24)%, 结合强度为(36.0±3.6) MPa, 介电强度为(29.74±2.01) kV/mm。在CF₄/Ar/O₂组成的混合等离子气体中, Y₂O₃涂层发生物理和化学反应, Ar⁺对涂层强烈冲击、轰击诱导, 使表面化学键断裂; CF₂*和F*使Y₂O₃不断被刻蚀, 生成的YF₃附着在涂层表面; 同时Ar⁺不断对涂层表面进行物理冲击, 去除YF₃层, 少量残余在涂层表面的YF₃被氧化形成了YOF, 最终导致涂层刻蚀率低至(11.48±5.21) nm/min。高致密性、低孔隙率、高均匀性的Y₂O₃涂层可以有效提高零件的耐等离子刻蚀性能, 对半导体工业具有重要意义。

关键词: 悬浮液等离子喷涂, Y₂O₃涂层, 孔隙率, 耐等离子刻蚀性

Abstract:

With the fierce competition of high-end chips, Y₂O₃coating is an important component of plasma etching cavity, corresponding research gradually becomes a research hotspot. Y₂O₃ coating was prepared on aluminum alloy surface by suspension plasma spraying (SPS). The effects of different process parameters on the phase composition, mechanical properties, microstructure, and dielectric strength of the coating were studied. The effect of microscopic porosity of Y₂O₃ coating on etching rate was analyzed after etching in CF₄/Ar/O₂ mixture for 30, 60 and 120 min, respectively. The microhardness, the porosity, the bonding strength, and the dielectric strength of Y₂O₃ coating prepared by the optimal process 1 (spraying distance 80 mm, liquid feed rate 35 mL/min, atomizing gas flow rate 15 L/min, horizontal gun moving speed 700 mm/s, vertical moving step 1 mm/step) is (3.78±0.36) GPa, (2.35±0.24)%, (36.0±3.6) MPa, and (29.74±2.01) kV/mm, respectively. In the mixed plasma gas composed of CF₄/Ar/O₂, the Y₂O₃ coating undergoes physical and chemical reactions, while Ar⁺ strongly shocks and bombards the coating to break the chemical bond on the surface. CF₂* and F* make Y₂O₃ continuously etched to form YF₃ attaching to the coating surface. At the same time, the physical impact of Ar⁺ constantly acts on the surface of the coating, removing the YF₃ layer, and a small amount of residual YF₃ on the surface of the coating is oxidized and finally forms YOF, resulting in a coating etching rate as low as (11.48±5.21) nm/min. Y₂O₃ coating with high density, low porosity and high uniformity can effectively improve the resistance of parts to plasma etching, which is of great significance in semiconductor industry.

Key words: suspension plasma spraying, Y₂O₃ coating, porosity, plasma etching resistance

中图分类号:

TQ174

马文, 申喆, 刘琪, 高元明, 白玉, 李荣星. 悬浮液等离子喷涂制备Y₂O₃涂层及耐等离子刻蚀性[J]. 无机材料学报, 2024, 39(8): 929-936.

MA Wen, SHEN Zhe, LIU Qi, GAO Yuanming, BAI Yu, LI Rongxing. Preparation of Y₂O₃ Coating by Suspension Plasma Spraying and Its Resistance to Plasma Etching[J]. Journal of Inorganic Materials, 2024, 39(8): 929-936.

图/表 10

表1 制备Y2O3涂层的固定工艺参数

Table 1 Fixed process parameters for preparing Y2O3 coating

Process parameter	Value
Gas volume ratio (Ar : N₂ : H₂)	6 : 3 : 1
Total gas flow/slpm	180
Arc current/A	220
Atomization gas flow rate/(L·min^-1)	15
Horizontal moving speed of spray gun/(mm·s^-1)	700

表2 Y2O3涂层的制备工艺参数

Table 2 Preparation process parameters of Y2O3 coating

Process	Spray distance/mm	Suspention injection rate/(mL·min^-1)	Vertical moving step/(mm·step^-1)
1	80	35	1.0
2	80	45	1.5
3	90	35	1.5
4	90	45	1.0

图1 原料粉末及四组工艺制备Y2O3涂层的XRD图谱

Fig. 1 XRD patterns of Y2O3 raw power and its coatings prepared by four processes

图2 四组工艺制备Y2O3涂层的截面形貌

Fig. 2 Cross-sectional microstructures of the Y2O3 coatings prepared by four processes (a) Process 1; (b) Process 2; (c) Process 3; (d) Process 4

图3 四组工艺制备的Y2O3涂层的结合强度和显微硬度

Fig. 3 Bonding strength and microhardness of the Y2O3 coatings prepared by four processes

图4 四组工艺制备的Y2O3涂层的孔隙率和介电强度

Fig. 4 Porosities and dielectric strengths of the Y2O3 coatings prepared by four processes

图5 刻蚀0、30、60和120 min后四组工艺制备的Y2O3涂层的表面形貌

Fig. 5 Surface microstructures of the Y2O3 coatings prepared by four processes after etching for 0, 30, 60 and 120 min

图6 四组工艺制的备Y2O3涂层的孔隙率和刻蚀率

Fig. 6 Porosities and etching rates of the Y2O3 coatings prepared by four processes

图7 四组工艺制备的Y2O3涂层刻蚀120 min后的XRD图谱

Fig. 7 XRD patterns of the Y2O3 coatings prepared by four processes after etching for 120 min

图8 四组工艺制备的Y2O3涂层刻蚀120 min后的EDS分析

Fig. 8 EDS analyses of the Y2O3 coatings prepared by four processes and etched for 120 min (a) Process 1; (b) Process 2; (c) Process 3; (d) Process 4

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悬浮液等离子喷涂制备Y₂O₃涂层及耐等离子刻蚀性

Preparation of Y₂O₃ Coating by Suspension Plasma Spraying and Its Resistance to Plasma Etching

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