193 nm激光下不同含量Y杂质CaF2晶体辐照损伤研究

doi:10.15541/jim20220300

无机材料学报 ›› 2023, Vol. 38 ›› Issue (2): 219-224.DOI: 10.15541/jim20220300

• 研究快报 • 上一篇

193 nm激光下不同含量Y杂质CaF₂晶体辐照损伤研究

王华进¹^,²(), 寇华敏²(), 王墉哲², 姜大朋², 张博², 钱小波², 王静雅², 朱琳玲⁴, 曾爱军⁴, 杨秋红¹, 苏良碧²^,³()

1.上海大学材料科学与工程学院, 上海 200444
2.中国科学院上海硅酸盐研究所, 透明光功能无机材料重点实验室, 上海 201899
3.中国科学院大学材料科学与光电工程中心, 北京 100049
4.中国科学院上海光学精密机械研究所, 上海 201800

收稿日期:2022-05-27 修回日期:2022-06-04 出版日期:2023-02-20 网络出版日期:2022-08-26
通讯作者: 寇华敏, 高级工程师. E-mail: huaminkou@mail.sic.ac.cn;
苏良碧, 研究员. E-mail: suliangbi@mail.sic.ac.cn
作者简介:王华进(1996-), 男, 硕士研究生. E-mail: wanghuajin@shu.edu.cn

Irradiation Damage of CaF₂ with Different Yttrium Concentrations under 193 nm Laser

WANG Huajin¹^,²(), KOU Huamin²(), WANG Yongzhe², JIANG Dapeng², ZHANG Bo², QIAN Xiaobo², WANG Jingya², ZHU Linling⁴, ZENG Aijun⁴, YANG Qiuhong¹, SU Liangbi²^,³()

1. School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China
2. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201899, China
3. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
4. Shanghai Institute of Optics and Fine Mechanics, Shanghai 201800, China

Received:2022-05-27 Revised:2022-06-04 Published:2023-02-20 Online:2022-08-26
Contact: KOU Huamin, associate professor. E-mail: huaminkou@mail.sic.ac.cn;
SU Liangbi, professor. E-mail: suliangbi@mail.sic.ac.cn
About author:WANG Huajin (1996-), male, Master candidate. E-mail: wanghuajin@shu.edu.cn
Supported by:
Strategic Priority Program of the Chinese Academy of Sciences(XDA25020313);National Natural Science Foundation of China(61925508);Science and Technology Commission of Shanghai Municipality(20501110300);Science and Technology Commission of Shanghai Municipality(20511107400);CAS Project for Young Scientists in Basic Research(YSBR-024)

摘要/Abstract

摘要：

氟化钙晶体的抗辐照性能是其在深紫外光刻应用中的关键性能之一, 目前氟化钙晶体在193 nm激光辐照下的损伤过程尚不清楚。本文报道了193 nm激光辐照下氟化钙晶体的损伤行为及影响损伤的关键缺陷因素。通过193 nm激光辐照试验, 发现晶体损伤主要表现为晶体内部产生的辐照诱导色心与表面产生的辐照诱导损伤坑。通过紫外-可见分光光度计对辐照诱导色心分析, 并将不同色心吸收系数与Y杂质含量进行线性拟合。结果表明: Y离子具有与F心结构波函数发生重叠的低位轨道, 两者发生轨道杂化易形成色心稳定结构; 线性拟合结果表明Y离子含量与氟化钙晶体本征色心之间存在线性关系, 说明Y元素是影响色心形成的关键杂质离子。实验表征了辐照诱导损伤坑的元素分布和结构缺陷。EDS结果表明损伤坑处伴随着钙元素含量上升和氟元素含量下降, 证实H心扩散、F心聚集导致了辐照损伤; EBSD结果表明表面辐照损伤优先在位错处产生。因此, 降低杂质含量及位错密度是提高氟化钙晶体在193 nm激光下抗辐照损伤性能的重要途径。

关键词: 氟化钙晶体, 色心, 激光辐照损伤, 杂质含量, 位错密度

Abstract:

Radiation resistance of CaF₂ crystal is one of the critical properties in the application of deep ultraviolet lithography, but the damage process under 193 nm laser irradiation is still unclear. This paper reports the damage behavior of CaF₂ crystals under 193 nm laser irradiation and the key defect factors affecting the damage. Through the 193 nm laser irradiation experiment, it is found that the crystal damage is mainly manifested as the radiation-induced color centers inside the crystal and the radiation-induced damage pits on the surface. Irradiation-induced color centers were analyzed by UV-visible spectrophotometer, and linear fitting was performed between absorption coefficients of different color centers and Y impurity contents. The results show that Y ion has a low-order orbit that overlaps with the F center structure wave function, and hybridizes to form a stable structure. There is a linear relationship between Y ions contents and intrinsic color centers of CaF₂ crystals, confirming that Y element is the key impurity ion affecting the formation of color centers. Energy dispersive X-ray spectrometer (EDS) results show that the content of calcium in the damage pits increases and the content of fluorine decreases, which confirms that the diffusion of H centers and the aggregation of F centers lead to irradiation damage. Electron backscatter diffraction (EBSD) results show that surface irradiation damage occurs preferentially at dislocations. Therefore, reducing the impurity content and dislocation density is an important way to improve the anti-irradiation damage performance of calcium fluoride crystals under 193 nm laser.

Key words: CaF₂ crystal, color center, laser irradiation damage, impurity content, dislocation density

中图分类号:

TQ174

王华进, 寇华敏, 王墉哲, 姜大朋, 张博, 钱小波, 王静雅, 朱琳玲, 曾爱军, 杨秋红, 苏良碧. 193 nm激光下不同含量Y杂质CaF₂晶体辐照损伤研究[J]. 无机材料学报, 2023, 38(2): 219-224.

WANG Huajin, KOU Huamin, WANG Yongzhe, JIANG Dapeng, ZHANG Bo, QIAN Xiaobo, WANG Jingya, ZHU Linling, ZENG Aijun, YANG Qiuhong, SU Liangbi. Irradiation Damage of CaF₂ with Different Yttrium Concentrations under 193 nm Laser[J]. Journal of Inorganic Materials, 2023, 38(2): 219-224.

图/表 8

Fig. 1 Absorption spectra and morphologies of samples before irradiation

Fig. 2 Radiation damage result (a) Damage morphology; (b) Relationship between Y ions and radiation resistance; (c) Damaged region absorption spectra mpps: million pulsesper second

Fig. 3 Schematic diagrams of the formation process of color centers (a) F center generated by self-excited defects formed by two-photon absorption; (b) defect-impurity orbital energy levels of the YFC

Fig. 4 Linear fitting of color center absorption coefficient and Y ion concentration

Fig. 5 SEM images of damaged area (a) Complete morphology of the damage pits; (b) Aggregate damage pits; (c) Single damage pit; (d) Etch pits of dislocations (HCl etching)

Fig. 6 Damage morphologies of sample 2# under different modes of SEM (a) Secondary electron image; (b) Stress distribution diagram, blue, green and red regions indicate the variation of stress from low to high, respectively

Table 1 Elastic stiffness constants cij and lattice constant of Ca and CaF2[28-29]

Crystal	c₁₁/GPa	c₁₂/GPa	Lattice constant/nm
CaF₂	165	46	0.546
Ca	16	8	0.558

Fig. 7 EDS analysis of sample 2# damage pits (a) EDS sampling location; (b) EDS results of elements at different positions Colorful figure is available on website

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193 nm激光下不同含量Y杂质CaF₂晶体辐照损伤研究

Irradiation Damage of CaF₂ with Different Yttrium Concentrations under 193 nm Laser

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