电子能量损失谱在BaTiO3基多层陶瓷电容器中的应用研究

doi:10.15541/jim20250021

无机材料学报 ›› 2025, Vol. 40 ›› Issue (6): 683-689.DOI: 10.15541/jim20250021

电子能量损失谱在BaTiO₃基多层陶瓷电容器中的应用研究

吴鲁康¹(), 傅正钱¹, 于子怡¹, 杨俊², 周斌¹, 陈学锋¹, 许钫钫¹()

1.中国科学院上海硅酸盐研究所, 上海 200050
2.深圳市宇阳科技发展有限公司, 深圳 523686

收稿日期:2025-01-15 修回日期:2025-03-05 出版日期:2025-06-20 网络出版日期:2025-03-06
通讯作者: 许钫钫, 研究员. E-mail: ffxu@mail.sic.ac.cn
作者简介:吴鲁康(2000-), 男, 博士研究生. E-mail: wulukang23@mails.ucas.ac.cn
基金资助:
国家重点研发计划(2023YFB3508200);上海市无机材料测试与表征技术平台(19DZ2290700)

Application of Electron Energy-loss Spectroscopy to BaTiO₃ Multi-layer Ceramic Capacitors

WU Lukang¹(), FU Zhengqian¹, YU Ziyi¹, YANG Jun², ZHOU Bin¹, CHEN Xuefeng¹, XU Fangfang¹()

1. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. Shenzhen Yuyang Technology Development Co., Ltd., Shenzhen 523686, China

Received:2025-01-15 Revised:2025-03-05 Published:2025-06-20 Online:2025-03-06
Contact: XU Fangfang, professor. E-mail: ffxu@mail.sic.ac.cn
About author:WU Lukang (2000-), male, PhD candidate. E-mail: wulukang23@mails.ucas.ac.cn
Supported by:
National Key R&D Program of China(2023YFB3508200);Shanghai Technical Platform for Testing and Charac- terization on Inorganic Materials(19DZ2290700)

摘要/Abstract

摘要：

消费电子、航空航天和国防科研等领域对BaTiO₃基多层陶瓷电容器(Multi-layer Ceramic Capacitor, MLCC)的性能要求日益提高。在MLCC复杂制作工艺过程中, 元素的分布和偏析会显著影响其相组成、微结构和性能, 亟需一个有效的分析手段在微观尺度上对MLCC进行元素精确解析。基于先进透射电镜(Transmission Electron Microscope, TEM)的元素分析技术因在亚埃尺度的超高空间分辨率而展现出独特优势。其中, X射线能谱(Energy Dispersive X-ray Spectroscopy, EDS)可快速定性分析金属元素, 但对轻元素O的检测灵敏度较低, 且因能量分辨率较低(~130 eV), 致使Ba和Ti元素存在谱峰重叠, 无法进行准确的定量分析。相比之下, 电子能量损失谱(Electron Energy-loss Spectroscopy, EELS)不仅具有超高能量分辨率(<1.0 eV), 而且能够给出化学价态等信息, 在MLCC微观尺度元素分析中具有较大的潜力与优势。本工作一方面利用EELS解决了EDS因谱峰重叠而不能区分Ba和Ti元素的问题; 另一方面通过EELS揭示了在较小晶粒中Ti³⁺离子占比更多, 且单晶粒的EELS线扫分析发现烧结过程中Ba的扩散比Ti更容易。基于高空间分辨率的EELS可以提供更为准确和丰富的元素和价态信息, 为MLCC的工艺改良和性能优化提供重要支撑。

关键词: 多层陶瓷电容器, 元素分析, 电子能量损失谱, BaTiO₃

Abstract:

BaTiO₃ multi-layer ceramic capacitors (MLCCs) are meeting the growing performance demands in consumer electronics, aerospace and defense research. Distribution and segregation of elements during complex fabrication process of MLCCs significantly affect the phase composition, microstructures and hence the performance, which necessitates an effective analytical means capable of accurately resolving elements of MLCCs at microscopic scales. Elemental analysis techniques integrated with modern transmission electron microscope (TEM) have unique advantages due to their ultra-high spatial resolution, reaching the sub-angström scale. Among them, energy dispersive X-ray spectroscopy (EDS) provides a simple and fast way for qualitative analysis of metallic elements. However, their limitations, such as low sensitivity for detecting the light element O, and more critically, low energy resolution (~130 eV), which results in the severe overlap of spectral peaks of Ba and Ti elements, hinder accurate quantitative analysis of BaTiO₃. In contrast, electron energy-loss spectroscopy (EELS) possesses ultra-high energy resolution (<1.0 eV), and can provide additional information regarding chemical valence, thus demonstrating enhanced potentials and advantages in the micro-scale elemental analysis of MLCC. In this work, EELS is employed to address the limitation of EDS in distinguishing between Ba and Ti elements due to the overlap of spectral peaks. In addition, EELS reveals that proportion of Ti³⁺ ions is higher in smaller BaTiO₃ grains. Meanwhile, EELS line-scan analysis of individual grains indicates that Ba element diffuses more easily than Ti during sintering process of ceramics. Given its high spatial resolution, EELS offers more accurate and comprehensive information on the elements and valence states, thereby providing potential support for the process improvement and performance optimization of MLCC.

Key words: multi-layer ceramic capacitor, elemental analysis, electron energy-loss spectroscopy, BaTiO₃

中图分类号:

TQ533
TM534

吴鲁康, 傅正钱, 于子怡, 杨俊, 周斌, 陈学锋, 许钫钫. 电子能量损失谱在BaTiO₃基多层陶瓷电容器中的应用研究[J]. 无机材料学报, 2025, 40(6): 683-689.

WU Lukang, FU Zhengqian, YU Ziyi, YANG Jun, ZHOU Bin, CHEN Xuefeng, XU Fangfang. Application of Electron Energy-loss Spectroscopy to BaTiO₃ Multi-layer Ceramic Capacitors[J]. Journal of Inorganic Materials, 2025, 40(6): 683-689.

图/表 8

图1 (a) TEM内高能入射电子与样品相互作用的示意图; (b) EDS和EELS的产生原理

Fig. 1 (a) Schematic illustration of interaction between high-energy incident electrons and sample within TEM; (b) Principles of EDS and EELS

图2 (a) MLCC低倍形貌的高角环形暗场(HAADF)照片(黄线-Ni电极层, 红线-BaTiO3介电层); (b)统计晶粒尺寸的示例区域及晶粒平均尺寸统计数据

Fig. 2 (a) Low magnified high angle annular dark field (HAADF) image of MLCC (yellow line is Ni electrode, red line is BaTiO3 dielectric layer); (b) Example area for grain size statistics and average grain size statistics Colorful figures are available on website

图3 (a) EDS面扫区域的HAADF照片; (b) EDS谱图(棕色峰标出Ba-L和Ti-K峰重叠); (c) Ba、Ti、O和Ni的EDS面分布图

Fig. 3 (a) HAADF image of EDS mapping region; (b) EDS spectra (brown peaks marking the overlap of Ba-L and Ti-K peaks); (c) EDS surface distributions of Ba, Ti, O, and Ni Colorful figures are available on website

图4 MLCC样品同一微区的EDS和EELS谱图

Fig. 4 EDS and EELS spectra of the same microregion of MLCC samples

图5 (a) MLCC截面样品的微区TEM照片; (b)图(a)中标识的BaTiO3单晶粒的EELS图谱; (c)100个BaTiO3晶粒的平均Ba/Ti原子比

Fig. 5 (a) Microregion TEM image of MLCC cross-section sample; (b) EELS spectrum of BaTiO3 single grain identified in (a); (c) Average Ba/Ti atomic ratios of 100 BaTiO3 grains

图6 BaTiO3单晶粒EELS线分析的HAADF照片和线扫测量的Ba/Ti原子比(橙线表示线扫位置)

Fig. 6 HAADF image of BaTiO3 single grain subjected to EELS line analysis and Ba/Ti ratios measured by line scanning (orange line indicating position of the line sweep)

图7 不同尺寸BaTiO3晶粒的EELS Ti-L2,3边精细结构

Fig. 7 EELS Ti-L2,3 edge fine structures of BaTiO3 grains with different sizes

图8 (a)电介质嵌入电极的示例HAADF照片; (b~g) 6个嵌入晶粒(图(a)中箭头所指)的EELS谱图

Fig. 8 (a) Example HAADF image of dielectric-embedded electrodes; (b-g) EELS spectra for six random embedding positions (indicated by arrows in (a))

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电子能量损失谱在BaTiO₃基多层陶瓷电容器中的应用研究

Application of Electron Energy-loss Spectroscopy to BaTiO₃ Multi-layer Ceramic Capacitors

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