无窗<i>X</i>射线能谱在荧光样品与金属锂成分分析中的优势与经验摸索

万鹏; 蔡蕊; 李勇; 孟祥玉; 周雨萌; 高晓霞; 徐强; 闫肃

doi:10.16495/j.1006-3757.2023.03.011

无窗X射线能谱在荧光样品与金属锂成分分析中的优势与经验摸索

doi: 10.16495/j.1006-3757.2023.03.011

万鹏^1,,
蔡蕊¹,
李勇²,
孟祥玉²,
周雨萌¹,
高晓霞¹,
徐强¹,
闫肃¹

1.
大连理工大学分析测试中心，辽宁大连　116024
2.
大连理工大学化工学院，辽宁大连　116024

详细信息

作者简介:
万鹏（1981−），女，博士，主要从事电子显微分析，E-mail：pengwan@dlut.edu.cn

中图分类号: O657. 62
计量
- 文章访问数: 18
- HTML全文浏览量: 9
- PDF下载量: 5
- 被引次数: 0
出版历程
- 收稿日期: 2023-05-26
- 录用日期: 2023-07-14
- 修回日期: 2023-07-14
- 刊出日期: 2023-09-25

Advantage and Experience of Windowless X-ray Energy Dispersive Spectroscopy at Composition Analysis of Fluorescent Sample and Lithium Metal

1.
Instrumental Analysis Center, Dalian University of Technology, Dalian 116024, Liaoning China
2.
School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning China

摘要

摘要: 用扫描电子显微镜搭载的有窗X射线能谱仪（EDS能谱）对荧光样品进行分析时，由于电子束的激发作用，样品受激自发产生的荧光将严重干扰EDS能谱探头对特征X射线的分析，最终导致定量困难甚至难以定性. 新型无窗EDS能谱由于其优异的低能量端信号采集与分析能力，结合单颗粒小区域采集的方法，可以成功实现荧光样品的正常EDS能谱分析. 由于无窗EDS能谱仪没有传统薄膜窗口的吸收作用，其最低可分析元素为锂. 通过优化加速电压，并借助样品表面钝化膜的保护作用，克服了背景噪音与样品污染的干扰，成功实现对单质锂的检测.
- X射线能谱分析 /
- 无窗EDS能谱仪 /
- 荧光粉 /
- 金属锂
Abstract: When the fluorescent samples were analyzed using a windowed X-ray energy dispersive spectrometer (EDS) equipped with a scanning electron microscope, due to the excitation of the electron beam, the stimulated fluorescence by sample stimulation will seriously interfere with the analysis of the characteristic X-rays by the EDS energy spectroscopy probe, which leads to qualitative and quantitative difficulties. The new windowless EDS combined with the method of single particle small region acquisition can successfully achieve normal EDS spectral analysis of fluorescent samples because of its excellent low-energy-end signal acquisition and analysis capability. Without the adsorption of the traditional ultra-thin window, the windowless EDS can analyze lithium metal. By optimizing the accelerating voltage and the protective effect of the passivation film on the sample surface, the interference of background noise and sample contamination were overcome, and the detection of elemental lithium was successfully realized.
- EDS /
- windowless EDS /
- fluorescent samples /
- lithium metal

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图 1 有窗EDS能谱在15 kV加速电压下分析两种荧光粉得到的异常EDS能谱图

（a）铈掺杂钇铝石榴石荧光粉的EDS能谱图，（a-1）为其荧光发射光谱图，（b）铕掺杂氮化物荧光粉的EDS能谱图，（b-1）为其荧光发射光谱图

Figure 1. Abnormal EDS spectra of two fluorescent powder samples obtained by windowed EDS at 15 kV

(a) EDS spectrum of Y₃Al₅O₁₂：Ce, (a-1) fluorescence spectrum of Y₃Al₅O₁₂：Ce, (b) EDS spectrum of SrAlSiN₃：Eu, (b-1) fluorescence spectrum of SrAlSiN₃：Eu

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图 2 电子束加速电压和采集区域大小对铈掺杂钇铝石榴石荧光粉EDS能谱分析的影响

(a-1) ~ (c-1)分别为大区域采集下电子束加速电压为15、10和5 kV时的EDS能谱图，(a-2) ~ (c-2)分别为单颗粒采集下电子束加速电压为15、10和5 kV时的EDS能谱图

Figure 2. Effect of accelerating voltages and scanning areas on EDS spectra of Y₃Al₅O₁₂：Ce

(a-1) ~ (c-1) accelerating voltages of 15, 10 and 5 kV, respectively, focused on large scanning area, (a-2) ~ (c-2) accelerating voltages of 15, 10 and 5 kV, respectively, focused on single particle

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图 3 利用无窗EDS能谱得到的无荧光干扰EDS能谱图

（a）铈掺杂钇铝石榴石荧光粉,（b）铕掺杂氮化物荧光粉

Figure 3. EDS spectra without fluorescence interference of (a) Y₃Al₅O₁₂：Ce and (b) SrAlSiN₃：Eu by windowless EDS

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图 4 不同条件下锂峰的出峰与峰形

（a）电子束加速电压为5 kV时样品表面氧化严重，电子束加速电压为（b）1 kV，（c）10 kV，（d）5 kV时受表面钝化膜保护的样品，电子束加速电压为（e）3 kV，（f）5 kV时样品表面经过长时间电子束辐照

Figure 4. Emergence and shape of peaks of lithium under different conditions (a) severely oxidized samples of surfaces under 5 kV, samples protected by passivation films under (b) 1 kV, (c) 10 kV, (d) 5 kV, sample areas of surfaces under repeated radiation by electron beam under (e) 3 kV, (f) 5 kV

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表 1 有窗EDS能谱在不同电子束加速电压下对铈掺杂钇铝石榴石荧光粉的定量分析结果

Table 1. Compositional analysis of Y₃Al₅O₁₂：Ce by windowed EDS under different accelerating voltages /%

	Y重量分数	Al重量分数	O重量分数	Ce重量分数	Y∶Al∶O原子比（理论值1∶1.67∶4）
15 kV大区域	Null	Null	Null	Null	Null
10 kV大区域	100	0	0	0	Null
5 kV大区域	51.0	22.0	24.0	2.9	1∶1.42∶2.64
15 kV单颗粒	51.0	24.1	23.1	1.0	1∶1.55∶1.78
10 kV单颗粒	48.0	23.1	27.4	1.5	1∶1.52∶1.64
5 kV单颗粒	48.3	21.3	28.9	1.5	1∶1.44∶3.30

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表 2 铈掺杂钇铝石榴石荧光粉和铕掺杂氮化物荧光粉的无窗EDS能谱定量分析结果

Table 2. Compositional analysis of Y₃Al₅O₁₂：Ce and SrAlSiN₃：Eu analyzed by windowless EDS /%

物质	元素	质量分数	原子百分比
Y₃Al₅O₁₂∶Ce（Y∶Al∶O原子比理论值为1∶1.67∶4）	Y	41	13.1
	Al	22.5	23.6
	O	35.6	63.1
	Ce	0.9	0.2
SrAlSiN₃∶Eu（Sr∶Al∶Si∶N原子比理论值为1∶1∶1∶3）	N	23.7	50.1
	Al	16	17.5
	Si	16.9	17.8
	Sr	42.1	14.3
	Eu	1.3	0.3

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参考文献(18)

[1]	Newbury D E, Ritchie N W M. Performing elemental microanalysis with high accuracy and high precision by scanning electron microscopy/silicon drift detector energy-dispersive X-ray spectrometry (SEM/SDD-EDS)[J]. Journal of Materials Science,2015,50 (2):493-518. doi: 10.1007/s10853-014-8685-2
[2]	Török S B, Lábár J, Injuk J, et al. X-ray spectrometry[J]. Analytical Chemistry,1996,68 (12):467-486. doi: 10.1021/a1960016q
[3]	焦汇胜, 李香庭. 扫描电镜能谱仪及波谱仪分析技术[M]. 长春: 东北师范大学出版社, 2011.
[4]	张大同. 扫描电镜与能谱仪分析技术[M]. 广州: 华南理工大学出版社, 2009.
[5]	Schreiner M, Melcher M, Uhlir K. Scanning electron microscopy and energy dispersive analysis: applications in the field of cultural heritage[J]. Analytical and Bioanalytical Chemistry,2007,387 (3):737-747. doi: 10.1007/s00216-006-0718-5
[6]	王忠. 扫描电子显微镜-能谱分析仪(SEM-EDS)中面扫描法在高分子材料失效分析中的应用[J]. 中国检验检测,2022,30(6):7-11.
[7]	赵东升, 郑海鹏, 雷振锋. 扫描电镜与能谱分析在碳酸盐岩储集层中的应用[J]. 电子显微学报,2001,20(4):389-390 ZHAO Dongsheng, ZHENG Haipeng, LEI Zhenfeng. Application of scanning electron microscope and spectrum analysis in carbonate rock reservoir[J]. Journal of Chinese Electron Microscopy Society,2001,20 (4):389-390.
[8]	Marks S, Jabar S, West G, et al. High resolution low kV SEM EDS-breaking convention with low working distance EDS[J]. Microscopy and Microanalysis,2020,26 (S2):2170-2172. doi: 10.1017/S1431927620020681
[9]	Newbury D E, Ritchie N W M. Is scanning electron microscopy/energy dispersive X-ray spectrometry (SEM/EDS) quantitative?[J]. Scanning,2013,35 (3):141-168. doi: 10.1002/sca.21041
[10]	Newbury D E, Ritchie N W M. Electron-excited X-ray microanalysis by energy dispersive spectrometry at 50: analytical accuracy, precision, trace sensitivity, and quantitative compositional mapping[J]. Microscopy and Microanalysis,2019,25 (5):1075-1105. doi: 10.1017/S143192761901482X
[11]	蔡志威, 梁键谋, 陈超. 扫描电子显微镜-能谱联用在鉴别药包材上的应用[J]. 分析测试技术与仪器,2022,28(3):260-266 CAI Zhiwei, LIANG Jianmou, CHEN Chao. Application of scanning electron microscopy-energy dispersive spectroscopy in identification of pharmaceutical packaging materials[J]. Analysis and Testing Technology and Instruments,2022,28 (3):260-266.
[12]	郑娜, 徐丽, 沈素丹, 等. 扫描电子显微镜和能谱分析高性能热塑性板材[J]. 分析测试技术与仪器,2022,28(3):254-259 ZHENG Na, XU Li, SHEN Sudan, et al. Analysis of high-performance thermoplastic plates based on scanning electron microscopy and energy dispersive spectrometry[J]. Analysis and Testing Technology and Instruments,2022,28 (3):254-259.
[13]	蔡志伟, 任小明, 禹宝军. 难检测样品的能谱分析技术研究[J]. 电子显微学报,2021,40(1):55-60 doi: 10.3969/j.issn.1000-6281.2021.01.011 CAI Zhiwei, REN Xiaoming, YU Baojun. Study on the energy spectrum analysis technology of difficult to detect samples[J]. Journal of Chinese Electron Microscopy Society,2021,40 (1):55-60. doi: 10.3969/j.issn.1000-6281.2021.01.011
[14]	Lin H W, Noguchi H, Uosaki K. Application of windowless energy dispersive spectroscopy to determine Li distribution in Li-Si alloys[J]. Applied Physics Letters,2018,112 (7):1-4.
[15]	Marshall A T. The windowless energy didpersive-X-ray detector-prospects for a role in biological X-ray-microanalysis[J]. Scanning Electron Microscopy, 1984: 493-504.
[16]	高尚, 黄梦诗, 杨振英, 等. 扫描电镜中X射线能谱仪的技术进展[J]. 分析科学学报,2022,38(1):115-121 GAO Shang, HUANG Mengshi, YANG Zhen-ying, et al. Technical progress of X-ray energy dispersive spectroscopy in scanning electron microscope[J]. Journal of Analytical Science,2022,38 (1):115-121.
[17]	唐靓, 叶慧琪, 肖东. 溶胶-凝胶法制备YAG: Ce, Yb纳米荧光粉及其发光性质研究[J]. 发光学报,2018,39(8):1051-1058 doi: 10.3788/fgxb20183908.1051 TANG Liang, YE Huiqi, XIAO Dong. YAG: Ce, Yb nano-phosphor synthesized by sol-gel method and its luminescence properties[J]. Chinese Journal of Luminescence,2018,39 (8):1051-1058. doi: 10.3788/fgxb20183908.1051
[18]	林海凤, 王海波, 张瑞西, 等. 白光LED用氮化物及氮氧化物红色荧光粉的研究现状[J]. 材料导报,2010,24(21):10-13 LIN Haifeng, WANG Haibo, ZHANG Ruixi, et al. Present research situation of the nitride and oxynitride red phosphors for white-LED[J]. Materials Reports,2010,24 (21):10-13.