Study on Reference Materials of Copper Content in Aluminum-Copper Thin Films
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摘要: 研制了一种X射线能谱仪/波谱仪校准用铝铜薄膜铜元素含量标准物质,使用电子探针对研制的铝铜薄膜铜元素含量标准物质进行均匀性、稳定性检验,使用电感耦合等离子体发射光谱仪(ICP-OES)对标准物质的铜元素含量(wt%)进行了定值,分析了名义值为49.5%的铝铜薄膜标准物质铜元素含量的不确定度来源,评定了标准物质的不确定度。研究结果表明:标准物质样品具有良好的均匀性和稳定性,标准物质的铜元素含量标准值为49.46 wt%,扩展不确定度为0.98 wt%(k=2)。研制的X射线能谱仪/波谱仪校准用铝铜薄膜铜元素含量标准物质,满足了X射线能谱仪/波谱仪定量分析过程中的校准需求,填补了X射线能谱仪/波谱仪校准用标准物质的国内空白,为我国科研产业的铜元素含量定量分析提供了量值保障和技术支撑。Abstract: An aluminum-copper (Al-Cu) thin film reference material for copper content, intended for the calibration of X-ray energy/wave spectrometers, was developed in this study. The uniformity and stability of the developed Al-Cu thin film reference material were evaluated using an electronic probe. An inductively coupled plasma emission spectrometer (ICP-OES) was employed to determine the copper content (wt%) of the reference material. The sources of uncertainty for the copper content in the Al-Cu film standard with a nominal value of 49.5% were examined, and the uncertainty of the reference material was evaluated. The findings indicate that the reference material displays good uniformity and stability. The copper content standard value of the reference material was found to be 49.46 wt%, with an extended uncertainty of 0.98 wt% (k=2). The developed Al-Cu thin film copper content reference material for X-ray energy/wave spectrometer calibration meets the calibration requirements for quantitative analyses conducted with X-ray energy/wave spectrometers. It fills a domestic gap in reference materials for X-ray energy/wave spectrometer calibration and provides a measurement assurance and technical support for the quantitative analysis of copper content in China's scientific research industry.
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Key words:
- metrology /
- copper /
- X-ray energy/wave spectrometers /
- reference material /
- calibration /
- uncertainty
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表 1 长期稳定性检验结果
Table 1. Results of long-term stability testing
检验日期(间隔/月) 铜元素含量(wt%) 平均值(wt%) 1 2 3 0 45.91 46.24 45.75 45.97 3 46.06 45.84 46.03 45.98 6 45.49 45.65 45.80 45.65 9 46.18 45.97 46.08 46.08 12 46.06 45.63 45.53 45.74 b1 −0.011844 t0.95, n-2 3.18 s(b1) 0.020848 t0.95, n−2∙s(b1) 0.066298 |b1|<t0.95, n−2·s(b1),斜率不显著,样品稳定性好
稳定性引入不确定度为us=s(b1) ·t,us−l=s(b1)·t =0.250%表 2 短期稳定性测量结果
Table 2. Results of short-term stability measurement
时间/天 1 3 7 铜元素含量(wt%) 45.93 46.14 45.94 45.95 45.98 46.13 46.12 46.13 45.97 平均值(wt%) 46.03 标准偏差(wt%) 0.09 表 3 铜元素含量名义值为49.5%的铝铜薄膜标准物质样品的铜元素含量ICP-OES测试结果
Table 3. ICP-OES measurement results of copper content in the Al-Cu thin film standard material sample with a nominal copper content of 49.5%
实验室编号 薄膜中铜元素含量(wt%) 平均值(wt%) 标准偏差(wt%) 1 48.942 49.178 49.090 48.978 49.147 49.102 49.073 0.09360 2 48.986 49.275 49.125 49.809 49.504 49.397 49.349 0.29173 3 49.689 50.005 49.829 49.832 49.493 49.674 49.754 0.17507 4 49.548 49.742 49.484 49.677 49.806 49.419 49.613 0.15267 5 49.387 49.355 49.387 49.355 49.452 49.419 49.392 0.03771 6 49.161 49.387 49.355 49.258 49.065 49.226 49.242 0.12027 7 49.606 49.300 49.316 49.413 49.781 49.800 49.536 0.22526 8 50.135 49.316 49.510 49.632 50.310 49.426 49.722 0.40545 8家实验室测量薄膜中铜元素含量平均值:49.46% 表 4 8家实验室ICP-OES测量铝铜薄膜铜元素含量标准曲线引入的不确定度
Table 4. Uncertainty introduced by the standard curve of copper content in Al-Cu film as measured by ICP-OES in eight laboratories
实验室编号 标准曲线 相关系数R ucurve(wt%) 1 y=2425.7x+77.722 0.99999 0.100 2 y=162014x+4317.6 0.99997 0.071 3 y=300172x-4532.5 0.99998 0.096 4 y=3446.6x-22.179 0.99999 0.072 5 y=30787x+2520 0.99998 0.085 6 y=142167x-1824.5 0.99999 0.061 7 y=2383.9x-41.19 0.99998 0.092 8 y=8505.3x-134.38 0.99999 0.068 表 5 名义值为49.5%的铝铜薄膜标准物质铜元素含量的不确定度
Table 5. Uncertainty in the copper content of the Al-Cu thin film standard material with a nominal value of 49.5%
实验室编号 1 2 3 4 5 6 7 8 A类不确定度(wt%) ur 0.0936 0.2917 0.1751 0.1527 0.0377 0.1203 0.2253 0.4055 B类不确定度(wt%) um 0.0463 uV-sample 0.0093 uCRM-cal / uCRM-dilution 0.2543 uCRM 0.0247 upipette 0.2473 uV-CRM 0.0536 ucurve 0.100 0.071 0.096 0.072 0.085 0.061 0.092 0.068 uh-mac(wt%) 0.196 uh-mic(wt%) 0.124 us-l(wt%) 0.250 us-s(wt%) 0.090 u(r+curve)(wt%) 0.1370 0.3002 0.1997 0.1688 0.0930 0.1349 0.2433 0.4111 u(r+curve)_average(wt%) 0.2110 uc(wt%) 0.49 表 6 铝铜薄膜标准物质铜元素含量的量值表达
Table 6. Expression of the copper content value in the Al-Cu thin film standard material
标准物质 特征量 标准值(wt%) 扩展不确定度U(wt%,k=2) 铝铜薄膜 铜元素含量 49.46 0.98 -
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