Glow Discharge Optical Emission Coded Aperture Spectroscopy

IF 6.7 1区 化学 Q1 CHEMISTRY, ANALYTICAL
Harsshit Agrawaal,  and , Gerardo Gamez*, 
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Abstract

Glow discharge optical emission spectrometry (GDOES) allows fast and simultaneous multielemental analysis directly from solids and depth profiling down to the nanometer scale, which is critical for thin-film (TF) characterization. Nevertheless, operating conditions for the best limits of detection (LODs) are compromised in lieu of the best sputtering crater shapes for depth resolution. In addition, the fast transient signals from ultra-TFs do not permit the optimal sampling statistics of bulk analysis such that LODs are further compromised. Furthermore, commercial GDOES instruments rely on a slit-based light dispersion that favors high spectral resolution at the expense of light throughput. Here, a new technique called glow discharge optical emission coded aperture spectrometry (GOCAS) is shown to allow both a higher spectral resolution and higher light throughput by using a coded aperture (CA) with multiple thin slits at the spectrograph’s entrance to measure the convoluted spectra and compressed sensing (CS) algorithms to recover the deconvoluted spectra from the full field of view. The effects of CA characteristics on spectral reconstruction fidelity were studied and showed the best fidelity for smaller slits, 50% transmittance, and wider CA with a higher number of slits. In addition, Shearlet enhanced snapshot compressive imaging (SeSCI)GPU showed the best performance of the CS algorithms studied, including SeSCICPU, two-step iterative shrinkage/thresholding (TwIST), and alternating direction method of multipliers total variation minimization (ADMM-TV). Moreover, GOCAS is shown to be very robust against increasing detector Gaussian noise. Finally, standard reference materials are used to show up to ∼30× improved S/N and an order-of-magnitude improved LODs, at the fastest acquisition times (fraction of a ms), which has the potential to be transformative for depth profiling of nanostructured materials.

Abstract Image

辉光放电光学发射编码孔径光谱学
辉光放电光学发射光谱法(GDOES)允许快速和同时的多元素分析,直接从固体和深度剖面到纳米尺度,这对薄膜(TF)表征至关重要。然而,最佳探测极限(lod)的操作条件受到损害,而不是最佳溅射陨石坑形状的深度分辨率。此外,来自超tf的快速瞬态信号不允许批量分析的最佳采样统计,从而进一步损害lod。此外,商用GDOES仪器依赖于基于狭缝的光色散,以牺牲光吞吐量为代价支持高光谱分辨率。本文介绍了一种名为辉光放电光学发射编码孔径光谱法(GOCAS)的新技术,该技术通过在光谱仪入口处使用带有多个细缝的编码孔径(CA)来测量卷积光谱,并使用压缩感知(CS)算法从整个视场中恢复反卷积光谱,从而实现更高的光谱分辨率和更高的光吞吐量。研究了CA特性对光谱重建保真度的影响,结果表明,较窄狭缝、50%透光率和较宽狭缝、较多狭缝的CA具有最佳的保真度。此外,Shearlet增强快照压缩成像(SeSCI)GPU在SeSCICPU、两步迭代收缩/阈值法(TwIST)和乘子总变化最小化交替方向法(ADMM-TV)等CS算法中表现出最好的性能。此外,GOCAS对增加的检测器高斯噪声具有很强的鲁棒性。最后,使用标准参考材料,在最快的采集时间(毫秒的几分之一)下,显示高达~ 30倍改进的信噪比和数量级改进的lod,这有可能改变纳米结构材料的深度剖面。
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来源期刊
Analytical Chemistry
Analytical Chemistry 化学-分析化学
CiteScore
12.10
自引率
12.20%
发文量
1949
审稿时长
1.4 months
期刊介绍: Analytical Chemistry, a peer-reviewed research journal, focuses on disseminating new and original knowledge across all branches of analytical chemistry. Fundamental articles may explore general principles of chemical measurement science and need not directly address existing or potential analytical methodology. They can be entirely theoretical or report experimental results. Contributions may cover various phases of analytical operations, including sampling, bioanalysis, electrochemistry, mass spectrometry, microscale and nanoscale systems, environmental analysis, separations, spectroscopy, chemical reactions and selectivity, instrumentation, imaging, surface analysis, and data processing. Papers discussing known analytical methods should present a significant, original application of the method, a notable improvement, or results on an important analyte.
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