{"title":"Glow Discharge Optical Emission Coded Aperture Spectroscopy","authors":"Harsshit Agrawaal, and , Gerardo Gamez*, ","doi":"10.1021/acs.analchem.4c0471810.1021/acs.analchem.4c04718","DOIUrl":null,"url":null,"abstract":"<p >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)<sub>GPU</sub> showed the best performance of the CS algorithms studied, including SeSCI<sub>CPU</sub>, 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.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"97 4","pages":"2078–2085 2078–2085"},"PeriodicalIF":6.7000,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Analytical Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.analchem.4c04718","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ANALYTICAL","Score":null,"Total":0}
引用次数: 0
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.
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.