Deep Learning Models for Data-Driven Laser Induced Breakdown Spectroscopy (LIBS) Analysis of Interstitial Oxygen Impurities in Czochralski-Si Crystals.

Analytical advantages of facile and expeditious spectral data collections from laser-induced breakdown spectroscopy (LIBS) are often offset by the low-accuracy quantitative analyses offered by the technique due to non-equilibrium plasma-matrix interactions. Herein, we developed a one-dimensional (1D) convolutional neural network (CNN) and a least absolute shrinkage and selection operator (LASSO) models for LIBS data analyses to predict trace amounts of interstitial oxygen impurities in commercial Czochralski-silicon (Cz-Si) crystals with known interstitial oxygen concentrations at 0-16 parts per million (ppm). While traditional spectral analyses from O(I) (777.2 nm) atomic lines offer poor accuracy, CNN and LASSO analyses generate excellent predictions for the interstitial oxygen concentrations. Specifically, CNN-based spectral analyses uniquely identified systematic alterations in LIBS fingerprints manifested by laser-matter interactions. Our results pave the path for combining facile and voluminous LIBS data collection with deep learning driven high-fidelity data analytics.

The performance of an inexpensive spark-induced breakdown spectroscopy instrument for near real-time analysis of toxic metal particles.

To meet the demand for identifying and controlling toxic air contaminants in environmental justice communities, we have recently developed a cost-effective spark-induced breakdown spectroscopy (SIBS) instrument for detecting and quantifying toxic metal air pollutants. We characterized the detection limit and linearity of this SIBS instrument by analyzing nebulized elemental standard solutions. The experimental parameters affecting SIBS performance were optimized, including the time delay to observation, the distance between electrodes, and the ablation voltage. The instrument successfully detected Cr, Cu, Mn, Fe, Zn, Co, and Ni, with limits of detection ranged from 0.05 µg m-3 to 0.81 µg m-3 at a flow rate of 15 l min-1 and a 30 min sampling duration. Similar to other investigations using ion breakdown spectroscopy, we did not observe strong emissions lines for As, Sb, Se, Hg, Pb, and Cd, which were likely due to spectral overlap, matrix effects, and the limited detection range of the optical components. Overall, SIBS is a promising technique for field measurements of toxic metals for environmental justice, industrial and urban applications.

Quantification of toxic metals using machine learning techniques and spark emission spectroscopy.

The United States Environmental Protection Agency (US EPA) list of hazardous air pollutants (HAPs) includes toxic metal suspected or associated with development of cancer. Traditional techniques for detecting and quantifying toxic metals in the atmosphere are either not real time, hindering identification of sources, or limited by instrument costs. Spark emission spectroscopy is a promising and cost-effective technique that can be used for analyzing toxic metals in real time. Here, we have developed a cost-effective spark emission spectroscopy system to quantify the concentration of toxic metals targeted by the US EPA. Specifically, Cr, Cu, Ni, and Pb solutions were diluted and deposited on the ground electrode of the spark emission system. The least absolute shrinkage and selection operator (LASSO) was optimized and employed to detect useful features from the spark-generated plasma emissions. The optimized model was able to detect atomic emission lines along with other features to build a regression model that predicts the concentration of toxic metals from the observed spectra. The limits of detections (LODs) were estimated using the detected features and compared to the traditional single-feature approach. LASSO is capable of detecting highly sensitive features in the input spectrum; however, for some toxic metals the single-feature LOD marginally outperforms LASSO LOD. The combination of low-cost instruments with advanced machine learning techniques for data analysis could pave the path forward for data-driven solutions to costly measurements.

Jolly green MOF: confinement and photoactivation of photosystem I in a metal-organic framework.

Photosystem I (PSI) is a ∼1000 kDa transmembrane protein that enables photoactivated charge separation with ∼1 V driving potential and ∼100% quantum efficiency during the photosynthetic process. Although such properties make PSI a potential candidate for integration into bio-hybrid solar energy harvesting devices, the grand challenge in orchestrating such integration rests on rationally designed 3D architectures that can organize and stabilize PSI in the myriad of harsh conditions in which it needs to function. The current study investigates the optical response and photoactive properties of PSI encapsulated in a highly stable nanoporous metal-organic framework (ZIF-8), denoted here as PSI@ZIF-8. The ZIF-8 framework provides a unique scaffold with a robust confining environment for PSI while protecting its precisely coordinated chlorophyll networks from denaturing agents. Significant blue shifts in the fluorescence emissions from UV-vis measurements reveal the successful confinement of PSI in ZIF-8. Pump-probe spectroscopy confirms the photoactivity of the PSI@ZIF-8 composites by revealing the successful internal charge separation and external charge transfer of P700 + and FB - even after exposure to denaturing agents and organic solvents. This work provides greater fundamental understanding of confinement effects on pigment networks, while significantly broadening the potential working environments for PSI-integrated bio-hybrid materials.

Detection of interstitial oxygen contents in Czochralski grown silicon crystals using internal calibration in laser-induced breakdown spectroscopy (LIBS).

We use an internal calibration approach in laser-induced breakdown spectroscopy (LIBS) for quantitative detection of dead load interstitial oxygen contents (Oi) in industrial-grade silicon (Si) crystal ingots. Si crystal samples were grown via Czochralski technique and supplied by SunEdison Semiconductor Ltd. with known Oi contents measured via gas fusion analysis (GFA) and Fourier transform infrared (FTIR) spectroscopy. The LIBS analyses reported here use and compare a direct approach based on the known oxygen atomic emission line at 777. 19 nm and an indirect approach based on an internal calibration technique using an emission line at 781 nm associated to Si I. Unlike the first direct approach, the latter exhibited much higher sensitivity, reliability and less error. In this approach, an internal calibration uses systematic variations in the 781 nm emission line in conjunction with observed changes in plasma excitation temperatures as a quantitative measure of changes in plasma conditions and laser-matter interactions due to varying Oi contents in the analyte matrix. Using this technique, we establish the detection limit of LIBS in measuring Oi in Si crystal ingots down to 8 ±â€¯1 ppma level. The approach assists to overcome the limitations of common industrial techniques such as FTIR that cannot provide accurate quantitative measurements for heavily doped Si crystals and GFA that is significantly cumbersome to be an online technique. Our results establish LIBS at the forefront of alternative industrial analytical tools heretofore not considered for rapid, potential on-line monitoring of dead loads in commercial grade Si wafers during their growth processes.

In-vitro analysis of early calcification in aortic valvular interstitial cells using Laser-Induced Breakdown Spectroscopy (LIBS).

Calcific aortic valve disease (CAVD) is a major cardiovascular disorder caused by osteogenic differentiation of valvular interstitial cells (VICs) within aortic valves. Conventional methods like colorimetric assays and histology fail to detect small calcium depositions during in-vitro VIC cultures. Laser-induced breakdown spectroscopy (LIBS) is a robust analytical tool used for inorganic materials characterizations, but relatively new to biomedical applications. We employ LIBS, for the first time, for quantitative in-vitro detection of calcium depositions in VICs at various osteogenic differentiation stages. VICs isolated from porcine aortic valves were cultured in osteogenic media over various days. Colorimetric calcium assays based on arsenazo dye and Von Kossa staining measured the calcium depositions within VICs. Simultaneously, LIBS signatures for Ca I (422.67 nm) atomic emission lines were collected for estimating calcium depositions in lyophilized VIC samples. Our results indicate excellent linear correlation between the calcium assay and our LIBS measurements. Furthermore, unlike the assay results, the LIBS results could resolve calcium signals from cell samples with as early as 2 days of osteogenic culture. Quantitatively, the LIBS measurements establish the limit of detection for calcium content in VICs to be ∼0.17±0.04 µg which indicates a 5-fold improvement over calcium assay. Picture: Quantitative LIBS enables in-vitro analysis for early stage detection of calcium deposition within aortic valvular interstitial cells (VICs).

Calibration-free quantitative analysis of elemental ratios in intermetallic nanoalloys and nanocomposites using Laser Induced Breakdown Spectroscopy (LIBS).

Intermetallic nanoalloys (NAs) and nanocomposites (NCs) have increasingly gained prominence as efficient catalytic materials in electrochemical energy conversion and storage systems. But their morphology and chemical compositions play critical role in tuning their catalytic activities, and precious metal contents. While advanced microscopy techniques facilitate morphological characterizations, traditional chemical characterizations are either qualitative or extremely involved. In this study, we apply Laser Induced Breakdown Spectroscopy (LIBS) for quantitative compositional analysis of NAs and NCs synthesized with varied elemental ratios by our in-house built pulsed laser ablation technique. Specifically, elemental ratios of binary PtNi, PdCo (NAs) and PtCo (NCs) of different compositions are determined from LIBS measurements employing an internal calibration scheme using the bulk matrix species as internal standards. Morphology and qualitative elemental compositions of the aforesaid NAs and NCs are confirmed from Transmission Electron Microscopy (TEM) images and Energy Dispersive X-ray Spectroscopy (EDX) measurements. LIBS experiments are carried out in ambient conditions with the NA and NC samples drop cast on silicon wafers after centrifugation to increase their concentrations. The technique does not call for cumbersome sample preparations including acid digestions and external calibration standards commonly required in Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES) techniques. Yet the quantitative LIBS results are in good agreement with the results from ICP-OES measurements. Our results indicate the feasibility of using LIBS in future for rapid and in-situ quantitative chemical characterizations of wide classes of synthesized NAs and NCs.