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At least 253 records · Page 14

Secondary Ion Mass Spectrometry (SIMS) for Chemical Characterization of Metal Halide Perovskites

Metal halide perovskite (MHP) solar cells have attracted much attention due to the rapidly growing power conversion efficiency that has reached 25.2% in a decade, comparable to established commercial photovoltaic modules. Compositional engineering is one of the most effective methods to boost the performance of MHP solar cells. Further improving the efficiency and the stability of MHP solar cells necessitates good understanding of the chemical–efficiency correlation and the chemical evolution during the degradation of MHP solar cells. In this regard, time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a powerful tool to investigate the chemical aspect of MHPs and has played an important role in advancing the development of MHP optoelectronics. However, up to date, a review that can guide future utilization of ToF-SIMS in the MHP development is missing. In this paper, the capabilities of ToF-SIMS in MHP investigations are summarized and analyzed from simple material synthesis and chemical distribution to more complicated device operation mechanism and stability. The strength of ToF-SIMS in resolving important issues in this field, such as interface composition, ion migration, and degradation in MHP is highlighted. Finally, an outlook with an emphasis on making the utmost of ToF-SIMS in developing MHP devices is provided.

36 MATERIALS SCIENCE↗

Elemental analysis of air-sensitive frozen molten salt samples using an inert transfer chamber for LIBS/LA-ICP-TOF-MS analysis

A novel inert sample transfer system was developed and employed to enable, for the first time, the analysis of air-sensitive salt samples in a two-volume ablation cell using simultaneous laser-induced breakdown spectroscopy (LIBS) and laser ablation (LA)-inductively coupled plasma (ICP)-time-of-flight (TOF)-mass spectrometry (MS) analysis. Molten salts are of growing interest as a medium for advanced nuclear reactors and nuclear fuel reprocessing technologies continue to be developed around their use. However, compositional analysis of molten salt samples can be challenging because of their air-sensitive nature and varying solubilities leading to inaccurate measurements when digested. LA-based analysis provides an alternate method to digestion and can provide rapid elemental information with little sample preparation. In this study, LIBS and LA-ICP-TOF-MS were used to analyze the Ce content in frozen salt samples taken from a series of electrochemical experiments. Calibrations were built for each technique, and the resulting limits of detection for Ce were estimated to be 107 and 58 µg g −1 for LIBS and LA-ICP-TOF-MS, respectively. Test samples from the electrochemical experiments were analyzed using these calibrations. The results matched bulk digestion-based ICP-optical emission spectroscopy values, and daily trends in Ce concentration changes were identified. Additionally, the LIBS and LA-ICP-TOF-MS analysis was demonstrated for identifying microgram per gram levels of components and detecting trace contaminants. The impurities detected by LIBS included Al, Mg, Ca, and Na. The impurities detected by LA-ICP-TOF-MS included W, Ag, Al, Fe, Ni, Mo, Nd, Sm, Th, and U.

Andrews, Hunter B. [Oak Ridge National Laboratory ↗

The roles of the binodal curve and the spinodal curve in expansions from the supercritical state with flashing

Data extracted from time-of-flight (TOF) measurements made on steady-state He free jets at Göttingen already in 1986 and for pulsed Ne free jets investigated recently at Tel Aviv have been added to an earlier plot of terminal condensed-phase mass fraction x{sub 2∞} as a function of the dimensionless scaling parameter Γ. Γ characterizes the source (fluid species, temperature, pressure and throat diameter); values of x{sub 2∞} are extracted from TOF measurements using conservation of energy in the free-jet expansion. For nozzles consisting of an orifice in a thin plate; the extracted data yield 22 data points which are correlated satisfactorily by a single curve. The Ne free jets were expanded from a conical nozzle with a 20° half angle; the three extracted data points stand together but apart from the aforementioned curve, indicating that the presence of the conical wall influences significantly the expansion and hence the condensation. The 22 data points for the expansions via an orifice consist of 15 measurements with expansions from the gas-phase side of the binodal curve which crossed the binodal curve downstream from the sonic point and 7 measurements with expansions of the gas-phase product of the flashing which occurred after an expansion from the liquid-phase side of the binodal curve crossed the binodal curve upstream from the sonic point. The association of these 22 points with a single curve supports the alternating-phase model for flows with flashing upstream from the sonic point proposed earlier. In order to assess the role of the spinodal curve in such expansions, the spinodal curves for He and Ne were computed using general multi-parameter Helmholtz-free-energy equation-of-state formulations. Then, for the several sets of source-chamber conditions used in the free-jet measurements, thermodynamic states at key locations in the free-jet expansions (binodal curve, sonic point and spinodal curve) were evaluated, with the expansion presumed to be metastable from the binodal curve to the spinodal curve. TOF distributions with more than two peaks (interpreted earlier as superimposed alternating-state TOF distributions) indicated flashing of the metastable flow downstream from the binodal curve but upstream from the sonic point. This relatively early flashing is due apparently to destabilizing interactions with the walls of the source. If the expansion crosses the binodal curve downstream from the nozzle, the metastable fluid does not interact with surfaces and flashing might be delayed until the expansion reaches the spinodal curve. It is concluded that, if the expansion crosses the binodal curve before reaching the sonic point, the resulting metastable fluid downstream from the binodal curve interacts with the adjacent surfaces and flashes into liquid and vapor phases which expand alternately through the nozzle; the two associated alternating TOF distributions are superposed by the chopping process so that the result has the appearance of a single distribution with three peaks.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

An integrated time-of-flight versus residual energy subsystem for a compact dual ion composition experiment for space plasmas

We have developed a novel concept for a Compact Dual Ion Composition Experiment (CoDICE) that simultaneously provides high quality plasma and energetic ion composition measurements over 6 decades in ion energy in a wide variety of space plasma environments. CoDICE measures the two critical ion populations in space plasmas: (1) mass and ionic charge state composition and 3D velocity and angular distributions of ∼10 eV/q–40 keV/q plasma ions—CoDICE-Lo and (2) mass composition, energy spectra, and angular distributions of ∼30 keV–10 MeV energetic ions—CoDICE-Hi. CoDICE uses a common, integrated Time-of-Flight (TOF) versus residual energy (E) subsystem for measuring the two distinct ion populations. This paper describes the CoDICE design concept, and presents results of the laboratory tests of the TOF portion of the TOF vs. E subsystem, focusing specifically on (1) investigation of spill-over and contamination rates on the start and stop microchannel plate (MCP) anodes vs. secondary electron steering and focusing voltages, scanned around their corresponding model-optimized values, (2) TOF measurements and resolution and angular resolution, and (3) cross-contamination of the start and stop MCPs’ singles rates from CoDICE-Lo and -Hi, and (4) energy resolution of avalanche photodiodes near the lower end of the CoDICE-Lo energy range. We also discuss physical effects that could impact the performance of the TOF vs. E subsystem in a flight instrument. Finally, we discuss advantages of the CoDICE design concept by comparing with capabilities and resources of existing flight instruments.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Diamond detectors for the TOTEM timing upgrade

This paper describes the design and the performance of the timing detector developed by the TOTEM Collaboration for the Roman Pots (RPs) to measure the Time-Of-Flight (TOF) of the protons produced in central diffractive interactions at the LHC . The measurement of the TOF of the protons allows the determination of the longitudinal position of the proton interaction vertex and its association with one of the vertices reconstructed by the CMS detectors. The TOF detector is based on single crystal Chemical Vapor Deposition (scCVD) diamond plates and is designed to measure the protons TOF with about 50 ps time precision. This upgrade to the TOTEM apparatus will be used in the LHC run 2 and will tag the central diffractive events up to an interaction pileup of about 1. A dedicated fast and low noise electronics for the signal amplification has been developed. The digitization of the diamond signal is performed by sampling the waveform. In conclusion, after introducing the physics studies that will most profit from the addition of these new detectors, we discuss in detail the optimization and the performance of the first TOF detector installed in the LHC in November 2015.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Performance of the Tachyon Time-of-Flight PET Camera

We have constructed and characterized a time-of-flight Positron Emission Tomography (TOF PET) camera called the Tachyon. The Tachyon is a single-ring Lutetium Oxyorthosilicate (LSO) based camera designed to obtain significantly better timing resolution than the ~ 550 ps found in present commercial TOF cameras, in order to quantify the benefit of improved TOF resolution for clinically relevant tasks. The Tachyon's detector module is optimized for timing by coupling the 6.15 ×25 mm 2 side of 6.15 ×6.15 ×25 mm 3 LSO scintillator crystals onto a 1-inch diameter Hamamatsu R-9800 PMT with a super-bialkali photocathode. We characterized the camera according to the NEMA NU 2-2012 standard, measuring the energy resolution, timing resolution, spatial resolution, noise equivalent count rates and sensitivity. The Tachyon achieved a coincidence timing resolution of 314 ps +/- 20 ps FWHM over all crystal-crystal combinations. Experiments were performed with the NEMA body phantom to assess the imaging performance improvement over non-TOF PET. We find that the results show that at a matched contrast, incorporating 314 ps TOF reduces the standard deviation of the contrast by a factor of about 2.3.

47 OTHER INSTRUMENTATION↗

Advanced Mass Spectrometry for Proteomics and Other Biological Applications

The purpose of the collaboration between Agilent Technologies and Battelle is to integrate Battelle’s unique electrospray ionization ion mobility spectrometry (ESI/IMS) technology with Agilent’s state-of-art time of flight mass spectrometry (TOF MS) to design and fabricate multiple ESI/IMS/TOF MS instrument platforms for large scale demonstration of proteomics analyses. The development is aimed at the firm foundation for a premium new IMS/MS product for Agilent and the dissemination of important analytical advances for the scientific community Three initial prototype systems are planned to be utilized as part of this effort. These are as follows: - Prototype 1: This prototype will based upon the integration of Battelle’s existing IMS Version 3 front-end with the latest version of Agilent’s TOF instrument (the SEIKO TOF) that will include an upgraded high-speed ADC. - Prototype 2: This prototype will be based on the integration of Battelle’s more advanced IMS Version 4 front-end with an existing Agilent TOF system already installed at PNNL. - Prototype 3: This prototype will be based on the integration of a modified IMS Version 4 front-end with Agilent’s most advanced TOF instruments. The collaboration consists of four tasks based on the prototypes and these are: - Task 1. Assembly and Testing of Prototype 1 - Task 2. Assembly and Testing of Prototype 2 - Task 3. Fabrication, Assembly, and Testing of Prototype 3 - Task 4. Final report

Baker, Erin Shammel↗

Trade Study for Neutron Transport at Low Earth Orbit: Adding Fidelity to DIORAMA

The Distributed Infrastructure Offering Real-Time Access to Modeling and Analysis (DIORAMA) software provides performance modeling capabilities of the United States Nuclear Detonation Detection System (USNDS) with a focus on the characterization of Space-Based Nuclear Detonation Detection (SNDD) instrument performance [1]. A case study was done to add the neutron propagation capabilities of DIORAMA to low earth orbit (LEO), and compare the back-calculated incident energy from the time-of- ight (TOF) spectrum with the scored incident energy spectrum. As the scoring altitude lowers, the time increase due to scattering takes up much more of the fraction of total TOF; whereas at geosynchronous earth orbit (GEO), the time increase due to scattering is a negligible fraction of the total TOF [2]. The scattering smears out the TOF enough to make the back-calculation of the initial energy spectrum from the TOF spectrum very convoluted.

79 ASTRONOMY AND ASTROPHYSICS↗

Integrated Spatial, Spectral, & Temporal Optical Reflectance System for Precision Occupancy & Location Sensing to Improve Building Energy Efficiency

Buildings consume approximately 35% of the electricity used in the U.S. and building owners can significantly reduce this energy use by providing services like heating, electrical power and lighting only when people are present. The ARPAe funded program titled “INTEGRATED SPATIAL, SPECTRAL, & TEMPORAL OPTICAL REFLECTANCE SYSTEM FOR PRECISION OCCUPANCY & LOCATION SENSING TO IMPROVE BUILDING ENERGY EFFICIENCY” demonstrates how a low cost sensor technology developed for measuring distances can be used to count and locate occupants with a high degree of precision with a very low error rates. This platform tells a building control system where occupants are located (but not who they are) so that energy consuming services can be provided only when the services are needed by building occupants. The original proof of concept involved using low cost, commercially available time-of-flight (TOF) sensors that measure distance, but the performance of these existing sensors was lacking, as they could not operate properly in the presence of sunlight, which blinded the simple TOF sensors and limited their utility in buildings. This project proposed a powerful new class of TOF sensors that used state-of-the-art integrated circuit (IC) fabrication processes that combined advanced photonics with conventional silicon chip circuitry for improved sensor performance. An equally important part of this project was to find ways to maximize occupant count and location accuracy while using the fewest number of sensors possible, in order to keep costs low. By using building blueprints to create digital twins of commercial building spaces, the team developed new algorithms to maximize occupant count and tracking accuracy by properly locating the minimum number of sensors at just the right spots in the building. This capability not only minimizes system costs but also simplified sensor installation and system commissioning. Our simulations of our sensor networks for a range of commercial floorplan designs demonstrated that our installed cost target of $0.08/sqft was attainable, though not fully demonstrated during the project. Finally, we noted that the TOF sensor concept could provide a valuable role in health and eldercare by tracking patients without the need for worn sensors and would be useful for fall detection and other patient safety metrics, including tracking healthcare/patient interactions. We feel that, when fully developed, this new class of sophisticated TOF sensors and support software will be a powerful new approach to improving building energy efficiency based on occupant centric control platforms and will also open new levels of patient safety in healthcare operations. To realize this potential, the team formed the Troy Sensor Company LLC to oversee licensing of the programs patents and continue to seek commercialization of this program’s activity sensing technologies.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Position-Dependent Neutron Time-of-Flight Deviation at VULCAN Diffractometer

In neutron diffraction, it is critical to precisely measure the lattice spacing, as it is an indicator of a material’s physical characteristics, such as lattice strain, thermal expansion, and phase structures. In time-of-flight (TOF) measurements, the lattice spacing is determined by the recorded TOF from a well-calibrated instrument. However, changes in neutron time-of-flight are sensitive to many factors, such as the alignment of instrument optics, temperature, sample positions, sample dimensions, internal strains, and chemical or physical heterogeneities at the grain level. At VULCAN (SNS, ORNL), which is a high-flux engineering neutron diffractometer, we used a 1-mm-diameter diamond powder sample to scan for changes in TOF by measuring d-spacing values at different sample positions under several configurations. The 2D map of the TOF deviation or d-spacing deviation, in terms of lattice shift/lattice strain, is reported. The change in TOF is dependent on the scanned location in the beam as well as on detector locations. The results are informative for experimental planning, data interpretation, and future instrument design.

36 MATERIALS SCIENCE↗

A Comparative Study on Computation of Cumulative Distribution Function in Predicting Time of Failure of Engineering Systems

Estimating accurate Time-of-Failure (ToF) of a system is key in making the decisions that impact operational safety and optimize cost. In this context, it is interesting to note that different approaches have been explored to tackle the problem of estimating ToF. The difference is in part characterized by different definitions of the hazard zones. The conventional definition for the cumulative distribution function (CDF) calculation is assumed to have well-defined hazard zones, that is, hazard zones defined as a function of the system state trajectory. An alternate method suggests the use of hazard zones defined as a function of the system state at time , instead of hazard zones defined as a function of system state up to and including time k (Acuna and Orchard 2018, 2017). This paper explores these differences and their impact on ToF estimation. Results for the conventional CDF definition indicated that, (i) the cumulative distribution function is always an increasing function of time, even when realizations of the degradation process are not monotonic, (ii) the sum of all probabilities is always 1 and does not need to be normalized, and (iii) all probabilities are positive and less than or equal to 1. Similar results are not observed for CDF calculation with hazard zones defined as a function only of the system state at time . Results for ToF estimation using Acuna's definition differ, suggesting that there is an underlying assumption of independence in the hazard zone definition. Therefore, we present an alternate definition of hazard zone which guarantees the properties of a well-defined CDF with a more straightforward ToF definition.

Hazard Zone↗

Development of picoseconds Time of Flight systems in Meson Test Beam Facility at Fermilab

The goal of the work is to develop time of flight (TOF) system with about 10 picosecond time resolution in real beam line when start and stop counters separated by some distance. We name the distance as 'base' for the TOF. This 'real' TOF setup is different from another one when start and stop counters located next to each other. The real TOF is sensitive to beam momentum spread, beam divergence, etc. Anyway some preliminary measurements are useful with close placement of start and stop counter. We name it 'close geometry'. The work started about 2 years ago at Fermilab Meson Test Beam Facility (MTBF). The devices tested in 'close geometry' were Microchannel Plate Photomultipliers (MCP PMT) with Cherenkov radiators. TOF counters based on Silicon Photomultipliers (SiPms) with Cherenkov radiators also in 'close geometry' were tested. We report here new results obtained with the counters in the MTBF at Fermilab, including beam line data.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Characterization of a double Time-Of-Flight detector system for accurate velocity measurement in a storage ring using laser beams

The Isochronous Mass Spectrometry (IMS) is a powerful tool for mass measurements of exotic nuclei with half-lives as short as several tens of micro-seconds in storage rings. In order to improve the mass resolving power while preserving the acceptance of the storage ring, the IMS with two Time-Of-Flight (TOF) detectors has been implemented at the storage ring CSRe in Lanzhou, China. Additional velocity information beside the revolution time in the ring can be obtained for each of the stored ions by using the double TOF detector system. In this paper, we introduced a new method of using a 658 nm laser range finder and a short-pulsed ultra-violet laser to directly measure the distance and time delay difference between the two TOF detectors which were installed inside the 10 -11 mbar vacuum chambers. Here, the results showed that the distance between the two ultra-thin carbon foils of the two TOF detectors was ranging from 18032.5 mm to 18035.0 mm over a measurable area of 20x20 mm 2 .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Molecular imaging of plant-microbe interactions on the Brachypodium seed surface

Plant growth-promoting rhizobacteria (PGPR) play a crucial role in biological control and pathogenic defense on and with-in plant tissues, however the mechanism(s) by which plants associate with PGPR to elicit such beneficial effects needs further study. Here, we present high mass resolution time-of-flight secondary ion mass spectrometry (ToF-SIMS) imaging of Brachypodium distachyon (Brachypodium) seeds with and without exposure to two model PGPR, i.e., Gram-negative Pseudomonas fluorescens SBW25::GFP (P.) and Gram-positive Arthrobacter chlorophenolicus A6::GFP (A.). Delayed image extraction was used to image PGPB-treated seed sections to reveal morphological changes. ToF-SIMS spectral compari-son, principal component analysis (PCA), and two-dimensional (2D) imaging show that the selected PGPR have different effects on the host seed surface, resulting in changes in chemical composition and morphology. Metabolite prod-ucts and biomarkers, such as flavonoids, phenolic com-pounds, fatty acids, and indole-3-acetic acid (IAA), were ob-served on the PGPR-treated seed surfaces. These compounds had different distributions on the Brachypodium seed surface for the two PGPR, indicating that the different bacteria elicited distinct responses from the host. Our results illustrate that ToF-SIMS is an effective tool to study plant-microbe interac-tions and to provide insightful information with submicrome-ter lateral resolution of the chemical distributions associated with morphological features, potentially offering a new way to study the mechanisms underlying beneficial roles of PGPR.

PGPR, Brachypodium distachyon, ToF-SIMS, metabolit↗

Chapter 13: Time-of-Flight Secondary-Ion Mass Spectrometry and Atom Probe Tomography

Time-of-flight secondary-ion mass spectrometry (TOF-SIMS) and atom probe tomography (APT) have many similarities. Both detect the chemical makeup of a solid material at ppm or better sensitivity, while retaining the spatial location information from the signal. Both use a similar principle to measure a signal associated with a given charged secondary ion—the flight time it takes a secondary ion to reach the detector after it is generated. Both are destructive techniques—albeit destructive of very small volumes—because the signal measured is generated by the removal of material from the sample itself. Importantly, both techniques require ultra-high vacuum (UHV) to ensure that the secondary ions, once generated, can reach the detector without collision with other atoms in the gas phase. In the case of TOF-SIMS, the samples can vary from several mm to several inches in size, whereas for APT, the samples are cones several hundred microns in size that are prepared in a special manner (covered in detail later in the chapter). We will discuss the basic fundamentals of each technique and cover several examples of the technique applied to photovoltaic materials, which should give a good idea of the types of information one can gain from TOF-SIMS and APT and how they are complementary as they both operate at different length scales: at the hundreds of microns to hundreds of nanometer scale for TOF-SIMS and at the nanometer to a few angstroms scale for APT.

41 EE - Solar Energy Technologies Office (EE-4S)↗

Molecular detection of per- and polyfluoroalkyl substances in water using time-of-flight secondary ion mass spectrometry

Detection of per- and polyfluoroalkyl substances (PFASs) is crucial in environmental mitigation and remediation of these persistent pollutants. We demonstrate that time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a viable technique to analyze and identify these substances at parts per trillion (ppt) level in real field samples without complicated sample preparation due to its superior surface sensitivity. Several representative PFAS compounds, such as perfluorooctanesulfonic acid (PFOS), perfluorobutanoic acid (PFBA), perfluoropentanoic acid (PFPeA), perfluoheptanoic acid (PFHpA), and perfluorononanoic acid (PFNA), and real-world groundwater samples collected from monitoring wells installed around at a municipal wastewater treatment plant located in Southern California were analyzed in this work. ToF-SIMS spectral comparison depicts sensitive identification of pseudo-molecular ions, characteristic of reference PFASs. Additionally, principal component analysis (PCA) shows clear discrimination among real samples and reference compounds. Our results show that characteristic molecular ion and fragments peaks can be used to identify PFASs. Furthermore, SIMS two-dimensional (2D) images directly exhibit the distribution of perfluorocarboxylic acid (PFCA) and PFOS in simulated mixtures and real wastewater samples. Such findings indicate that ToF-SIMS is useable to determine PFAS compounds in complex environmental water samples. In conclusion, ToF-SIMS provides simple sample preparation and high sensitivity in mass spectral imaging, offering an alternative solution for environmental forensic analysis of PFASs in wastewater in the future.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solvent effects on differentiation of mouse brain tissue using laser microdissection ‘cut and drop’ sampling with direct mass spectral analysis

Rationale: Laser microdissection-liquid vortex capture/electrospray ionization mass spectrometry (LMD-LVC/ESI-MS) has potential for on-line classification of tissue but an investigation into what analytical conditions provide best spectral differentiation has not been conducted. The effects of solvent, ionization polarity, and spectral acquisition parameters on differentiation of mouse brain tissue regions are described.Methods: Individual 40 × 40 μm microdissections from cortex, white, grey, granular, and nucleus regions of mouse brain tissue were analyzed using different capture/ESI solvents, in positive and negative ion mode ESI, using time-of-flight (TOF)-MS and sequential window acquisitions of all theoretical spectra (SWATH)-MS (a permutation of tandem-MS), and combinations thereof. Principal component analysis-linear discriminant analysis (PCA-LDA), applied to each mass spectral dataset, was used to determine the accuracy of differentiation of mouse brain tissue regions. Results: Mass spectral differences associated with capture/ESI solvent composition manifested as altered relative distributions of ions rather than the presence or absence of unique ions. In negative ion mode ESI, 80/20 (v/v) methanol/water yielded spectra with low signal/noise ratios relative to other solvents. PCA-LDA models acquired using 90/10 (v/v) methanol/chloroform differentiated tissue regions with 100% accuracy while data collected using methanol misclassified some samples. The combination of SWATH-MS and TOF-MS data improved differentiation accuracy.Conclusions: Combined TOF-MS and SWATH-MS data differentiated white, grey, granular, and nucleus mouse tissue regions with greater accuracy than when solely using TOF-MS data. Using 90/10 (v/v) methanol/chloroform, tissue regions were perfectly differentiated. Lastly, these results will guide future studies looking to utilize the potential of LMD-LVC/ESI-MS for tissue and disease differentiation.

47 OTHER INSTRUMENTATION↗