Line Intensities Research Articles

Assessment of the possibility of X-ray fluorescence analysis before conducting the experimental work

The article proposes an approach to the development of a method for X-ray fluorescence analysis of an object using crystal-diffraction spectrometers prior to the experimental work. In case when the X-ray fluorescence analysis method is intended as a substitute for an existing method, then for the object being analyzed the statistical characteristics of the material for which the X-ray fluorescence analysis method is being developed, i.e. the average content of the elements to be determined, the dispersion and the range of the elements content, the requirements for the accuracy of determination, and some others, are calculated on the basis of archival data of the analytical laboratory (or an array of selected calibration samples). In case when a new method is developed, technical requirements for the product allowing estimating these characteristics are sufficient. Analytical characteristics, such as basic instrumental error, sensitivity, spectral resolution, contrast, must be measured and calculated over the entire operating range of the measured analytical lines for the spectrometer used. Metrological characteristics of the method for determining the elements, i.e. detection limit, differential sensitivity, instrumental reproducibility of content measurement at the selected exposure time, are evaluated on the basis of these data. At this stage the question concerning the necessity of diluting the samples with a heavy or light diluent for obtaining satisfactory differential sensitivity may be resolved. The regimes for recording the analytical signal for the elements to be analyzed, i.e. analytical lines, analyzer crystals, X-ray tube operating modes, are determined, the probability of overlapping spectral lines is estimated, and the background measurement points are selected. Calculation of theoretical and simulation of experimental intensities for selected calibration and test samples and calculation of theoretical coefficients of influence are carried out. The expected error of the analysis is estimated on the basis of the statistical characteristics of the material and the theoretical coefficients of influence, and the need to take into account the relationship between the interfering elements in the equations is determined for achieving the required accuracy of determining the elements. Selection of regression or theoretical coupling equations, which provide the required accuracy of determining the elements, is carried out on the basis of the simulated experimental intensities of the analytical lines of the elements. Such approach allows a priory estimate the possibility of developing an X-ray fluorescence analysis technique for an object selected, and can significantly reduce time for performing the experimental work. Keywords: X-ray fluorescence analysis, method of analysis, analyzed object, X-ray spectrometer, analysis characteristics, forecast of experimental intensities, estimation of expected error, modes of registration of the analytical signal, coupling equations.

Color-tunable luminescence and temperature sensing properties of Bi3+/Sm3+ or Bi3+/Eu3+ codoped Ba2Gd2Ge4O13 phosphors.

Novel temperature-sensitive luminescent materials, Ba2Gd2Ge4O13 doped with Bi3+, Bi3+/Sm3+ or Bi3+/Eu3+ ions, have been prepared using a conventional solid-state reaction technique. The XRPD study has verified that all the synthesized germanates crystallize in the monoclinic system (space group C2/c, Z = 4). The crystal lattice of the compounds consists of zigzag chains of edge-sharing Me2O7 (Me = Bi3+, Eu3+ or Sm3+) dimers, [Ge4O13] units, and ten-coordinated Ba atoms. Under UV excitation the powders exhibit the luminescence corresponding to the 3P1 → 1S0 (310-550 nm) transition in Bi3+ and 4G5/2 → 6HJ (550-730 nm) in Sm3+ or 5D0 → 7FJ (570-720 nm) transitions in Eu3+ ions. Heating of Ba2Gd1.94Bi0.01Sm0.05Ge4O13 and Ba2Gd1.89Bi0.01Eu0.1Ge4O13 phosphors leads to an irregular decrease in the intensity of the main emission lines. It has been found that the fluorescence intensity ratio between a wide band in the 310-530 nm region and peaks at longer wavelengths may be successfully used as a temperature-dependent characteristic. Absolute/relative sensitivity values for Ba2Gd1.94Bi0.01Sm0.05Ge4O13 and Ba2Gd1.89Bi0.01Eu0.1Ge4O13 germanates reach 0.19% K-1/0.80% K-1 and 2.21% K-1/0.58% K-1, respectively. The above parameters indicate that Ba2Gd2Ge4O13:Bi3+/Sm3+ or Bi3+/Eu3+ samples can be used as potential luminescent materials for non-contact temperature measurement.

First measurements of an imaging heavy ion beam probe at the ASDEX Upgrade tokamak.

The imaging heavy ion beam probe (i-HIBP) diagnostic has been successfully commissioned at ASDEX Upgrade. The i-HIBP injects a primary neutral beam into the plasma, where it is ionized, leading to a fan of secondary (charged) beams. These are deflected by the magnetic field of the tokamak and collected by a scintillator detector, generating a strike-line light pattern that encodes information on the density, electrostatic potential, and magnetic field of the plasma edge. The first measurements have been made, demonstrating the proof-of-principle of this diagnostic technique. A primary beam of 85/87Rb has been used with energies ranging between 60 and 72keV and extracted currents up to 1.5 mA. The first signals have been obtained in experiments covering a wide range of parameter spaces, with plasma currents (Ip) between 0.2 and 0.8 MA and on-axis toroidal magnetic field (Bt) between 1.9 and 2.7T. Low densities appear to be critical for the performance of the diagnostic, as signals are typically observed only when the line integrated density is below 2.0-3.0 × 1019m-2 in the central interferometer chord, depending on the plasma shape. The strike line moves as expected when Ip is ramped, indicating that current measurements are possible. Additionally, clear dynamics in the intensity of the strike line are often observed, which might be linked to changes in the edge profile structure. However, the signal-to-background ratio of the signals is hampered by stray light, and the image guide degradation is due to neutron irradiation. Finally, simulations have been carried out to investigate the sensitivity of the expected signals to plasma density and temperature. The results are in qualitative agreement with the experimental observations, suggesting that the diagnostic is almost insensitive to fluctuations in the temperature profile, while the signal level is highly determined by the density profile due to the beam attenuation.

EXPERIMENTAL AND THEORETICAL STUDY OF THE BEHAVIOR OF GALLIUM IN A DISCHARGE PLASMA AT ICP-AES DETERMINATION

In the case of inductively coupled plasma atomic emission determination of gallium in metallurgical materials, matrix components can have a significant influence on the determination results. In addition to matrix spectral interference, there may also be non-spectral interference from macrocomponents. The element present in the discharge plasma at high concentrations can lead to a change in the conditions for excitation of the emission spectra, which will lead to a distortion of the intensity of the spectral lines of gallium. It has been established that the spectral lines of gallium are not free from spectral overlap from macrocomponents (iron, chromium, molybdenum, tungsten, nickel and cobalt). As a result, experimental study of non-spectral interference using gallium spectral lines is impossible. Using thermodynamic modeling, a quasi-analyte element was selected, which was proposed to be used to study the non-spectral matrix effect on the analytical signal of gallium during its atomic emission determination with inductively coupled plasma. Indium was proposed as a quasi-analyte. Based on the results of thermodynamic modeling, it was established that when varying the operating parameters of the atomic emission spectrometer (plasma temperature, argon and aerosol flow rate), the spectral behavior of gallium and the proposed indium quasi-analyte in argon plasma is similar. In this case, there is no spectral interference from the quasi-analyte on the spectral lines of gallium, and the increase in the value of the matrix interference estimate observed in some cases is random, which may be due to the time drift of the operating parameters of the atomic emission spectrometer. Thus, it is proposed to use indium as a quasi-analyte for the experimental study of non-spectral interference from matrix components (iron, chromium, molybdenum, tungsten, nickel and cobalt) instead of detectable gallium in metallurgical materials.

Simultaneous detection of two subtypes of extracellular vesicles using ultrabright fluorescent nanosphere-based test strips.

In recent years, the cargo profiles of extracellular vesicles (EVs), which were inherited from their parent cells, have emerged as a reliable biomarker for liquid biopsy (LB) in disease diagnosis, prognosis, and treatment monitoring. EVs secreted by different cells exhibit distinct characteristics, particularly in terms of disease diagnosis and prediction. However, currently available techniques for the quantitative analysis of EV cargoes, including enzyme-linked immunosorbent assay (ELISA), cannot specifically identify the cellular origin of EVs, thus seriously affecting the accuracy of EV-based liquid biopsy. In light of this, we here developed ultrabright fluorescent nanosphere (FNs)-based test strips which have the unique capability to specifically assess the levels of PD-L1-positive EVs (PD-L1+ EVs) derived from both tumor cells and immune cells in bodily fluids. The levels of PD-L1+ EV subpopulations in human saliva were quantified using the ultrabright fluorescent nanosphere-based test strips with more convenience and higher efficiency (detection time <30 min). Results demonstrated that the fluorescence intensity of the test line exhibited a good linear relationship respectively with the PD-L1 levels of tumor cell- (R2 = 0.993) and immune cell-derived EVs (R2 = 0.982) in human saliva. By assessing the levels of PD-L1+ EV subpopulations, our test strips hold immense potential for advancing the application of PD-L1+ EV subpopulation-based predictions in tumor diagnosis and prognosis evaluation. In summary, by integrating the benefits of FNs and lateral flow chromatography, we here provide a strategy to accurately measure the cargo levels of EVs originating from diverse cell sources in bodily fluids.

A simplified lateral flow immunosensor for the assay of carcinoembryonic antigen in low-resource settings.

Carcinoembryonic antigen (CEA) is a glycoprotein widely used as a tumor marker. In this work, a colorimetric lateral flow immunosensor is developed for rapid and low-cost quantification of CEA in human blood serum. The immunosensor consists of a glass fiber sample/conjugation pad, a nitrocellulose detection pad and a cellulose absorption pad. The detection is based on a sandwich immunoreaction: the sample/conjugation pad is modified with gold nanoparticles (GNPs)-labeled anti-CEA conjugate probes which bind to the CEA target molecules in the sample and the complexes are captured at capture anti-CEA immobilized at the test line. The color intensity of the test line, measured from a scanned image of the strip, is related to the CEA concentration in the sample. The different assay parameters are studied in detail. The linearity holds from 1.25 to 640 ng mL-1 of CEA, the instrumental and visual limits of detection are 0.45 and 0.63 ng mL-1, respectively, and the total assay time is 15 min. The specificity of the immunoassay versus other cancer biomarkers is satisfactory. The recovery in samples of human serum spiked with CEA is in the range of 81-118% and the coefficient of variation of the method is ≤10%. Results obtained with the lateral flow immunosensor correlated well with a reference radioimmunoassay method (R2 = 0.99). This immunosensor can be readily applied to CEA monitoring at the point-of-care (POC) or in resource-limited settings thanks to its low-cost and simplicity.

Investigation of the temperature of electrons in a glow discharge plasma at direct current Ar and Ar/C2H2

This paper presents the results of the study of the electron temperature in argon and argon-acetylene plasma of DC glow discharge. The optical-emission method was used to determine the main parameter of the complex plasma. The dependence of the electron temperature on the operating pressure, voltage, and discharge time was determined from the intensity of spectral lines. The source voltage was varied from 1 kV to 1.5 kV, and the pressure was maintained between 0.1-1 torr. As a time-dependent function, the electron temperature was calculated every 20 seconds during a 200-second discharge. The results showed that in argon plasma, as the pressure increases, the electron temperature decreases up to a pressure value of 0.4 torr, subsequent increase leads to an increase in temperature. Also, with the increase in source voltage, a decrease in electron temperature within the error limits is observed. In addition, in dust plasma (PECVD in Ar-C2H2), the electron temperature as a function of pressure and source voltage showed a trend similar to that observed in argon plasma. However, the electron temperature in dust plasma increases as a function of time at the initial moment, after which it decreases sharply with time.

Extreme N-emitters at high redshift: Possible signatures of supermassive stars and globular cluster or black hole formation in action

Context. Recent James Webb Space Telescope (JWST) spectroscopic observations of the z = 10.6 galaxy GN-z11 have revealed a very peculiar UV spectrum exhibiting intense emission lines of nitrogen, which are not typically detected in galaxy spectra. This observation indicates a super-solar N/O abundance ratio at low metallicity, which only resembles the abundances seen in globular cluster (GC) stars. This discovery suggests that we might be seeing proto-GCs in formation or possibly even signatures of supermassive stars. Aims. To examine whether other objects with strong N IV and/or N III emission lines (N-emitters, hereafter) exist and to better understand their origin and nature, we have examined the available JWST spectra and data from the literature. Methods. Using the NIRSpec/JWST observations from CEERS, we found an extreme N-emitter, CEERS-1019 at z = 8.6782, showing intense N IV] λ1486 and N III] λ1750 emission. From the observed rest-UV and optical lines, we conclude that it is compatible with photoionization from stars and we have determined accurate abundances for C, N, O, and Ne, relative to H. We also (re-)analyzed other N-emitters from the literature, including three lensed objects at z = 2.3 − 3.5 (Sunburst cluster, SMACS2031, and Lynx arc) and a low-redshift compact galaxy, Mrk 996. We carried out a comparison among the observed abundance ratios to observations from normal star-forming galaxies, predicted wind yields from massive stars, and predictions from supermassive stars (SMS with ∼104 − 105M⊙). Results. For CEERS-1019, we find a highly supersolar ratio log(N/O)= − 0.18 ± 0.11, and abundances of log(C/O)= − 0.75 ± 0.11 and log(Ne/O)= − 0.63 ± 0.07, which are normal compared to other galaxies at the low metallicity (12 + log(O/H) = 7.70 ± 0.18) of this galaxy. The three lensed N-emitters also show strongly enhanced N/O ratios and two of them normal C/O. The high N/O abundances can be reproduced by massive star winds assuming a special timing and essentially no dilution with the ambient interstellar medium (ISM). Alternatively, these N/O ratios can be explained by mixing the ejecta of SMS with comparable amounts of unenriched ISM. Massive star ejecta (from WR stars) are needed to explain the galaxies with enhanced C/O (Lynx arc, Mrk 996). On the other hand, a SMS in the “conveyer-belt model” (put forward to explain globular clusters) would predict a high N/O and small changes in C/O, compatible with CEERS-1019, the Sunburst cluster, SMACS2031, and GN-z11. Based on the chemical abundances, possible enrichment scenarios, and other properties (e.g., their compactness and high ISM density), we discuss which objects could contain proto-GCs. We suggest that this is the case for CEERS-1019, SMACS2031, and the Sunburst cluster. Enrichment in the Lynx arc and Mrk 996 is likely due to normal massive stars (WR), which implies that the star-forming regions in these objects cannot become GCs. Finally, we propose that some N-emitters enriched by SMS could also have formed intermediate mass black holes and we suggest that this might be the case for GN-z11. Conclusions. Our observations and analysis reinforce the suggested link between some N-emitters and proto-GC formation, which is supported both by empirical evidence and quantitative models. Furthermore, the observations provide possible evidence for the presence of supermassive stars in the early Universe (z &gt; 8) and at z ∼ 2 − 3. Our analysis also suggests that the origin and nature of the N-emitters is diverse, including objects such as GN-z11, which may possibly host an active galactic nucleus (AGN).

Spacecraft Outgassing Observed by the BepiColombo Ion Spectrometers

AbstractDuring the first flyby of the BepiColombo composite spacecraft at Mercury in October 2021 ion spectrometers observed two intense spectral lines with energies between 10 and 70 eV. The spectral lines persisted also at larger distances from Mercury and were observed again at lower intensity during cruise phase in March 2022 and at the second and third Mercury flyby as a single band. The ion composition indicates that water is the dominant gas source. The outgassing causes the composite spacecraft to charge up to a negative potential of up to −50 V. The distribution and intensity of the lower energy signal depends on the intensity of low energy electron fluxes around the spacecraft which again depend on the magnetic field orientation. We interpret the observation as being caused by water outgassing from different source locations on the spacecraft being ionized in two different regions of the surrounding potential. The interpretation is confirmed by two dimensional particle‐in‐cell simulations.

Structural and spectroscopic insights into the performance of K3Tb(PO4)2 green phosphor.

A narrow-band green emitting K3Tb(PO4)2 phosphor has been synthesized by a novel single-crystal growth approach involving the application of an inert flux. Its structural and spectroscopic peculiarities have been systematically studied by means of single-crystal X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy analysis, and diffuse reflectance, infrared and photoluminescence spectroscopy. The layered framework of the title compound is organized by linking together slightly distorted phosphate tetrahedra with non-condensed TbO7 polyhedra into [Tb(PO4)2]3- sheets interconnected by potassium cations. K3Tb(PO4)2 reveals an intense slow green photoluminescence (PL) (decay time constant τ is near 2.6 ms) under excitation in the range from VUV (100 nm) up to blue light (484 nm). Intensive narrow lines of the 5D4 → 7F6-0 (4f8 → 4f8) radiative transitions in Tb3+ ions form the PL spectra. Besides, fast violet PL (time constant τ < 20 ns) occurs under PL excitations in a narrow range from 250 to 325 nm. Dependencies of the PL quantum yield, and the green and violet PL decays on the excitation wavelength have been analyzed taking into account the multi-phonons, cross-relaxation processes and exciting light absorption by the inherent defects in the K3Tb(PO4)2 crystal lattice. The dependency of the complex characteristics of PL quantum yield on the excitation wavelength and violet photoluminescence is ascribed to the formation of Tb4+ ions. The color coordinates and color purity of the emission were estimated for the cases of PL excitation in the 160-371 nm spectral range. It has been shown that these characteristics are similar to or even better than those reported for conventional commercial green phosphors. The high values of correlated color temperature (T> 4863 K) of the emission indicates the potential use of K3Tb(PO4)2 for enhancing cold-light emitting devices.

Identification of Different Classes of VOCs Based on Optical Emission Spectra Using a Dielectric Barrier Helium Plasma Coupled with a Mini Spectrometer.

In this study, a micro helium dielectric barrier discharge (μHDBD) plasma device fabricated using 3D printing and molding techniques was coupled with a mini spectrometer to detect and identify different classes of volatile organic compounds (VOCs) using optical emission spectrometry (OES). We tested 11 VOCs belonging to three different classes (straight-chain alkanes, aromatics, and polar organic compounds). Our results clearly demonstrate that the optical emission spectra of different classes of VOCs show clear differences, and therefore, can be used for identification. Additionally, the emission spectra of VOCs with a similar structure (such as n-pentane, n-hexane, n-heptane, n-octane, and n-nonane) have similar optical emission spectrum shape. Acetone and ethanol also have similar emission wavelengths, but they show different line intensities for the same concentrations. We also found that the side-chain group of aromatics will also affect the emission spectra even though they have a similar structure (all have a benzene ring). Moreover, our μHDBD-OES system can also identify multiple compounds in VOC mixtures. Our work also demonstrates the possibility of identifying different classes of VOCs by the OES shape.

Product branching in the photodissociation of oxazole detected by broadband rotational spectroscopy.

The photodissociation of oxazole (c-C3H3NO) following excitation at 193 nm is studied using mm-Wave rotational spectroscopy in a uniform supersonic flow. Molecules entrained in the flow are excited to a ππ* state after which it is believed most relax back to the ground state via ring opening at the O-C[N] bond with subsequent fragmentation. From the line intensities of the probed products, we obtained the branching fractions for seven different products which are the result of five different dissociation pathways. The detected photoproducts and respective branching fractions (%) are the following: HCN (70.4), HCO (22.8), CH2CN (4.2), CH2CO (1.0), CH3CN (1.0), HNC (0.9), HNCO (0.08). We suspect much of the HCO may be formed in conjunction with the isocyanomethyl radical, CH2NC, which we did not probe. We discuss our results in relation to previous work, in particular our own study on the related isomer isoxazole, as well as direct dynamics theoretical simulations from the literature. We also studied the relaxation of a number of vibrationally excited levels of HCN produced at 20 K.

Astrochemical Diagnostics of the Isolated Massive Protostar G28.20-0.05

We study the astrochemical diagnostics of the isolated massive protostar G28.20-0.05. We analyze data from Atacama Large Millimeter/submillimeter Array 1.3 mm observations with a resolution of 0.″2 (∼1000 au). We detect emission from a wealth of species, including oxygen-bearing (e.g., H2CO, CH3OH, CH3OCH3), sulfur-bearing (SO2, H2S), and nitrogen-bearing (e.g., HNCO, NH2CHO, C2H3CN, C2H5CN) molecules. We discuss their spatial distributions, physical conditions, correlation between different species, and possible chemical origins. In the central region near the protostar, we identify three hot molecular cores (HMCs). HMC1 is part of a millimeter continuum ring-like structure, is closest in projection to the protostar, has the highest temperature of ∼300 K, and shows the most line-rich spectra. HMC2 is on the other side of the ring, has a temperature of ∼250 K, and is of intermediate chemical complexity. HMC3 is further away, ∼3000 au in projection, cooler (∼70 K), and is the least line-rich. The three HMCs have similar mass surface densities (∼10 g cm−2), number densities (n H ∼ 109 cm−3), and masses of a few solar masses. The total gas mass in the cores and in the region out to 3000 au is ∼25 M ⊙, which is comparable to that of the central protostar. Based on spatial distributions of peak line intensities as a function of excitation energy, we infer that the HMCs are externally heated by the protostar. We estimate column densities and abundances of the detected species and discuss the implications for hot core astrochemistry.

Targeted fluorescence imaging using bevacizumab‐800CW within neovascular age‐related macular degeneration (AMD) patients to evaluate the upregulation of vascular endothelial growth factor (VEGF‐A) (preliminary results)

Aims/Purpose: With this phase 1 study, we aim to gain insight into the feasibility of using bevacizumab‐800CW to visualize the upregulation of VEGF‐A in AMD patients for treatment optimization.Methods: First, six wet AMD patients who are currently undergoing treatment with anti‐VEGF agents were included to evaluate the optimal tracer dose and received either 4.5 or 15 mg bevacizumab‐800CW. For the ongoing analysis of targeted tracer accumulation, three additional on‐therapy and three naïve patients will be included with the optimal dose of 15 mg. Fluorescence images (Heidelberg Spectralis) were taken before, up to 60 min and 3–4 days after intravenous injection of bevacizumab‐800CW. The target‐to‐background ratios (TBR) were calculated and compared between dose groups to evaluate the optimal dose. To investigate targeted tracer uptake, images of different time points are normalized and aligned, and a fluorescence intensity line is plotted over the active lesion to locate interesting areas for further quantification.Results: The preliminary results showed a clear inflow of the tracer into the eye vasculature after administration of 15 mg bevacizumab‐800CW. The fluorescence remains visible up to 1 h after tracer administration. Visual image comparison and TBR calculation in the first six patients showed that 15 mg bevacizumab‐800CW was the optimal tracer dose. In patients who received 15 mg bevacizumab‐800CW, accumulation of fluorescence signal in a smaller area within the active lesion was seen after 3–4 days.Conclusions: For the first time, we show that bevacizumab‐800CW (4.5 mg/15 mg) can be imaged in AMD patients using a commercially available system. An increase in signal intensity 3–4 days after bevacizumab‐800CW injection predicts tracer accumulation in the diseased area indicating ongoing active disease. VEGF‐A imaging can act as a proof of concept and pave the way for a broad application to track the performance of drugs by fluorescence molecular imaging.

Non-Gaussian Signal Statistics’ Impact on LIBS Analysis

A detailed study has been carried out to reveal signal statistics’ impact on analysis sensitivity in laser-induced breakdown spectroscopy (LIBS) measurements. For several signals measured simultaneously, it was demonstrated that space-, spectra- and time-integrated plasma emission followed a normal distribution while the spectra- and time-resolved LIBS signal (atomic line intensity, plasma background emissions) distribution functions were biased compared to a Gaussian distribution function. For the first time in LIBS, the impact of a non-Gaussian distribution function on the limit of detection (LOD)’s determination has been studied in detail for single-shot spectra as well as for averaged spectra. Here, we demonstrated that the non-symmetrical distribution of the LIBS signals influenced the estimated LODs, so knowledge of a LIBS signal’s distribution function provides more reliable results, and the analysis sensitivity can be wrongly estimated if Gaussian distribution is presumed.

NATURE OF ZINC OXIDE COLLOIDAL NANOCRYSTALS PHOTOLUMINESCENCE

The purpose of the study is to determine the nature of the radiative transitions responsible for the visible radiation of zinc oxide nanocrystals. Show that the size of nanocrystallites does not affect the spectral composition and location of long-wave luminescence. ZnO nanocrystals obtained by the method of colloidal synthesis with or without gelatin stabilization were investigated in the paper. The size of the nanocrystallites was determined in the approximation of the effective masses by the magnitude of the fundamental absorption edge shift. The results of calculating the size of nanocrystallites agree well with the results of SEM studies. It is shown that the main factor affecting the size of nanocrystallites is the concentration of precursors. Photoluminescence spectra of colloidal ZnO nanocrystals were studied in two spectral regions – ultraviolet and visible. Photoluminescence spectra in the ultraviolet region are characterized by three emission lines, the location of which depends on the concentration of precursors, that is, on the width of the band gap. Analysis of the energy states of intrinsic defects in nanostructured zinc oxide showed that the first two emission lines are associated with radiative transitions of excitons bound on neutral interstitial zinc atoms and on neutral zinc vacancies. The third line of ultraviolet radiation is caused by radiative transitions with the participation of deep donors, which are interstitial zinc atoms in the +2 charge state. The visible radiation spectra of colloidal ZnO nanocrystals are characterized by broad non-elemental emission bands in the blue-green and yellow-red regions of the spectrum. A detailed analysis of the spectra at different concentrations of precursors showed that the change in concentrations of precursors does not affect the spectral location of elementary emission lines. The absence of impurity absorption lines indicates that the centers responsible for visible radiation are donor-acceptor pairs. The analysis of the ratio of the emission lines intensities with increasing concentrations of the precursors shows that interstitial zinc and oxygen atoms dominate in the studied nanocrystals at high concentrations. As a result, in samples with a high concentration of precursors, blue radiation dominates over yellow and green. Thus, the study shows that by changing the concentrations of precursors, it is possible to influence both the spectral location of the edge ultraviolet luminescence and the intensity of individual long-wave luminescence components. The resulting colloidal ZnO nanocrystals can be used as luminescent sensors.

Effect of proton irradiation on the cathodoluminescence of gallium nitride films

In this work, we studied the effect of 350 keV proton irradiation with two different fluences of 1013 cm−2 and 1015 cm−2 on the cathodoluminescence (CL) spectrum of GaN. Three lines were observed in the CL spectra of virgin and proton pre-irradiated samples - band edge line (3.4 eV), blue line (2.8 eV) and yellow line (2.15 eV). A strong decrease in the CL intensity for samples pre-irradiated by protons, especially at high proton fluence of 1015 cm−2, is shown. The evolution of the cathodoluminescence spectra during electron irradiation demonstrates a further decrease in all line intensities. It was shown that virgin and proton pre-irradiated GaN samples were not charged under electron irradiation. The cathodoluminescence signal drop can be caused by a decrease in the concentration of initial luminescence centers associated with intrinsic and impurity defects due to their transformation under proton bombardment and electron-stimulated diffusion implanted H+ ions.

Optical emission spectroscopy of vanadium cathodic arc plasma at different nitrogen pressure

Optical emission spectroscopy studies of vanadium plasma in a cathodic-arc discharge in a nitrogen atmosphere have been carried out. Spectral lines of neutral atoms and ions of the cathode material V, V1+, and V2+, and nitrogen N2 and N2+ were observed in the discharge plasma. Analysis and comparison of the intensity of vanadium and nitrogen spectral lines as a function of nitrogen pressure showed that in vacuum excited ions V2+ and V+ are registered, with increasing pressure, the lines V+*, N2*, and N2+* are observed, and at pressures above 0.5 Pa, the neutral vanadium lines are additionally registered. The electron temperature of Te decreases from 5.9 to 3–4 eV with increasing pressure. Studies of cross-sectional scanning electron microscopy images of VN coatings deposited at different nitrogen pressures have shown that a dense, homogeneous, fine-grained microstructure is formed in the coating when the number of neutral V in the plasma is low, while in the presence of a large number of neutrals, the coating structure changes to a dense structure with columnar growth.

LED-based Fourier transform spectroscopy of 14N216O in the 9750-12050 cm−1 region

The five bands of the nitrous oxide molecule (ν1+4ν3,ν1+4ν20+3ν3, 3ν1+3ν3, ν1+5ν3 and 6ν1+2ν3) were studied in the 9750–12,050 cm−1 region using a Bruker IFS-125 M Fourier Transform Spectrometer. High brightness LEDs used as the light sources, which have provided a high signal-to-noise ratio and made it possible to record weak lines with intensities of the order of 1 × 10−26 cm/molecule at 296 K. Each spectrum was obtained by averaging over 33,120 scans. The line parameters (centers and intensities) were recovered from the observed spectra. The spectroscopic constants of the upper vibrational states together with the vibrational transition dipole moments were fitted to the measured line positions and intensities, respectively. It was found that the ν1+5ν3 band is in an interpolyad resonance anharmonic interaction with the 6ν1+2ν3 band.

Exploring the Degradation Mechanism on PtxCoy Alloy Catalysts for Oxygen Reduction Reaction by Operando X-Ray Absorption Spectroscopy

At present, alloying the Pt with 3d-transition metal, such as Co, has been demonstrated as an efficacious approach in enhancing the activity of the cathodic catalysts and diminishing the cost of Pt through ligand effect and strain effect. However, these catalysts were facing with a substantial challenge of the limited durability, primarily attributed to the leaching of the 3d-transition metal under the rigorous electrochemical conditions for the proton exchange membrane fuel cells (PEMFCs)[1]. Herein, we applied both operando conventional XAS and high energy resolution fluorescence detection (HERFD) XAS to identify the electro-chemical behaviors of subsize (about 2.5 nm) PtxCoy alloy catalysts with different Co content and associated with the Pt1Co3@Pt core-shell (CS) nanostructure catalysts obtained by simple displacement reaction. We find that the introduction of Co helps to modify the structure of PtCo alloy catalysts and benefit the activity, however, the increase content of Co brings to the heavier oxidation of Pt, which accelerate the degradation of the PtCo alloy catalysts. While the structure with Pt-rich shell suggested a high tolerance to the Pt oxidation which benefits both stability and activity. Based on these findings, we demonstrate the significance of designing PtCo CS nanostructure with high Co content to achieve optimal performance in PEMFCs. Our research provides valuable insights in designing the catalysts combined with operando XAS analysis and paves the way for the development for the large-scale application for PEMFCs. For the typical synthesis of PtCox alloy catalysts, the Pt(acac)2 and Co(acac)3 were used as Pt and Co precursors. 4mL ethanol was added to the pre-mixed Pt and Co precursors and heated up to 60 °C with magnetic stirring. After the precursors completely dissolved, certain amount of Vulcan 72 was added into the solution. Then repeat ultrasonication and magnetic stirring in 60 °C until the solution converted into slurry statement, dried the product in 30 °C over night. Next, the above well-milled products were treated at 700 °C for 2h in Ar atmosphere to transfer into alloy particles. According to the introduced ratio between Pt and Co, the catalysts were noted as Pt3Co1, Pt1Co1, and Pt1Co3. The contribution of CS nanostructure of Pt1Co3 was applied by simple displacement reaction using H2PtCl6 solution as Pt source. The production was annealed in H2 for 30 min. Operando conventional XAS (at BL36XU in Spring 8) was performed to investigate the electronic statement and structure changes during the operation. Operando HERFD XAS (at BL39XU in Spring 8) further identified the formation of metal Pt with chemisorbed O and Pt oxidation during the polarization varying different Co content and Pt-rich shell. The electronic performance of PtCo alloy catalysts was evaluated in rotating disk electrode, gas diffusion electrode, and membrane electrode assembly, which exhibited a higher performance (about 5 times higher than Pt/C) for Pt1Co3@Pt catalyst. Fig. 1a shows the STEM mapping results for Pt1Co3@Pt catalysts, the linear scanning profile is shown in the mix-image, and the signal intensity between the Pt L-edge and Co K-edge indicates the Pt-rich shell and Pt and Co core structure, which suggested the successful synthesis of Pt-rich shell with high Co content. To further analyze the electronic-behavior for the catalysts, the operando HERFD-XAS analysis was performed on Pt1Co3 and Pt1Co3@Pt catalysts, which provides a higher signal-to-noise ratio and detailed information about the electronic statement of Pt atom[2]. As shown in Figure 1b and c, the main Pt L3-edge white line intensity continuously increased and positively shifted, which suggested the increasing coverage of chemisorbed O or OH onto the Pt surface and the generation of oxidic component at high polarization potential for Pt1Co3 catalyst. While less changes were shown in Pt1Co3@Pt catalyst, which implied the formation of Pt-rich shell could help to suppress the oxidation of Pt in PtCo alloy catalysts and benefit the catalytic performance.