Retrieval of Optical Constants of Undoped Flash-Evaporated Lead Iodide Films from an Analysis of Their Normal Incidence Transmission Spectra Using Swanepoel’s Transmission Envelope Theory of Non-Uniform Films

Normal-incidence transmission-wavelength (T_exp (λ)-λ) spectra of 1 and 1.2 m thick flash-evaporated lead iodide (PbI2) films on 1.1 mm thick glass slides held at 200 ℃ display well-spaced several interference-fringe maxima and minima in the λ-range 520-900 nm, without exhibiting a transparent region and with the maxima lying well below the substrate transmission. Below 520 nm, these T_exp (λ)-λ curves drop steeply to zero (at λ ≼ 505 nm), signifying crystalline-like PbI2 film absorption. As corrections of measured (PbI2 film/substrate) transmittance data for substrate absorption and spectrometer slit-width effect were marginal over the studied λ-range, the observed low transmittance of (PbI2 film/substrate) system was related to PbI2 film thickness non-uniformity (∆d), which causes shrinkage of both maxima and minima and leads to significant film optical absorption that reduces both maxima and minima. The McClain ENVELOPE algorithm was utilized, with a minor modification, to construct maxima T_M (λ_max/λ_min) and minima T_m (λ_min/λ_max) envelope curves, which were analyzed by Swanepoel’s envelope method of non-uniform films using an approach that takes account of dispersive substrate refractive index n_s (λ) and circumvents the non-availability of a high-λ transparency region. In such analytical approach, ∆d was varied till a re-generated T_gen (λ)-λ curve matches the T_exp (λ)-λ curve. An average thickness d ̅ of the film, besides its refractive index n(λ) and absorption coefficient α(λ) in the weak, medium and strong absorption regions, were then obtained. The energy-dependence of α(λ) is discussed in view of interband electronic transition models. The obtained results are consistent with other literature studies on similar flash-evaporated PbI2 films. Keywords: PbI2, Optical constants and bandgap, Swanepoel's transmission envelope method, Non-uniform films.

Slit homogenizer introduced performance gain analysis based on the Sentinel-5/UVNS spectrometer

Spatially heterogeneous Earth radiance scenes affect the atmospheric composition measurements of high-resolution Earth observation spectrometer missions. The scene heterogeneity creates a pseudo-random deformation of the instrument spectral response function (ISRF). The ISRF is the direct link between the forward radiative transfer model, used to retrieve the atmospheric state, and the spectra measured by the instrument. Hence, distortions of the ISRF owing to radiometric inhomogeneity of the imaged Earth scene will degrade the precision of the Level-2 retrievals. Therefore, the spectral requirements of an instrument are often parameterized in the knowledge of the ISRF over non-uniform scenes in terms of shape, centroid position of the spectral channel and the full width at half maximum (FWHM). The Sentinel-5/UVNS instrument is the first push-broom spectrometer that makes use of a concept referred to as a slit homogenizer (SH) for the mitigation of spatially non-uniform scenes. This is done by employing a spectrometer slit formed by two parallel mirrors scrambling the scene in the along track direction (ALT) and hence averaging the scene contrast only in the spectral direction. The flat mirrors do not affect imaging in the across track direction (ACT) and thus preserve the spatial information in that direction. The multiple reflections inside the SH act as coherent virtual light sources and the resulting interference pattern at the SH exit plane can be described by simulations using scalar diffraction theory. By homogenizing the slit illumination, the SH strongly modifies the spectrograph pupil illumination as a function of the input scene. In this work we investigate the impact and strength of the variations of the spectrograph pupil illumination for different scene cases and quantify the impact on the ISRF stability for different types of aberration present in the spectrograph optics.

Slit homogenizer introduced performance gain analysis based on Sentinel-5/UVNS spectrometer

The spectral accuracy of high resolution Earth observation spectrometer missions is affected by the impact of spatially heterogeneous Earth radiance scenes on the instrument spectral response function (ISRF). As the ISRF is the direct link between the forward radiative transfer model and the spectra measured by the instrument, distortions of the iSRF owing to radiometric inhomogeneity of the imaged Earth scene will degrade the precision of the Level-2 retrievals. Therefore, the spectral requirements of an instrument are often parametrized in the knowledge of the ISRF over non-uniform scenes in terms of shape, centroid position of the spectral channel and the Full Width at Half Maximum (FWHM). The Sentinel-5/UVNS instrument is the first push-broom spectrometer that makes use of a concept referred as slit homogenizer (SH) for the mitigation of spatially non-uniform scenes. This is done by employing a spectrometer slit formed by two parallel mirrors, scrambling the scene in along track direction (ALT) and hence averaging the scene contrast only in the spectral direction. The flat mirrors do not affect imaging in the across track direction (ACT) and thus preserve the spatial information in that direction. The multiple reflections inside the SH act as coherent virtual light sources and the resulting interference pattern at the SH exit plane can be described by simulations using scalar diffraction theory. By homogenizing the slit illumination, the SH moreover strongly modifies the spectrograph pupil as a function of the input scene. In this work we investigate the impact and strength of spectrograph pupil variations for different scene cases and quantify the impact on the ISRF stability for different type of aberrations present in the spectrograph optics.

An Optical Model for Quantitative Raman Microspectroscopy

Raman spectroscopy is an invaluable technique for identifying compounds by the unique pattern of their molecular vibrations and is capable of quantifying the individual concentrations of those compounds provided that certain parameters about the sample and instrument are known. We demonstrate the development of an optical model to describe the intensity distribution of incident laser photons as they pass through the sample volume, determine the limitations of that volume that may be detected by the spectrometer optics, and account for light absorption by molecules within the sample in order to predict the total Raman intensity that would be obtained from a given, uniform sample such as an aqueous solution. We show that the interplay between the shape and divergence of the laser beam, the position of the focal plane, and the dimensions of the spectrometer slit are essential to explaining experimentally observed trends in deep ultraviolet Raman intensities obtained from both planar and volumetric samples, including highly oriented pyrolytic graphite and binary mixtures of organic nucleotides. This model offers the capability to predict detection limits for organic compounds in different matrices based on the parameters of the spectrometer, and to define the upper/lower limits within which concentration can be reliably determined from Raman intensity for such samples. We discuss the potential to quantify more complex samples, including as solid phase mixtures of organics and minerals, that are investigated by the unique instrument parameters of the Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) investigation on the upcoming Mars 2020 rover mission.

Magnetic reconnection processes induced by a CME expansion

On 10–11 December 2005 a slow CME occurred in the Western Hemisphere in between two coronal streamers. SOHO/MDI magnetograms show a multipolar magnetic configuration at the photosphere: a complex of active regions located at the CME source and two bipoles at the base of the lateral coronal streamers. White light observations reveal that the CME expansion affects both of them and induces the release of plasma within or close to the nearby streamers. These transient phenomena are possibly due to magnetic reconnections induced by the CME expansion and occurring inside the streamer current sheet or between the CME flanks and the streamer. These events have been observed by the SOHO/UVCS with the spectrometer slit centered at 1.8 R⊙ over about a full day. In this work we focus on the interaction between the CME and the streamer: the UVCS spectral interval included UV lines from ions at different temperatures of maximum formation such as O VI, Si XIII and Al Xi. These data gave us the opportunity to infer the evolution of plasma temperature and density at the reconnection site and adjacent regions. These are relevant to characterize secondary reconnection processes occurring during a CME development.

Determination of Chlorinity in Aqueous Fluids Using Raman Spectroscopy of the Stretching Band of Water at Room Temperature: Application to Fluid Inclusions

A new analytical method, based on the Raman spectroscopy of the ν(OH) stretching vibration of water, has been developed for the determination of the concentration of chloride in aqueous solutions with the goal of reconstructing the bulk ion content of fluid inclusions that are relics of paleo-fluid circulation in rocks. The method involves calibrating the area of one band of the spectrum difference between pure water and solutions of appropriate composition with respect to the chloride concentration. Calibration curves were constructed for the major geological chemical salts LiCl, NaCl, KCl, CaCl2, and MgCl2, and NaCl–CaCl2 systems. The application to fluid inclusions has been confirmed using synthetic fluid inclusions. For cubic minerals such as fluorite, the calibration curve for the NaCl system correctly estimates the chlorinity. For birefringent minerals, such as quartz, the Raman spectrum of the aqueous solution depends on the orientation of the host crystal. The crystal must be oriented in such a way that one axis of the ellipse of the indicatrix projects parallel to the spectrometer slit. This method complements micro-thermometric data and allows the determination of chlorinity when ice-melting temperature cannot be used.

Effects of Sampling Parameters on Principal Components Analysis of Raman Line Images

Raman images of the distribution of materials in a sample prepared from 10-μm-diameter polystyrene spheres embedded in epoxy were reconstructed from sets of line-scanned images, with the use of univariate and multivariate processing of the spectral data. Multiple sets of microscopic Raman spectral line images were acquired by using line-focused illumination with a cylindrical lens, a motorized translation stage to move the sample perpendicular to the illumination line, and a holographic imaging spectrograph equipped with a 2D charge-coupled device (CCD) detector. Repeat sets of data were obtained at different spectrometer slit width settings and different magnification. The raw spectral data were processed by using both a simple univariate method (single-band integration) and a more sophisticated multivariate method [principal components analysis (PCA) with eigenvector rotation] to generate 2D Raman images representing spatial distribution of the individual polymeric constituents. The repeat data sets were compared to ascertain the effects of the sampling parameters on the PCA method. The results indicated that spectrometer slit width and magnification affect the sampling depth and spatial resolution, but have little effect on the PCA. Moreover, digital sampling (i.e., number of PCA wavelength variables) could be significantly reduced with little or no degradation of the PCA-generated images, particularly if key bands were represented.