Synergetic interfacial conductivity modulation dictating hysteresis evolution in perovskite solar cells under operation.

In this work, the configuration of compact TiO2 coating (c-TiO2) interface as electron transport layer (ETL) in giving rise to loss and gain of fill factor (FF) and therefore modulation of hysteresis behavior in perovskite solar cells (PSCs) is investigated. For this purpose, PSCs based on planar compact TiO2 (c-TiO2) as well as a scaffold-based architecture are studied. In the latter case c-TiO2 coats a hydrothermally grown titania nanorod scaffold. The results demonstrate that when c-TiO2 is used in planar configuration, FF considerably improves with prolonged light soaking which is in sharp contrast to what is observed for scaffold-based PSCs. Moreover, higher thickness of planar c-TiO2 is shown to be beneficial for sustaining FF in forward scan. Finally, through studying the intricate interfacial dynamics utilizing electrochemical impedance spectroscopy (EIS), it was concluded that for a PSC under operation, the cumulative effect of conductivity modulation at the perovskite with transport layer interfaces, for their respective charge carriers, determines the loss and gain in performance depending on scan rate, applied bias and prolonged light soaking. This work points towards multiple factors affecting PSC output, which could work either in confluence or against one another depending on the interfacial configuration of transport layers.

ZAFG Method for Quantitative Characterization of Spherical Particles: Deriving a Universal Equation for Geometrical Correction.

This study introduces a universal equation to calculate the geometrical correction factor (G) as the fourth factor in the conventional ZAF method for quantifying spherical particles (specifically, NIST-K411 glass microspheres mounted on bulk carbon substrate). Note that the fluorescence correction factor (F) is not considered in this study. Our findings demonstrate that the G factor, as a function of the particle diameter (D) and the range of emitted X-rays in a bulk sample (Xe), provides the best model. Xe depends on the chemical composition and accelerating voltage. We observed excellent agreement between the G factor predicted by our model and experimental data obtained from NIST-K411 standard particles. Our results show that when Xe is greater than D, the G factor decays exponentially, independent of the incident electron energy, X-ray lines, and chemical composition of the particles. We also found that when DXe > 1, the particle behaves as a bulk sample, and G = 1. Notably, our data indicate that the G factor depends only on DXe, not on the chemical composition or beam energy.

Secondary Fluorescence of 3D Heterogeneous Materials Using a Hybrid Model.

In electron probe microanalysis or scanning electron microscopy, the Monte Carlo method is widely used for modeling electron transport within specimens and calculating X-ray spectra. For an accurate simulation, the calculation of secondary fluorescence (SF) is necessary, especially for samples with complex geometries. In this study, we developed a program, using a hybrid model that combines the Monte Carlo simulation with an analytical model, to perform SF correction for three-dimensional (3D) heterogeneous materials. The Monte Carlo simulation is performed using MC X-ray, a Monte Carlo program, to obtain the 3D primary X-ray distribution, which becomes the input of the analytical model. The voxel-based calculation of MC X-ray enables the model to be applicable to arbitrary samples. We demonstrate the derivation of the analytical model in detail and present the 3D X-ray distributions for both primary and secondary fluorescence to illustrate the capability of our program. Examples for non-diffusion couples and spherical inclusions inside matrices are shown. The results of our program are compared with experimental data from references and with results from other Monte Carlo codes. They are found to be in good agreement.

The Impact of Chemical Bonding on Mass Absorption Coefficients of Soft X-rays.

Accurate elemental quantification of materials by X-ray detection techniques in electron microscopes or microprobes can only be carried out if the appropriate mass absorption coefficients (MACs) are known. With continuous advancements in experimental techniques, databases of MACs must be expanded in order to account for new detection limits. Soft X-ray emission spectroscopy (SXES) is a characterization technique that can detect emitted X-rays whose energies are in the range of 10 eV to 2 keV by using a varied-line-spaced grating. Transitions producing soft X-rays can be detected and accurate MACs are required for use in quantification. This work uses Monte Carlo modeling coupled with multivoltage SXES measurements in an electron probe micro-analyzer (EPMA) to compute MACs for the L2,3-M and Li Kα transitions in a variety of aluminum alloys. Electron depth distribution curves obtained by the software MC X-ray are used in a parametrized fitting equation. The MACs are calculated using a least-squares regression analysis. It is shown that X-ray distribution cross-sections at such low energies need to take into account additional contributions, such as Coster­Kronig transitions, Auger yields, and wave function effects in order to be accurate.

The f-Ratio Quantification Method for X-ray Microanalysis Applied to Mg-Al-Zn Alloys.

The f-ratio quantitative X-ray microanalysis method has been recently developed for binary systems based on a scanning electron microscope/energy dispersive spectroscopy (SEM/EDS) system. This method incorporates traditional EDS experiments and Monte Carlo simulations, and calibration factors are calculated with standard samples to evaluate the differences between them. In this work, the f-ratio method was extended to Mg-Al-Zn multi-element systems using a cold field emission SEM and a tungsten emission SEM. Results show that the stability of the beam current does not influence the f-ratio quantification accuracy. Thus, the f-ratio method is suitable for quantitative X-ray mapping with a long-time acquisition or even an unstable beam current. Comparing with other quantitative techniques including the routine standardless analysis and the standard-based k-ratio method, the f-ratio method is a simple and accurate quantification method.

Secondary Fluorescence Correction for Characteristic and Bremsstrahlung X-Rays Using Monte Carlo X-ray Depth Distributions Applied to Bulk and Multilayer Materials.

Secondary fluorescence effects are important sources of characteristic X-ray emissions, especially for materials with complicated geometries. Currently, three approaches are used to calculate fluorescence X-ray intensities. One is using Monte Carlo simulations, which are accurate but have drawbacks such as long computation times. The second one is to use analytical models, which are computationally efficient, but limited to specific geometries. The last approach is a hybrid model, which combines Monte Carlo simulations and analytical calculations. In this article, a program is developed by combining Monte Carlo simulations for X-ray depth distributions and an analytical model to calculate the secondary fluorescence. The X-ray depth distribution curves of both the characteristic and bremsstrahlung X-rays obtained from Monte Carlo program MC X-ray allow us to quickly calculate the total fluorescence X-ray intensities. The fluorescence correction program can be applied to both bulk and multilayer materials. Examples for both cases are shown. Simulated results of our program are compared with both experimental data from the literature and simulation data from PENEPMA and DTSA-II. The practical application of the hybrid model is presented by comparing with the complete Monte Carlo program.

In-Situ Characterization of Lithium Native Passivation Layer in A High Vacuum Scanning Electron Microscope.

A technique to characterize the native passivation layer (NPL) on pure lithium metal foils in a scanning electron microscope (SEM) is described in this paper. Lithium is a very reactive metal, and consequently, observing and quantifying its properties in a SEM is often compromised by rapid oxidation. In this work, a pure lithium energy-dispersive x-ray spectrum is obtained for the first time in a high vacuum SEM using a cold stage/cold trap with liquid nitrogen reservoir outside the SEM chamber. A nanomanipulator (OmniProbe 400) inside the microscope combined with x-ray microanalysis and windowless energy dispersive spectrometer is used to fully characterize the NPL of lithium metal and some of its alloys by a mechanical removal procedure. The results show that the native films of pure lithium and its alloys are composed of a thin (25 nm) outer layer that is carbon-rich and an inner layer containing a significant amount of oxygen. Differences in thickness between laminated and extruded samples are observed and vary depending on the alloy composition.

In Situ Scanning Electron Microscopy Detection of Carbide Nature of Dendrites in Li-Polymer Batteries.

Li metal batteries suffer from dendrite formation which causes short circuit of the battery. Therefore, it is important to understand the chemical composition and growth mechanism of dendrites that limit battery efficiency and cycle life. In this study, in situ scanning electron microscopy was employed to monitor the cycling behavior of all-solid Li metal batteries with LiFePO4 cathodes. Chemical analyses of the dendrites were conducted using a windowless energy dispersive spectroscopy detector, which showed that the dendrites are not metallic lithium as universally recognized. Our results revealed the carbide nature of the dendrites with a hollow morphology and hardness greater than that of pure lithium. These carbide-based dendrites were able to perforate through the polymer, which was confirmed by milling the polymer using focused ion beam. It was also shown that applying pressure on the battery can suppress growth of the dendrites.

Use of an Annular Silicon Drift Detector (SDD) Versus a Conventional SDD Makes Phase Mapping a Practical Solution for Rare Earth Mineral Characterization.

A number of techniques for the characterization of rare earth minerals (REM) have been developed and are widely applied in the mining industry. However, most of them are limited to a global analysis due to their low spatial resolution. In this work, phase map analyses were performed on REM with an annular silicon drift detector (aSDD) attached to a field emission scanning electron microscope. The optimal conditions for the aSDD were explored, and the high-resolution phase maps generated at a low accelerating voltage identify phases at the micron scale. In comparisons between an annular and a conventional SDD, the aSDD performed at optimized conditions, making the phase map a practical solution for choosing an appropriate grinding size, judging the efficiency of different separation processes, and optimizing a REM beneficiation flowsheet.

The qualitative f-ratio method applied to electron channelling-induced x-ray imaging with an annular silicon drift detector in a scanning electron microscope in the transmission mode.

Electron channelling is known to affect the x-ray production when an accelerated electron beam is applied to a crystalline material and is highly dependent on the local crystal orientation. This effect, unless very long counting time are used, is barely noticeable on x-ray energy spectra recorded with conventional silicon drift detectors (SDD) located at a small elevation angle. However, the very high count rates provided by the new commercially available annular SDDs permit now to observe this effect routinely and may, in some circumstances, hide the true elemental x-ray variations due to the local true specimen composition. To circumvent this issue, the recently developed f-ratio method was applied to display qualitatively the true net intensity x-ray variations in a thin specimen of a Ti-6Al-4V alloy in a scanning electron microscope in transmission mode. The diffraction contrast observed in the x-ray images was successfully cancelled through the use of f-ratios and the true composition variations at the grain boundaries could be observed in relation to the dislocation alignment prior to the ß-phase nucleation. The qualitative effectiveness in removing channelling effects demonstrated in this work makes the f-ratio, in its quantitative form, a possible alternative to the ZAF method in channelling conditions.

About the contrast of δ' precipitates in bulk Al-Cu-Li alloys in reflection mode with a field-emission scanning electron microscope at low accelerating voltage.

Characterising the impact of lithium additions in the precipitation sequence in Al-Li-Cu alloys is important to control the strengthening of the final material. Since now, transmission electron microscopy (TEM) at high beam voltage has been the technique of choice to monitor the size and spatial distribution of δ' precipitates (Al3 Li). Here we report on the imaging of the δ' phase in such alloys using backscattered electrons (BSE) and low accelerating voltage in a high-resolution field-emission scanning electron microscope. By applying low-energy Ar+ ion milling to the surface after mechanical polishing (MP), the MP-induced corroded layers were efficiently removed and permitted the δ's to be visible with a limited impact on the observed microstructure. The resulting BSE contrast between the δ's and the Al matrix was compared with that obtained using Monte Carlo modelling. The artefacts possibly resulting from the sample preparation procedure were reviewed and discussed and permitted to confirm that these precipitates were effectively the metastable δ's. The method described in this report necessitates less intensive sample preparation than that required for TEM and provides a much larger field of view and an easily interpretable contrast compared to the transmission techniques.

Monte Carlo Simulations of Electron Energy-Loss Spectra with the Addition of Fine Structure from Density Functional Theory Calculations.

A new approach is presented to introduce the fine structure of core-loss excitations into the electron energy-loss spectra of ionization edges by Monte Carlo simulations based on an optical oscillator model. The optical oscillator strength is refined using the calculated electron energy-loss near-edge structure by density functional theory calculations. This approach can predict the effects of multiple scattering and thickness on the fine structure of ionization edges. In addition, effects of the fitting range for background removal and the integration range under the ionization edge on signal-to-noise ratio are investigated.

Characterization of Amorphous Oxide Nano-Thick Layers on 316L Stainless Steel by Electron Channeling Contrast Imaging and Electron Backscatter Diffraction.

Characterization of the topmost surface of biomaterials is crucial to understanding their properties and interactions with the local environment. In this study, the oxide layer microstructure of plasma-modified 316L stainless steel (SS316L) samples was analyzed by a combination of electron backscatter diffraction and electron channeling contrast imaging using low-energy incident electrons. Both techniques allowed clear identification of a nano-thick amorphous oxide layer, on top of the polycrystalline substrate, for the plasma-modified samples. A methodology was developed using Monte Carlo simulations combined with the experimental results to estimate thickness of the amorphous layer for different surface conditions. X-ray photoelectron spectroscopy depth profiles were used to validate these estimations.