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Understanding Measurement Artifacts Causing Inherent Cation Gradients in Depth Profiles of Perovskite Photovoltaics with TOF-SIMS
Time-of-flight secondary-ion mass spectrometry (TOF-SIMS) is one of the few techniques that can obtain chemical information from the hybrid organic-inorganic perovskite solar cells (PSCs) in one dimension (standard depth profiling), two dimensions (high-resolution 100-nm imaging), as well as three dimensions (tomography combining high-resolution imaging with depth profiling). We have very recently developed thermo-mechanical methods to cleave perovskite samples at the back transparent conducting oxide/PSC interface. This allowed for depth-profiling from the back of the device to the front. The resultant profiles answered the lingering question of the apparent A-site cation gradient typically seen in TOF-SIMS depth profiles. In fact, this gradient is a measurement artifact due to beam damage that the community should be informed of as TOF-SIMS data become more commonly employed. Methods of mitigating this artifact by altering the measurement conditions are also presented.
Interpreting inorganic compositional depth profiles to understand the rate-limiting step in vapor phase infiltration processes
Vapor phase infiltration (VPI) is a post-polymerization modification technique that infuses inorganics into polymers to create organic–inorganic hybrid materials with new properties. Much is yet to be understood about the chemical kinetics underlying the VPI process. The aim of this study is to create a greater understanding of the process kinetics that govern the infiltration of trimethyl aluminum (TMA) and TiCl 4 into PMMA to form inorganic-PMMA hybrid materials. To gain insight, this paper initially examines the predicted results for the spatiotemporal concentrations of inorganics computed from a recently posited reaction–diffusion model for VPI. This model provides insight on how the Damköhler number (reaction versus diffusion rates) and non-Fickian diffusional processes (hindering) that result from the material transforming from a polymer to a hybrid can affect the evolution of inorganic concentration depth profiles with time. Subsequently, experimental XPS depth profiles are collected for TMA and TiCl 4 infiltrated PMMA films at 90 °C and 135 °C. The functional behavior of these depth profiles at varying infiltration times are qualitatively compared to various computed predictions and conclusions are drawn about the mechanisms of each of these processes. TMA infiltration into PMMA appears to transition from a diffusion-limited process at low temperatures (90 °C) to a reaction-limited process at high temperatures (135 °C) for the film thicknesses investigated here (200 nm). While TMA appears to fully infiltrate these 200 nm PMMA films within a few hours, TiCl 4 infiltration into PMMA is considerably slower, with full saturation not occurring even after 2 days of precursor exposure. Infiltration at 90 °C is so slow that no clear conclusions about mechanism can be drawn; however, at 135 °C, the TiCl 4 infiltration into PMMA is clearly a reaction-limited process, with TiCl 4 permeating the entire thickness (at low concentrations) within only a few minutes, but inorganic loading continuously increasing in a uniform manner over a course of 2 days. Near-surface deviations from the uniform-loading expected for a reaction-limited process also suggest that diffusional hindering is high for TiCl 4 infiltration into PMMA. In conclusion, these results demonstrate a new, ex situ analysis approach for investigating the rate-limiting process mechanisms for vapor phase infiltration.
Cation- and lattice-site-selective magnetic depth profiles of ultrathin Fe 3 O 4 (001) films
A detailed understanding of ultrathin film surface properties is crucial for the proper interpretation of spectroscopic, catalytic, and spin-transport data. We present x-ray magnetic circular dichroism (XMCD) and x-ray resonant magnetic reflectivity (XRMR) measurements on ultrathin Fe 3 O 4 films to obtain magnetic depth profiles for the three resonant energies corresponding to the different cation species F e o c t 2 + , F e t e t 3 + , and F e o c t 3 + located on octahedral and tetrahedral sites of the inverse spinel structure of Fe 3 O 4 . By analyzing the XMCD spectrum of Fe 3 O 4 using multiplet calculations, the resonance energy of each cation species can be isolated. Performing XRMR on these three resonant energies yields magnetic depth profiles that each correspond to one specific cation species. The depth profiles of both kinds of Fe 3+ cations reveal a (3.9 ± 1.0) -Å -thick surface layer of enhanced magnetization, which is likely due to an excess of these ions at the expense of the F e o c t 2 + species in the surface region. The magnetically enhanced F e t e t 3 + layer is additionally shifted about 2.9 ± 0.4 Å farther from the surface than the F e o c t 3 + layer.
D retention and depth profile behavior for single crystal tungsten with high temperature neutron irradiation
Single crystalline W (tungsten) samples irradiated at 633, 963 and 1073 K by neutrons to a damage level of 0.1 dpa were exposed to a high-flux D (deuterium) plasma at 673, 873 and 973 K, respectively, in TPE (Tritium Plasma Experiment) at INL (Idaho National Laboratory). Deuterium desorption was analyzed by TDS (Thermal Desorption Spectroscopy), and D depth profiles were determined by NRA (Nuclear Reaction Analysis) at SNL (Sandia National Laboratories). HIDT (Hydrogen Isotope Diffusion and Trapping) simulation code was applied to evaluate D behavior for neutron-damaged W at higher temperature. The D retention at depths up to 3 f.tm for the neutron-damaged sample at 673 K was two orders of magnitude larger than that for undamaged tungsten, and its D desorption spectrum had a single broad stage at around 900 K. As the neutron irradiation/plasma exposure temperature increased, D retention was largely reduced, and the desorption temperature was increased to higher temperatures above 1100 K. The D depth profiles by NRA also showed D migration toward bulk by higher temperature irradiation, compared to undamaged W. The HIDT simulation indicated that the major binding energy of D was changed from 1.43 eV to 2.07 eV at higher neutron irradiation and plasma exposure temperatures, suggesting that some vacancies and small vacancy clusters would aggregate to form larger voids, or depopulation of weak traps at high D plasma exposure temperatures. It can be said that more stable trapping sites played dominant roles in the D retention at higher neutron irradiation and plasma exposure temperature. The binding energy by HIDT simulation was almost consistent with the reported value by TMAP, but the consideration of not only total D retention measured by TDS but also D depth profile by NRA led to the more accurate D behavior in neutron-damaged W.
Depth profiling and standardization from the back side of a sample for accurate analyses: Emphasis on quantifying low‐fluence, shallow implants in diamond‐like carbon
Rationale Back‐side thinning of wafers is used to eliminate issues with transient sputtering when analyzing near‐surface element distributions. Precise and accurate calibrated implants are created by including a standard reference material during the implantation. Combining these methods allows accurate analysis of low‐fluence, shallow features even if matrix effects are a concern. Methods Implanted Na (<2.0 × 10 11 ions/cm 2 , peaking <50 nm) in diamond‐like carbon (DLC) film on silicon (solar wind returned by NASA's Genesis mission) was prepared for measurement as follows. Implanted surfaces of samples were epoxied to wafers and back‐side‐thinned using physical or chemical methods. Thinned samples were then implanted with reference ions for accurate quantification of the solar wind implant. Analyses used a CAMECA IMS 7f‐GEO SIMS in depth‐profiling mode. Results Back‐side‐implanted reference ions reduced the need to change sample mounts or stage position and could be spatially separated from the solar wind implant even when measuring monoisotopic ions. Matrix effects in DLC were mitigated and the need to find an identical piece of DLC for a reference implant was eliminated. Accuracy was only limited by the back‐side technique itself. Conclusions Combining back‐side depth profiling with back‐side‐implanted internal standards aides quantification of shallow mono‐ and polyisotopic implants. This technique helps mitigate matrix effects and keeps measurement conditions consistent. Depth profile acquisition times are longer, but if sample matrices are homogeneous, procedural changes can decrease measurement times.
Controlling Magnetization Vector Depth Profiles of La 0.7 Sr 0.3 CoO 3 /La 0.7 Sr 0.3 MnO 3 Exchange Spring Bilayers via Interface Reconstruction
The La 0.7 Sr 0.3 CoO 3–δ /La 0.7 Sr 0.3 MnO 3–δ (LSCO/LSMO) bilayer system is an ideal perovskite oxide platform for investigating interface reconstruction and its effect on their magnetic properties. Previous studies have shown that LSCO can separate into magnetic sublayers, which possess distinct trends as the total LSCO thickness increases. Here, we used polarized neutron reflectometry to quantify changes in the magnetic and chemical depth profiles, and it confirms the formation of ~12 Å-thick interfacial LSCO and LSMO layers, characterized by a decreased nuclear scattering length density compared to the bulk of the layers. This decrease is attributed to the combined effects of oxygen vacancy formation and interfacial charge transfer, which lead to magnetically active Co 2+ ions with ionic radii larger than the Co 3+ /Co 4+ ions typically found in bulk LSCO or single-layer films. The interfacial magnetization values, as well as Co 2+ ion and oxygen vacancy concentrations, depend strongly on the LSCO layer thickness. These results highlight the sensitive interplay of the cation valence states, oxygen vacancy concentration, and magnetization at interfaces in perovskite oxide multilayers, demonstrating the potential to tune their functional properties via careful design of their structure.
Active microbial biomass decreases, but microbial growth potential remains similar across soil depth profiles under deeply-vs. shallow-rooted plants
Climate-smart land management practices that replace shallow-rooted annual crop systems with deeply-rooted perennial plants can contribute to soil carbon sequestration. However, deep soil carbon accrual may be influenced by active microbial biomass and their capacity to assimilate fresh carbon at depth. Incorporating active microbial biomass, dormancy, and growth in microbially-explicit models can improve our ability to predict soil's capacity to store carbon. But, so far, the microbial parameters that are needed for such modeling are poorly constrained, especially in deep soil layers. Here, we used a lab incubation experiment and growth kinetics model to estimate how microbial parameters vary along 240 cm of soil depth in profiles under shallow- (soy) and deeply-rooted (switchgrass) plants 11 years after plant cover conversion. We also assessed resource origin and availability (total organic carbon, 14 C, extractable organic carbon, specific UV absorbance of K 2 SO 4 extractable organic C, total nitrogen, total dissolved nitrogen) along the soil profiles to examine associations between soil chemical and biological parameters. Even though root biomass was greater and rooting depth was deeper under switchgrass than soy, resource availability and microbial growth parameters were generally similar between vegetation types. Instead, depth significantly influenced soil chemical and biological parameters. For example, resource availability and total and relative active microbial biomass decreased with soil depth. Decreases in the relative active microbial biomass coincided with increased lag time (response time to external carbon inputs) along the soil profiles. Even at a depth of 210–240 cm, microbial communities were activated to grow by added resources within a day. Maximum specific growth rate decreased to a depth of 90 cm and then remained consistent in deeper layers. Our findings show that >10 years of vegetation and rooting depth changes may not be long enough to alter microbial growth parameters, and suggest that at least a portion of the microbial community in deep soils can grow rapidly in response to added resources. Our study determined microbial growth parameters that can be used in microbially-explicit models to simulate carbon dynamics in deep soil layers.
High resolution depth profiling using near-total-reflection hard x-ray photoelectron spectroscopy
By adjusting the incidence angle of incoming x rays near the critical angle of x-ray total reflection, photoelectron intensity is strongly modulated due to the variation of x-ray penetration depth. Photoelectron spectroscopy combined with near-total reflection exhibits tunable surface sensitivity, providing depth-resolved information. In this Review, we first describe the experimental setup and specific data analysis process. We then review three different examples that show the broad application of this method. Furthermore, the emphasis is on its applications correlated to oxide heterostructures, especially quantitative depth analyses of compositions and electronic states. In the last part, we discuss the limitations of this technique, mostly in terms of the range of samples that can be studied.
Improved quantitation of SIMS depth profile measurements of niobium via sample holder design improvements and characterization of grain orientation effects
The importance of SIMS analyses for “N-doped” impurity alloyed niobium and other surface-alloyed materials continues to increase. A major hurdle is the uncertainty of instrument calibration due to changes in sample height either from sample surface topography or from the sample holder itself. The CAMECA sample holder design allows for many types of samples to be analyzed. However, a drawback is that the holder faceplate can bend, contributing an uncertainty in the relative sensitivity factor (RSF) used to quantify the SIMS results. Here, we describe an improved sample holder having a reinforced faceplate, which prevents deflection and reduces uncertainty. Simulations show that the new design significantly reduces deflection from 10 μm to 5 nm. Sample measurements show a reduction of RSF uncertainty from this source from 4.1% to 0.95%. Grain orientation has long been suspected to affect RSF measurement as well. A bicrystal implant standard, consisting of randomly oriented and [001] grains, was successively rotated 15° between analyses. It was observed that 20% of the analyses performed on the randomly oriented grain exhibited anomalously high RSF values as well as slow sputter rates. These features were associated with the changing grain normal orientation with respect to the primary Cs + beam. The grain orientation associated with the rise in RSF was simulated and determined to be the [101] crystallographic plane, thus indicating that ion channeling was responsible for the significantly increased RSF. Focused ion beam analysis confirmed slower sputter rates for the cardinal crystallographic orientations, indicating that ion channeling occurred for each.
ToF-SIMS Depth Profiling to Measure Nanoparticle and Polymer Diffusion in Polymer Melts
Not provided.
Characterizing the Roles of Biogeochemical Cycling and Ocean Circulation in Regulating Marine Copper Distributions
Copper (Cu) is a key micronutrient for marine phytoplankton. Its oceanic biogeochemical cycle has elicited considerable attention due to dissolved Cu exhibiting a unique linear profile with depth. Several processes have been proposed for explaining this behavior. Here, in this study, we characterize the relationships between the observed Cu, PO 4 3– , and Si on a global scale. We find that the depth profiles of Cu resemble those of Si more than of PO 4 3– in the global ocean. To understand their relationships, we couple the biogeochemical and internal circulation processes in a model, fitting optimal Cu:PO 4 3– uptake ratios and remineralization length-scales to replicate the marine Cu distributions. The modeling results suggest that Cu uptake needs in the Southern Ocean are substantially higher than those in other oceanic regions. In addition, our modeling results indicate a deep Cu remineralization in the global ocean. We offer an alternative mechanism that relies on biogeochemical cycling and internal circulation to produce the linear depth profiles of dissolved Cu. Our results suggest that diatoms are likely the major phytoplankton dominating oceanic Cu cycling.
Physics-Informed and Data-Driven Prediction of Residual Stress in Three-Dimensional Machining
Efficient and reliable prediction of machining-induced residual stress (RS) is a key requirement for truly integrated computational materials engineering (ICME). Currently available process modeling approaches, including empirical, analytical, and numerical methodologies lack predictive power and require substantial calibration and validation data. Moreover, most model-based approaches consider only two-dimensional (2D) (i.e., orthogonal), cutting processes. Meanwhile, industrial processes such as milling, turning, and drilling are inherently three-dimensional (3D). The present work attempts to bridge the gap between 2D and 3D through careful consideration of the process physics, including geometric, kinematic, and size-effect constraints to realize robust prediction of how RS develops in 3D machining. Using a novel in-situ experimental technique and digital image correlation (DIC) to determine equivalent Hertzian contact widths, contact pressures, and friction coefficients, the proposed methodology leverages a discretized conversion algorithm that includes multi-pass shakedown effects. This paper presents a semi-analytical model to predict machining-induced RS in 3D turning operations, which are used representatively for 3D processes more generally. Rather than follow a ‘brute force’ 3D FEM approach or conduct countless experiments to train a purely data-driven machine learning algorithm, the proposed approach builds on previous 2D modeling work. Through careful consideration of the process physics, including complex geometry/kinematic considerations of 3D turning, the authors demonstrated an experimentally calibrated approach, as well as validation based on published RS data. Model predictions and previously published measurement data of RS depth profiles for turning of Inconel 718 were compared for a range of process parameters. Correlation between the proposed 3D model and validation data was found to be within the margin of experimental error for most conditions. The proposed model appears to capture the overall behavior of 3D RS depth profiles with acceptable accuracy, particularly the key metrics of near-surface stress, peak stress magnitude and location, as well as overall stress profile depth. This report presents a physics-informed, data-driven approach for efficient calibration of a 2D model for machining-induced RS through DIC analysis of in-situ characterized subsurface displacement fields.
Antarctic permafrost processes and antiphase dynamics of cold-based glaciers in the McMurdo Dry Valleys inferred from 10 Be and 26 Al cosmogenic nuclides
Abstract. Soil and sediment mixing and associated permafrost processes are not widely studied or understood in the McMurdo Dry Valleys of Antarctica. In this study, we investigate the stability and depositional history of near-surface permafrost sediments to ∼ 3 m depth in the Pearse and lower Wright valleys using measured cosmogenic 10Be and 26Al depth profiles. In Pearse Valley, we estimate a minimum depositional age of ∼ 74 ka for the active layer and paleoactive-layer sediments (< 0.65 m). Combined depth profile modelling of 10Be and 26Al gives a depositional age for near-surface (< 1.65 m) permafrost in Pearse Valley of 180 +20/-40 ka, implying that the deposition of permafrost sediments predates MIS 5 advances of Taylor Glacier. Deeper permafrost sediments (> 2.09 m) in Pearse Valley are thus inferred to have a depositional age of > 180 ka. At a coastal, lower-elevation site in neighbouring lower Wright Valley, 10Be and 26Al depth profiles from a second permafrost core exhibit near-constant concentrations with depth and indicate the sediments are either vertically mixed after deposition or sufficiently young so that post-depositional nuclide production is negligible relative to inheritance. 26Al/10Be concentration ratios for both depth profiles range between 4.0 and 5.2 and are all lower than the nominal surface production rate ratio of 6.75, indicating that prior to deposition, these sediments experienced complex, yet similar, exposure–burial histories. Assuming a single-cycle exposure–burial scenario, the observed 26Al/10Be ratios are equivalent to a total minimum exposure–burial history of ∼ 1.2 Myr. In proximity to the depth profile core site, we measured cosmogenic 10Be and 26Al in three granite cobbles from thin, patchy drift (Taylor 2 Drift) in Pearse Valley to constrain the timing of retreat of Taylor Glacier. Assuming simple continuous exposure, our minimum, zero-erosion exposure ages suggest Taylor Glacier partially retreated from Pearse Valley no later than 65–74 ka. The timing of retreat after 65 ka and until the Last Glacial Maximum (LGM) when Taylor Glacier was at a minimum position remains unresolved. The surface cobble ages and permafrost processes reveal Taylor Glacier advances during MIS 5 were non-erosive or mildly erosive, preserving the underlying permafrost sediments and peppering boulders and cobbles upon an older, relict surface. Our results are consistent with U/Th ages from central Taylor Valley and suggest changes in moisture delivery over Taylor Dome during MIS 5e, 5c, and 5a appear to be associated with the extent of the Ross Ice Shelf and sea ice in the Ross Sea. These data provide further evidence of antiphase behaviour through retreat of a peripheral lobe of Taylor Glacier in Pearse Valley, a region that was glaciated during MIS 5. We suggest a causal relationship of cold-based glacier advance and retreat that is controlled by an increase in moisture availability during retreat of sea ice and perhaps the Ross Ice Shelf, as well as, conversely, a decrease during times of sea ice and Ross Ice Shelf expansion in the Ross Sea.
Data associated with Quaternary Research manuscript Latest Pleistocene glacial chronology and paleoclimate reconstruction for the East River watershed, Colorado, USA
The data here are associated with Quaternary Research manuscript Latest Pleistocene glacial chronology and paleoclimate reconstruction for the East River watershed, Colorado, USA and include data associated with cosmogenic exposure and depth profile dating as well as glacier-climate numerical modeling. Reconstructing Pleistocene glaciation timing and extent is vital for understanding paleoclimate. While late Pleistocene glaciation has been studied extensively in western North American mountain ranges, the glacial history of the western Elk Range in Colorado remains understudied, particularly in the East River watershed, a site of intense scientific focus. Here we use cosmogenic nuclide exposure and depth–profile dating methods to determine the timing of glaciation in the East River watershed. We use glacier modeling to reconstruct paleoglacier extents and quantify past climate conditions. Our findings indicate that the East River glacier retreated from its maximum position approximately 17–18 ka, moving to recessional positions between 13–15 ka, before experiencing more substantial retreat to high-elevation cirques around 12.9 ka. Glacier modeling suggests that the maximum ice extents at 17–18 ka could have been sustained by temperature depressions of approximately −6.5°C compared to modern conditions, assuming consistent precipitation. Additionally, the ice position at 13–15 ka could have been supported by temperature depressions of around −4.0°C. These results offer insights into the deglaciation timeline in the East River watershed and broader western Elk Range as well as paleoclimate conditions during the late Pleistocene, which may aid future research on critical zone evolution in the East River watershed.The data files include: 1. Table 1 In situ-produced 10Be sample data (.pdf, .csv, .xlsx)2. Table 2 In situ-produced 10Be exposure age results (.pdf, .csv, .xlsx)3. S1_A CRONUS calculator input assuming no erosion (.csv)4. S1_B CRONUS calculator input assuming erosion (.csv)5. S1_C CRONUS calculator results and comparison (.csv)6. S2_A In situ-produced 10Be sample data for depth profile (.csv)7. S2_B In situ-produced 10Be depth profile model input (.csv)8. S2_C In situ-produced 10Be depth profile model results (.csv)9. S3 Monthly cloudiness, rH, and windspeed data used in glacier climate model (.csv)10. S4 Glacier climate model results (.csv)
Constraining Erosion Rates and Landscape Evolution With In Situ 10 Be and 26 Al Cosmogenic Nuclides at Table Mountain, Antarctica
Abstract This study investigates surface weathering and sediment preservation at Table Mountain, a high‐elevation, hyperarid, polar landscape in the Transantarctic Mountains. We report cosmogenic nuclide concentrations ( 10 Be and 26 Al) in quartz from bedrock surfaces, erratic boulder lag, and cobbles embedded within Sirius Group sediments to quantify erosion rates. In situ 10 Be and 26 Al depth profiles from a 2.95 m permafrost core in the Sirius Group further constrain surface erosion rates and elucidate landscape stability. Measured 10 Be and 26 Al concentrations from two sandstone bedrock surfaces adjacent to Sirius Group sediments give erosion rates of 0.18–0.28 m/Myr. An erratic sandstone boulder within the lag above the Sirius Group yields erosion rates of ∼0.42 ± 0.03 m/Myr, whereas two cobbles embedded within the Sirius Group yield higher rates of 0.81–1.12 m/Myr. Depth profiles of in situ 10 Be and 26 Al indicate no vertical mixing of Sirius Group permafrost since deposition. Depth profile models are best explained by erosion rates of 0.53 +0.13 / −0.12 m/Myr, and an exposure age of 0.78 +0.06 / −0.08 Ma. We view the model “age” to represent the ∼0.8‐million‐year time‐scale for surface lowering equivalent to one attenuation length of cosmic ray production to achieve steady‐state conditions. Continual exhumation of embedded clasts from within the Sirius Group results in an accumulation of clasts forming the observed erosional lag deposit covering the landscape. Our erosion rates of the Sirius Group surface based on in situ 10 Be and 26 Al depth profiles are an order‐of‐magnitude larger than those based on meteoric 10 Be infiltration and further clarification is required.
Best practices for operando depth-resolving battery experiments
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