Depth Profile Measurements Research Articles

Quantification of Ag/Ni Auger electron spectroscopy depth profiles upon preferential sputtering with non-stationary roughness

The measured Auger electron spectroscopy (AES) depth profiles of the as-deposited Ag/Ni multilayers demonstrate a strong preferential sputtering effect. In the framework of the Mixing-Roughness-Information depth (MRI) model, the influence of preferential sputtering on the “measured” depth profile is quantitatively evaluated. The mass conservation upon AES preferential sputtering is verified and applied to obtain the true layer thickness from the measured depth profiling data (i.e. intensity or composition as a function of sputtering time). Meanwhile the influences of preferential sputtering and non-stationary roughness effects on the depth resolution are also quantitatively evaluated. Based on the developed model, the measured AES depth profiles of the Ag/Ni multilayers as-deposited and annealed at different temperatures are fitted and the interdiffusion coefficients are obtained accordingly.

Confocal Raman Microscopy for the Analysis of the Three-Dimensional Shape of Polymeric Microsphere Layers.

The reconstruction of the three-dimensional (3D) morphology of polymeric microsphere layers based on confocal Raman microscopy was studied. Refraction of the Raman laser beam at the curved surface of the spheres broadens the focus volume inside the sphere. Compared to planar layers, the focus gets trapped inside the spheres such that the measured depth profiles are shifted and broadened. Additionally, the Raman signal of the underlying substrate is already observed for nominal focus positions above the microsphere layer. The results are successfully modeled with ray-optical simulations that allow for a clear understanding of the relevant mechanisms that lead to the generation of the Raman signals in the complex three-dimensional structures.

A distributed temperature profiling system for vertically and laterally dense acquisition of soil and snow temperature

Abstract. Measuring soil and snow temperature with high vertical and lateral resolution is critical for advancing the predictive understanding of thermal and hydro-biogeochemical processes that govern the behavior of environmental systems. Vertically resolved soil temperature measurements enable the estimation of soil thermal regimes, frozen-/thawed-layer thickness, thermal parameters, and heat and/or water fluxes. Similarly, they can be used to capture the snow depth and the snowpack thermal parameters and fluxes. However, these measurements are challenging to acquire using conventional approaches due to their total cost, their limited vertical resolution, and their large installation footprint. This study presents the development and validation of a novel distributed temperature profiling (DTP) system that addresses these challenges. The system leverages digital temperature sensors to provide unprecedented, finely resolved depth profiles of temperature measurements with flexibility in system geometry and vertical resolution. The integrated miniaturized logger enables automated data acquisition, management, and wireless transfer. A novel calibration approach adapted to the DTP system confirms the factory-assured sensor accuracy of ±0.1 ∘C and enables improving it to ±0.015 ∘C. Numerical experiments indicate that, under normal environmental conditions, an additional error of 0.01 % in amplitude and 70 s time delay in amplitude for a diurnal period can be expected, owing to the DTP housing. We demonstrate the DTP systems capability at two field sites, one focused on understanding how snow dynamics influence mountainous water resources and the other focused on understanding how soil properties influence carbon cycling. Results indicate that the DTP system reliably captures the dynamics in snow depth and soil freezing and thawing depth, enabling advances in understanding the intensity and timing in surface processes and their impact on subsurface thermohydrological regimes. Overall, the DTP system fulfills the needs for data accuracy, minimal power consumption, and low total cost, enabling advances in the multiscale understanding of various cryospheric and hydro-biogeochemical processes.

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.

Multiwavelength Ablation/Ionization and Mass Spectrometric Analysis of 1.88 Ga Gunflint Chert.

The investigation of chemical composition on planetary bodies without significant sample processing is of importance for nearly every mission aimed at robotic exploration. Moreover, it is a necessary tool to achieve the longstanding goal of finding evidence of life beyond Earth, for example, possibly preserved microbial remains within martian sediments. Our Laser Ablation Ionization Mass Spectrometer (LIMS) is a compact time-of-flight mass spectrometer intended to investigate the elemental, isotope, and molecular composition of a wide range of solid samples, including e.g., low bulk density organic remains in microfossils. Here, we present an overview of the instrument and collected chemical spectrometric data at the micrometer level from a Precambrian chert sample (1.88 Ga Gunflint Formation, Ontario, Canada), which is considered to be a martian analogue. Data were collected from two distinct zones-a silicified host area and a carbon-bearing microfossil assemblage zone. We performed these measurements using an ultrafast pulsed laser system (pulse width of ∼180 fs) with multiple wavelengths (infrared [IR]-775 nm, ultraviolet [UV]-387 nm, UV-258 nm) and using a pulsed high voltage on the mass spectrometer to reveal small organic signals. We investigated (1) the chemical composition of the sample and (2) the different laser wavelengths' performance to provide chemical depth profiles in silicified media. Our key findings are as follows: (1) microfossils from the Gunflint chert reveal a distinct chemical composition compared with the host mineralogy (we report the identification of 24 elements in the microfossils); (2) detection of the pristine composition of microfossils and co-occurring fine chemistry (rare earth elements) requires utilization of the depth profiling measurement protocol; and (3) our results show that, for analysis of heterogeneous material from siliciclastic deposits, siliceous sinters, and cherts, the most suitable wavelength for laser ablation/Ionization is UV-258 nm.

Design and production of tungsten-carbide rich coating layers

Ion beam induced mixing (IBM) can be used for making protecting coating layers at room temperature. We have studied the production of tungsten-carbide, having high strength and low friction, by IBM since this material is also a candidate for protective coatings. WC rich layers have been produced by irradiating C/W multilayer of various structures (with individual layer thicknesses from 10 to 20 nm) by noble gases using medium energy projectiles. The resulting alterations of the samples have been measured by Auger electron spectroscopy (AES) depth-profiling. TRIDYN simulations, with some parametrization, were applied to determine the elemental in-depth distribution after IBM; the compound formation was calculated by a simple model. The calculated and measured depth profiles were compared and excellent agreement has been found for a rich dataset differing in layer structures, projectiles, ion fluences and energies. The good agreement in a wide parameter range validates our procedure and allows the design of the WC-rich layers and also enables the significant decrease of the experimental work.

Electrochemical codeposition of arsenic from acidic copper sulfate baths: The implications for sustainable copper electrometallurgy

• The main source of arsenic contamination is codeposition during the nucleation stage. • Convection and concentrated Cu(II) electrolytes mitigate arsenic contamination. • The reduction of As(III) to metallic As does not occur readily. • Fast removal of As(III) possible by copper-arsenic codeposition. Copper producers face increased demand associated with increasing complexity in feedstock composition, including high amounts of impurity metals. In this work, linear sweep voltammetry was used to study the electrodeposition behavior of copper and arsenic, define strategies for the production of grade A copper, and the removal of arsenic from complex electrolytes. Our results show that the copper concentration is a key parameter to control in the electrodeposition process. The continuous deposition of arsenic from the electrolyte requires copper in solution (≤10 g L −1 Cu(II) for 2 g L −1 As(III)) to form copper arsenides . The deposition of metallic arsenic does not occur readily. Conversely, the use of a concentrated Cu(II) solution (e.g. 40 g L −1 ) resulted in grade A copper from an electrolyte with a maximum of 2 g L −1 As(III) under galvanostatic control at a current density of – 42 mA cm −2 . Time-of-Flight Secondary Ion Mass Spectrometry depth profile measurements on copper deposits revealed that arsenic contamination was entirely concentrated near the substrate side of the deposit and progressively decreased further into the deposit. The codeposition of arsenic occurred along with the initial copper nucleation, when the electrochemical potential for electrodepostion under galvanostatic control is temporarily lower. These findings provide important insights for future sustainable copper electrodeposition technologies from complex feedstocks.

Enhanced thin film analysis via High Resolution RBS using the NEC CARBS system

Advancements in thin film deposition techniques can now produce films of only a few monolayers in thicknesses, with multiple applications emerging in the nano technology field. This maturing manufacturing technique is driving the need for diagnostics tools able to accurately measure depth profiles. To meet this need, the Compact Automated Rutherford Back-Scattering (CARBS) system is under development at National Electrostatics Corp. (NEC) for nanometer thin film analysis using High-resolution RBS (HRBS) within a 4 x 4meter footprint. We present the recent development of the system and demonstrate a study of HRBS applied to a 30nm CoAl alloy film. We compare the performance of the CARBS system with the conventional NEC HRBS end station and discuss the advantages of HRBS over SIMS method.

An approach for 3-D distribution measurement of tritium in tungsten by chemical etching and imaging plate technique

Measurement of tritium distribution details both on surface and in bulk of tungsten is of great importance for studies on the retention properties of plasma facing materials (PFMs) in magnetic fusion reactors. An attempt was made to determine the tritium 3-D distribution in tungsten sample through layer by layer chemical etching method (LLCE) and imaging plate technique (IP). As chemical etching method has been rarely employed for tritium measurement in tungsten, the influence of key experimental parameters were evaluated. And the tritium 3-D distribution in a tungsten sample was obtained by LLCE and IP. It is found that LLCE is a promising and reliable method for tritium depth profile measurement. The relative error of tritium content in each layer is approximately 5.2% when the thickness of erosion layer is 0.4 μm. Combined with IP technique, the detailed 3-D distribution could be obtained and it is clearly indicated that tritium is unevenly distributed on the radial section of this sample. In addition, the good agreement of tritium depth profile by LLCE and IP shows the reliability of this approach.

Relating tensile strength to acoustic and biological properties of sediments along a mud-sand gradient in Mobile Bay, AL

Nearshore and estuarine sediments experience varying sediment inputs that create sharp gradients in sediment properties over fairly small vertical and horizontal distances. In this study, we explored the sand-mud transition in sediment cores collected from Mobile Bay, AL, with acoustic and geotechnical approaches. A custom built instrument was used to measure depth profiles of tensile strength at cm-scale resolution. These measurements were compared to acoustic sound speed and attenuation across a range of frequencies. Cores collected exhibited a horizontal gradient from sand to mud across the study area with a sandy layer on top of muddier sediment in most cores. This study explicitly examines the relationship between acoustic sound speed and attenuation and strength-related properties of sediments such as cohesion that can be measured in situ more easily than textural properties (e.g., porosity and grain size). We compare our data to in situ normal incidence measurements and portable free fall penetrometer data as well as infaunal community composition to better relate acoustic, geotechnical, and biological properties across a gradient of sediments.

Defect depth profiling of sputter-deposited Cu/Nb bilayers using a positron accelerator

Ultrathin bilayers of Cu/Nb viz. Nb/Cu/Si and Cu/Nb/Si have been deposited on Si substrate using DC and RF magnetron sputtering. The structural characterization of bilayers has been carried out using X-ray reflectivity (XRR) to determine the thickness and density of individual layers. The thickness of Nb and Cu layer in the bilayers ranges from ∼ 44–71 nm and 6–11 nm, respectively. Defect depth profiling of bilayers has been carried out using a positron accelerator. The measured depth profiles, i.e., S-parameter profiles have been fitted using VEPFIT, a program that factors the positron implantation profile and its annihilation to estimate S-parameter and positron diffusion length in individual layers. We present a detailed and systematic analysis of the measured S-profiles using VEPFIT to evaluate S-parameter and positron diffusion length in individual layers of the bilayer structures. These parameters are representative of defect characteristics of the layers. In this work we also highlight the nuances of VEPFIT analysis useful to extract defect characteristics in bilayers. The results indicate that defect microstructure of the layer depends on the thickness, deposition method and irradiation. Defect density is seen to increase with the reduction of thickness of the layer. RF sputtered layer has more defects as compared to DC sputtered layers. Positron depth profiling does not reveal distinct interface between the two metallic layers as well as layer and the substrate. A systematic characterization of defect in ultrathin structures is crucial to establish a correlation between defect microstructure and properties of nanolayer composites for advanced applications.

Growth and Characterisation Studies of Eu3O4 Thin Films Grown on Si/SiO2 and Graphene.

We report the growth, structural and magnetic properties of the less studied Eu-oxide phase, EuO, thin films grown on a Si/SiO substrate and Si/SiO/graphene using molecular beam epitaxy. The X-ray diffraction scans show that highly textured crystalline EuO(001) films are grown on both substrates, whereas the film deposited on graphene has a better crystallinity than that grown on the Si/SiO substrate. The SQUID measurements show that both films have a Curie temperature of ∼ K, with a magnetic moment of ∼ emu/cm at 2 K. The mixed valence of the Eu cations has been confirmed by the qualitative analysis of the depth-profile X-ray photoelectron spectroscopy measurements with the : ratio of . However, surprisingly, our films show no metamagnetic behaviour as reported for the bulk and powder form. Furthermore, the microscopic optical images and Raman measurements show that the graphene underlayer remains largely intact after the growth of the EuO thin films.

Feasibility study of an efficient method to measure depth profile of particle ions using a wedge-shaped acrylic block

The depth-profile measurement of particle ions is a time- and labor-consuming task, and thus an efficient method is desired. To solve this problem, we propose a new method to measure depth profiles and test it for carbon ions. In our method, we use a thin silver-activated zinc sulfide (ZnS(Ag)) scintillator plate set against the inner top side of a black box and irradiate a uniform carbon-ion beam to this plate from the upper side. On the ZnS(Ag) plate, a wedge-shaped acrylic block is set to absorb the carbon ions depending on the plate’s position. The scintillation light’s image is reflected by a surface mirror set below the ZnS(Ag) plate and then detected by a cooled charge-coupled device (CCD) camera from the side. We irradiate carbon ions for 6 s and measure the ZnS(Ag) image that is partially attenuated by the wedge-shaped acrylic block. By setting the profile on the measured image, we could estimate the depth profile of the carbon-ion beam, although a quenching of the scintillator is observed around the Bragg peak area. We conclude that our proposed method is promising for efficiently measuring the depth profile of particle ions.

Commissioning of an ultra-high dose rate pulsed electron beam medical LINAC for FLASH RT preclinical animal experiments and future clinical human protocols.

To present the acceptance and the commissioning, to define the reference dose, and to prepare the reference data for a quality assessment (QA) program of an ultra-high dose rate (UHDR) electron device in order to validate it for preclinical animal FLASH radiotherapy (FLASH RT) experiments and for FLASH RT clinical human protocols. The Mobetron® device was evaluated with electron beams of 9MeV in conventional (CONV) mode and of 6 and 9MeV in UHDR mode (nominal energy). The acceptance was performed according to the acceptance protocol of the company. The commissioning consisted of determining the short- and long-term stability of the device, the measurement of percent depth dose curves (PDDs) and profiles at two different positions (with two different dose per pulse regimen) and for different collimator sizes, and the evaluation of the variability of these parameters when changing the pulse width and pulse repetition frequency. Measurements were performed using a redundant and validated dosimetric strategy with alanine and radiochromic films, as well as Advanced Markus ionization chamber for some measurements. The acceptance tests were all within the tolerances of the company's acceptance protocol. The linearity with pulse width was within 1.5% in all cases. The pulse repetition frequency did not affect the delivered dose more than 2% in all cases but 90Hz, for which the larger difference was 3.8%. The reference dosimetry showed a good agreement within the alanine and films with variations of 2.2% or less. The short-term (resp. long-term) stability was less than 1.0% (resp. 1.8%) and was the same in both CONV and UHDR modes. PDDs, profiles, and reference dosimetry were measured at two positions, providing data for two specific dose rates (about 9Gy/pulse and 3Gy/pulse). Maximal beam size was 4 and 6cm at 90% isodose in the two positions tested. There was no difference between CONV and UHDR mode in the beam characteristics tested. The device is commissioned for FLASH RT preclinical biological experiments as well as FLASH RT clinical human protocols.

Synthesis and study of highly dense and smooth TiN thin films

This study aims towards a systematic reciprocity of the tunable synthesis parameters - partial pressure of N2 gas, ion energy (Ei) and Ti interface in TiN thin film samples deposited using ion beam sputtering at ambient temperature (300 K). At the optimum partial pressure of N2 gas, samples were prepared with or without Ti interface at Ei = 1.0 or 0.5 keV. They were characterized using x-ray reflectivity (XRR) to deduce thickness, roughness and density. The roughness of TiN thin films was found to be below 1 nm, when deposited at the lower Ei of 0.5 keV and when interfaced with a layer of Ti. Under these conditions, the density of TiN sample reaches to 5.80(±0.03) g cm−3, a value highest hitherto for any TiN sample. X-ray diffraction and electrical resistivity measurements were performed. It was found that the cumulative effect of the reduction in Ei from 1.0 to 0.5 keV and the addition of Ti interface favors (111) oriented growth leading to dense and smooth TiN films and a substantial reduction in the electrical resistivity. The reduction in Ei has been attributed to the surface kinetics mechanism (simulated using SRIM) where the available energy of the sputtered species (<Esp>) leaving the target at Ei = 0.5 keV is the optimum value favoring the growth of defects free homogeneously distributed films. Secondary ion mass spectroscopy depth profile measurements confirm the uniform distribution of N and Ti across the depth of a sample. The electronic structure of samples was probed using N K-edge and Ti L-edge absorption spectroscopy and the information about the crystal field and spin-orbit splitting confirmed TiN phase formation. In essence, through this work, we demonstrate the role of <Esp> and Ti interface in achieving highly dense and smooth TiN thin films with low resistivity without the need of a high temperature or substrate biasing during the thin film deposition process.

A method to reduce the error due to the angular dependencies of Cerenkov-light in water for optical imaging of X-rays from high-energy medical linear accelerators (LINAC)

Determining the absorbed dose distributions in phantoms for X-ray beams of high-energy medical linear accelerators (LINAC) is an important task in the quality control of a system. Although optical imaging of water during irradiation of X-ray beams from a LINAC is a promising method, depth dose profiles show underestimation in the deeper parts of the water, mainly due to the angular dependency of Cerenkov-light produced in water. To solve this problem, the authors change camera angles from 0 degree to 10 degrees and obtain optical images with a high-sensitivity cooled charge coupled device (CCD) camera during X-ray beam irradiation. Furthermore, the authors calculate the Cerenkov-light distributions with different camera angles using Monte Carlo simulation and the obtained depth profiles. Then, these depth profiles are evaluated and compared with those of a planning system. In both measured and simulated distributions, the light intensity increases as the angle increases. The measured depth profile of 10 degrees was nearly identical to the planning system. The percentage differences of depth profile between the measured optical image at the angle of 10 degrees and the planning system was -1.7 % at 100 mm depth, and the average difference was 0.8 %. We conclude that optical imaging with that angle is a promising method for reducing the error due to the angular dependency of Cerenkov-light.

Development of &lt;i&gt;Spatiotemporal&lt;/i&gt; Measurement and Analysis Techniques in X-ray Photoelectron Spectroscopy ∼From NAP-HARPES to 4D-XPS∼

We have developed spatiotemporal measurement and analysis techniques in x-ray photoelectron spectroscopy. To begin with, time-division depth profiles of gate stacked film interfaces have been achieved by NAP-HARPES (Near Ambient Pressure Hard x-ray Angle-Resolved PhotoEmission Spectroscopy) data. We then have promoted our methods to quickly perform peak fittings and depth profiling from time-division ARPES data, which enables us to realize 4D-XPS analysis. It is found that the traditional maximum entropy method (MEM) combined with Jackknife averaging of sparse modeling in NAP-HARPES data is effective to perform dynamic measurement of depth profiles with high precision.

Preferential sputtering in quantitative sputter depth profiling of multi-element thin films

Preferential sputtering plays an important role in the quantification of measured depth profiles. The distortion of the measured depth profile as compared to the original one has to be evaluated upon preferential sputtering in depth profiling. In the framework of the mixing-roughness-information depth (MRI) model, the influences of preferential sputtering on the depth profile of multi-element thin films are quantitatively evaluated as demonstrated for a layered structure of three elements with different sputtering rates and subsequent interfaces as A/BC/A. Moreover, the mass conservation upon Auger electron spectroscopy/X-ray photoelectron spectroscopy depth profiling of multi-element structure is discussed with respect to the preferential effect. Finally, as an example, the measured glow discharge optical emission spectroscope depth profiling data of 60x(3.0 nm Mo/0.3 nm B4C/3.7 nm Si)/Si(111) multilayer structure are quantitatively evaluated using the extended MRI model.

Competing Segregation of Br- and Cl- to a Surface Coated with a Cationic Surfactant: Direct Measurements of Ion and Solvent Depth Profiles.

Ion-surface scattering experiments can be used to measure elemental depth profiles on the angstrom scale in complex liquid mixtures. We employ NICISS (neutral impact collision ion scattering spectroscopy) to measure depth profiles of dissolved ions and solvent in liquid glycerol containing the cationic surfactant tetrahexylammonium bromide (THA+/Br-) at 0.013 M and mixtures of NaBr + NaCl at 0.4 M total concentration. The experiments reveal that Br- outcompetes Cl- in its attraction to surface THA+, and that THA+ segregates more extensively when more Br- ions are present. Intriguingly, the depths spanned by THA+, Br-, and Cl- ions generally increase with Br- bulk concentration, expanding from ∼10 to ∼25 Å for both Br- and Cl- depth profiles. This broadening likely occurs because of an increasing pileup of THA+ ions in a multilayer region that spreads the halide ions over a wider depth. The experiments indicate that cationic surfactants enhance Br- and Cl- concentrations in the surface region far beyond their bulk-phase values, making solutions coated with these surfactants potentially more reactive toward gases that can oxidize the halide ions.

Precision of Hole-Drilling Residual Stress Depth Profile Measurements and an Updated Uncertainty Estimator

Measurement precision and uncertainty estimation are important factors for all residual stress measurement techniques. The values of these quantities can help to determine whether a particular measurement technique would be viable option. This paper determines the precision of hole-drilling residual stress measurement using repeatability studies and develops an updated uncertainty estimator. Two repeatability studies were performed on test specimens extracted from aluminum and titanium shot peened plates. Each repeatability study included 12 hole-drilling measurements performed using a bespoke automated milling machine. Repeatability standard deviations were determined for each population. The repeatability studies were replicated using a commercially available manual hole-drilling milling machine (RS-200, Micro-Measurements). An updated uncertainty estimator was developed and was assessed using an acceptance criterion. The acceptance criterion compared an expected percentage of points (68%) to the fraction of points in the stress versus depth profile where the measured stresses ± its total uncertainty contained the mean stress of the repeatability studies. Both repeatability studies showed larger repeatability standard deviations at the surface that decay quickly (over about 0.3 mm). The repeatability standard deviation was significantly smaller in the aluminum plate (max ≈ 15 MPa, RMS ≈ 6.4 MPa) than in the titanium plate (max ≈ 60 MPa, RMS ≈ 21.0 MPa). The repeatability standard deviations were significantly larger when using the manual milling machine in the aluminum plate (RMS ≈ 21.7 MPa), and for the titanium plate (RMS ≈ 18.9 MPa). The single measurement uncertainty estimate met a defined acceptance criterion based on the confidence interval of the uncertainty estimate.