Composition Depth Profiles Research Articles

Corrosion resistance and biocompatibility of carbon ion implanted AZ31B magnesium alloy

The poor corrosion resistance of magnesium limits its clinical applications. Accordingly, in the present study, carbon ions were incorporated into a AZ31b magnesium alloy surface via carbon plasma immersion ion-implantation to improve its corrosion resistance and biocompatibility. The surface morphology and properties of the modified alloy were evaluated by field-emission scanning electron microscopy, water contact angle measurement, Raman scattering, X-ray photoelectron spectroscopy, and energy dispersive X-ray spectroscopy. Furthermore, compositional depth profiles were obtained by glow discharge optical emission spectroscopy, revealing a Gaussian-like distribution of carbon concentration. Electrochemical and hydrogen-evolution analysis demonstrated the successfully improved corrosion resistance of the AZ31b Mg alloy, while its biocompatibility was demonstrated by MTT and cell-adherence assays.

Evaluating Nondestructive Quantification of Composition Gradients in Metal-Organic Frameworks by MeV Ion Microbeam Analysis.

We evaluate a method to quantify composition depth gradients in intact metal-organic framework (MOF) single crystals and thereby derive diffusion coefficients of postsynthetically incorporated active sites by nondestructive ion-beam microanalysis. Zr-based UiO-67-bpy (bpy = 2,2'-bipyridine-5,5'-dicarboxylic acid) MOFs were synthesized on Si substrates and then metalated postsynthetically with NiCl2 for 2-48 h, resulting in different Ni depth distributions. Simultaneous micro-Rutherford backscattering spectrometry (μ-RBS) and micro-particle induced X-ray emission (μ-PIXE) analysis were used for the spatially resolved chemical analysis of the MOF single crystals. Qualitative assessment of the μ-RBS spectra indicated the presence of elemental depth gradients and hinted at the governing process of the postsynthetic Ni incorporation, in the present case, molecular diffusion. Quantitative evaluation of the resulting composition depth profiles directly provided the diffusion length and, thereby, the diffusion coefficient of the system. Virtual gradients caused by overhanging tips/edges of the truncated octahedral crystal shape are considered. Furthermore, in the case of insufficient probing depth for μ-RBS, μ-PIXE was still capable of providing qualitative information. In the present system the diffusion coefficient for NiCl2 is found to be (1.72 ± 0.18) × 10-16 m2s-1. The long-term stability of the synthesized and postsynthetically modified MOFs is proved by repeated measurements.

Structural and phase transformations in Fe-Pd-Ag layered thin films by grain boundary diffusion

The influence of the stacking order and of an additional Ag layer on the formation of ordered phases in thin (< 50 nm) layered Fe/Pd and Fe/Ag/Pd films was investigated at 460 °C. The samples were prepared by magnetron sputtering at room temperature on Si/SiO2 substrate and were post-annealed in vacuum. Composition depth profiling and x-ray diffraction were used to characterize the processes. It has been shown, that the stacking order strongly influences the formation of ordered phases both in Fe/Pd bilayered and Fe/Ag/Pd trilayered films. In bilayered Fe/Pd films for both stacking orders the FePd3 phase appeared and it also showed L12 ordering for one stacking order. Addition of Ag layer between the Fe and Pd layers found to promote the formation of FePd phase which showed L10 ordering or A1 disordered structure depending on stacking order. Based on the analysis of the chemical depth profiles and XRD patterns the transformations were interpreted by grainboundary diffusion mechanisms including grainboundary diffusion induced grainboundary migration and solid state reaction.

Quantification of Hydrogen and Transition Metals in the Cathode Catalyst Layer of Anion Exchange Membrane Electrolyzer By Ion Beam Techniques

Anion Exchange Membrane Water Electrolyzer (AEMWE) has increased interest in H2 production at low cost and high scalability. The efficiency is strongly dependent on the membrane electrode assembly (MEA) with appropriate ionomer and catalyst layers. Herein, we report AEMWE with MoNi4-MoO2 cathode catalyst layer in ionomer-free Catalyst Coated Substrate (CCS) configuration. The optimized MEA for AEMWE demonstrated the superior performance of 225 mA/cm2 at 2V with more than 48 hours of durability. The X-ray diffraction confirmed the NiMoO4 phase transformation to MoNi4-MoO2 and SEM-EDS was used to study the morphology and elemental composition of the deposited catalyst. X-ray photoelectron Spectroscopy demonstrated the dominant metallic MoO2 formed after H2/Ar annealing. Rutherford Backscattering Spectroscopy (RBS) was also employed to measure the depth composition profile of the catalyst layer exhibiting the reduction of Ni concentration in the bulk after annealing. Further, we introduce hydrogen depth profiling by Nuclear Reaction Analysis (NRA) via the resonant 1H(15N,αγ)12C reaction as a versatile method for the highly depth-resolved visualization of hydrogen(H) in the near-surface region, including transitions of hydrogen between the surface and the bulk, and between shallow interfaces of the nanostructured cathode catalyst layer. The diffusion of the H atoms was observed with a 40% atomic percent of Hydrogen after H2/Ar annealing of the catalyst for 180 minutes (about 3 hours) and decreased to 10% atomic percent of hydrogen after 24 hours of electrolyzer operation. This technique also enabled the measurement of the zero-point vibrational energy of hydrogen atoms absorbed on the surfaces of the catalyst layer. Overall, this work better explains the cathode catalyst degradation effects and hydrogen diffusion in the cathode catalyst layer responsible for voltage and mass transfer losses in AEM electrolyzers.

Practical guides for x-ray photoelectron spectroscopy: Use of argon ion beams for sputter depth profiling and cleaning

Ion beams are used in x-ray photoelectron spectroscopy (XPS) to clean samples and perform compositional sputter depth profiles. The purpose of this article is to compile good practice, recommendations, and useful information related to the use of argon ion sources for inexperienced users of XPS instrumentation. The most used type of ion source generates monoatomic argon ions at a range of energies from a fixed direction relative to the instrument. The angle and direction of the ion beam with respect to the surface are normally altered by manipulating the sample, and this may involve tilting the sample to change the angle of incidence or rotating the sample to change the azimuthal incidence angle. Atomic argon ion beams cause damage to the structure of the material surface, which may exhibit itself as a change in stoichiometry or topography as well as the implantation of argon atoms. Therefore, caution is required in the interpretation of XPS depth profiles. Gas cluster ion sources offer new possibilities and choices to XPS users. Gas cluster sources enable the sputtering of organic materials with high yield in comparison to inorganic materials and offer the potential for nearly damage-free depth profiling of delicate organic materials as well as low damage cleaning of inorganic materials. It may be possible to use argon clusters to reduce damage during the depth profiling of inorganic materials, but there is currently insufficient evidence to make any general recommendations.

The Influence of Annealing on the Compositional and Crystallographic Properties of Sputtered Li–Al–O Thin Films

Li–Al–O materials are interesting for several applications. Herein, a Li–Al–O thin‐film materials library, deposited by inert magnetron sputtering and postdeposition annealing in O2 atmosphere, is used to study the effects of different annealing temperatures (300–850 °C) and durations (1 min to 7 h) on crystallinity and composition of the films. X‐ray photoelectron spectroscopy depth profiling reveals inhomogeneous compositional depth profiles of conventionally annealed films (300–650 °C, 3–7 h) with increased Li contents toward the film surface and increased Al contents toward the film–substrate interface, as confirmed by a combination of Rutherford backscattering spectrometry and deuteron‐induced nuclear reaction analysis. The minimum temperature for the formation of crystalline LiAlO2 in the otherwise amorphous films is 550 °C. The undesired inhomogeneous depth profiles are transformed into homogeneous ones by rapid thermal annealing (750–850 °C, 1–10 min), while simultaneously causing the formation of crystalline LiAlO2. Therefore, rapid thermal annealing is shown to be more suitable than conventional annealing for the thermal processing of Li–Al–O thin films. Moreover, this conclusion is expected to have broader relevance beyond Li–Al–O materials, as it is likely to apply to other Li metal oxides, of which there are many technologically relevant ones.

Viscous Sintering of Acid Leached Glass Powders

The process of viscous flow sintering is a phenomenon that is closely linked to the surface properties of the glass particles. In this work, we studied the extreme case of acid-leaching of soda-lime-silicate glass beads of two different particle size distributions and its effects on non-isothermal viscous sintering of powder compacts. Depth profiling of the chemical composition after leaching revealed a near-surface layer depleted in alkali and alkaline earth ions, associated with concurrent hydration as mass loss was detected by thermogravimetry. Heating microscopy showed that acid treatment of glasses shifted the sinter curves to higher temperatures with increasing leaching time. Modelling of the shrinkage with the cluster model predicted a higher viscosity of the altered surface layer, while analysis of the time scales of mass transport of mobile species (Na+, Ca2+ and H2O) during isochronous sintering revealed that diffusion of Na+ can compensate for concentration gradients before sintering begins. Also, exchanged water species can diffuse out of the altered layer, but the depletion of Ca2+ in the altered surface layer persists during the sinter interval, resulting in a glass with higher viscosity, which causes sintering to slow down.

Investigation of interdiffusion in thin films of ZnO/ZnCdO grown by molecular beam epitaxy

Rutherford backscattering spectrometry (RBS) was used to determine the composition, uniformity, impurity, and elemental depth profiles of Zn, Cd, and O in ZnCdO/ZnO thin film deposited on differently oriented Al2O3 substrates using molecular beam epitaxy technique. For the films deposited under the same condition, it was observed that the variation of Zn/Cd/O ratios is dependent on substrate orientation and highly depends on the growth parameters. The composition and thickness variation, in relationship with two different substrates orientations, were explored with RBS, scanning electron microscopy, and photoluminescence measurements. It was found that ZnCdO films deposited on r- oriented ZnO buffers exhibit much less surface roughness and intermixing after the rapid thermal processing annealing is less extensive.

Composition and thermoelectric properties of structures based on iron silicide grown by pulse laser deposition

Silicon compounds have a wide range of electrical properties. In particular, the possibility of creating thermoelectric converters based on them looks extremely attractive. The use of most silicides as thermoelectrics today is limited by their low efficiency. The development of approaches consisting in the creation of low-dimensional structures using non-equilibrium formation methods is one of the priority directions for improving the properties of thermoelectric generators. Determination of the effect of technological regimes on the structure, phase-chemical composition and thermoelectric properties of metal-silicide structures is a key task, the solution of which will allow creating highly efficient thermoelectric generators based on them. Thin-film structures with a layer thickness of ~50 nm formed at different growth temperatures by pulsed laser deposition on two types of substrates: sapphire and gallium arsenide coated with an Al2O3 nanolayer were studied in this work. On the formed samples, a chemical analysis and a study of the phase composition were performed. Chemical analysis was carried out by X-ray photoelectron spectroscopy with the chemical composition depth profiling. The phase composition was studied by Raman spectroscopy. In addition, analysis of the elements in the films was carried out by X-ray spectral microanalysis based on a scanning electron microscope. To determine the thermoelectric properties of the formed thin-film structures, the temperature dependences of the Seebeck coefficient and the electrical conductivity coefficient were recorded. The dependence of the thermoelectric characteristics of iron silicide films on the phase composition is analyzed. In particular, measurements of the thermoelectric properties of FeSix thin-film structures registered the manifestation of a strong thermoelectric effect in layers with the maximum number of chemical bonds between iron and silicon. The parameters of the growth process at which the most effective formation of iron-silicon chemical bonds is achieved were determined using the method of X-ray photoelectron spectroscopy. Line shifts from the beta phase of iron disilicide were found in the Raman spectra and the reasons for their appearance were proposed

Measurement of the Dzyaloshinskii-Moriya Interaction in Mn4N Films That Host Skyrmions.

Mn4N thin film is one of the potential magnetic mediums for spintronic devices due to its ferrimagnetism with low magnetization, large perpendicular magnetic anisotropy (PMA), thermal stability, and large domain wall velocity. Recent experiments confirmed the existence of tunable magnetic skyrmions in MgO/Mn4N/CuxPt1-x(x = 0, 0.5, 0.9, 0.95), and density functional theory (DFT) calculation provided a large theoretical value of the interfacial Dzyaloshinskii-Moriya interaction (iDMI) of Mn4N/Pt, which is consistent with the predicted chemical trend of the DMI in transition metal/Pt films. So far, the measured DMI has not been reported in Mn4N, which is needed in order to support the predicted large DMI value. This paper reports the average DMI of MgO/Mn4N(17 nm)/CuxPt1-x(3 nm) extracted from the anomalous Hall effect with various tilted angles, which is based on magnetic droplet theory with DMI effects. The DMI decreases from 0.267 mJ/m2 to 0.011 mJ/m2 with non-linear tendencies as Cu concentration in the CuxPt1-x capping layer increases from 0 to 1, demonstrating the control of the DMI through the CuxPt1-x capping layer. Furthermore, a solid solution model is developed based on an X-ray photoelectron spectroscopy (XPS) compositional depth profile to analyze the possible effects on the DMI from the mixing layers at the surface of Mn4N. After taking into account the mixing layers, the large DMI in Mn4N film with Pt capping is consistent with the predicted DMI.

Elemental and chemical depth profiling of high-build single-component (1K) polyester-polyurethane coil coatings

The interior structure and chemistry of single-component (1K) polyester-polyurethane (PU) coil coatings, which find preferred application in the construction industry, was comprehensively investigated by energy-dispersive X-ray spectroscopy (EDX), Fourier-transform infrared (FTIR) spectroscopy and X-ray electron spectroscopy (XPS). Fabrication of extended tapers in the millimetre-range through a double-layered coating system with a total dry film thickness of 50 μm was achieved by cryo-ultra-low-angle microtomy (cryo-ULAM). The linearity and surface topography of shallow angle ULAM cuts created at different preparation conditions were examined at mesoscopic and microscopic scale by coherence scanning interferometry, atomic force microscopy (AFM) and scanning electron microscopy (SEM). EDX mappings recorded on the exposed sections enabled to determine the elemental structure and the distribution of embedded fillers at plane-view. Focal plane array (FPA) FTIR spectroscopy in attenuated total reflection (ATR) mode was used to acquire high-resolution chemical data from the fabricated taper, revealing the clustering of nitrogen-containing groups. Compositional depth profiling of the investigated high-build PU coating system was achieved by performing XPS line scans on the exposed sections. Depth analysis at a chemical level was obtained by means of evaluating the high-resolution carbon C1s spectra, which showed an enhancement of nitrogen and oxygen containing functionalities near the primer/substrate interface. All methods of this correlative work of analysis consistently indicate the presence of chemical gradients related to the cross-linking agent.

Stratified and gradient films by evaporation-induced stratification of bimodal latexes. Potential of confocal and scanning electron microscopy for compositional depth profiling

In the field of bimodal latex film's formation, finding methods to quantify particle concentration profiles within the film thickness is a challenge. Herein the advantages and limitations of confocal fluorescence microscopy (CFM) and scanning electron microscopy (SEM) are presented. Films are prepared from a bimodal fluorescent acrylic mixture of large non-deformable particles and small deformable particles having high Péclet numbers. A fixed volume fraction of large particles (ΦL) in the dispersion is used with increasing volume fractions of small particles latex (ΦS). At low ΦS, a surface stratification of large particles occurs with thicknesses up to several micrometers, allowing detection by both CFM and SEM. Small particles form a stratified surface layer above a threshold ΦS value. Its thickness of less than 500 nm is evidenced only by SEM due to the resolution limit of the confocal scan. SEM is also able to reveal concentration gradients of large particles below the “small-on-top” stratified layer.

In Situ Neutron Reflectometry Study of a Tungsten Oxide/Li-Ion Battery Electrolyte Interface.

The solid electrolyte interface/interphase (SEI) is of great importance to the viable operation of lithium-ion batteries. In the present work, the interface between a tungsten oxide electrode and an electrolyte solution consisting of LiPF6 in a deuterated ethylene carbonate/diethyl carbonate solvent was characterized with in situ neutron reflectometry (NR) at a series of applied electrochemical potentials. NR data were fit to yield neutron scattering length density (SLD) depth profiles in the surface normal direction, from which composition depth profiles were inferred. The goals of this work were to characterize SEI formation on a model transition-metal oxide, an example of a conversion electrode, to characterize the lithiation of WO3, and to help interpret the results of an earlier study of tungsten electrodes without an intentionally grown surface oxide. The WO3 electrode was produced by thermal oxidation of a W thin film. Co-analysis of NR and X-ray reflectivity data indicated that the stoichiometry of the thermal oxide was WO3. As the electrode was polarized to progressively more reducing potentials, starting from open circuit and down to +0.25 V versus Li/Li+, the layer that was originally WO3 expanded and increased in lithium content. The reduced electrode consisted of two to three layers: an inner layer (the evolving conversion electrode) which may have been mixed W and Li2O and unreacted WO3 or LixWO3, a layer rich in protons and/or lithium, possibly corresponding to LiOH or LiH (the inner SEI), and an outermost layer adjacent to the solution with an SLD close to that of the solution, possibly consisting of lower SLD species with solution-filled porosity or deuteron-rich species derived from the solvents (the outer SEI), though the presence of this layer was tenuous. For the steps in the direction of more oxidizing potentials, the evolution of the layer structure was qualitatively the reverse of that seen when stepping toward more negative potentials, though with hysteresis. The SLD gradient suggested that the reaction was not limited by diffusion within the film. No clear phase boundary was evident in the evolving conversion electrode.

Dynamic character of compositional sputter depth profiling by SIMS: A comparison of different models for quantitative profile evaluation

We are dealing with some new insights in the quantification of sputter depth profiles obtained by secondary ion mass spectroscopy, which can be easily extended to XPS or AES. Recent publications present a rather negative image of the mixing-roughness-information depth (MRI) model of quantitative sputter depth profile evaluation in conjunction with Dowsett’s up-and-down slope (UDS) model, at first we attempt to point out the merits of the MRI model. Since these publications come up with a new, alternative model [called roughness-mixing-recoil model (RMR)], we discuss in detail the flaws of both the UDS and the RMR models. In conclusion, we present some instructive examples that show the decisive validity of the MRI model in describing the nature of the process of sputter depth profiling.

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 TiCl4 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 TiCl4 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, TiCl4 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 TiCl4 infiltration into PMMA is clearly a reaction-limited process, with TiCl4 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 TiCl4 infiltration into PMMA. These results demonstrate a new, ex situ analysis approach for investigating the rate-limiting process mechanisms for vapor phase infiltration.

XPS investigation of 5N purity Al thin foils for MEMS devices

Thin Al foils are promising materials for applications in devices of microelectromechanical systems (MEMS). In this work, three foils of high purity (5N) Al with different thickness (10, 50, and 125 μm) were analyzed by means of X‐ray photoelectron spectroscopy (XPS), before and after annealing (720 K for 30 min). XPS surface analysis and depth profiling of chemical composition were performed to investigate the distribution of Al oxide. Electron energy loss spectroscopy (EELS) measurements were also carried out in order to identify the plasmon losses and chemical state of Al. The loss peaks in the 5N‐Al thin foils were compared with those of an Al foil of commercial purity (99.95 wt%). The thickness of the oxide layer on the sample surface of all the samples is not constant and oxide is thicker in the samples of high purity than in those of commercial quality. Moreover, the thinnest foils of 5N‐Al (10 μm) exhibit the thinnest oxide layer. These findings have been discussed by considering the size effect, that is, mechanical properties of thin foils are improving as the thickness decreases. The complex morphology of the metal‐oxide interface may contribute to enhance the mechanical performances of Al foils with a thickness below ~50 μm, because the free dislocations pile up against the interface which represents an obstacle for their motion hindering plastic deformation. Obtained results suggest that Al foils to be used in MEMS devices should be of high purity and annealed to get a surface completely covered by the oxide layer.

Microtopography Matters: Belowground CH4 Cycling Regulated by Differing Microbial Processes in Peatland Hummocks and Lawns

AbstractWater table depth and vegetation are key controls of methane (CH4) emissions from peatlands. Microtopography integrates these factors into features called microforms. Microforms often differ in CH4 emissions, but microform‐dependent patterns of belowground CH4 cycling remain less clearly resolved. To investigate the impact of microtopography on belowground CH4 cycling, we characterized depth profiles of the community composition and activity of CH4‐cycling microbes using 16S rRNA amplicon sequencing, incubations, and measurements of porewater CH4 concentration and isotopic composition from hummocks and lawns at Sallie's Fen in NH, USA. Geochemical proxies of methanogenesis and methanotrophy indicated that microforms differ in dominant microbial CH4 cycling processes. Hummocks, where water table depth is lower, had higher porewater redox potential (Eh) and higher porewater δ13C‐CH4 values in the upper 30 cm than lawns, where water table depth is closer to the peat surface. Porewater δ13C‐CH4 and δD‐CH3D values were highest at the surface of hummocks where the ratio of methanotrophs to methanogens was also greatest. These results suggest that belowground CH4 cycling in hummocks is more strongly regulated by methanotrophy, while in lawns methanogenesis is more dominant. We also investigated controls of porewater CH4 chemistry. The ratio of the relative abundance of methanotrophs to methanogens was the strongest predictor of porewater CH4 concentration and δ13C‐CH4, while vegetation composition had minimal influence. As microbial community composition was strongly influenced by redox conditions but not vegetation, we conclude that water table depth is a stronger control of belowground CH4 cycling across microforms than vegetation.

Portable NMR for quantification of breast density in vivo: Proof-of-concept measurements and comparison with quantitative MRI

Mammographic Density (MD) is the degree of radio-opacity of the breast in an X-ray mammogram. It is determined by the Fibroglandular: Adipose tissue ratio. MD has major implications in breast cancer risk and breast cancer chemoprevention. This study aimed to investigate the feasibility of accurate, low-cost quantification of MD in vivo without ionising radiation.We used single-sided portable nuclear magnetic resonance (“Portable NMR”) due to its low cost and the absence of radiation-related safety concerns. Fifteen (N = 15) healthy female volunteers were selected for the study and underwent an imaging routine consisting of 2D X-ray mammography, quantitative breast 3T MRI (Dixon and T1-based 3D compositional breast imaging), and 1D compositional depth profiling of the right breast using Portable NMR. For each participant, all the measurements were made within 3–4 h of each other. MRI-determined tissue water content was used as the MD-equivalent quantity. Portable NMR depth profiles of tissue water were compared with the equivalent depth profiles reconstructed from Dixon and T1-based MR images, which were used as the MD-equivalent reference standard.The agreement between the depth profiles acquired using Portable NMR and the reconstructed reference-standard profiles was variable but overall encouraging. The agreement was somewhat inferior to that seen in breast tissue explant measurements conducted in vitro, where quantitative micro-CT was used as the reference standard. The lower agreement in vivo can be attributed to an uncertainty in the positioning of the Portable NMR sensor on the breast surface and breast compression in Portable NMR measurements.The degree of agreement between Portable NMR and quantitative MRI is encouraging. While the results call for further development of quantitative Portable NMR, they demonstrate the in-principle feasibility of Portable NMR-based quantitative compositional imaging in vivo and show promise for the development of safe and low-cost protocols for quantification of MD suitable for clinical applications.

Phase control of heterogeneous Hf x Zr(1−x)O2 thin films by machine learning

AbstrsctPolymorphic Hf x Zr(1−x)O2 thin films have been widely used as dielectric layers in the semiconductor industry for their high-k, ferroelectric, and antiferroelectric properties in the metastable non-monoclinic phases. To maximize the non-monoclinic components, we optimize the composition depth profile of 20 nm PVD Hf x Zr(1−x)O2 through closed-loop experiments by using parallel Bayesian optimization (BO) with the advanced noisy expected improvement acquisition function. Within 40 data points, the ratio of non-monoclinic phases is improved from ∼30% in pure 20 nm HfO2 and ZrO2 to nearly 100%. The optimal sample has a 5 nm Hf0.06Zr0.94O2 capping layer over 15 nm Hf0.91Zr0.09O2. The composition and thickness effect of the capping layer has been spontaneously explored by BO. We prove that machine-learning-guided fine-tuning of composition depth profile has the potential to improve film performance beyond uniform or laminated pure crystals and lead to the discovery of novel phenomena.

Effect of Ti/Si and Ti/TiN/Si interlayers on the structure, properties, and tribological behavior of an a-C film deposited onto a C17200 copper-beryllium alloy

Reduced hardness and wear resistance may limit SAE C17200 copper‐beryllium alloy use in manufacturing applications, such as plunger tips of die casting machines and as cores and inserts for steel dies in injection molding processes. In order to improve the surface properties of Cu—Be alloys, amorphous carbon (a-C) films have been selected since these coatings may show high hardness, low wear rate and low coefficient of friction. However, the adhesion of carbonaceous films on Cu—Be alloys remains a challenge. Two interlayer compositions (Ti/Si and Ti/TiN/Si) were deposited onto Cu—Be disks and silicon wafers to assess amorphous carbon adhesion on substrates made of Cu—Be alloy. The microstructure and topography of the coatings were examined by Field Emission Scanning Electron Microscopy (FESEM) coupled with X-ray dispersive energy spectroscopy (EDS). The chemical composition depth profile was measured by glow discharge optical emission spectroscopy (GDOES), which confirmed distinct coating layers of Ti, Si, a-C (C1 and C2 conditions-pDCMS). A TiN extra layer presence was obtained for the C3 and C4 conditions-pDCMS reactive, confirmed by small angle XRD analysis. Raman scattering spectroscopy showed a higher quantity of sp3 carbon bonds for C3 and C4 coating conditions compared to C1 and C2. Instrumented indentation tests indicated a higher hardness and reduced elastic modulus for C3 and C4 coating systems, corroborating Raman results, in terms of a higher concentration of sp3 bonds. Scanning electron microscopy (SEM), atomic force microscopy (AFM), and coherence correlation interferometry (CCI) were used to characterize the coatings' surface features and scratch tracks after the tests. In addition, ramp load scratch tests were conducted to assess coating adhesion to the Cu—Be alloy substrate by measuring critical loads and the coefficient of friction. The highest critical loads to failure (Lc2) and (Lc3) were found for the Ti/TiN/Si interlayer sample (C4 condition), indicating that this interlayer improved the coating contribution to a gradual increase in the hardness and promotion of an enhanced adhesion strength of the a-C coating.