RESUMEN

Copper Sulfide (CuS) semiconductors have garnered interest, but the effect of transition metal doping on charge carrier kinetics and bandgap remains unclear. In this study, the interactions between dopant atoms (Nickel, Cobalt, and Manganese) and the CuS lattice using spectroscopy and electrochemical analysis are explored. The findings show that sp-d exchange interactions between band electrons and the dopant ions, which replace Cu2+, are key to altering the material's properties. Specifically, these interactions result in a reduced bandgap by shifting the conduction and valence band edges and increasing carrier concentration. It is observed that undoped CuS nanoflowers exhibit a carrier lifetime of 2.16 ns, whereas Mn-doped CuS shows an extended lifetime of 2.62 ns. This increase is attributed to longer carrier scattering times (84 ± 5 fs for Mn-CuS compared to 53 ± 14 fs for CuS) and slower trapping (∼1.5 ps) with prolonged de-trapping (∼100 ps) rates. These dopant-induced energy levels enhance mobility and carrier lifetime by reducing recombination rates. This study highlights the potential of doped CuS as cathode materials for sodium-ion batteries and emphasizes the applicability of metal sulfides in energy solutions.

RESUMEN

In this work, a simple rectangular milling technique was demonstrated to prepare needle shape atom probe tomography (APT) specimens from Al alloys by focused-ion-beam (FIB) milling using Ga+ ions at room temperature. Ga has high miscibility in Al owing to which electropolishing technique is preferred over Ga+ ion FIB instruments for the fabrication of APT specimens. Although, site specific sample preparation is not possible by the electropolishing technique. This led to the motivation to demonstrate a new rectangular milling technique using Ga+ FIB instrument that resulted a significant reduction of Ga+ ion impregnation into the specimens. This is attributed to the reduction of milling time (<30 s at 30 kV acceleration voltage) and the use of lower currents (<0.3 nA) compared to the conventional annular milling method. The yield of specimens during field evaporation in APT was also significantly increased from around 8 million ions to more than 86 million ions due to the avoidance of Ga+ ion embrittlement. Therefore, the currently demonstrated rectangular milling technique can be used to prepare APT specimens from Al-alloys and obtained accurate compositions of matrix, phases, and hetero-phase interfaces with Ga < 0.1 at%. RESEARCH HIGHLIGHTS: Feasibility of using Ga+ ions for the preparation of needle shaped specimens at room temperature from aluminum alloys. Demonstration of using a rectangular milling technique instead of annular milling technique that led to a significant reduction in impregnation of Ga+ ions into the specimen needles. Due to very low Ga+ ion damage, the yield of the APT data increased by 10-12 times.

RESUMEN

The antagonism between strength and resistance to hydrogen embrittlement in metallic materials is an intrinsic obstacle to the design of lightweight yet reliable structural components operated in hydrogen-containing environments. Economical and scalable microstructural solutions to this challenge must be found. Here, we introduce a counterintuitive strategy to exploit the typically undesired chemical heterogeneity within the material's microstructure that enables local enhancement of crack resistance and local hydrogen trapping. We use this approach in a manganese-containing high-strength steel and produce a high dispersion of manganese-rich zones within the microstructure. These solute-rich buffer regions allow for local micro-tuning of the phase stability, arresting hydrogen-induced microcracks and thus interrupting the percolation of hydrogen-assisted damage. This results in a superior hydrogen embrittlement resistance (better by a factor of two) without sacrificing the material's strength and ductility. The strategy of exploiting chemical heterogeneities, rather than avoiding them, broadens the horizon for microstructure engineering via advanced thermomechanical processing.

Asunto(s)

RESUMEN

Atom probe tomography (APT) provides three-dimensional compositional mapping with sub-nanometre resolution. The sensitivity of APT is in the range of parts per million for all elements, including light elements such as hydrogen, carbon or lithium, enabling unique insights into the composition of performance-enhancing or lifetime-limiting microstructural features and making APT ideally suited to complement electron-based or X-ray-based microscopies and spectroscopies. Here, we provide an introductory overview of APT ranging from its inception as an evolution of field ion microscopy to the most recent developments in specimen preparation, including for nanomaterials. We touch on data reconstruction, analysis and various applications, including in the geosciences and the burgeoning biological sciences. We review the underpinnings of APT performance and discuss both strengths and limitations of APT, including how the community can improve on current shortcomings. Finally, we look forwards to true atomic-scale tomography with the ability to measure the isotopic identity and spatial coordinates of every atom in an ever wider range of materials through new specimen preparation routes, novel laser pulsing and detector technologies, and full interoperability with complementary microscopy techniques.

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An amendment to this paper has been published and can be accessed via a link at the top of the paper.

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Single crystal Ni-based superalloys have long been an essential material for gas turbines in aero engines and power plants due to their outstanding high temperature creep, fatigue and oxidation resistance. A turning point was the addition of only 3 wt.% Re in the second generation of single crystal Ni-based superalloys which almost doubled the creep lifetime. Despite the significance of this improvement, the mechanisms underlying the so-called "Re effect" have remained controversial. Here, we provide direct evidence of Re enrichment to crystalline defects formed during creep deformation, using combined transmission electron microscopy, atom probe tomography and phase field modelling. We reveal that Re enriches to partial dislocations and imposes a drag effect on dislocation movement, thus reducing the creep strain rate and thereby improving creep properties. These insights can guide design of better superalloys, a quest which is key to reducing CO2 emissions in air-traffic.

RESUMEN

Although atom probe tomography (APT) reconstructions do not directly influence the local elemental analysis, any structural inferences from APT volumes demand a reliable reconstruction of the point cloud. Accurate estimation of the reconstruction parameters is crucial to obtain reliable spatial scaling. In the current work, a new automated approach of calibrating atom probe reconstructions is developed using only one correlative projection electron microscopy (EM) image. We employed an algorithm that implements a 2D cross-correlation of microstructural features observed in both the APT reconstructions and the corresponding EM image. We apply this protocol to calibrate reconstructions in a Cu(In,Ga)Se2-based semiconductor and in a Co-based superalloy. This work enables us to couple chemical precision to structural information with relative ease.