| 1. |
- Bericat Vadell, Robert, et al.
(författare)
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Single-electron transfer reactions on surface-modified gold plasmons
- 2023
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Ingår i: Materials Today Chemistry. - : Elsevier. - 2468-5194. ; 34
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Tidskriftsartikel (refereegranskat)abstract
- Photoredox catalysis's relevance in organic synthesis research and innovation will increase in the coming decades. However, the processes rely almost exclusively on expensive noble metal complexes, most notably iridium complexes, to absorb light and transfer a single charge to a substrate or a catalyst to initiate cascade transformations. Light-triggered plasmon resonances generate a non-Fermi-Dirac energy distribution with many hot carriers that decay in similar to 1 ps. Their ultrafast relaxation makes performing single electron transfer (SET) transformations challenging. Herein, a novel photosystem is proposed based on surface-modified gold nanoparticles (aka plasmon "molecularization"), which improved charge separation and, more importantly, enabled SET reactions, expanding the portfolio of photocatalysts available for photoredox catalysis. The photosystem was made into an electrode, permitting its use in photoelectrochemical arrangements that leverage electro- and photo-chemical approaches' benefits and chemical engineering solutions, helping the synthetic chemistry efforts towards greener synthesis and synthesis of more complex structures on a scale.
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| 2. |
- Dey, Ananta, et al.
(författare)
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Exploiting hot electrons from a plasmon nanohybrid system for the photoelectroreduction of CO2
- 2024
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Ingår i: Communications Chemistry. - : Springer Nature. - 2399-3669. ; 7:1
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Tidskriftsartikel (refereegranskat)abstract
- Plasmonic materials convert light into hot carriers and heat to mediate catalytic transformation. The participation of hot carriers (photocatalysis) remains a subject of vigorous debate, often argued on the basis that carriers have ultrashort lifetime incompatible with drive photochemical processes. This study utilises plasmon hot electrons directly in the photoelectrocatalytic reduction of CO2 to CO via a Ppasmonic nanohybrid. Through the deliberate construction of a plasmonic nanohybrid system comprising NiO/Au/ReI(phen-NH2)(CO)3Cl (phen-NH2 = 1,10-Phenanthrolin-5-amine) that is unstable above 580 K; it was possible to demonstrate hot electrons are the main culprit in CO2 reduction. The engagement of hot electrons in the catalytic process is derived from many approaches that cover the processes in real-time, from ultrafast charge generation and separation to catalysis occurring on the minute scale. Unbiased in situ FTIR spectroscopy confirmed the stepwise reduction of the catalytic system. This, coupled with the low thermal stability of the ReI(phen-NH2)(CO)3Cl complex, explicitly establishes plasmonic hot carriers as the primary contributors to the process. Therefore, mediating catalytic reactions by plasmon hot carriers is feasible and holds promise for further exploration. Plasmonic nanohybrid systems can leverage plasmon’s unique photophysics and capabilities because they expedite the carrier’s lifetime.
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| 3. |
- Fritze, Stefan, et al.
(författare)
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Elemental distribution and fracture properties of magnetron sputtered carbon supersaturated tungsten films
- 2024
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Ingår i: Surface & Coatings Technology. - : Elsevier BV. - 0257-8972 .- 1879-3347. ; 477
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Tidskriftsartikel (refereegranskat)abstract
- The combination of strength and toughness is a major driving force for alloy design of protective coatings, and nanocrystalline tungsten (W)-alloys have shown to be promising candidates for combining strength and toughness. Here we investigate the elemental distribution and the fracture toughness of carbon (C) alloyed W thin films prepared by non-reactive magnetron sputtering. W:C films with up to ~4 at.% C crystallize in a body-centered-cubic structure with a strong 〈hh0〉texture, and no additional carbide phases are observed in the diffraction pattern. Atom probe tomography and X-ray photoelectron spectroscopy confirmed the formation of such a supersaturated solid solution. The pure W film has a hardness ~13 GPa and the W:C films exhibit a peak hardness of ~24 GPa. In-situ micromechanical cantilever bending tests show that the fracture toughness decreases from ~4.5 MPa·m1/2 for the W film to ~3.1 MPa·m1/2 for W:C films. The results show that C can significantly enhance the hardness of W thin films while retaining a high fracture toughness.
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| 4. |
- Gopakumar, Geethanjali, 1992-, et al.
(författare)
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X-ray Induced Fragmentation of Protonated Cystine
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- Protein structure determination using high-intensity X-ray sources induces damage in the protein. Disulfide bridges, formed between two cysteine amino acid residues stabilize the protein structure. Owing to the higher absorption cross-section of sulfur for X-ray photons, and a large number of electrons released from sulfur atoms, these disulfide bridges are hot spots for a higher level of noise in structural studies. But it is yet to be understood how exactly the damage occurs through the interaction of the disulfide bridges with photons. Here we study the fragmentation of protonated cystine in the gas phase, which is the dimer of cysteine, by irradiation with X-rays across the sulfur L-edge using an electrospray ionization source (ESI) in combination with an ion trap. This is complemented with the calculation of the sulfur NEXAFS spectrum on the level of Restricted Open-Shell Configuration Interaction (ROCIS) and Density Functional Theory (DFT) calculations for molecular orbital visualization as well as Molecular Dynamics (MD) simulations for the fragmentation of triply charged cystine ions. We have deduced a possible pathway of fragmentation upon excitation and ionization of S 2p electrons by combining the experiments and simulations. The disulfide bridge breaks for resonant excitation at lower energies but remains intact upon higher energy resonant excitation and upon ionization of S 2p. The larger fragments formed subsequently break into smaller fragments.
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| 5. |
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| 6. |
- Kalha, Curran, et al.
(författare)
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Hard x-ray photoelectron spectroscopy : a snapshot of the state-of-the-art in 2020
- 2021
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Ingår i: Journal of Physics. - : Institute of Physics Publishing (IOPP). - 0953-8984 .- 1361-648X. ; 33:23
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Forskningsöversikt (refereegranskat)abstract
- Hard x-ray photoelectron spectroscopy (HAXPES) is establishing itself as an essential technique for the characterisation of materials. The number of specialised photoelectron spectroscopy techniques making use of hard x-rays is steadily increasing and ever more complex experimental designs enable truly transformative insights into the chemical, electronic, magnetic, and structural nature of materials. This paper begins with a short historic perspective of HAXPES and spans from developments in the early days of photoelectron spectroscopy to provide an understanding of the origin and initial development of the technique to state-of-the-art instrumentation and experimental capabilities. The main motivation for and focus of this paper is to provide a picture of the technique in 2020, including a detailed overview of available experimental systems worldwide and insights into a range of specific measurement modi and approaches. We also aim to provide a glimpse into the future of the technique including possible developments and opportunities.
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| 7. |
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| 8. |
- Villamayor, Michelle Marie S., et al.
(författare)
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Wafer-sized WS2 monolayer deposition by sputtering
- 2022
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Ingår i: Nanoscale. - : Royal Society of Chemistry (RSC). - 2040-3364 .- 2040-3372. ; 14:17, s. 6331-6338
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Tidskriftsartikel (refereegranskat)abstract
- We demonstrate that tungsten disulphide (WS2) with thicknesses ranging from monolayer (ML) to several monolayers can be grown on SiO2/Si, Si, and Al2O3 by pulsed direct current-sputtering. The presence of high quality monolayer and multilayered WS2 on the substrates is confirmed by Raman spectroscopy since the peak separations between the A(1g)-E-2g and A(1g)-2LA vibration modes exhibit a gradual increase depending on the number of layers. X-ray diffraction confirms a textured (001) growth of WS2 films. The surface roughness measured with atomic force microscopy is between 1.5 and 3 angstrom for the ML films. The chemical composition WSx (x = 2.03 +/- 0.05) was determined from X-ray Photoelectron Spectroscopy. Transmission electron microscopy was performed on a multilayer film to show the 2D layered structure. A unique method for growing 2D layers directly by sputtering opens up the way for designing 2D materials and batch production of high-uniformity and high-quality (stochiometric, large grain sizes, flatness) WS2 films, which will advance their practical applications in various fields.
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| 9. |
- von Fieant, Kristina, et al.
(författare)
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In Situ Formation of Ge Nanoparticles by Annealing of Al-Ge‑N ThinFilms Followed by HAXPES and XRD
- 2019
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 58:16, s. 11100-11109
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Tidskriftsartikel (refereegranskat)abstract
- Ge nanoparticles embedded in thin films have attracted a lot of attention due to their promising optical and electronic properties that can be tuned by varying the particle size and choice of matrix material. In this study, Ge nanoparticle formation was investigated for Al-Ge-N based thin films by simultaneous measurements of HAXPES and grazing incidence XRD during in situ annealing in vacuum conditions. As-deposited Al-Ge-N thin films, synthesized by reactive dc magnetron sputtering, consisted of a nanocrystalline (Al1–xGex)Ny solid solution and an amorphous tissue phase of Ge3Ny. Upon annealing to 750 °C, elemental Ge was formed shown by both HAXPES and XRD measurements, and N2 gas was released as measured by a mass spectrometer. Postannealed ex situ analysis by SEM and TEM showed that the elemental Ge phase formed spherical nanoparticles on the surface of the film, with an average size of 210 nm. As the annealing temperature increased further to 850 °C, the Ge particles on the film surface evaporated, while the phase segregation of Ge still could be observed within the film. Thus, these results show the possibility for a controlled synthesis of Ge nanoparticles through annealing of Al-Ge-N thin films to produce materials suitable for use in electronic or optoelectronic devices.
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| 10. |
- Bylin, Johan, et al.
(författare)
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The influence of hydrogen on the electronic structure in transition metallic glasses
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- We investigate the influence of hydrogen on the electronic structure of a binary transition metallic glass of V80Zr20. We examine the hybridization between the hydrogen and metal atoms with the aid of hard x-ray photoelectron spectroscopy. Combined with ab initio density functional theory, we are able to show and predict the formation of s-d hybridized energy states. With optical transmission and resistivity measurements, we investigate the emergent electronic properties formed out of those altered energy states, and together with the theoretical calculations of the frequency-dependent conductivity tensor, we qualitatively support the observed strong wavelength-dependency of the hydrogen-induced changes on the optical absorption and a positive parabolic change in resistivity with hydrogen concentration.
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| 11. |
- Casillas Trujillo, Luis, et al.
(författare)
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Experimental and theoretical evidence of charge transfer in multi-component alloys : how chemical interactions reduce atomic size mismatch
- 2021
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Ingår i: Materials Chemistry Frontiers. - : Royal Society of Chemistry. - 2052-1537. ; 5:15, s. 5746-5759
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Tidskriftsartikel (refereegranskat)abstract
- Ab initio simulations of a multi-component alloy using density functional theory (DFT) were combined with experiments on thin films of the same material using X-ray photoelectron spectroscopy (XPS) to study the connection between the electronic and atomic structures of multi-component alloys. The DFT simulations were performed on an equimolar HfNbTiVZr multi-component alloy. Structure and charge transfer were evaluated using relaxed, non-relaxed, as well as elemental reference structures. The use of a fixed sphere size model allowed quantification of charge transfer, and separation into different contributions. The charge transfer was generally found to follow electronegativity trends and results in a reduced size mismatch between the elements, and thus causes a considerable reduction of the lattice distortions compared to a traditional assumption based on tabulated atomic radii. A calculation of the average deviation from the average radius (i.e. the so-called δ-parameter) based on the atomic Voronoi volumes gave a reduction of δ from ca. 6% (using the volumes in elemental reference phases) to ca. 2% (using the volumes in the relaxed multi-component alloy phase). The reliability of the theoretical results was confirmed by XPS measurements of a Hf22Nb19Ti18V19Zr21 thin film deposited by sputter deposition. The experimentally observed core level binding energy shifts (CLS), as well as peak broadening due to a range of chemical surroundings, for each element showed good agreement with the calculated DFT values. The single solid solution phase of the sample was confirmed by X-ray diffraction (XRD) and transmission electron microscopy (TEM) including energy dispersive spectroscopy (EDS) with nm-resolution. These observations show that the HfNbTiVZr solid solution phase is non-ideal, and that chemical bonding plays an important part in the structure formation, and presumably also in the properties. Our conclusions should be transferable to other multi-component alloy systems, as well as some other multi-component material systems, and open up interesting possibilities for the design of material properties via the electronic structure and controlled charge transfer between selected metallic elements in the materials.
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| 12. |
- Couto, Rafael Carvalho, et al.
(författare)
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Breaking inversion symmetry by protonation : Experimental and theoretical NEXAFS study of the diazynium ion, N2H
- 2021
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 23:32, s. 17166-17176
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Tidskriftsartikel (refereegranskat)abstract
- As an example of symmetry breaking in NEXAFS spectra of protonated species we present a high resolution NEXAFS spectrum of protonated dinitrogen, the diazynium ion N2H+. By ab initio calculations we show that the spectrum consists of a superposition of two nitrogen 1s absorption spectra, each including a π∗ band, and a nitrogen 1s to H+ charge transfer band followed by a weak irregular progression of high energy excitations. Calculations also show that, as an effect of symmetry breaking by protonation, the π∗ transitions are separated by 0.23 eV, only slightly exceeding the difference in the corresponding dark (symmetry forbidden) and bright (symmetry allowed) core excitations of neutral N2. By DFT and calculations and vibrational analysis, the complex π∗ excitation band of N2H+ is understood as due to the superposition of the significantly different vibrational progressions of excitations from terminal and central nitrogen atoms, both leading to bent final state geometries. We also show computationally that the electronic structure of the charge transfer excitation smoothly depends on the nitrogen-proton distance and that there is a clear extension of the spectra going from infinity to close nitrogen-proton distance where fine structures show some, although not fully detailed, similarities. An interesting feature of partial localization of the nitrogen core orbitals, with a strong, non-monotonous, variation with nitrogen-proton distance could be highlighted. Specific effects could be unraveled when comparing molecular cation NEXAFS spectra, as represented by recently recorded spectra of N2+ and CO+, and spectra of protonated molecules as represented here by the N2H+ ion. Both types containing rich physical effects not represented in NEXAFS of neutral molecules because of the positive charge, whereas protonation also breaks the symmetry. The effect of the protonation on dinitrogen can be separated in charge, which extends the high-energy part of the spectrum, and symmetry-breaking, which is most clearly seen in the low-energy π∗ transition.
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| 13. |
- Couto, Rafael Carvalho, et al.
(författare)
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The carbon and oxygen K-edge NEXAFS spectra of CO
- 2020
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 22:28, s. 16215-16223
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Tidskriftsartikel (refereegranskat)abstract
- We present and analyze high resolution near edge X-ray absorption fine structure (NEXAFS) spectra of CO+ at the carbon and oxygen K-edges. The spectra show a wealth of features that appear very differently at the two K-edges. The analysis of these features can be divided into three parts; (i) repopulation transition to the open shell orbital – here the C(1s) or O(1s) to 5σ transition, where the normal core hole state is reached from a different initial state and different interaction than in X-ray photoelectron spectroscopy; (ii) spin coupled split valence bands corresponding to C(1s) or O(1s) to π* transitions; (iii) remainder weak and long progressions towards the double ionization potentials containing a manifold of peaks. These parts, none of which has correspondence in NEXAFS spectra of neutral molecules, are dictated by the localization of the singly occupied 5σ orbital, adding a dimension of chemistry to the ionic NEXAFS technique.
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| 14. |
- Delcey, Mickael G, 1988-, et al.
(författare)
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Soft X-ray signatures of cationic manganese–oxo systems, including a high-spin manganese(v) complex
- 2022
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 24:6, s. 3598-3610
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Tidskriftsartikel (refereegranskat)abstract
- Limitations in synthesis of high-valent metal–oxo complexes are circumvented by trapping a series of ionic Mn–oxo complexes. One of them is a rare high-spin Mn(v)–oxo, which can serve as a template to identify similar intermediates in catalysis.
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| 15. |
- Fernandes, Arthur B., et al.
(författare)
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Recoverable and Reusable Polymer Microbead-Supported Metal Nanocatalysts for Redox Chemical Transformations
- 2020
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Ingår i: ACS APPLIED NANO MATERIALS. - : AMER CHEMICAL SOC. - 2574-0970. ; 3:2, s. 1722-1730
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Tidskriftsartikel (refereegranskat)abstract
- Metal nanoparticles have been widely exploited in catalysis, but their full impact on the environment and human health is still under debate. Here we describe the one-step fabrication of recoverable and reusable polymer microbead-supported metal and metal oxide nanocatalysts for application in batch reactions and flow systems. Au, Ag, and Fe3O4 nanoparticles were prepared directly at the surface of commercial benzylamine-coated spherical polymer beads in water by using low-energy microwave radiation for 5 min. The functionalization of microbead surface with betalamic acid, an antioxidant from plant origin, before irradiation changes the morphology and catalytic properties of the grafted nanoparticles. No leaching of the active phase was observed during the application of these effective and ready-to-use nanocatalysts on the reduction of 4-nitrophenol and oxidation of dihydrorhodamine 123. The supported nanocatalysts were recovered by filtration and/or magnetic separation and reused up to three times without significant drop in catalytic performance. These results can stimulate the controlled and facile synthesis of recoverable microbead-supported magnetic and nonmagnetic nanocatalysts that can be applied under myriad reaction conditions and reused multiple times.
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| 16. |
- Heintz, Mads C., et al.
(författare)
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Photovoltaic Wafering Silicon Kerf Loss as Raw Material : Example of Negative Electrode for Lithium‐Ion Battery
- 2023
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Ingår i: ChemElectroChem. - : Wiley-VCH Verlagsgesellschaft. - 2196-0216. ; 10:19
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Tidskriftsartikel (refereegranskat)abstract
- Silicon powder kerf loss from diamond wire sawing in the photovoltaic wafering industry is a highly appealing source material for use in lithium-ion battery negative electrodes. Here, it is demonstrated for the first time that the kerf particles from three independent sources contain ~50 % amorphous silicon. The crystalline phase is in the shape of nano-scale crystalline inclusions in an amorphous matrix. From literature on wafering technology looking at wafer quality, the origin and mechanisms responsible for the amorphous content in the kerf loss powder are explained. In order to better understand for which applications the material could be a valuable raw material, the amorphicity and other relevant features are thoroughly investigated by a large amount of experimental methods. Furthermore, the kerf powder was crystallized and compared to the partly amorphous sample by operando X-ray powder diffraction experiments during battery cycling, demonstrating that the powders are relevant for further investigation and development for battery applications.
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| 17. |
- Lindblad, Rebecka, 1984-
(författare)
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Electronic Structures and Energy Level Alignment in Mesoscopic Solar Cells : A Hard and Soft X-ray Photoelectron Spectroscopy Study
- 2014
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Photoelectron spectroscopy is an experimental method to study the electronic structure in matter. In this thesis, a combination of soft and hard X-ray based photoelectron spectroscopy has been used to obtain atomic level understanding of electronic structures and energy level alignments in mesoscopic solar cells. The thesis describes how the method can be varied between being surface and bulk sensitive and how to follow the structure linked to particular elements. The results were discussed with respect to the material function in mesoscopic solar cell configurations.The heart of a solar cell is the charge separation of photoexcited electrons and holes, and in a mesoscopic solar cell, this occurs at interfaces between different materials. Understanding the energy level alignment between the materials is important for developing the function of the device. In this work, it is shown that photoelectron spectroscopy can be used to experimentally follow the energy level alignment at interfaces such as TiO2/metal sulfide/polymer, as well as TiO2/perovskite.The electronic structures of two perovskite materials, CH3NH3PbI3 and CH3NH3PbBr3 were characterized by photoelectron spectroscopy and the results were discussed with support from quantum chemical calculations. The outermost levels consisted mainly of lead and halide orbitals and due to a relatively higher cross section for heavier elements, hard X-ray excitation was shown useful to study the position as well as the orbital character of the valence band edge.Modifications of the energy level positions can be followed by core level shifts. Such studies showed that a commonly used additive in mesoscopic solar cells, Li-TFSI, affected molecular hole conductors in the same way as a p-dopant. A more controlled doping can also be achieved by redox active dopants such as Co(+III) complexes and can be studied quantitatively with photoelectron spectroscopy methods.Hard X-rays allow studies of hidden interfaces, which were used to follow the oxidation of Ti in stacks of thin films for conducting glass. By the use of soft X-rays, the interface structure and bonding of dye molecules to mesoporous TiO2 or ZnO could be studied in detail. A combination of the two methods can be used to obtain a depth profiling of the sample.
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| 18. |
- Lindblad, Rebecka, Dr, 1984-, et al.
(författare)
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Experimental and theoretical near-edge x-ray-absorption fine-structure studies of NO
- 2022
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Ingår i: Physical Review A: covering atomic, molecular, and optical physics and quantum information. - : American Physical Society. - 2469-9926 .- 2469-9934. ; 106:4
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Tidskriftsartikel (refereegranskat)abstract
- Experimental near-edge x-ray-absorption fine-structure (NEXAFS) spectra of the nitrosonium NO+ ion are presented and theoretically analyzed. While neutral NO has an open shell, the cation is a closed-shell species, which for NEXAFS leads to the simplicity of a closed-shell spectrum. Compared to neutral NO, the electrons in the cation experience a stronger Coulomb potential, which introduces a shift of the ionization potential towards higher energies, a depletion of intensity in a large interval above the pi* resonance, and a shift of the sigma* resonance from the continuum to below the ionization threshold. NEXAFS features at the nitrogen and oxygen K edges of NO+ are compared, as well as NEXAFS features at the nitrogen edges of the isoelectronic closed-shell species NO+, N2, and N2H+.
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| 19. |
- Osinger, Barbara, et al.
(författare)
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Charge transfer effects in (HfNbTiVZr)C – shown by ab-initio calculations and X-ray photoelectron spectroscopy
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Tidskriftsartikel (övrigt vetenskapligt/konstnärligt)abstract
- Considering charge transfer effects and the variability of the bonding between elements with different electronegativity opens up a deeper understanding of the electronic structure and as a result many of the properties in high entropy related materials. This study investigates the importance of the diverse bonding and chemical environments when discussing multicomponent carbide materials. A combination of ab initio calculations and X-ray photoelectron spectroscopy (XPS) was used to investigate the electronic structure of multicomponent thin films based on the (HfNbTiVZr)C system. The charge transfer was quantified theoretically using relaxed and non-relaxed multicomponent as well as binary carbide reference structures, employing a fixed sphere model. High-resolution XPS spectra from (HfNbTiVZr)C magnetron sputtered thin films displayed core level binding energy shifts and broadening effects as a result of the complex chemical environment. Charge transfer effects and a changed electronic structure in the multicomponent material, compared with the reference binary carbides, are observed both experimentally and in the DFT simulations. The observed effects loosely follow electronegativity considerations, leading to a deviation from an ideal solid solution structure assuming non-distinguishable chemically equivalent environments.
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| 20. |
- Paschalidou, Eirini-Maria, et al.
(författare)
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Corrosion studies on multicomponent CoCrFeMnNi(C) thin films in acidic environments
- 2022
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Ingår i: Electrochimica Acta. - : Elsevier. - 0013-4686 .- 1873-3859. ; 404
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Tidskriftsartikel (refereegranskat)abstract
- The corrosion resistances of near equimolar CoCrFeMnNi magnetron-sputtered thin films with different carbon concentrations were examined in 0.05 M HCl and 0.05 M H2SO4. Polarization curves were recorded with different scan rates with and without reducing the native oxide. The results showed that the carbon concentration and the experimental conditions affected the electrochemical behaviour mainly in the Cr transpassive region. At potentials above 850 mV, the carbon-containing films were more corrosion resistant in 0.05 M HCl than in 0.05 M H2SO4 due to a lower carbon oxidation rate in 0.05 M HCl, facilitating the formation of a Mn-rich oxide layer. (C)& nbsp;2021 The Author(s). Published by Elsevier Ltd.& nbsp;
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| 21. |
- Srinath, Aishwarya, et al.
(författare)
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Influence of the nitrogen content on the corrosion resistances of multicomponent AlCrNbYZrN coatings
- 2021
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Ingår i: Corrosion Science. - : Elsevier BV. - 0010-938X .- 1879-0496. ; 188
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Tidskriftsartikel (refereegranskat)abstract
- In this study, the relationship between the nitrogen content and the corrosion resistances of non-equimolar multicomponent AlCrNbYZrN films (N = 13-49 at.%) is probed. While there was no linear relationship between nitrogen content and corrosion resistance, the results clearly show that the corrosion resistances of the films were instead determined by their nitrogen-induced porosities i.e. the less porous the sample, the higher the corrosion resistance. The 23, 30 and 37 at.% N samples were denser while the 13 at.% N sample was porous and the 49 at.% N film had an underdense nanocrystalline columnar cross section permitting the ingress of electrolyte.
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| 22. |
- Srinath, Aishwarya
(författare)
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Investigations of the corrosion resistances of magnetron sputtered multicomponent materials : A study on high entropy alloys, high entropy sublattice ceramics, and metallic glasses
- 2022
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The corrosion resistances of sputter deposited AlCrNbYZrN, CrNbTiTaWC and TaNiSiC alloys were assessed in acidic and alkaline environments. Compositionally complex alloying strategies, and whether they produced coatings with superior corrosion resistances, were explored. Another priority was to determine if the formation of a random solid solution was necessary for the design of corrosion resistant multicomponent alloys. The results showed that successful surface passivation/oxidation was the key factor determining corrosion resistance. The corrosion resistance was maximised when coating porosity was minimised, spontaneously passivating elements were used, and the oxide solubility in the electrolyte was low. The benefits of multicomponent alloying were demonstrated through the protective effect of oxides of more stable elements (Cr, Nb, Ta) reducing the loss of less corrosion resistant elements (Al, Ti). The supersaturation of nitrogen, carbon and/or silicon affected coating morphologies, surface repassivation rates, and even directly corrosion resistances, e.g. when silicon oxides were formed on TaNiSiC films.The N content (0-50 at.% N) in AlCrNbYZrN films affected the film porosity, the absence of which led to high corrosion resistances in 1.0 M HCl. The formation of a single phase did not govern the corrosion resistances. It was more important that the coatings were dense, as this permitted the formation of an impervious passive layer. The addition of 8 at.% C to nearequimolar CrNbTiTaW alloys affected surface repassivation rates of films whose oxide had been partially removed by chronoamperometry in a 1.0 M HCl electrolyte. However, the effect of carbon on the corrosion properties was minor. A comparison of the nearequimolar CrNbTiTaW, Nb and TaW alloys with their native oxides revealed comparable corrosion resistances in 0.01 M HCl + 0.1 M NaCl. The nearequimolar CrNbTiTaW, Nb, and TaW alloys also showed no evidence of pitting in 1.0 M HCl. The high corrosion resistances in CrNbTiTaW alloys was due to the presence of extremely stable surface oxides abundant in Cr, Nb, and Ta. TaNiSiC films with Si contents above 12 at.%, and C contents lower than 11 at.% showed high corrosion resistances in 10 mM sodium borate due to the formation of silicon oxides, even after three polarisations from −0.7 to +1.5 V vs. Ag/AgCl (3 M NaCl) and 50+ hours of immersion. Microscopy of the Si-rich TaNiSiC film showed negligible differences in surface condition before and after corrosion in sodium borate, while films with lower Si contents or higher Ta contents were more severely corroded.
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| 23. |
- Srinath, Aishwarya, et al.
(författare)
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Near-surface analysis of magnetron sputtered AlCrNbYZrNx high entropy materials resolved by HAXPES
- 2024
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Ingår i: Applied Surface Science. - : Elsevier. - 0169-4332 .- 1873-5584. ; 666
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Tidskriftsartikel (refereegranskat)abstract
- Hard X-ray photoelectron spectroscopy (HAXPES) was used to perform a non-destructive depth profile of AlCrNbYZrNx (x = 0 to ∼50 at.%) thin films. The outermost native oxide of the pristine thin films contained the highest coordination oxides of every metal. Substoichiometric oxides or oxynitrides were found underneath. After exposure to 1.0 M HCl, increases in the most highly coordinated oxides of Cr, Nb, and Al in films with up to 37 at.% N were observed, suggesting that the low coordination oxides and oxynitrides in the subsurface had been further oxidised and were intermediary compounds in the passivation process. Al and Y oxides were lost to the HCl electrolyte, in agreement with their respective Pourbaix diagrams. The film with 49 at.% N showed little to no change in the data due to its high porosity which led to the oxide being detected at all probed depths. The metal core level spectra revealed a preferential order in which nitrogen bonded with the different metals. Nitrogen interacted first with Y, then Zr, then Al and Nb, and lastly Cr as the nitrogen content was increased.
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| 24. |
- Svensson, Pamela, et al.
(författare)
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Heavy element incorporation in nitroimidazole radiosensitizers : molecular-level insights into fragmentation dynamics
- 2024
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 26:2, s. 770-779
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Tidskriftsartikel (refereegranskat)abstract
- The present study investigates the photofragmentation behavior of iodine-enhanced nitroimidazole-based radiosensitizer model compounds in their protonated form using near-edge X-ray absorption mass spectrometry and quantum mechanical calculations. These molecules possess dual functionality: improved photoabsorption capabilities and the ability to generate species that are relevant to cancer sensitization upon photofragmentation. Four samples were investigated by scanning the generated fragments in the energy regions around C 1s, N 1s, O 1s, and I 3d-edges with a particular focus on NO2+ production. The experimental summed ion yield spectra are explained using the theoretical near-edge X-ray absorption fine structure spectrum based on density functional theory. Born-Oppenheimer-based molecular dynamics simulations were performed to investigate the fragmentation processes.
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| 25. |
- Yang, Lei, et al.
(författare)
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Experimental and Theoretical Investigation of the Function of 4- tert -Butyl Pyridine for Interface Energy Level Adjustment in Efficient Solid-State Dye-Sensitized Solar Cells
- 2018
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society. - 1944-8244 .- 1944-8252. ; 10:14, s. 11572-11579
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Tidskriftsartikel (refereegranskat)abstract
- 4-tert-Butylpyridine (t-BP) is commonly used in solid state dye-sensitized solar cells (ssDSSCs) to increase the photovoltaic performance. In this report, the mechanism how t-BP functions as a favorable additive is investigated comprehensively. ssDSSCs were prepared with different concentrations of t-BP, and a clear increase in efficiency was observed up to a maximum concentration and for higher concentrations the efficiency thereafter decreases. The energy level alignment in the complete devices was measured using hard X-ray photoelectron spectroscopy (HAXPES). The results show that the energy levels of titanium dioxide are shifted further away from the energy levels of spiro-OMeTAD as the t-BP concentration is increased. This explains the higher photovoltage obtained in the devices with higher t-BP concentration. In addition, the electron lifetime was measured for the devices and the electron lifetime was increased when adding t-BP, which can be explained by the recombination blocking effect at the surface of TiO2. The results from the HAXPES measurements agree with those obtained from density functional theory calculations and give an understanding of the mechanism for the improvement, which is an important step for the future development of solar cells including t-BP.
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| 26. |
- Zendejas Medina, León, 1993-, et al.
(författare)
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Elemental distribution in carbon-supersaturated high entropy alloycoatings: A synchrotron-based study
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- The properties of high entropy alloys (HEAs) are strongly affected by the addition of carbon past the solubility limit. Despite this is the local chemistry in these meta-stable materials not well-characterized. To better understand how carbon affects the elemental distribution of alloys whose constituent elements have widely varying carbon affinities, this paper studies amorphous sputter-deposited coatings of CoCrFeMnNi with concentrations of up to 11\% carbon. Hard x-ray photoelectron spectroscopy (HAXPES), near-edge x-ray absorption fine structure (NEXAFS), and transmission electron microscopy (TEM) were used to determine how each metallic element is affected by the presence of carbon. As-deposited samples are also compared to annealed samples to study the thermal stability and the Calphad method was used to predict the thermodynamic equilibrium state. All five component metals had weak interaction with carbon, including Ni which had a less metallic character in the carbon-containing samples. While elemental segregation is expected at all temperatures at thermodynamic equilibrium, carbon did not promote segregation in the as-deposited samples. During annealing, however, the elements rearranged and formed a mixture of alloy phases and crystalline Cr-rich carbides. Rearrangement of the elements also occurred in the surface oxide, where Mn became dominant. The combination of techniques to characterize HEAs revealed promising trends for future research into these important materials.
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| 27. |
- Öhman, Sebastian, 1991-, et al.
(författare)
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Role of Oxygen in Vacancy-Induced Phase Formation and Crystallization of Al2TiO5-Based Chemical Vapor-Deposited Coatings
- 2023
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 127:13, s. 6456-6465
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Tidskriftsartikel (refereegranskat)abstract
- Oxygen is a commonly overlooked element influencing the properties of many metal oxides. By combining several analytical in situ techniques and theoretical calculations, we demonstrate that oxygen plays a vital part in the phase formation and crystallization of Al2TiO5-based chemical vapor-deposited coatings. Rutherford backscattering spectrometry (RBS) corroborates a polymorphic transformation during crystallization. Subsequent hard X-ray photoelectron spectroscopy (HAXPES) shows that crystallization occurs through a displacive (diffusionless) mechanism. Coupled with theoretical calculations, the crystallization and co-formation of Al2TiO5, Al6Ti2O13, and Al16Ti5O34 are suggested to be driven by the migration of oxygen ions and their corresponding vacancies.
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