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A search for high-speed and low-energy memory devices puts antiferromagnetic thin films at the forefront of spintronic research. Here, we develop a material model of a granular antiferromagnetic thin film with uniaxial anisotropy and provide fundamental insight into the interaction of antiferromagnetic domain walls with grain boundaries. This model is validated on thin films of the antiferromagnetic insulator \ch{Cr2O3}, revealing complex maze-like domain patterns hosting localized nanoscale domains down to 50 nm. We show that the inter-grain magnetic parameters can be estimated based on an analysis of high-resolution images of antiferromagnetic domain patterns examining the domain patterns' self-similarity and the statistical distribution of domain sizes. Having a predictive material model and understanding of the pinning of domain walls on grain boundaries, we put forth design rules to realize granular antiferromagnetic recording media.

Electrochemiluminescence (ECL) represents a widely explored technique to generate light, in which the emission intensity relies critically on the charge-transfer reactions between electrogenerated radicals. Two types of charge-transfer mechanisms have been postulated for ECL generation, but the manipulation and effective probing of these routes remain a fundamental challenge. Here, we demonstrate the design of quantum dot (QD) aerogels as novel ECL luminophores via a versatile water-induced gelation strategy. The strong electronic coupling between adjacent QDs enables efficient charge transport within the aerogel network, leading to the generation of highly efficient ECL based on the selectively improved interparticle chargetransfer route. This mechanism is further verified by designing CdSe-CdTe mixed QD aerogels, where the two mechanistic routes are clearly decoupled for ECL generation. We anticipate our work will advance the fundamental understanding of ECL and prove useful for designing next-generation QD-based devices.

The use of metal nanoparticles (NPs) as antimicrobial agents has become a promising alternative to the problem of antibiotic-resistant bacteria and other applications. Silver nanoparticles (AgNPs) are well-known as one of the most universal biocide compounds. However, selenium nanoparticles (SeNPs) recently gained more attention as effective antimicrobial agents. This study aims to investigate the antibacterial activity of SeNPs with different surface coatings (BSA-coated, chitosan-coated, and undefined coating) on the Gram-negative Stenotrophomonas bentonitica and the Gram-positive Lysinibacillus sphaericus in comparison to AgNPs. The tested NPs had similar properties, including shape (spheres), structure (amorphous), and size (50−90 nm), but differed in their surface charge. Chitosan SeNPs exhibited a positive surface charge, while the remaining NPs assayed had a negative surface charge. We have found that cell growth and viability of both bacteria were negatively affected in the presence of the NPs, as indicated by microcalorimetry and flow cytometry. Specifically, undefined coating SeNPs displayed the highest percentage values of dead cells for both bacteria (85−91%). An increase in reactive oxygen species (ROS) production was also detected. Chitosan-coated and undefined SeNPs caused the highest amount of ROS (299.7 and 289% over untreated controls) for S. bentonitica and L. sphaericus, respectively. Based on DNA degradation levels, undefined-SeNPs were found to be the most hazardous, causing nearly 80% DNA degradation. Finally, electron microscopy revealed the ability of the cells to transform the different SeNP types (amorphous) to crystalline SeNPs (trigonal/monoclinical Se), which could have environmentally positive implications for bioremediation purposes and provide a novel green method for the formation of crystalline SeNPs. The results obtained herein demonstrate the promising potential of SeNPs for their use in medicine as antimicrobial agents, and we propose S. bentonitica and L. sphaericus as candidates for new bioremediation strategies and NP synthesis with potential applications in many fields.

The microbial reduction of U(VI) to U(IV) can decrease the mobility of U contaminants in the environment and may have a significant impact on the safety of a nuclear waste repository, as well as, the potential to serve as a component in bioremediation strategies for U-contaminated environments. In this study, we show significant differences in the reduction mechanisms for iron- and sulfate-reducing bacteria, highlighting the importance of investigating microbe-uranium interaction of different bacterial genera. Moreover, we introduce the use of artificial bio-constructs to study U reduction by microbial communities to gain insights into the complex interactions in a multi-species environment. To gain molecular process understanding regarding microbial U reduction Desulfosporosinus and Desulfitobacterium spp. were chosen as important representatives of sulfate- and iron-reducing bacteria in anaerobic environments. Furthermore, their U reduction capabilities were investigated using artificial bio-constructs with different other microbial species. Time-dependent experiments of pure cultures in bicarbonate buffer (30 mM, 100 µM U(VI), 10 mM lactate) showed a decrease of U concentrations in the supernatant of Desulfitobacterium sp. G1-2, whereas no changes occurred for Desulfosporosinus hippei DSM 8344T. In contrast, in artificial Opalinus Clay pore water (100 µM U(VI), pH 5.5, 10 mM lactate) up to 80% of the radionuclide got removed by both microorganisms. UV/Vis studies verified the reduction of U(VI) to U(IV) in the cell pellets. STEM-EDXX revealed the presence of two different U-containing aggregates inside the cells of Desulfitobacterium sp. G1-2, while cells of Desulfosporosinus hippei DSM 8344T showed almost no U uptake but U-aggregates on the cell surface. First experiments with artificial bio-constructs that were formed from different bacterial genera using polyelectrolyte-controlled aggregation showed a promising U reduction capacity. Such artificial biostructures, in the form of aggregates or artificial biofilms, have a potential in investigating the complex interactions in multi-species environments and to utilize beneficial microbes in remediation strategies, even if they do not form biofilms themselves.

Developing efficient and stable Pt-based oxygen reduction reaction (ORR) electrocatalysts via both economical and controllable routes is critical for the practical application of electrochemical energy devices. Herein, a scalable, controllable, and general ambient-O2-involved aqueous-solution cultivating strategy to prepare PtxMy (M = Ni, Fe, Co) bunched-nanocages aerogels (BNCs AG) is demonstrated, based on a newly established high-M-to-Pt-precursor-ratio-and-B-incorporation-facilitated M-rich core and Pt-rich shell hydrogel formation process. The Pt83Ni17 BNCs AG shows prominent ORR performance with a mass activity (MA) of 1.95 A mgPt−1 and specific activity of 3.55 mA cm−2, which are 8.9-times and 9.6-times that of Pt supported on carbon (Pt/C), respectively. Particularly, the Pt83Ni17 BNCs AG displays greatly enhanced durability (MA 82.6% retention) compared to Pt/C (MA 31.8% retention) after a 20 000-cycles accelerated durability test. Systematic studies including density functional theory calculations uncover that the excellent activity is closely related to the optimized ligand and strain effects with the optimized Ni content in this aerogel; the outstanding durability is endowed by the lowered-down Ni leaching with the optimized Pt/Ni ratio and the inhibited sintering due to its appropriate porosity. This work provides new perspectives on the development of electrocatalysts with both high performance and low cost.

Chemoenzymatic cascades are an important tool for advanced synthesis in chemistry. However, these cascades are often limited due to the incompatibility issue between two distinct catalysts and reactions. To address this issue, we present a simple multistep one-pot platform, in which nanoparticle catalysts are prepared to allow chemo- and biocatalytic reactions performed sequentially in water and Pickering emulsions. The preparation of particle catalysts is accomplished in just two steps by polymer modifications and [RuCl2(pcymene)]2 coordination, while the benefits of using them for chemoenzymatic synthesis are multifaceted. They act not only as asymmetric catalysts for asymmetric transfer hydrogenation from acetophenone to 1-phenylethanol in water with up to 99 % conversion and 93 % ee, but also as an emulsifier to form stable Pickering emulsions. By the addition of Candida antarctica lipase B into the emulsions, the second-step reaction of enantioselective acylation was achieved with 38 % conversion and 99 % ee. Therefore, we successfully present a simple method to enable chemoenzymatic cascades by combining particle catalysts and enzymes in water and Pickering emulsions in a sequential fashion, which can be generalized for other cascade syntheses with different chemo- and biocatalysts in the future.

Electrochemical upgrading of ethanol to acetic acid provides a promising strategy to couple with the current hydrogen production from water electrolysis. This work reports the design of a series of bimetallic Pt-Hg aerogels, where the PtHg aerogel exhibits a 10.5-times higher mass activity than that of commercial Pt/C toward ethanol oxidation. More impressively, the PtHg aerogel demonstrates nearly 100% selectivity toward the production of acetic acid. The operando infrared spectroscopic studies and nuclear magnetic resonance analysis verify the preferable C2 pathway mechanism during the reaction. This work opens an avenue for the electrochemical synthesis of acetic acid via ethanol electrolysis.

In this work, we report on the preparation of Te-hyperdoped Si. The hyperdoped Si layers are homogeneous, do not show cellular breakdown, and have a flat surface. Based on the obtained materials, we demonstrate a room-temperature mid-wavelength infrared Si p-n photodiode working in photovoltaic mode. The fabricated photodiode exhibits enhanced performance, e.g. regarding spectral photoresponse, specific detectivity, bandwidth and response speed. Moreover, inherited from the high free carrier concentration, mid-infrared-localized surface plasmon resonances (LSPR) are also observed in hyperdoped Si. We show that the mid-infrared LSPR can be further enhanced and spectrally extended to the far-infrared range by fabricating two-dimensional arrays of micrometer-sized antennas on a Te-hyperdoped Si chip. Since Te-hyperdoped Si can also work as an infrared photodetector, we believe that our results will unlock the route toward the direct integration of plasmonic sensors within a one-chip CMOS platform, greatly advancing the possibility of mass manufacturing of Si-based infrared photonic systems.

Understanding behavior of magnetic texture in antiferromagnetic nanostructures and thin films is crucial for the design of novel magnetic data storage and logic devices. Here, we derive the boundary conditions for the Néel vector in a two-sublattice antiferromagnet (AFM) and apply them to describe the shape of the domain walls [1,2] and skyrmions [2] in confined samples. In general, the surface of a 3D domain wall behaves as an elastic ribbon which bends in response on the topographic features of the single crystal Cr2 O3 [1]. In presence of the Dzyaloshinskii-Moriya interaction, topologically non-trivial AFM textures possess broadening near the surface. In thin films, the sample’s granularity becomes crucial. We present a model of a granular AFM and, by comparison with Nitrogen Vacancy magnetometry of 200-nm-thick Cr2O3 films, estimate the inter-grain exchange strength. The grain boundaries act as strong pinning sites for the AFM texture. [1] N. Hedrich et al., Nat. Phys. 17, 574 (2021); [2] O. Pylypovskyi et al., Phys. Rev. B 103, 134413 (2021).

Layered van der Waals crystals host unique properties making them attractive for applications in nanoelectronics, optoelectronics, and sensing. The integration of two-dimensional materials with complementary metal-oxide-semiconductor (CMOS) technology requires controllable n- and p-type doping. In this work, we demonstrate the fabrication of vertical p-n heterojunctions made of p-type tin monoselenide (SnSe) and n-type tin diselenide (SnSe2). The p-n heterojunction is created in a single flake by the NH3-plasma-assisted phase transformation from SnSe2 to SnSe. We show that the transformation rate and crystal quality strongly depend on the plasma parameters like plasma power, temperature, partial pressure, NH3 flow, and duration of plasma treatment. With optimal plasma parameters, the full transformation of SnSe2 flakes to SnSe is achieved within a few seconds. The crystal quality and the topography of the fabricated SnSe-SnSe2 heterostructures are investigated using micro-Raman spectroscopy and cross-sectional transmission electron microscopy. The formation of a p-n junction is verified by current-voltage measurements.

In situ Rutherford Backscattering Spectrometry (RBS) and Spectroscopic Ellipsometry (SE) were applied to study the compositional and optical stability of a WAlSiN-based solar-selective coating (SSC) at high temperatures in vacuum. The samples were exposed to heating-cooling cycles between quasi room temperature and stepwise-increased high temperatures of 450 °C, 650 °C, and 800 °C, respectively. In situ RBS revealed full compositional stability of the SSC during thermal cycling. In situ SE indicated full conservation of the optical response at 450 °C and 650 °C, and minimal changes at 800 °C. The analysis of the ex situ optical reflectance spectra after the complete thermal cycling gave an unchanged solar absorptance of 0.94 and a slightly higher calculated thermal emittance at 800 °C of 0.16 compared to 0.15 after deposition. Cross-sectional element distribution analysis performed in scanning transmission electron microscopy mode confirmed the conservation of the SSC’s microstructure after the heating – cooling cycles. The study demonstrates compositional, optical, and structural stability of the WAlSiN-based solar-selective coating at temperatures targeted for the next generation of concentrated solar power plants.

Decentralized electrochemical production of hydrogen peroxide (H2O2) is an attractive alternative to the industrial anthraquinone process, the application of which is hindered by the lack of high-performance electrocatalysts in acidic media. Herein, a novel catalyst design strategy is reported to optimize the Pd sites in pure metallic aerogels by tuning their geometric environments and electronic structures. By increasing the Hg content in the Pd-Hg aerogels, the Pd-Pd coordination is gradually diminished, resulting in isolated, single-atom-like Pd motifs in the Pd2Hg5 aerogel. Further heterometal doping leads to a series of M-Pd2Hg5 aerogels with an unalterable geometric environment, allowing for sole investigation of the electronic effects. Combining theoretical and experimental analyses, a volcano relationship is obtained for the M-Pd2Hg5 aerogels, demonstrating an effective tunability of the electronic structure of the Pd active sites. The optimized Au-Pd2Hg5 aerogel exhibits an outstanding H2O2 selectivity of 92.8% as well as transferred electron numbers of ≈2.1 in the potential range of 0.0-0.4 VRHE. This work opens a door for designing metallic aerogel electrocatalysts for H2O2 production and highlights the importance of electronic effects in tuning electrocatalytic performances.

Most industrial processes are generating waste heat that can be converted into electrical energy with thermoelectric generators (TEGs). For efficient energy harvesting, it is necessary to significantly improve the properties like Seebeck coefficient, electrical and thermal conductivity of the thermoelectric materials in the TEGs. One promising approach are thermoelectric nanostructures to reduce the thermal conductivity while maintaining constant electrical conductivity and Seebeck coefficient. For that reason, this study investigated the possibility of preparing nanowires of the thermoelectric material iron antimonide (FeSb₂) on crystalline gallium arsenide GaAs(001) substrates with ion-induced surface nanopatterning. The GaAs(001) substrates were pre-patterned using 1 keV Ar⁺ ion irradiation. By using an ion source with a broad, unfocused ion beam at normal incidence, the patterned area can be scaled to nearly any size. The self-organized surface structure is formed by reverse epitaxy and is characterized by almost perfectly parallel-aligned ripples at the nanometer scale. For the fabrication of FeSb₂ nanowires, iron and antimony were successively deposited on the prepatterned GaAs substrates at grazing incidence and then annealed. They were characterized using transmission electron microscopy (TEM), in particular high-resolution TEM imaging for structure analysis and spectrum imaging analysis based on energy-dispersive X-ray spectroscopy for element characterization. With the presented fabrication method, FeSb₂ nanowires were produced successfully on GaAs(001) substrates with an ion-induced nanopatterned surface. The nanowires have a polycristalline structure and a cross-sectional area which is scalable up to 22×22nm². Due to the highly ordered nanostructure of the GaAs substrates, the nanowires have a length of several micrometer. These bottom-up nanofabrication based on ion-induced patterning can be a viable alternative to top-down procedures regarding to efficiency and costs.

Actinide und Lanthanide spielen eine wichtige Rolle bei vielen industriellen Anwendungen und können durch den Abbau, die Nutzung und Entsorgung in die Umwelt gelangen. Genaue Kenntnisse über das komplexe Verhalten und die Wechselwirkung dieser Metalle mit der Biosphäre, z.B. mit Bakterien, Pilzen und Pflanzen sind notwendig, um ein mögliches Gefährdungspotential für den Menschen abschätzen und entsprechende Schutzmaßnahmen ergreifen zu können. Darüber hinaus ermöglicht dieses Wissen die Entwicklung biologischer Verfahren zur Entfernung radioaktiver und toxischer Metalle und Schadstoffe aus Abwässern und kontaminierten Böden. Nach den Unfällen in Tschernobyl und Fukushima ist deutlich geworden, dass insbesondere Pilze große Mengen an Radionukliden und Schwermetallen aufnehmen und anreichern können, allerdings sind die zugrundeliegenden Prozesse noch nicht gut verstanden. Ziel dieser Studie war es die Wechselwirkungen von Myzel ausgewählter holz- und bodenbewohnender Pilze mit Uran und Europium als Analogon für die dreiwertigen Actinide Americium und Curium zu untersuchen. Neben der Bestimmung der Metall-komplexe in den Sorptionslösungen wurden die gebildeten Metall-Pilzspezies mittels Rastertransmissionselektronenmikroskopie gekoppelt mit energiedispersiver Röntgen-mikroanalyse, zeitaufgelöster laser-induzierter Fluoreszenzspektroskopie und chemischer Mikroskopie charakterisiert. Schizophyllum commune zeigte signifikant höhere Metall-Bindungskapazitäten im Vergleich zu den anderen holzbewohnenden Pilzen Pleurotus ostreatus und Lentinus tigrinus sowie zu dem bodenbewohnenden Pilz Leucoagaricus naucinus. Die Metalle werden insbesondere an der Zelloberfläche, in den Zellmembranen und Membranen verschiedener Organellen, aber teilweise auch im Zytoplasma gebunden. Die spektroskopischen Untersuchungen des metallbelasteten Pilzmyzels haben gezeigt, dass Phosphatgruppen verschiedener Biomoleküle neben den Carboxylgruppen eine große Rolle bei der Immobilisierung des Urans und des Europiums durch Pilze spielen.

Superconductivity in group IV semiconductors is desired for hybrid devices combining both semiconducting and superconducting properties. Following boron-doped diamond and Si, superconductivity has been observed in gallium-doped Ge; however, the obtained specimen is in polycrystalline form [Phys. Rev. Lett. 102, 217003 (2009)]. Here we present superconducting single-crystalline Ge hyperdoped with gallium or aluminum by ion implantation and rear-side flash lamp annealing. The maximum concentration of Al and Ga incorporated into substitutional positions in Ge is 8 times higher than the equilibrium solid solubility. This corresponds to a hole concentration above 1021cm-3. Using density functional theory in the local-density approximation and pseudopotential plane-wave approach, we show that the superconductivity in p-type Ge is phonon mediated. According to the ab initio calculations, the critical superconducting temperature for Al- and Ga-doped Ge is in the range of 0.45 K for 6.25at.% of dopant concentration, being in qualitative agreement with experimentally obtained values. Being Si-chip technology compatible, superconducting Ge can find wide applications in quantum technology.

Axial heterostructures have diverse functionality in electronic and optoelectronic devices. Implementing such systems in freestanding semiconducting nanowires further broadens the scope of potential applications, for example: distributed Bragg reflectors, high-efficiency light-emitting diodes, and quantum dot heterostructures. The challenge, however, lies in reducing the compositional grading effect of the constituent heterostructure materials across the interfaces in nanowires grown in vapor-liquid-solid mode. Here, our previously developed nanowire growth technique called droplet-confined alternate pulsed-epitaxy [1] (an adaptation of conventional molecular beam epitaxy), which grants precise control over the axial growth rate and droplet composition, is employed to grow Al(x)Ga(1-x)As axial insertions in self-catalyzed GaAs nanowires. A full nanowire with six insertions is shown in Figure 1 (top). High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and nanowire growth models are utilized to gain an understanding of the compositional grading mechanism and its dependence on the growth temperature (TG), the nanowire radius (RNW), and the amount of supplied Al. Figure 1 (bottom) is an example HAADF-STEM image showing two atomically resolved Al(x)Ga(1-x)As insertions embedded in a zincblende GaAs nanowire, whereas Figure 2 shows the extracted Al-content (x) axial profiles for three selected insertions with different TG and RNW (the same amount of supplied Al). We show that lower TG and/or smaller RNW result in sharper interfaces, with a more profound improvement for the AlxGa1-xAs-to-GaAs interface. In the best case, almost symmetric insertions with interface thicknesses of only 2 – 3 monolayers are achieved, approaching the absolute limit of atomically sharp interfaces. Thermodynamics, kinetics, and nanowire geometry are all factors considered during the formation of our Al(x)Ga(1-x)As insertions. Using two existing heterostructure growth models [2, 3] to fit our experimental data we can extract valuable quantitative information regarding the interface characteristics. Our results show for the first time that not only TG, but also size effects, i.e. a decreasing RNW, play a large role in the thermodynamic stability at the liquid-solid interface, setting previously unknown limitations on the maximum attainable interface sharpness. These findings and their implications will be discussed in detail. The functionality of our insertions is successfully tested via their employment as axial barriers in quantum dot nanowire heterostructures. By growing the quantum dot heterostructure at 350 °C, consequently sharpening the quantum dot interfaces, we observe a one order of magnitude decrease in quantum dot emission linewidth (Figure 3) in comparison to a similar system grown at 550 °C. 1. Balaghi et al., Nano Lett. 16, 4032 (2016) 2. Luna et al., Phys. Rev. Lett. 109, 126101 (2012) 3. Priante et al., Nano Lett. 16, 1917 (2016)

High-entropy alloys (HEAs) are a relatively new class of metal alloys composed of several principal elements, usually at (near) equiatomic ratios. It has previously been reported that some HEAs display superior radiation damage resistance, with composition and microstructure being cited as contributing factors, though the precise mechanism is still unknown. To study the influence of the crystal structure on the response to radiation, we have chosen FeCoCrNiV as a model system. While FeCoCrNi has a face-centred cubic (fcc) structure, adding V leads to a structural transformation towards a body-centred tetragonal (bct) structure with both phases present at near-stochiometric composition. The as-cast sample was characterised by energy-dispersive X-ray spectroscopy (EDXS) and electron backscatter diffraction in a scanning electron microscope confirming the presence of both phases. Irradiations were performed with a focussed He beam provided by a helium ion microscope (HIM) at temperatures between 20°C and 500°C. The fluence was varied between 6×10^17 ions/cm² and 1×10^20 ions/cm². High-resolution images of the irradiated areas were taken with the same HIM as shown in Fig. 1a. Selected irradiated areas were additionally studied by transmission electron microscopy (TEM) in combination with EDXS. Under irradiation, pores start to be generated in the material with pore sizes differing significantly between the two phases. At higher fluences and above a critical temperature, a tendril structure as exemplary shown for the bct phase in Fig. 1a forms in both phases. TEM images reveal that these tendrils span the whole depth of the irradiated area (Fig. 1b) and are accompanied by bubbles of various sizes. Scanning TEM-based EDXS of these structures indicates a He-induced change in composition.

For a comprehensive safety assessment of a nuclear repository, the influence of naturally occurring microorganisms from deep geological layers has to be taken into account. Clay rock represents a suitable host rock for the long-term storage of high-level radioactive waste with bentonite as backfill material. In the event of a worst-case scenario, water can enter the repository, solubilize components of the waste, and transport it into the surrounding barriers. In this case, microorganisms can interact with the radionuclides and thereby change the chemical speciation or induce redox reactions. Desulfosporosinus species represent important members of anaerobic, sulfate-reducing bacteria present in both, clay rock and bentonite. They occur, among others, in the pore water of Opalinus Clay and in the Bavarian bentonite B25. [1,2] Desulfosporosinus hippei DSM 8344T is a close phylogenetic relative to an isolated bacterium from bentonite samples. [3] Therefore, this strain was selected to get a more profound insight into the uranium(VI) interactions, especially regarding the reduction to the less mobile uranium(IV). Artificial Opalinus Clay pore water [4] served as background electrolyte for the reduction experiments (100 µM uranium(VI), pH 5.5), in which the uranium concentrations in the supernatants decreased rapidly. Time-resolved laser-induced fluorescence spectroscopy showed the presence of a uranyl lactate and a uranyl carbonate complex as aqueous species in the supernatant. While the proportion of the uranyl lactate complex decreased with the incubation time, the uranyl carbonate fraction remained almost constant. UV/Vis studies of the dissolved cell pellets provided clear proof of a partial reduction of uranium(VI) to uranium(IV) of up to 39% in the samples. Therefore, a combined association-reduction process is a possible interaction mechanism. TEM images showed the presence of uranium-containing aggregates on the cell surface. To mitigate encrustation, cells released membrane vesicles as a possible defense mechanism. In addition, uranium(VI) reduction was confirmed by HERFD-XANES measurements. Moreover, uranium(V) could be detected as an intermediate, providing first evidence of the involvement of uranium(V) in uranium(VI) reduction by sulfate-reducing microorganisms. EXAFS measurements helped to identify different cell-related uranium species. This study helps to improve the understanding of the complexity of uranium-microbe interactions relevant to the long-term storage of high-level radioactive waste in clay rock and therefore contributes to a safety concept for a nuclear repository in this host rock. References: [1] Bagnoud et al. (2016) Nat. Commun 7, 1–10. [2] Matschiavelli et al. (2019) Environ. Sci. Technol. 53, 10514–10524. [3] Vatsurina et al. (2008) Int. J. Syst. Evol. Microbiol. 58, 1228–1232. [4] Wersin et al. (2011) Appl. Geochemistry 26, 931–953.

Optical pump – THz probe spectroscopy has been established as a tool for contactless probing of electronic transport in semiconductor nanowires (NWs) [1]. Particularly in III-V NWs, scattering rates of charge carriers, as well as their plasmonic resonances for typical doping levels, are located in the THz range. The analysis of the optical conductivity spectra using the localized surface plasmon model provides an estimation of the carrier density and the mobility. Here, we employ THz spectroscopy to study electron mobility in the strained GaAs core of GaAs/InAlAs core/shell nanowires. Owing to the lattice mismatch between the core and the shell in these NWs, the bandgap energy in the strained GaAs core exhibits a reduction by up to 40% [2]. Our results demonstrate that this effect is accompanied by a notable increase in the electron mobility by 30-50% with respect to a bulk GaAs [3]. We discuss the role of various scattering mechanisms and their dependence on strain and temperature. In addition to the homogeneous plasmon broadening caused by the carrier scattering, we also observe an inhomogeneous broadening in dense ensembles of NWs as illustrated in Fig. 1(a). Our modelling demonstrates that such broadening stems from the plasmonic interaction between neighboring NWs leading to the shift of the plasmon frequency as shown in Fig. 1(b). This effect has to be considered in the analysis of THz response of NWs since it may result in a significant underestimation of the mobility values.

The aggressive reduction of the channel length in transistors needs the high doping of the channel region, while the contact area requires doping beyond 1020 cm-3 to ensure low-resistance ohmic contacts. Similar problems apply to wide-band gap semiconductors where the p-type doping is challenging, mainly due to the high activation energy for acceptors, low equilibrium solid solubility and deactivation of acceptors by the formation of acceptor-vacancy clusters. Recently, we have shown that ultra-doped n-type and p-type Ge with a carrier concentration above 1020 cm-3 can be achieved by applying non-equilibrium methods like ion implantation followed by millisecond-range flash-lamp annealing (FLA) [1-3]. The n-type doping of Ge is a self-limiting process due to the formation of vacancy-donor complexes (DnV with n ≤ 4) that deactivates the donors [4]. Based on data density functional theory calculations, at temperature higher than 850 K, the concentration of D4V clusters progressively decreases liberating unbounded vacancies and donor atoms. The same effect is observed for p-type Ge and in III-V semiconductors. Here, we report on experiments and theoretical calculations solving the basic problem of donors and acceptors deactivation in heavily doped semiconductors. The dissolution of donor/acceptor-vacancy clusters in heavily doped semiconductors is achieved by ms-range FLA with a peak temperature close to the melting point of the semiconductor. Positron annihilation lifetime spectroscopy (PALS) reveals that dopant-vacancy clusters are the main defect centers deactivating both acceptors and donors. Millisecond-range high-temperature treatment dissociates the dopant-V clusters and, as shown by SIMS, fully suppresses the dopant diffusion in both group IV semiconductors and III-V compound semiconductors. For the first time, using structural characterization (PALS, SIMS) and electrochemical capacitance-voltage profiling combined with DFT calculations, we were able to address, understand, and solve the fundamental problem hindering the doping of semiconductors above the solid solubility limit.

Axial heterostructures have diverse functionality in electronic and optoelectronic devices. Implementing such systems in freestanding semiconducting nanowires further broadens the scope of potential applications, for example: distributed Bragg reflectors, high-efficiency light-emitting diodes, and quantum dot heterostructures. The challenge, however, lies in reducing the compositional grading effect of the constituent heterostructure materials across the interfaces in nanowires grown in vapor-liquid-solid mode. Here, our previously developed nanowire growth technique called droplet-confined alternate pulsed-epitaxy [1] (an adaptation of conventional molecular beam epitaxy), which grants precise control over the axial growth rate and droplet composition, is employed to grow Al(x)Ga(1-x)As axial insertions in self-catalyzed GaAs nanowires. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and nanowire growth models are utilized to gain an understanding of the compositional grading mechanism and its dependence on the growth temperature (TG), the nanowire radius (RNW), and the amount of supplied Al. Figure 1 (a) is an example HAADF-STEM image showing two Al(x)Ga(1-x)As insertions embedded in a zincblende GaAs nanowire, whereas Figure 1 (b) shows the extracted Al-content (x) axial profiles for three selected insertions with different TG and RNW (the same amount of supplied Al). We show that lower TG and/or smaller RNW result in sharper interfaces, with a more profound improvement for the AlxGa1-xAs-to-GaAs interface. In the best case, almost symmetric insertions with interface thicknesses of only 2 – 3 monolayers are achieved, approaching the absolute limit of atomically sharp interfaces. The fitting of our experimental data with existing heterostructure growth models [2, 3] is suggestive of different mechanisms behind the compositional grading of the two interfaces and will be discussed in detail. The functionality of our insertions is successfully tested via their employment as axial barriers in quantum dot nanowire heterostructures. By growing the quantum dot heterostructure at 350 °C, consequently sharpening the quantum dot interfaces, we observe a one order of magnitude decrease in quantum dot emission linewidth (Figure 1 (c)) in comparison to a similar system grown at 550 °C. [1] Balaghi et al., Nano Lett. 16, 4032 (2016) [2] Luna et al., Phys. Rev. Lett. 109, 126101 (2012) [3] Priante et al., Nano Lett. 16, 1917 (2016)

Silicon doped with Tellurium (Te), a deep level impurity, at concentrations higher than the solid solubility limit (hyperdoping) was prepared by ion-implantation and nanosecond pulsed laser melting. The resulting materials exhibit strong sub-bandgap optical absorption showing potential for room-temperature broadband infrared photodetectors. As a thermodynamically metastable system, an impairment of the optoelectronic properties in hyperdoped Si materials occurs upon subsequent high-temperature thermal treatment. The substitutional Te atoms that cause the sub-bandgap absorption are removed from the substitutional sites to form Te-related complexes. In this work, we explore the phase evolution and the electrical deactivation of Te-hyperdoped Si layers upon furnace annealing through the analysis of optical and microstructural properties as well as positron annihilation lifetime spectroscopy. Particularly, Te-rich clusters are observed in samples thermally annealed at temperature reaching 950 °C and above. Combining the analysis of polarized Raman spectra and transmission electron microscopy, the observed crystalline clusters are suggested to consist of Si2Te3. The defect characterization using positron lifetime spectroscopy suggests the generation of vacancy complexes as a function of temperature, leading to the decrease of sheet carrier concentration.

Low-power logic and memory circuits remain a main task for the next generations of energy-efficient electronic devices. Single Electron Transistors (SETs) are extremely low energy dissipation devices. However, SETs operate usually at cryogenic temperatures and have some serious drawbacks. Fortunately, Field Effect Transistors (FETs) and SETs are complementary: The SET is the champion of low-power consumption while FETs advantages, like high-speed, driving, voltage gain and input impedance can compensate exactly for SET's intrinsic drawbacks. To overcome the drawback of cryogenic temperature operation, each SET has to be manufactured with a quantum dot of a size of just a few nanometers, and this dot has to be located not more than about one nanometer apart from the electrodes. The large-scale implementation of SETs in room-temperature electronics is hampered by its unresolved manufacturability because such requirements are beyond the limits of present lithography. We employed self-organization to overcome the present-day limits of lithography. On 5…8nm thick SiO2 layers of (001)Si wafers about 30nm thick a-Si layers have been deposited and subsequently irradiated with 50 keV Si+ ions. The irradiation leads to ion beam mixing at the upper and lower Si/SiO2 interfaces and transforms the buried SiO2 layer to SiOx with x~1. Then, pillar arrays have been fabricated from such layer stacks using electron beam lithography and plasma etching. Arrays of pillars with different diameters from 100nm down to less than 20nm have been produced, where the smallest pillar diameters have been further reduced to ~10nm by plasma oxidation and selective oxide etching (sacrificial oxidation). In this manner we manufactured SiOx disks of ~10nm diameter and 5nm thickness sandwiched between the Si of the pillars. During Rapid Thermal Processing (RTP) of such pillars at 1050°C for 60s, phase separation SiOx  (1-x/2)Si + x/2SiO2 occurs via formation of Si nuclei and Ostwald ripening. Close to the SiO2/Si interfaces the Si excess of SiOx condensates on the upper/lower Si of the pillar, i.e. no Si nuclei can form there. The nucleation rate at the rim of the disk is reduced too, especially if there are traces of oxygen in the ambient. Thus, in nanopillars of ~10nm diameter a single Si dot of ~3nm forms in the ~5nm thick SiO2 disk, whereas in thicker pillars a few dots are found. From such nanopillars vertical nanowire Gate-All-Around SETs (nw GAA-SETs) are fabricated by gate oxide formation using plasma oxidation and gate layer deposition followed by contact formation. The nw GAA-SETs can be combined with nw GAA FETs to fabricate integrated hybrid SET/FET devices, where the FETs are responsible for current amplification. The funding from the European Union’s Horizon 2020 research and innovation program under grand agreement Nº 688072 (project acronym: Ions4SET) is gratefully acknowledged.

Raw data for the publication: "Epitaxial lateral overgrowth of tin spheres driven and directly observed by helium ion microscopy". It contains helium ion microscopy, transmission electron microscopy, scanning electron microscopy as well as gallium focused ion microscopy images and XPS data. It shows how the irradiation of tin spheres with keV He ions causes epitaxial lateral overgrowth.

Antiferromagnetic insulators are a prospective material science platform for magnonics, spin superfluidity, THz spintronics, and non-volatile data storage. A magnetomechanical coupling in antiferromagnets offers vast advantages in the control and manipulation of the primary order parameter yet remains largely unexplored both fundamentally and technologically. Here, we discover a new member in the family of flexoeffects in thin films of technologically relevant antiferromagnetic Cr2O3. We demonstrate that a gradient of mechanical strain can impact the magnetic phase transition resulting in the distribution of the N ́eel temperature along the thickness of a 50-nm-thick film and induces a sizable flexomagnetic coefficient of about 15 μb/nm2 originating from the inhomogeneous reduction of the antiferromagnetic order parameter. The antiferromagnetic ordering in inhomogeneously strained thin films of Cr2O3 can persist up to 100◦ C, rendering Cr2O3 relevant for industrial electronics applications. The presence of a strain gradient in thin films of Cr2O3 may therefore allow for the realization of reconfigurable antiferromagnetic racetracks, magnonic waveguides and magnon crystals. The presence of a strain gradient in ultrathin films of Cr2O3 enables new fundamental research directions on magnetomechanics and thermodynamics of antiferromagnetic solitons, spin waves and artificial spin ice systems in magnetic materials with continuously graded parameters.

Optical pump – Terahertz (THz) probe (OPTP) spectroscopy has proven efficacy for contactless probing of electronic transport in semiconductor NWs [1]. Particularly in III-V NWs, scattering rates of charge carriers, as well as their plasmonic resonances for typical doping levels, are located in the THz range. The analysis of the optical conductivity spectra using the localized surface plasmon model allows estimating the carrier lifetime and the carrier mobility. Here, OPTP spectroscopy is employed to study two unique phenomena in GaAs/(In,Al,Ga)As core/shell nanowires. First, it is demonstrated that the mobility of electrons in the hydrostaticallystrained GaAs core (owing to the lattice mismatch between the core and the shell [2]) exceeds the mobility in bulk GaAs by 30-50% [3]. The role of the various scattering mechanisms is analyzed as a function of strain and temperature. Depending on the density of NWs in the probed sample, some of them can form bundles or touch each other, leading to an inhomogeneous broadening of the plasmon resonance. We discuss the role of this effect and its impact on the estimation of carrier mobility [3, 4]. Second, we demonstrate a strong THz nonlinearity using single-cycle intense THz pulses with peak electric fields reaching up to 0.6 MV/cm. With the increase of the driving THz field, we observe a systematic redshift of the plasmon frequency, accompanied by a gradual suppression of the spectral weight. Remarkably, the spectral weight does not remain proportional to the square of the plasmon frequency when the driving electric field exceeds 0.4 MV/cm, indicating an onset of a spatially inhomogeneous carrier distribution across the NW. The observed behavior can be ascribed to nonlinear effects caused by the scattering of electrons from the Gamma- to L-valley occurring in the high electric field regime. However, in contrast to bulk semiconductors, this effect initially sets in at hot spots of the NW, where the local electric field is enhanced by the plasmonic resonance [5]. All in all, our findings provide important guidelines for the exploitation of nanowires in high-frequency electronics, but also underline the unique strengths of OPTP spectroscopy for the study of electronic transport in nanowires. [1] H. J. Joyce et al., Semicond. Sci. Technol. 31, 103003 (2016). [2] L. Balaghi et al., Nat. Commun. 10, 2793 (2019). [3] L. Balaghi et al., Nat. Commun. 12, 6642 (2021). [4] I. Fotev et al., Nanotechnology 30, 244004 (2019). [5] R. Rana et al., Nano Lett. 20, 3225 (2020).

The mining and industrial use of heavy metals lead to locally high heavy metal contamination with serious consequences for the environment and local population. The high potential of biological remediation processes, in particular, the use of magnetotactic bacteria of heavy metal and radionuclide-contaminated waters has recently been discussed. Yet, the molecular reactions involved in the uptake of radionuclides, especially U, by these bacteria are unknown. The present work is a multidisciplinary approach combining wet chemistry, microscopy, and spectroscopy methods. Our findings suggest that the cell wall plays a prominent role in the bioassociation of U(VI). In time-dependent bioassociation studies, up to 95 % of the initial U(VI) was removed from the suspension within the first hours by Magnetospirillum magneticum AMB-1. PARAFAC analysis of TRLFS data highlights that peptidoglycan is the most important ligand involved, showing a stable immobilization of U(VI) over a wide pH range with the formation of three characteristic species. In addition, in-situ ATR FT-IR reveals the predominant binding to carboxylic functionalities, at higher pH polynuclear species seem to play an important role. This comprehensive molecular study may initiate in future new remediation strategies on effective immobilization of U in combination with the bacteria´s magnetic properties.

Due to their self-supporting and nanoparticulate structure, metal aerogels have emerged as excellent electrocatalysts, especially in the light of the shift to renewable energy cycles. While a large number of synthesis parameters have already been studied in depth, only superficial attention has been paid to the solvent. In order to investigate the influence of this parameter with respect to the gelation time, crystallinity, morphology, or porosity of metal gels, AuxCuy aerogels were prepared in water and ethanol. It was shown that although gelation in water leads to highly porous gels (60 m2g-1), a CuO phase forms during this process. The undesired oxide could be selectively removed using a post-washing step with formic acid. In contrast, the solvent change to EtOH led to a halving of the gelation time and the suppression of Cu oxidation. Thus, pure Cu aerogels were synthesized in addition to various bimetallic Au3X (X = Ni, Fe, Co) gels. The faster gelation, caused by the lower permittivity of EtOH, led to the formation of thicker gel strands, which resulted in a lower porosity of the AuxCuy aerogels. The advantage given by the solvent choice simplifies the preparation of metal aerogels and provides deeper knowledge about their gelation.

The physical downscaling of CMOS technology has reached its limitations. Subsequently, the quest for alternative technological solutions based on new materials and device concepts augment the downscaling of integrated circuits. One such concept is the reconfigurable FET (RFET), which can be dynamically programmed to n- or p-polarity by applying an electrostatic potential [1]. In this work, we present the idea of a novel mixed dimensional RFET device, which explores the potential of both one-dimensional (1D) channel materials (like silicon (Si) or silicon-germanium (SiGe) based nanowires) and two-dimensional (2D) materials. In the most generic process, an RFET device is based on intrinsic Si or SiGe nanowire with Nickel (Ni) placed on both ends. Subsequent annealing results in the formation of silicide regions in the nanowire. The junction of the silicide to Si or SiGe is a typical Schottky junction. By controlling the Schottky junction with the help of gating architectures, the flow of charge carriers within the channel can be modulated. For ambipolarity, an electrostatic potential on the back-gate or a single top-gate enables the n- or p-transport depending on the polarity of the gate voltage. The main aim of this work is to optimize the RFET architecture based on 2D materials like hexagonal boron nitride (hBN) as a dielectric and encapsulating layer instead of thermally grown oxide around the nanowire. 2D hBN comprises a structure very similar to graphene with its sub lattice consisting of boron or nitrogen atoms. However, contrary to graphene, hBN acts as an insulator with dielectric constant between 3-4 (similar to SiO2). The properties of atomically thin hBN like the absence of dangling bonds, resistance to oxidation and chemical stability makes it an ideal gate dielectric material for flexible electronics. Top-down fabrication of RFETs is an essential requirement for large-scale device integration. The Si or SiGe nanowires are fabricated using electron beam lithography and reactive ion etching [2]. As reported in our previous works, the formation of silicided Schottky junctions by flash lamp annealing (FLA) yields better control over the silicide progression in the nanowire compared to rapid thermal annealing (RTA) [3,4]. This work focuses on the application of 2D hBN as a dielectric layer for nanowire-based devices. The devices fabricated and characterized consist of a mechanically exfoliated 2D hBN flake deposited on the single Si or SiGe nanowire-based devices by the dry viscoelastic stamping transfer technique. The thickness of the hBN flakes, investigated by atomic force microscopy and transmission electron microscopy, was between 5-10 nm (shown in figure 1). The energy dispersive X-ray analysis (EDX) was also carried out on the cross-sectioned devices for investigating the elemental distribution (figure 2). The ambipolar transfer characteristics of the Si-hBN devices with different gating architectures (compared in figure 3) show a significant improvement in subthreshold swing value due to the 2D encapsulation and passivation. The fabricated SiGe-hBN based devices also show an improvement of p and n on-currents and ION/IOFF ratio through back-gating due to the encapsulation and passivation of the nanowire by the hBN flake (figure 4).

The efficient integration of transition metal dichalcogenides (TMDs) into the current electronic device technology requires mastering the techniques of effective tuning of their optoelectronic properties. Specifically, controllable doping is essential. For conventional bulk semiconductors, ion implantation is the most developed method offering stable and tunable doping. In this work, we demonstrate n-type doping in MoSe2 flakes realized by low-energy ion implantation of Cl+ ions followed by millisecond-range flash lamp annealing (FLA). We further show that FLA for 3 ms with a peak temperature of about 1000 °C is enough to recrystallize implanted MoSe2. The Cl distribution in few-layer-thick MoSe2 is measured by secondary ion mass spectrometry. An increase in the electron concentration with increasing Cl fluence is determined from the softening and red shift of the Raman-active A1g phonon mode due to the Fano effect. The electrical measurements confirm the n-type doping of Cl-implanted MoSe2. A comparison of the results of our density functional theory calculations and experimental temperature-dependent micro-Raman spectroscopy data indicates that Cl atoms are incorporated into the atomic network of MoSe2 as substitutional donor impurities.

High-entropy alloys (HEAs) are a relatively new class of metal alloys composed of several principal elements, usually at (near) equiatomic ratios. It has previously been reported that some HEAs display superior radiation damage resistance, with composition and microstructure being cited as contributing factors, though the precise mechanism is still unknown. To study the influence of the crystal structure on the response to radiation, we have chosen FeCoCrNiV as a model system. While FeCoCrNi has a face-centred cubic (fcc) structure, adding V leads to a structural transformation towards a body-centred tetragonal (bct) structure with both phases present at near-stochiometric composition [1]. The as-cast sample was characterised by energy-dispersive X-ray spectroscopy (EDXS) and electron backscatter diffraction (EBSD) in a scanning electron microscope (SEM) confirming the presence of both phases. Irradiations were performed with a focussed He beam provided by a helium ion microscope (HIM) at temperatures between room temperature and 500°C. The irradiation fluence was varied between 6x1017 ions/cm2 and 1x1020 ions/cm2. High-resolution images of the irradiated areas were taken with the same HIM, and an example is shown in Fig. 1a. Selected irradiated areas were additionally studied by transmission electron microscopy (TEM) in combination with EDXS. Under irradiation, pores start to be generated in the material with pore sizes differing significantly between the two phases. At higher fluences and above a critical temperature, a tendril structure as exemplary shown for the bct phase in Fig. 1a forms in both phases. We have found that the critical temperature depends on the phase and is lower for fcc. TEM images reveal that the tendrils span the whole depth of the irradiated area and are accompanied by bubbles of various sizes as shown in Fig. 1b for the bct phase. Scanning TEM-based EDXS of these structures indicates a He-induced change in composition. A.G. acknowledges support by the Royal Academy of Engineering and the Leverhulme Trust.

Advanced energy materials and effective manufacturing facilities of battery cells production are key parameters to overcome the economic barrier to entry into the market. This poster shows an annealing technology using the millisecond range flash lamp annealing (FLA), which takes place without preheating and can be both a vacuum and vacuum-free method. This procedure at a pilot stage is characterized by significant savings in time, energy, resource and production costs enabling to enhance the sustainability of the battery production generally. It will review, as example, the advances that are obtained using FLA on new materials for high energy density thin film electrodes based on silicon. These new materials have the capability of realizing an excellent performance of the energy storage system, e.g. of lithium ion batteries and beyond, for vehicles and stationary applications. It will be demonstrated how it is possible to develop a silicon metal electrode (SiMe) with outstanding properties with a higher capacity than the standard of the day, compatible to many variants of lithium cells, solvents free, cost-effective and capable to be integrated on roll-to- roll processing.

The interaction of tobacco (Nicotiana tabacum) BY-2 cells with uranyl(VI) nitrate in phosphate-deficient medium was investigated. The hypothesis was that endocytosis is a means of uranium uptake in these cells. Analysis was in the form of physiological studies (growth and viability), electron microscopy, proteomics and biochemical studies.

The safe disposal of high-level radioactive waste represents a significant scientific and societal challenge. According to geological, geochemical, and geophysical properties, clay formations represent a suitable host rock for the long-term storage of this waste. However, for a comprehensive safety assessment, the influence of naturally occurring microorganisms in clay rock and in the backfill material bentonite must be taken into account. Desulfosporosinus species play a crucial role in the community of sulfate-reducing bacteria present in clay rock and bentonite.[1,2] Desulfosporosinus hippei DSM 8344T is a close relative of the isolated species and was originally found in permafrost soils.[3] Desulfitobacterium sp. G1-2 has been isolated from bentonite samples and is an important representative of iron-reducing bacteria. As members of the microbial community from deep geological layers, these strains were selected to get a more profound knowledge about their interactions with U(VI). During time-dependent experiments in bicarbonate buffer (30 mM, 100 µM U(VI)), Desulfitobacterium sp. G1-2 showed a removal of up to 80% within 5 days. UV/Vis studies of the dissolved cell pellets verified the formation of U(IV) during the process. In contrast to these findings, Desulfosporosinus hippei DSM 8344T was not able to reduce U(VI) in the presence of bicarbonate. Therefore, experiments in artificial Opalinus Clay pore water [4] (100 µM U(VI), pH 5.5) were conducted. Determinations of the U concentrations showed a removal of up to 80% of the radionuclide from the supernatants within only 48 h. UV/Vis studies of the dissolved cell pellets provided clear proof of a partially reduction of U(VI) to U(IV), although bands of U(VI) were also still observable. These findings propose a combined association-reduction process as a possible interaction mechanism for this microorganism. TEM images combined with EDX analysis revealed the presence of two different U-containing aggregates inside cells of Desulfitobacterium sp. G1-2. Furthermore, cells of Desulfosporosinus hippei DSM 8344T released membrane vesicles as a possible defense mechanism against encrustation by U precipitates on the cell surface. However, cells showed almost no uptake of U. In this study, different analytical methods were used to better understand the U(VI) reduction by sulfate- and iron-reducing bacteria. Significant differences in the occurring mechanisms were evident between both microorganisms, highlighting the importance of studies on the U(VI) interactions of different microorganisms present in clay rock. Moreover, these results contribute to a safety concept for a nuclear repository in clay formations and for final disposal sites using bentonite as backfill material. References: [1] Bagnoud et al. (2016) Nat. Commun 7, 1–10. [2] Matschiavelli et al. (2019) Environ. Sci. Technol. 53, 10514–10524. [3] Vatsurina et al. (2008) Int. J. Syst. Evol. Microbiol. 58, 1228–1232. [4] Wersin et al. (2011) Appl. Geochemistry 26, 931–953.