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Epitaxial growth of the three-dimensional topological semimetal Cd3As2 on semiconductor substrates enables its use and integration in device applications. Epitaxy also provides an avenue for varying and controlling point defects through modification of the chemical potential during growth. In turn, knowledge of the point defects that are generated in Cd3As2 epilayers will aid the interpretation of electron transport behavior and guide growth efforts to produce material with low defect densities. Point defects in Cd3As2 epilayers grown by molecular beam epitaxy with varying As/Cd flux ratios are probed by positron annihilation spectroscopy. We find that lower As/Cd flux ratios produce higher concentrations of point defects. Remarkably, the measurements indicate that the average defect size is larger than a monovacancy. The data presented here contribute to an evolving picture of vacancy point defects in Cd3As2 and can be used to direct future investigation of the defect-transport relationships in this emerging electronic material.

Abstract The oxidation of chromium in air at 700 °C was investigated with a focus on point defect behavior and transport during oxide layer growth. A comprehensive set of characterization techniques targeted characteristics of chromium oxide microstructure and chemical composition analysis. TEM showed that the oxide was thicker with longer oxidation times and that, for the thicker oxides, voids formed at the metal/oxide interface. PAS revealed that the longer the oxidation time, there was an overall reduction in vacancy-type defects, though chromium monovacancies were not found in either case. EIS found that the longer oxidized material was more electrochemically stable and that, while all oxides displayed p-type character, the thicker oxide had an overall lower charge carrier density. Together, the results suggest anion oxygen interstitials and chromium vacancy cluster complexes drive transport in an oxidizing environment at this temperature, providing invaluable insight into the mechanisms that regulate corrosion.

Pure W and W-Cr-Hf alloy which are prospective materials for nuclear fusion reactors, such as DEMO, were irradiated at room temperature with 5 MeV Au2+ ions with fluences between 4 × 1014 and 1.3 × 1016 ions.cm−2 to generate various levels of lattice damage from about units up to tens of dpa. The distinct character of radiation damage accumulation, microstructure and defect nature have been observed in both pure W and W-Cr-Hf alloys, the latter exhibited interesting ability of damage reorganisation and defect size decrease at the higher ion fluences as determined by positron annihilation spectroscopy (PAS). High radiation damage rate in the irradiated layer has been evidenced in the W samples already at the lower Au-ion fluences compared to W-Cr-Hf samples, where the damage increased in steps with the increasing Au-ion fluence. The distinct defect accumulation was accompanied with the different Au-ion implanted distribution in the irradiated layer determined by Secondary Ion Mass Spectrometry (SIMS) as well as the thermal properties have shown the consequent worsening in the depth in good agreement with the Au-depth concentration profiles. TEM corroborated above mentioned findings, where the sub-surface layer exhibited defect release after the irradiation, the maximum of dislocation loop density has been identified in the depth according the predicted dpa (displacement particles per atom) maximum for the lower Au-ion fluences. Moreover, TEM shows the dislocation density band structure appeared in W-Cr-Hf samples exhibiting the high density defect band according the projected range of the Au-ions simultaneously with the additional layer with larger isolated dislocations pronounced in the higher depth as a growing function of Au-ion fluence. Such phenomenon was not observed in W samples.

We demonstrate the manipulation of magnetic phases in FeRh thin films through atomic displacements and the distribution of structural defects. Atomic scale disorder can be controlled via irradiation with light noble gas ions, producing depth-varying nanoscale phase configurations of distinct antiferromagnetic, ferromagnetic, and paramagnetic regions. Here, we perform a spatial characterization of the magnetic phases and the local magnetic environment around the Fe atoms, as well as the variation of the open-volumes around atomic sites. Thus, a direct correspondence between the existence of the three magnetic phases and lattice defects is revealed. By careful selection of the irradiating fluence, we show that it is possible to produce simple and thermally stable magnetic configurations, such as uniform magnetization or a bilayer phase structure. Furthermore, the thin film surface and interfaces are observed as the nucleation sites for the transitions between the phases. These results demonstrate a sensitive nanoscale manipulation of magnetic properties, shedding light on magnetic ordering in alloy lattices and broadening the scope for applications.

Germanium (Ge), the next-in-line group-IV material, bears great potential to add functionality and performance to next-generation nanoelectronics and solid-state quantum transport based on silicon (Si) technology. Here, we investigate the direct epitaxial growth of two-dimensional high-quality crystalline Ge layers on Si deposited at ultralow growth temperatures ( T Ge = 100-350 °C) and pristine growth pressures (≲10 -10 mbar). First, we show that a decreasing T Ge does not degrade the crystal quality of homoepitaxial Ge/Ge(001) by comparing the point defect density using positron annihilation lifetime spectroscopy. Subsequently, we present a systematic investigation of the Ge/Si(001) heteroepitaxy, varying the Ge coverage (Θ Ge, 1, 2, 4, 8, 12, and 16 nm) and T Ge (100-300 °C, in increments of 50 °C) to assess the influence of these parameters on the layer's structural quality. Atomic force microscopy revealed a rippled surface topography with superimposed grainy features and the absence of three-dimensional structures, such as quantum dots. Transmission electron microscopy unveiled pseudomorphic grains of highly crystalline growth separated by defective domains. Thanks to nanobeam scanning X-ray diffraction measurements, we were able to evidence the lattice strain fluctuations due to the ripple-like structure of the layers. We conclude that the heteroepitaxial strain contributes to the formation of the ripples, which originate from the kinetic limitations of the ultralow temperatures., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

This study is the first one that investigates in detail the bacterial intercellular response to the high density of crystallographic defects including vacancies created in Cu by high pressure torsion. To this aim, samples were deformed by high pressure torsion and afterward, their antibacterial properties against Staphylococcus aureus were analyzed in adhesion tests. As a reference an annealed sample was applied. To avoid the influence of surface roughness, specially elaborated conditions for surface preparation were employed, which do not introduce defects and assure comparable surface roughness. The analysis of the chemical composition and thickness of passive layers by X-ray photoelectron spectroscopy showed that they were comparable for nanostructured and micrograined samples, consisting of Cu 2 O and CuO, and a thickness of 6 nm. The interface bacterium-substrate was prepared by a focused ion beam and further analyzed by scanning transmission electron microscopy and energy dispersive spectroscopy. High pressure torsion processed Cu shows enhanced anti-adhesion properties while in contact with S. aureus than micrograined Cu. There is a linear correlation between luminous intensity and grain size -0.5 . The bacterial intercellular defence mechanism includes the creation of Cu 2 O nanoparticles and the increased concentration of sulphur-rich compounds near these nanoparticles., (© 2024. The Author(s).)

LiMn 2 O 4 (LMO) cathodes present large stability when cycled in aqueous electrolytes, contrasting with their behavior in conventional organic electrolytes in lithium-ion batteries (LIBs). To elucidate the mechanisms underlying this distinctive behavior, we employ unconventional characterization techniques, including variable energy positron annihilation lifetime spectroscopy (VEPALS), tip-enhanced Raman spectroscopy (TERS), and macro-Raman spectroscopy (with tens of μm-size laser spot). These still rather unexplored techniques in the battery field provide complementary information across different length scales, revealing previously hidden features. VEPALS offers atomic-scale insights, uncovering cationic defects and subnanometer pores that tend to collapse with cycling. TERS, operating in the nanometric range at the surface, captured the presence of Mn 3 O 4 and its dissolution with cycling, elucidating dynamic changes during operation. Additionally, TERS highlights the accumulation of SO 4 2- at grain boundaries. Macro-Raman spectroscopy focuses on the micrometer scale, depicting small changes in the cathode's long-range order, suggesting a slow but progressive loss of crystalline quality under operation. Integrating these techniques provides a comprehensive assessment of LMO cathode stability in aqueous electrolytes, offering multifaceted insights into phase and defect evolution that can help to rationalize the origin of such stability when compared with conventional organic electrolytes. Our findings advance the understanding of LMO behavior in aqueous environments and provide guidelines for its development for next-generation LIBs., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Introduction: The pathogenesis of chronic subdural hematoma (CSDH) has not been completely understood. However, different mechanisms can result in space-occupying subdural fluid collections, one pathway can be the transformation of an original trauma-induced acute subdural hematoma (ASDH) into a CSDH., Materials and Methods: All patients with unilateral CSDH, requiring burr hole trephination between 2018 and 2023 were included. The population was distributed into an acute-to-chronic group (group A, n = 41) and into a conventional group (group B, n = 282). Clinical and radiographic parameters were analyzed. In analysis A, changes of parameters after trauma within group A are compared. In analysis B, parameters between the two groups before surgery were correlated., Results: In group A, volume and midline shift increased significantly during the progression from acute-to-chronic (p < 0.001, resp.). Clinical performance (modified Rankin scale, Glasgow Coma Scale) dropped significantly (p = 0.035, p < 0.001, resp.). Median time between trauma with ASDH and surgery for CSDH was 12 days. Patients treated up to the 12th day presented with larger volume of ASDH (p = 0.012). Before burr hole trephination, patients in group A presented with disturbance of consciousness (DOC) more often (p = 0.002), however less commonly with a new motor deficit (p = 0.014). Despite similar midline shift between the groups (p = 0.8), the maximal hematoma width was greater in group B (p < 0.001)., Conclusion: If ASDH transforms to CSDH, treatment may become mandatory early due to increase in volume and midline shift. Close monitoring of these patients is crucial since DOC and rapid deterioration is common in this type of SDH., (© 2024. The Author(s).)

Metal-organic frameworks (MOFs) stand as pivotal porous materials with exceptional surface areas, adaptability, and versatility. Positron Annihilation Lifetime Spectroscopy (PALS) is an indispensable tool for characterizing MOF porosity, especially micro- and mesopores in both open and closed phases. Notably, PALS offers porosity insights independent of probe molecules, which is vital for detailed characterization without structural transformations. This study explores how metal ion states in MOFs affect PALS results. We find significant differences in measured porosity due to paramagnetic or oxidized metal ions compared to simulated values. By analyzing CPO-27(M) (M = Mg, Co, Ni), with identical pore dimensions, we observe distinct PALS data alterations based on metal ions. Paramagnetic Co and Ni ions hinder and quench positronium (Ps) formation, resulting in smaller measured pore volumes and sizes. Mg only quenches Ps, leading to underestimated pore sizes without volume distortion. This underscores the metal ions' pivotal role in PALS outcomes, urging caution in interpreting MOF porosity.

The effect of annealing temperature on the microstructure, defects and optical properties of ZnO thin films are investigated using sol-gel based spin coating method for a range of annealing temperatures from 200 ∘ C to 500 ∘ C. The correlation among the microstructure, defects, impurity content and the optical band gap of films of thickness about 10-12 nm is elucidated. The particle size increases and the optical band gap reduces with the annealing temperature. At 200 ∘ C, amorphous films were formed with particle size less than 10 nm with an optical band gap of about 3.41 eV. As the temperature increases the grain size increases and the defect, impurity content as well as the optical band gap reduces. This could be due to the reduction in the lattice strain. For an average grain size of about 35 nm and above, the band gap asymptotically approaches the theoretical value of ZnO (3.37 eV). The photoluminescence (PL) spectra show a systematic red-shift in the excitonic levels corresponding to the variation in the optical band-gap. The defect emission from Zn-vacancies is observed in the PL spectra and are further supported by the positron annihilation measurements., (© 2023 IOP Publishing Ltd.)

Atmospheric water harvesting with metal-organic frameworks (MOFs) is a new technology providing a clean, long-term water supply in arid areas. In-situ positron annihilation lifetime spectroscopy (PALS) is proposed as a valid methodology for the mechanistic understanding of water sorption in MOFs and the selection of prospective candidates for desired applications. DUT-67-Zr and DUT-67-Hf frameworks are used as model systems for method validation because of their hierarchical pore structure, high adsorption capacity, and chemical stability. Both frameworks are characterized using complementary techniques, such as nitrogen (77 K) and water vapor (298 K) physisorption, SEM, and PXRD. DUT-67-Zr and DUT-67-Hf are investigated by PALS upon exposure to humidity for the first time, demonstrating the stepwise pore filling mechanism by water molecules for both MOFs. In addition to exploring the potential of PALS as a tool for probing MOFs during in situ water loading, this work offers perspectives on the design and use of MOFs for water harvesting.

Flash lamp annealing (FLA) with millisecond pulse durations is reported as a novel curing method for pore precursor's degradation in thin films. A case study on the curing of dielectric thin films is presented. FLA-cured films are being investigated by means of positron annihilation spectroscopy (PAS) and Fourier-transform infrared (FTIR) spectroscopy in order to quantify the nm-scale porosity and post-treatment chemistry, respectively. Results from positron annihilation reveal the onset of the formation of porous voids inside the samples at 6 ms flash treatment time. Moreover, parameter's adjustment (flash duration and energy density) allows for identifying the optimum conditions of effective curing. Within such a systematic investigation, positron results indicate that FLA is able to decompose the porogen (pore precursors) and to generate interconnected (open porosity) or isolated pore networks with self-sealed pores in a controllable way. Furthermore, FTIR results demonstrate the structural evolution after FLA, that help for setting the optimal annealing conditions whereby only a residual amount of porogen remains and at the same time a well-densified matrix, and a hydrophobic porous structures are created. Raman spectroscopy suggests that the curing-induced self-sealing layer developed at the film surface is a graphene oxide-like layer, which could serve as the outside sealing of the pore network from intrusions., (© 2023. The Author(s).)

Magneto-ionics refers to the control of magnetic properties of materials through voltage-driven ion motion. To generate effective electric fields, either solid or liquid electrolytes are utilized, which also serve as ion reservoirs. Thin solid electrolytes have difficulties in (i) withstanding high electric fields without electric pinholes and (ii) maintaining stable ion transport during long-term actuation. In turn, the use of liquid electrolytes can result in poor cyclability, thus limiting their applicability. Here we propose a nanoscale-engineered magneto-ionic architecture (comprising a thin solid electrolyte in contact with a liquid electrolyte) that drastically enhances cyclability while preserving sufficiently high electric fields to trigger ion motion. Specifically, we show that the insertion of a highly nanostructured (amorphous-like) Ta layer (with suitable thickness and electric resistivity) between a magneto-ionic target material ( i . e ., Co 3 O 4 ) and the liquid electrolyte increases magneto-ionic cyclability from <30 cycles (when no Ta is inserted) to more than 800 cycles. Transmission electron microscopy together with variable energy positron annihilation spectroscopy reveals the crucial role of the generated TaO x interlayer as a solid electrolyte ( i.e ., ionic conductor) that improves magneto-ionic endurance by proper tuning of the types of voltage-driven structural defects. The Ta layer is very effective in trapping oxygen and hindering O 2- ions from moving into the liquid electrolyte, thus keeping O 2- motion mainly restricted between Co 3 O 4 and Ta when voltage of alternating polarity is applied. We demonstrate that this approach provides a suitable strategy to boost magneto-ionics by combining the benefits of solid and liquid electrolytes in a synergetic manner.

A set of GaN layers prepared by metalorganic vapor phase epitaxy under different technological conditions (growth temperature carrier gas type and Ga precursor) were investigated using variable energy positron annihilation spectroscopy (VEPAS) to find a link between technological conditions, GaN layer properties, and the concentration of gallium vacancies (V Ga ). Different correlations between technological parameters and V Ga concentration were observed for layers grown from triethyl gallium (TEGa) and trimethyl gallium (TMGa) precursors. In case of TEGa, the formation of V Ga was significantly influenced by the type of reactor atmosphere (N 2 or H 2 ), while no similar behaviour was observed for growth from TMGa. V Ga formation was suppressed with increasing temperature for growth from TEGa. On the contrary, enhancement of V Ga concentration was observed for growth from TMGa, with cluster formation for the highest temperature of 1100 °C. From the correlation of photoluminescence results with V Ga concentration determined by VEPAS, it can be concluded that yellow band luminescence in GaN is likely not connected with V Ga ; additionally, increased V Ga concentration enhances excitonic luminescence. The probable explanation is that V Ga prevent the formation of some other highly efficient nonradiative defects. Possible types of such defects are suggested.

Cuprous oxide (Cu 2 O) is a promising p-type semiconductor material for many applications. So far, the lowest resistivity values are obtained for films deposited by physical methods and/or at high temperatures (~1000 °C), limiting their mass integration. Here, Cu 2 O thin films with ultra-low resistivity values of 0.4 Ω.cm were deposited at only 260 °C by atmospheric pressure spatial atomic layer deposition, a scalable chemical approach. The carrier concentration (7.10 14 -2.10 18  cm -3 ), mobility (1-86 cm 2 /V.s), and optical bandgap (2.2-2.48 eV) are easily tuned by adjusting the fraction of oxygen used during deposition. The properties of the films are correlated to the defect landscape, as revealed by a combination of techniques (positron annihilation spectroscopy (PAS), Raman spectroscopy and photoluminescence). Our results reveal the existence of large complex defects and the decrease of the overall defect concentration in the films with increasing oxygen fraction used during deposition., (© 2022. The Author(s).)

Extending the potential window toward the 3 V plateau below the typically used range could boost the effective capacity of LiMn 2 O 4 spinel cathodes. This usually leads to an "overdischarge" of the cathode, which can cause severe material damage due to manganese dissolution into the electrolyte and a critical volume expansion (induced by Jahn-Teller distortions). As those factors determine the stability and cycling lifetime for all-solid-state batteries, the operational window of LiMn 2 O 4 is usually limited to 3.5-4.5 V versus Li/Li + in common battery cells. However, it has been reported that nano-shaped particles and thin films can potentially mitigate these detrimental effects. We demonstrate here that porous LiMn 2 O 4 thin-film cathodes with a certain level of off-stoichiometry show improved cycling stability for the extended cycling range of 2.0-4.5 V versus Li/Li + . We argue through operando spectroscopic ellipsometry that the origin of this stability lies in the surprisingly small volume change in the layer during lithiation.

Thin films of the magnetoelectric insulator α-Cr 2 O 3 are technologically relevant for energy-efficient magnetic memory devices controlled by electric fields. In contrast to single crystals, the quality of thin Cr 2 O 3 films is usually compromised by the presence of point defects and their agglomerations at grain boundaries, putting into question their application potential. Here, the impact of the defect nanostructure, including sparse small-volume defects and their complexes is studied on the magnetic properties of Cr 2 O 3 thin films. By tuning the deposition temperature, the type, size, and relative concentration of defects is tailored, which is analyzed using the positron annihilation spectroscopy complemented with electron microscopy studies. The structural characterization is correlated with magnetotransport measurements and nitrogen-vacancy microscopy of antiferromagnetic domain patterns. Defects pin antiferromagnetic domain walls and stabilize complex multidomain states with a domain size in the sub-micrometer range. Despite their influence on the domain configuration, neither small open-volume defects nor grain boundaries in Cr 2 O 3 thin films affect the Néel temperature in a broad range of deposition parameters. The results pave the way toward the realization of spin-orbitronic devices where magnetic domain patterns can be tailored based on defect nanostructures without affecting their operation temperature., (© 2022 The Authors. Small published by Wiley-VCH GmbH.)

Magneto-ionics allows for tunable control of magnetism by voltage-driven transport of ions, traditionally oxygen or lithium and, more recently, hydrogen, fluorine, or nitrogen. Here, magneto-ionic effects in single-layer iron nitride films are demonstrated, and their performance is evaluated at room temperature and compared with previously studied cobalt nitrides. Iron nitrides require increased activation energy and, under high bias, exhibit more modest rates of magneto-ionic motion than cobalt nitrides. Ab initio calculations reveal that, based on the atomic bonding strength, the critical field required to induce nitrogen-ion motion is higher in iron nitrides (≈6.6 V nm -1 ) than in cobalt nitrides (≈5.3 V nm -1 ). Nonetheless, under large bias (i.e., well above the magneto-ionic onset and, thus, when magneto-ionics is fully activated), iron nitride films exhibit enhanced coercivity and larger generated saturation magnetization, surpassing many of the features of cobalt nitrides. The microstructural effects responsible for these enhanced magneto-ionic effects are discussed. These results open up the potential integration of magneto-ionics in existing nitride semiconductor materials in view of advanced memory system architectures.

The excess energy emitted during the positronium (Ps) formation in condensed matter may be released as light. Spectroscopic analysis of this light can be a new method of studying the electronic properties of materials. We report the first experimental attempt, according to our knowledge, to verify the existence of this emission process. As a result, the possibility of the emission of photons during Ps formation is within the experimental uncertainty in two different solids: an n-alkane and porous silica. However, it seems that the Ps formation on the alkane surface is not accompanied by the emission of photons with energy in the detection range of 1.6-3.8 eV. Various processes that can influence the energy of the photon emitted during the Ps formation are discussed to elucidate this issue. To aid future experiments, equations were developed to estimate the expected ratio of light emission events to annihilation events with the presence or absence of a photon during the Ps formation.

The nondestructive investigation of single vacancies and vacancy clusters in ion-irradiated samples requires a depth-resolved probe with atomic sensitivity to defects. The recent development of short-pulsed positron beams provides such a probe. Here, we combine depth-resolved Doppler broadening and positron annihilation lifetime spectroscopies to identify vacancy clusters in ion-irradiated Fe and measure their density as a function of depth. Despite large concentrations of dislocations and voids in the pristine samples, positron annihilation measurements uncovered the structure of vacancy clusters and the change in their size and density with irradiation dose. When combined with transmission electron microscopy measurements, the study demonstrates an association between the increase in the density of small vacancy clusters with irradiation and a remarkable reduction in the size of large voids. This, previously unknown, mechanism for the interaction of cascade damage with voids in ion-irradiated materials is a consequence of the high porosity of the initial microstructure., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

A recently discovered modified low-temperature baking leads to reduced surface losses and an increase of the accelerating gradient of superconducting TESLA shape cavities. We will show that the dynamics of vacancy-hydrogen complexes at low-temperature baking lead to a suppression of lossy nanohydrides at 2 K and thus a significant enhancement of accelerator performance. Utilizing Doppler broadening Positron Annihilation Spectroscopy, Positron Annihilation Lifetime Spectroscopy and instrumented nanoindentation, samples made from European XFEL niobium sheets were investigated. We studied the evolution of vacancies in bulk samples and in the sub-surface region and their interaction with hydrogen at different temperature levels during in-situ and ex-situ annealing.

Of 1270 consecutive patients with liver diseases of various types we have examined the blood serum on autoimmune antibodies against cell nuclei (ANA), smooth muscle (SMA) and vascular endothelium. 98 patients (7.7%) had antibodies of one of the above. These patients were matched with patients with the same liver diagnosis without antibodies following the matched pair technique. 3-5 years later both were examined by the family doctor. It remained a collection of 58 pairs. The examined criteria were compared pair by pair. We conclude the existence of autoimmune antibodies from type ANA, SMA or vascular endothelium is without prognostic prediction. The outcome of chronic active hepatitis was in majority benign, but the outcome of alcohol-toxic hepatitis was bad, because the people were unable to stop the alcoholism.