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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.

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.

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).)

Methylammonium lead tribromide (MAPbBr 3 ) stands out as the most easily grown wide-band-gap metal halide perovskite. It is a promising semiconductor for room-temperature gamma-ray (γ-ray) spectroscopic detectors, but no operational devices are realized. This can be largely attributed to a lack of understanding of point defects and their influence on detector performance. Here, through a combination of crystal growth design and defect characterization, including positron annihilation and impedance spectroscopy, the presence of specific point defects are identified and correlated to detector performance. Methylammonium (MA) vacancies, MA interstitials, and Pb vacancies are identified as the dominant charge-trapping defects in MAPbBr 3 crystals, while Br vacancies caused doping. The addition of excess MABr reduces the MA and Br defects and so enables the detection of energy-resolved γ-ray spectra using a MAPbBr 3 single-crystal device. Interestingly, the addition of formamidinium (FA) cations, which converted to methylformamidinium (MFA) cations by reaction with MA + during crystal growth further reduced MA defects. This enabled an energy resolution of 3.9% for the 662 keV 137 Cs line using a low bias of 100 V. The work provides direction toward enabling further improvements in wide-bandgap perovskite-based device performance by reducing detrimental defects., (© 2024 Wiley‐VCH GmbH.)

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.)

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.)

Direct-band-gap Germanium-Tin alloys (Ge 1- x Sn x ) with high carrier mobilities are promising materials for nano- and optoelectronics. The concentration of open volume defects in the alloy, such as Sn and Ge vacancies, influences the final device performance. In this article, we present an evaluation of the point defects in molecular-beam-epitaxy grown Ge 1- x Sn x films treated by post-growth nanosecond-range pulsed laser melting (PLM). Doppler broadening - variable energy positron annihilation spectroscopy and variable energy positron annihilation lifetime spectroscopy are used to investigate the defect nanostructure in the Ge 1- x Sn x films exposed to increasing laser energy density. The experimental results, supported with ATomic SUPerposition calculations, evidence that after PLM, the average size of the open volume defects increases, which represents a raise in concentration of vacancy agglomerations, but the overall defect density is reduced as a function of the PLM fluence. At the same time, the positron annihilation spectroscopy analysis provides information about dislocations and Ge vacancies decorated by Sn atoms. Moreover, it is shown that the PLM reduces the strain in the layer, while dislocations are responsible for trapping of Sn and formation of small Sn-rich-clusters., (Creative Commons Attribution license.)

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.

Antiferromagnetic insulators are a prospective materials 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. Here, we discover a new member in the family of flexoeffects in thin films of Cr 2 O 3 . We demonstrate that a gradient of mechanical strain can impact the magnetic phase transition resulting in the distribution of the Néel temperature along the thickness of a 50-nm-thick film. The inhomogeneous reduction of the antiferromagnetic order parameter induces a flexomagnetic coefficient of about 15 μ B  nm -2 . The antiferromagnetic ordering in the inhomogeneously strained films can persist up to 100 °C, rendering Cr 2 O 3 relevant for industrial electronics applications. Strain gradient in Cr 2 O 3 thin films enables fundamental research on magnetomechanics and thermodynamics of antiferromagnetic solitons, spin waves and artificial spin ice systems in magnetic materials with continuously graded parameters., (© 2022. The Author(s).)

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.

Ion intercalation of perovskite oxides in liquid electrolytes is a very promising method for controlling their functional properties while storing charge, which opens up its potential application in different energy and information technologies. Although the role of defect chemistry in oxygen intercalation in a gaseous environment is well established, the mechanism of ion intercalation in liquid electrolytes at room temperature is poorly understood. In this study, the defect chemistry during ion intercalation of La 0.5 Sr 0.5 FeO 3-δ thin films in alkaline electrolytes is studied. Oxygen and proton intercalation into the La 1- x Sr x FeO 3-δ perovskite structure is observed at moderate electrochemical potentials (0.5 to -0.4 V), giving rise to a change in the oxidation state of Fe (as a charge compensation mechanism). The variation of the concentration of holes as a function of the intercalation potential is characterized by in situ ellipsometry, and the concentration of electron holes is indirectly quantified for different electrochemical potentials. Finally, a dilute defect chemistry model that describes the variation of defect species during ionic intercalation is developed.

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.)

Background:  The objective was to compare computed tomography (CT)-guided thoracic sympathicolysis (CTSy) and video-assisted thoracoscopic sympathectomy (VATS) with regard to their feasibility, the occurrence of minor and major complications, and the clinical outcome., Materials and Methods:  In this study, 88 patients treated by CTSy and 86 patients treated by VATS were retrospectively included. CTSy was performed after establishing the entry plane below the level of the intervertebral space T2/3 via a dorsolateral approach using a 22-G coaxial needle. On average of 5 mL of a sympathicolytic mixture was instilled. VATS was performed under intubation anesthesia. After insertion of the instruments via a minithoracotomy, the parietal pleura was dissected and the sympathetic trunk severed below T2. The interventions were performed unilaterally, the contralateral side being treated after approximately 6 weeks. All patients evaluated their sense of discomfort before treatment as well as 2 days, 6, and 12 months after, on the basis of a Dermatology Quality of Life Index and additionally the side effects that occurred., Results:  Both treatments led to a marked reduction of symptoms, whereby mild recurrent sweating occurred over the further course, significantly higher in the CTSy patient group. Short-term miosis and ptosis were rarely found in both groups. As the most common side effect, transient compensatory sweating was reported by 16/88 patients after CTSy and 10/86 patients after VATS. Pneumothoraces developed postoperatively in 7/86 cases. Temporary pain after thoracotomy was experienced by 12/86 patients., Conclusion:  For patients with palmar hyperhidrosis, CTSy and VATS represented a minimally invasive treatment option that provided a high and largely equivalent level of benefit., Competing Interests: None declared., (Thieme. All rights reserved.)

The effect of in situ annealing is investigated in Gd 0.1 Ca 0.9 MnO 3 (GCMO) thin films in oxygen and vacuum atmospheres. We show that the reduction of oxygen content in GCMO lattice by vacuum annealing induced more oxygen complex vacancies in both subsurface and interface regions and larger grain domains when compared with the pristine one. Consequently, the double exchange interaction is suppressed and the metallic-ferromagnetic state below Curie temperature turned into spin-glass insulating state. In contrast, the magnetic and resistivity measurements show that the oxygen treatment increases ferromagnetic phase volume, resulting in greater magnetization ( M S ) and improved magnetoresistivity properties below Curie temperature by improving the double exchange interaction. The threshold field to observe the training effect is decreased in oxygen treated film. In addition, the positron annihilation spectroscopy analysis exhibits fewer open volume defects in the subsurface region for oxygen treated film when compared with the pristine sample. These results unambiguously demonstrate that the oxygen treated film with significant spin memory and greater magnetoresistance can be a potential candidate for the future memristor applications., (© 2022 IOP Publishing Ltd.)

The interplay of structure, composition and electrical conductivity was investigated for Fe-doped SrTiO 3 thin films prepared by pulsed laser deposition. Structural information was obtained by reciprocal space mapping while solution-based inductively-coupled plasma optical emission spectroscopy and positron annihilation lifetime spectroscopy were employed to reveal the cation composition and the predominant point defects of the thin films, respectively. A severe cation non-stoichiometry with Sr vacancies was found in films deposited from stoichiometric targets. The across plane electrical conductivity of such epitaxial films was studied in the temperature range of 250-720 °C by impedance spectroscopy. This revealed a pseudo-intrinsic electronic conductivity despite the substantial Fe acceptor doping, i.e. conductivities being several orders of magnitude lower than expected. Variation of PLD deposition parameters causes some changes of the cation stoichiometry, but the films still have conductivities much lower than expected. Targets with significant Sr excess (in the range of several percent) were employed to improve the cation stoichiometry in the films. The use of 7% Sr-excess targets resulted in near-stoichiometric films with conductivities close to the stoichiometric bulk counterpart. The measurements show that a fine-tuning of the film stoichiometry is required in order to obtain acceptor doped SrTiO 3 thin films with bulk-like properties. One can conclude that, although reciprocal space maps give a first hint whether or not cation non-stoichiometry is present, conductivity measurements are more appropriate for assessing SrTiO 3 film quality in terms of cation stoichiometry., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

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.

Alumina thin films are synthesized by combustion synthesis of mixtures of aluminium nitrate (ALN) and methylcarbazate (MCZ). The interdependence of the ratio of oxidizer and reducing agent on composition, microstructure and electronic properties of the resulting oxide layers is investigated. The dielectric and insulating behaviour is improved by addition of different amounts of MCZ (MCZ : ALN = 0.67 or 2.5). In this way films (thickness ∼140 nm) with a dielectric constant κ of 9.7 and a dielectric loss tan δ below 0.015 can be achieved. Medium concentrations of MCZ (MCZ : ALN = 1.0 or 1.5) lead to films with lower performance, though. Our studies indicate two opposing effects of the organic additive. Removal of organic residues during film formation as combustion gases is potentially detrimental. Larger amounts of MCZ, however, cause condensation reactions in the precusor mixture, which improve the microstructure. The porosity of the films can be sucessfully analyzed by positron annihilation liftetime studies. In this way the impact of the organic ligand sphere on the resulting microstructure can be quantified. Samples prepared from ALN alone exhibit mesopores and also larger micropores. In contrast, the formation of mesopores can be inhibited by addition of MCZ.

The effect of in situ oxygen and vacuum annealings on the low bandwidth manganite Gd 1- x Ca x MnO 3 (GCMO) thin film with x = 0.4 was investigated. Based on the magnetic measurements, the AFM-FM coupling is suppressed by the vacuum annealing treatment via destroying the double exchange interaction and increasing the unit cell volume by converting the Mn 4+ to the Mn 3+ . Consequently, resistance increases significantly compared to pristine film. The results are explained by a model obtained from the positron annihilation studies, where the vacuum annealing increased the annihilation lifetime in A and B sites due to the formation of vacancy complexes V A,B - V O , which was not the case in the pristine sample. The positron annihilation analysis indicated that most of the open volume defects have been detected in the interface region rather than on the subsurface layer and this result is confirmed by detailed x-ray reflection analysis. On the other hand, the effect of oxygen annealing on the unit cell volume and magnetization was insignificant. This is in agreement with positron annihilation results which demonstrated that the introduction of oxygen does not change the number of cation vacancies significantly. This work demonstrates that the modification of oxygen vacancies and vacancy complexes can tune magnetic and electronic structure of the epitaxial thin films to provide new functionalities in future applications., (© 2021 IOP Publishing Ltd.)

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.

Invited for the cover of this issue is Jörg J. Schneider and co-workers at Technical University Darmstadt, Helmholtz-Zentrum Dresden-Rossendorf and KIT Karlsruhe. The image depicts the application of high energy generated electron/positron couples which are able to detect defects sites in semiconducting zinc oxide thin films. Read the full text of the article at 10.1002/chem.202004270., (© 2021 Wiley-VCH GmbH.)

Machine learning is changing how we design and interpret experiments in materials science. In this work, we show how unsupervised learning, combined with ab initio random structure searching, improves our understanding of structural metastability in multicomponent alloys. We focus on the case of Al-O-N alloys where the formation of aluminum vacancies in wurtzite AlN upon the incorporation of substitutional oxygen can be seen as a general mechanism of solids where crystal symmetry is reduced to stabilize defects. The ideal AlN wurtzite crystal structure occupation cannot be matched due to the presence of an aliovalent hetero-element into the structure. The traditional interpretation of the c -lattice shrinkage in sputter-deposited Al-O-N films from X-ray diffraction (XRD) experiments suggests the existence of a solubility limit at 8 at % oxygen content. Here, we show that such naive interpretation is misleading. We support XRD data with accurate ab initio modeling and dimensionality reduction on advanced structural descriptors to map structure-property relationships. No signs of a possible solubility limit are found. Instead, the presence of a wide range of non-equilibrium oxygen-rich defective structures emerging at increasing oxygen contents suggests that the formation of grain boundaries is the most plausible mechanism responsible for the lattice shrinkage measured in Al-O-N sputtered films. We further confirm our hypothesis using positron annihilation lifetime spectroscopy.

Magneto-ionics, understood as voltage-driven ion transport in magnetic materials, has largely relied on controlled migration of oxygen ions. Here, we demonstrate room-temperature voltage-driven nitrogen transport (i.e., nitrogen magneto-ionics) by electrolyte-gating of a CoN film. Nitrogen magneto-ionics in CoN is compared to oxygen magneto-ionics in Co 3 O 4 . Both materials are nanocrystalline (face-centered cubic structure) and show reversible voltage-driven ON-OFF ferromagnetism. In contrast to oxygen, nitrogen transport occurs uniformly creating a plane-wave-like migration front, without assistance of diffusion channels. Remarkably, nitrogen magneto-ionics requires lower threshold voltages and exhibits enhanced rates and cyclability. This is due to the lower activation energy for ion diffusion and the lower electronegativity of nitrogen compared to oxygen. These results may open new avenues in applications such as brain-inspired computing or iontronics in general.

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.

Advancement of optoelectronic and high-power devices is tied to the development of wide band gap materials with excellent transport properties. However, bipolar doping (n-type and p-type doping) and realizing high carrier density while maintaining good mobility have been big challenges in wide band gap materials. Here P-type and n-type conductivity was introduced in β-Ga 2 O 3 , an ultra-wide band gap oxide, by controlling hydrogen incorporation in the lattice without further doping. Hydrogen induced a 9-order of magnitude increase of n-type conductivity with donor ionization energy of 20 meV and resistivity of 10 -4 Ω.cm. The conductivity was switched to p-type with acceptor ionization energy of 42 meV by altering hydrogen incorporation in the lattice. Density functional theory calculations were used to examine hydrogen location in the Ga 2 O 3 lattice and identified a new donor type as the source of this remarkable n-type conductivity. Positron annihilation spectroscopy measurements confirm this finding and the interpretation of the experimental results. This work illustrates a new approach that allows a tunable and reversible way of modifying the conductivity of semiconductors and it is expected to have profound implications on semiconductor field. At the same time, it demonstrates for the first time p-type and remarkable n-type conductivity in Ga 2 O 3 which should usher in the development of Ga 2 O 3 devices and advance optoelectronics and high-power devices.

Atomic scale defects generated using focused ion as well as laser beams can activate ferromagnetism in initially non-ferromagnetic B2 ordered alloy thin film templates. Such defects can be induced locally, confining the ferromagnetic objects within well-defined nanoscale regions. The characterization of these atomic scale defects is challenging, and the mechanism for the emergence of ferromagnetism due to sensitive lattice disordering is unclear. Here we directly probe a variety of microscopic defects in systematically disordered B2 FeRh thin films that are initially antiferromagnetic and undergo a thermally-driven isostructural phase transition to a volatile ferromagnetic state. We show that the presence of static disorder i.e. , the slight deviations of atoms from their equilibrium sites is sufficient to induce a non-volatile ferromagnetic state at room temperature. A static mean square relative displacement of 9 × 10 -4 Å -2 is associated with the occurrence of non-volatile ferromagnetism and replicates a snapshot of the dynamic disorder observed in the thermally-driven ferromagnetic state. The equivalence of static and dynamic disorder with respect to the ferromagnetic behavior can provide insights into the emergence of ferromagnetic coupling as well as achieving tunable magnetic properties through defect manipulations in alloys., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Striving to improve the critical current density Jc of superconducting YBa 2 Cu 3 O 6+x (YBCO) thin films via enhanced vortex pinning, the interplay between film growth mechanisms and the formation of nanosized defects, both natural and artificial, is systematically studied in undoped and BaZrO 3 (BZO)-doped YBCO thin films. The films were grown via pulsed laser deposition (PLD), varying the crystal grain size of the targets in addition to the dopant content. The microstructure of the PLD target has been observed to have a great impact on that of the deposited thin films, including the formation of vortex pinning centers, which has direct implications on the superconducting performance, especially on the isotropy of flux pinning properties. Based on experimentally measured angular dependencies of Jc, coupled with a molecular dynamics (MD) simulation of flux pinning in the YBCO films, we present a quantitative model of how the splay and fragmentation of BZO nanorods artifically introduced into the YBCO film matrix explain the majority of the observed critical current anisotropy.

Modifications of magnetic and magneto-optical properties of Pt/Co(d Co )/Pt upon Ar + irradiation (with energy 1.2, 5 and 30 keV) and fluence, F at the range from 2 · 10 13 -2 · 10 16 Ar + cm -2 ) were studied. Two 'branches' of increased perpendicular magnetic anisotropy (PMA) and enhanced magneto-optical response are found on 2D (d Co , F) diagrams. The difference in F between 'branches' is driven by ion energy. Structural features correlated with magnetic properties have been analysed thoroughly by x-ray diffraction, Rutherford backscattering spectrometry and positron annihilation spectroscopy. Experimental results are in agreement with TRIDYN numerical calculations of irradiation-induced layers intermixing. Our work discusses particularly structural factors related to crystal lattice defects and strain, created and modified by irradiation, co-responsible for the increase in the PMA.

Electric-field-controlled magnetism can boost energy efficiency in widespread applications. However, technologically, this effect is facing important challenges: mechanical failure in strain-mediated piezoelectric/magnetostrictive devices, dearth of room-temperature multiferroics, or stringent thickness limitations in electrically charged metallic films. Voltage-driven ionic motion (magneto-ionics) circumvents most of these drawbacks while exhibiting interesting magnetoelectric phenomena. Nevertheless, magneto-ionics typically requires heat treatments and multicomponent heterostructures. Here we report on the electrolyte-gated and defect-mediated O and Co transport in a Co 3 O 4 single layer which allows for room-temperature voltage-controlled ON-OFF ferromagnetism (magnetic switch) via internal reduction/oxidation processes. Negative voltages partially reduce Co 3 O 4 to Co (ferromagnetism: ON), resulting in graded films including Co- and O-rich areas. Positive bias oxidizes Co back to Co 3 O 4 (paramagnetism: OFF). This electric-field-induced atomic-scale reconfiguration process is compositionally, structurally, and magnetically reversible and self-sustained, since no oxygen source other than the Co 3 O 4 itself is required. This process could lead to electric-field-controlled device concepts for spintronics.

Neuroendocrine tumours (NET) are clinically challenging due to their unpredictable behaviour. Nomograms, grading and staging systems are predictive tools with multiple roles in clinical practice, including patient prognostication. The NET nomogram allocates scores for various clinicopathological parameters, calculating percentage estimates for 5- and 10-year disease-specific survival of patients with small bowel (SB) NET. We evaluated the clinical utility of three prognostic systems in 70 SB NET patients: the NET nomogram, the World Health Organisation (WHO)/European Neuroendocrine Tumour Society (ENETS) grading system and the American Joint Commission on Cancer (AJCC)/Union Internationale Contre le Cancer (UICC) TNM staging method. Using Kaplan-Meier methodology, neither the WHO/ENETS grade ( P  = 0.6) nor the AJCC/UICC stage ( P  = 0.276) systems demonstrated significant differences in patient survival in the cohort. The NET nomogram was well calibrated to our data set, displaying favourable prediction accuracy. Harrel's C-index for the nomogram (a measure of predictive power) was 0.65, suggesting good prediction ability. On Kaplan-Meier analyses, there were significant differences in patient survival when stratified into nomogram score-based risk groups: low-, medium- and high-risk tumours were associated with median estimated survivals of 156, 129 and 112 months, respectively ( P  = 0.031). Our data suggest that a multivariable analysis-based NET nomogram may be clinically useful for patient survival prediction. This study identifies the limitations of the NET nomogram and the imperfections of other currently used single or binary parameter methodologies for assessing neuroendocrine disease prognosis. The future addition of other variables to the NET nomogram will likely amplify the accuracy of this personalised tool., (© 2017 The authors.)

Magnetic random access memory schemes employing magnetoelectric coupling to write binary information promise outstanding energy efficiency. We propose and demonstrate a purely antiferromagnetic magnetoelectric random access memory (AF-MERAM) that offers a remarkable 50-fold reduction of the writing threshold compared with ferromagnet-based counterparts, is robust against magnetic disturbances and exhibits no ferromagnetic hysteresis losses. Using the magnetoelectric antiferromagnet Cr 2 O 3 , we demonstrate reliable isothermal switching via gate voltage pulses and all-electric readout at room temperature. As no ferromagnetic component is present in the system, the writing magnetic field does not need to be pulsed for readout, allowing permanent magnets to be used. Based on our prototypes, we construct a comprehensive model of the magnetoelectric selection mechanisms in thin films of magnetoelectric antiferromagnets, revealing misfit induced ferrimagnetism as an important factor. Beyond memory applications, the AF-MERAM concept introduces a general all-electric interface for antiferromagnets and should find wide applicability in antiferromagnetic spintronics.

The luminescence and scintillation properties of ZnO single crystals were studied by photoluminescence and X-ray-induced luminescence (XRIL) techniques. XRIL allowed a direct comparison to be made between the near-band emission (NBE) and trap emissions providing insight into the carrier recombination efficiency in the ZnO crystals. It also provided bulk luminescence measurements that were not affected by surface states. The origin of a green emission, the dominant trap emission in ZnO, was then investigated by gamma-induced positron spectroscopy (GIPS) - a unique defect spectroscopy method that enables positron lifetime measurements to be made for a sample without contributions from positron annihilation in the source materials. The measurements showed a single positron decay curve with a 175 ps lifetime component that was attributed to Zn vacancies passivated by hydrogen. Both oxygen vacancies and hydrogen-decorated Zn vacancies were suggested to contribute to the green emission. By combining scintillation measurements with XRIL, the fast scintillation in ZnO crystals was found to be strongly correlated with the ratio between the defect luminescence and NBE. This study reports the first application of GIPS to semiconductors, and it reveals the great benefits of the XRIL technique for the study of emission and scintillation properties of materials.

Small bowel neuroendocrine tumours are the commonest malignancy arising in the small intestine and have substantially increased in incidence in recent decades. Patients with small bowel neuroendocrine tumours commonly develop lymph node and/or distant metastases. Here, we examine the role of staging in 84 surgically treated patients with small bowel neuroendocrine tumours, comparing diagnostic information yielded from morphological, functional and endoscopic modalities. Furthermore, we correlate pre-operative staging with intra-operative findings in a sub-cohort of 20 patients. The vast majority of patients had been histologically confirmed to have low-grade (Ki-67 <2%) disease; however, lymph node and distant metastases were observed in 74 (88.1%) and 51 (60.7%) of patients at presentation, respectively. Liver metastases were evident in 48 (57.1%) patients, with solely peritoneal and bone metastases observed in 2 (2.4%) and 1 (1.2%) patients, respectively. Forty patients (47.6%) received multimodal treatment. In our sub-cohort analysis, pre-operative imaging understaged disease in 14/20 (70%) when compared with intra-operative findings. In patients with multifocal primary tumours and miliary liver metastases, no imaging modality was able to detect entire disease spread. Overall, presently available imaging modalities heavily underestimate disease stage, with meticulous intra-operative abdominal examination being superior to any imaging technology. Multimodal treatment has an important role in prolonging survival.

One of the solutions enabling performance progress, which can overcome the downsizing limit in silicon technology, is the integration of different functional optoelectronic devices within a single chip. Silicon with its indirect band gap has poor optical properties, which is its main drawback. Therefore, a different material has to be used for the on-chip optical interconnections, e.g. a direct band gap III-V compound semiconductor material. In the paper we present the synthesis of single crystalline InP nanodots (NDs) on silicon using combined ion implantation and millisecond flash lamp annealing techniques. The optical and microstructural investigations reveal the growth of high-quality (100)-oriented InP nanocrystals. The current-voltage measurements confirm the formation of an n-p heterojunction between the InP NDs and silicon. The main advantage of our method is its integration with large-scale silicon technology, which allows applying it for Si-based optoelectronic devices.

InAs with an extremely high electron mobility (up to 40,000 cm(2)/V s) seems to be the most suitable candidate for better electronic devices performance. Here we present a synthesis of inverted crystalline InAs nanopyramids (NPs) in silicon using a combined hot ion implantation and millisecond flash lamp annealing techniques. Conventional selective etching was used to form the InAs/Si heterojunction. The current-voltage measurement confirms the heterojunction diode formation with the ideality factor of η = 4.6. Kelvin probe force microscopy measurements indicate a type-II band alignment of n-type InAs NPs on p-type silicon. The main advantage of our method is its integration with large-scale silicon technology, which also allows applying it for Si-based electronic devices.

Sub-100-nm magnetic dots embedded in a non-magnetic matrix are controllably generated by selective ion irradiation of paramagnetic Fe(60)Al(40) (atomic %) alloys, taking advantage of the disorder-induced magnetism in this material. The process is demonstrated by sequential focused ion beam irradiation and by in-parallel broad-beam ion irradiation through lithographed masks. Due to the low fluences used, this method results in practically no alteration of the surface roughness. The dots exhibit a range of magnetic properties depending on the size and shape of the structures, with the smallest dots (<100 nm) having square hysteresis loops with coercivities in excess of micro(0)H(C) = 50 mT. Importantly, the patterning can be fully removed by annealing. The combination of properties induced by the direct magnetic patterning is appealing for a wide range of applications, such as patterned media, magnetic separators, or sensors.