Variable-energy Positron Annihilation Research Articles

Defect characterizations of N-rich GaNAs ternary alloys

This paper presents a comprehensive analysis of defects in As-diluted GaN alloys. GaNAs crystal layers with an arsenic content of 1.8, 2.9, 4.1, and 5.5 % are grown on GaN buffer layers using the metalorganic vapour-phase epitaxy (MOVPE) method. Since these alloys have potential in electronics due to the modification of the electronic structure caused by As, it is extremely important to determine their quality. Complementary techniques for the characterization of the alloys are used. Densities of screw and edge dislocations are obtained using X-ray diffraction measurements performed, respectively, from the surface and edge of samples. In turn, a population of vacancies is determined by Doppler broadening variable energy positron annihilation spectroscopy (DB-VEPAS) and variable energy positron lifetime positron annihilation spectroscopy (VEPALS), which provide the distribution of vacancies as a function of depth. An increase in dislocation density is observed accompanied by a rise in the concentration of vacancy agglomerations and reduction in Ga-vacancy-hydrogen associates in the function of As-content.

Insights into the LiMn2O4 Cathode Stability in Aqueous Electrolytes.

LiMn2O4 (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 Mn3O4 and its dissolution with cycling, elucidating dynamic changes during operation. Additionally, TERS highlights the accumulation of SO4 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.

Hydrogen-Induced Microstructure Changes in Zr/Nb Nanoscale Multilayer Structures

Zr/Nb nanoscale multilayer coatings (NMCs) were studied after hydrogenation in a gaseous environment at 400 °C. The hydrogen distribution and content were determined by pressure and hydrogenation time. Increasing the pressure from 0.2 to 2 MPa resulted in different hydrogen distribution within the Zr/Nb NMCs, while the concentration remained constant at 0.0150 ± 0.0015 wt. %. The hydrogen concentration increased from 0.0165 ± 0.001 to 0.0370 ± 0.0015 wt. % when the hydrogenation time was extended from 1 to 7 h. The δ-ZrH hydride phase was formed in the Zr layers with Zr crystals reorienting towards the [100] direction. The Nb(110) diffraction reflex shifted towards smaller angles and the interplanar distance in the niobium layers increased, indicating significant lateral compressive stresses. Despite an increase in pressure, the nanohardness and Young’s modulus of the Zr/Nb NMCs remained stable. Increasing the hydrogen concentration to 0.0370 ± 0.0015 wt. % resulted in a 40% increase in nanohardness. At this concentration, the relative values of the Doppler broadening variable energy positron annihilation spectroscopy (S/S0) increased above the initial level, indicating an increase in excess free volume due to hydrogen-induced defects and changes. However, the predominant positron capture center remained intact. The Zr/Nb NMCs with hydrogen content ranging from 0.0150 ± 0.0015 to 0.0180 ± 0.001 wt. % exhibited a decrease in the free volume probed by positrons, as demonstrated by the Doppler broadening variable energy positron annihilation spectroscopy. This was evidenced by opposite changes in S and W (S↓W↑). The microstructural changes are attributed to defect annihilation during hydrogen accumulation near interfaces with the formation of hydrogen–vacancy clusters and hydrides.

Evolution of point defects in pulsed-laser-melted Ge1-x Sn x probed by positron annihilation lifetime spectroscopy

Direct-band-gap Germanium-Tin alloys (Ge1-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 Ge1-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 Ge1-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.

Hydrogen sensing capabilities of highly nanoporous black gold films

Hydrogen sensing is a crucial topic for many industrial and environmental applications regarding the green deal and the use of hydrogen as a next-generation energy source/energy-storage medium. Therefore, many different approaches are being used to find sensitive, reliable and inexpensive devices for hydrogen detection. One such approach is the use of chemiresistive nanostructured materials that provide a large surface area for hydrogen adsorption. In this paper, we present a detailed study of the hydrogen sensing capabilities of highly nanoporous black gold films that show fast response and recovery times (0.5 min) while operating at low temperatures (40 °C). To investigate the sensing properties of black gold, films with different levels of nanoporosity were prepared and tested to a hydrogen concentration in the range of 0.25–0.95 %. Film morphology was characterised by AFM, SEM and XPS. To correctly examine the nanopores and defects in prepared films, Variable Energy Positron Annihilation Spectroscopy (VEPAS) was used. We found that nanoporous black gold is suitable as an active layer of chemiresistor for hydrogen sensing and that its sensitivity is the function of the film nanoporosity. Possible mechanisms of hydrogen-gold interactions are discussed.

Characterization of defect microstructure in MgRE (RE=Ce, Nd) alloys after processing by high-pressure torsion using positron annihilation spectroscopy and a high resolution X-ray diffraction

Two MgRE (RE = Ce, Nd) alloys with ultrafine-grain (UFG) microstructures were prepared by high-pressure torsion (HPT) at room temperature. The in-depth distribution of defects was characterized by Doppler broadening –variable energy positron annihilation spectroscopy (DB-VEPAS). The characteristic S parameter increases in bulk after HPT processing relative to an as-received sample and shows a relative stability between ½ and 10 turns, which suggests a rise in the open volume defect density. However, a theoretical analysis of the S(E) depth profile reveals an increase in the positron diffusion length from ∼115 nm for the as-received state to ∼207 nm after 10 HPT turns. Almost all the open volume defect consisted of dislocations (positron lifetime of τ = 260 ps). The dislocation density deduced from high-resolution X-ray diffraction in the HPT disc radial direction was reasonably homogeneous (around 4–6 × 1014 m−2).

Regulating Oxygen Ion Transport at the Nanoscale to Enable Highly Cyclable Magneto-Ionic Control of Magnetism.

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., Co3O4) 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 TaOx 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 O2- ions from moving into the liquid electrolyte, thus keeping O2- motion mainly restricted between Co3O4 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.

Relation between Ga Vacancies, Photoluminescence, and Growth Conditions of MOVPE-Prepared GaN Layers.

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 (VGa). Different correlations between technological parameters and VGa concentration were observed for layers grown from triethyl gallium (TEGa) and trimethyl gallium (TMGa) precursors. In case of TEGa, the formation of VGa was significantly influenced by the type of reactor atmosphere (N2 or H2), while no similar behaviour was observed for growth from TMGa. VGa formation was suppressed with increasing temperature for growth from TEGa. On the contrary, enhancement of VGa concentration was observed for growth from TMGa, with cluster formation for the highest temperature of 1100 °C. From the correlation of photoluminescence results with VGa concentration determined by VEPAS, it can be concluded that yellow band luminescence in GaN is likely not connected with VGa; additionally, increased VGa concentration enhances excitonic luminescence. The probable explanation is that VGa prevent the formation of some other highly efficient nonradiative defects. Possible types of such defects are suggested.

Characterizing heavy ions-irradiated Zr/Nb: Structure and mechanical properties

In this work, the radiation responses of Zr/Nb nanostructured metallic multilayers (NMMs) are studied. The nanostructures with different layer thicknesses were deposited on Si (111) substrate by using magnetron sputtering and were subjected to heavy-ion irradiation at room temperature with different fluences. Nanoindentation, XRD, DFT, SIMS, and Variable Energy Positron Annihilation Spectroscopy (VEPAS) techniques were used to study the type and distribution of defects, and strain within the material as well as the changes in the hardness of the structures as a function of damage. Our results suggest that the strain and the irradiation hardening are layer thickness- and damage-dependent while they are independent of the type of irradiated ions. The magnitude of hardening decreases with decreasing individual layer thickness indicating that the number of interfaces has a direct effect on the radiation tolerance enhancement. For thin layers with a periodicity of 27 nm (Zr/Nb27), a transition from hardening to softening occurs at high fluence, and a saturation point is reached in thick layers with a periodicity of 96 nm (Zr/Nb96). The as-deposited thin multilayers presented a significantly higher atomic-scale disorder which increases with ion irradiation compared to the thick multilayers. VEPAS reveals the vacancy defects before and after irradiation that contribute to the presented strain. Based on the findings, thin nanostructured Zr/Nb multilayered structures possess excellent radiation resistance due to the high density of interfaces that act as sinks for radiation-induced point defects.

Precipitation of supersaturated solute in H ion irradiated Fe-Au and Fe-Au-W alloys studied by positron annihilation spectroscopy

The effect of thermal aging of homogenized Fe-Au and Fe-Au-W alloys, irradiated at room temperature with hydrogen ions, was studied for an aging treatment at 300 °C for aging times up to 100 h. The aging behavior of the Fe-based alloys is compared to the results for pure Fe. The precipitation behavior of Au-rich and W-rich precipitates and its correlation to the H+ irradiation-induced defects is investigated by variable energy positron annihilation spectroscopy (VEPAS). The formation of open-volume defects after irradiation is monitored by an increase in the S parameter, while the recovery of the vacancy-like defects and the formation of precipitates are signalled by an increase in the W parameter. Au-rich precipitation continuously develops during long-term aging, as indicated by the increase in the W parameter. The change of the W parameter in the Fe-Au-W alloy is not only due to the effect of solute W on the Au precipitates, but also because of the interface of W-rich Laves phase with matrix.

Exploring the anti-site disorder and oxygen vacancies in Sr[formula omitted]FeMoO[formula omitted] thin films

To address the importance of nanoscale defects in complex magnetic oxides, we present an effective tool, variable energy positron annihilation spectroscopy, for probing the relatively small changes in anti-site disorder and oxygen vacancies of the in situ annealed double perovskite Sr2FeMoO6 thin films. By controlling the annealing conditions in wide pressure and temperature ranges and thus affecting the amount of nanoscale defects, we show that the magnetic properties of Sr2FeMoO6 thin films can be modified, particularly with the oxygen nonstoichiometry, and hence their spintronic functionality can be improved. On the basis of our findings together with proposed mechanism, we suggest that the annealing treatments can also be scaled to other complex magnetic perovskites to engineer nanoscale defects and thus improve their usability in future spintronic applications.

Mediation of high temperature radiation damage in bcc iron by Au or Cu precipitation

High temperature radiation damage in binary bcc Fe alloys containing 1 atomic % Au or Cu due to Fe ion irradiation at 550 °C to a peak dose of 2.8 and 8.3 dpa is studied. The precipitation behavior of gold and copper and its correlation to the irradiation-induced defects is studied by transmission electron microscopy and variable energy positron annihilation spectroscopy (VEPAS). The increase of S parameters from VEPAS indicates the formation of open volume defects upon irradiation. Disc-shaped Au precipitates, grown from the irradiation induced dislocations, are observed in the Fe-Au alloy. In the Fe-Cu alloy, spherical Cu particles are formed but no direct connection between Cu precipitates and radiation damage is detected. For the Fe-Au alloy, the surface hardness dramatically increases for a dose of 2.8 dpa, with a slight decrease as the irradiation dose is enhanced to 8.3 dpa. In the Fe-Cu alloy, radiation hardening increases continuously.

Improvement of luminescence properties of n-GaN using TEGa precursor

Abstract The aim of this work is to compare and improve optical and structural properties of GaN layers prepared using TMGa or TEGa precursors. MOVPE grown GaN buffer layers on sapphire substrates are usually grown from TMGa precursor at the temperatures above 1000 °C. These layers contain deep and shallow acceptor levels which are responsible for blue and yellow defect bands in luminescent spectra. Both defect bands are detrimental for all major nitride device applications. Especially n-doped GaN layers suffer from strong yellow defect bands. In this work, it is shown that yellow band photoluminescence intensity can be suppressed by using TEGa precursor during the growth of n–doped GaN layers. Different kinds of growth parameters, such as growth temperature or growth rate, have been studied. It is also shown that the change of carrier gas (H2 or N2) has very strong influence on the layer quality. H2 carrier gas increased intensity of yellow band in sample grown from TEGa precursor while N2 carrier gas had the same effect for sample grown from TMGa precursor. Variable energy positron annihilation spectroscopy showed creation of single VGa in H2 atmosphere and clustering of VGa to big complexes ((VGa)3(VN)n) in N2 atmosphere.

Self healing of radiation-induced damage in Fe–Au and Fe–Cu alloys: Combining positron annihilation spectroscopy with TEM and ab initio calculations

Self healing of early stage radiation damage by site selective solute segregation is a promising approach to extend the lifetime of nuclear reactor components. In the present study, the creation and autonomous healing of irradiation-induced damage is investigated in pure Fe and high purity Fe–Au and Fe–Cu model alloys. To create radiation damage samples are irradiated at 550 °C by 120 keV He+ ions with fluences of 5.0 × 1015, 1.0 × 1016 and 5.0 × 1016 ions/cm2. The observed increase in the S and W parameters determined in the variable energy positron annihilation spectroscopy measurements indicates the formation of vacancy-like defects, precipitates and vacancy-solute complexes. The presence of substitutionally dissolved Au is found to reduce the formation of radiation defects more efficiently than solute Cu. Site-specific Au precipitation at defect sites is indicated, which results in damage healing with a reduced swelling, whereas Cu precipitates and radiation damage only show weak interaction. Ab initio calculations show that the binding energies of Au solutes to vacancy clusters (Au-Vn) are significantly larger than those of Cu solutes (Cu-Vn) whereas the binding energies of helium filled vacancy clusters Au-HenVn and Cu-HenVn are comparable.

Insights into Hydrogen Gas Environment-Promoted Nanostructural Changes in Stressed and Relaxed Palladium by Environmental Transmission Electron Microscopy and Variable-Energy Positron Annihilation Spectroscopy.

Environmental transmission electron microscopy (ETEM) and variable-energy positron annihilation spectroscopy (VEPAS) are used to observe hydrogen-induced microstructural changes in stress-free palladium (Pd) foils and stressed Pd thin films grown on rutile TiO2 substrates. The microstructural changes in Pd strongly depend on the hydrogen pressure and on the stress state. At room temperature, enhanced Pd surface atom mobility and surface reconstruction is seen by ETEM already at low hydrogen pressures ( pH < 10 Pa). The observations are consistent with molecular dynamics simulations. A strong increase of the vacancy density was found, and so-called superabundant vacancies were identified by VEPAS. At higher pressures, migration and vanishing of intrinsic defects is observed in Pd free-standing foils. The Pd thin films demonstrate an increased density of dislocations with increase of the H2 pressure. The comparison of the two studied systems demonstrates the influence of the mechanical stress on structural evolution of Pd catalysts.

Positron annihilation study of cavities in black Au films

Defects in a black Au film were studied using variable energy positron annihilation spectroscopy. Black Au films exhibit porous morphology similar to cauliflower. This type of structure enhances the optical absorption due to a multiple reflections in the micro-cavities. A nanostructured black Au film was compared with conventional smooth Au films with high reflectivity. The black Au film exhibited a remarkably enhanced S-parameter in sub-surface region. This is caused by a narrow para-Positronium contribution to the annihilation peak.

Shallow nitrogen ion implantation: Evolution of chemical state and defect structure in titanium

Evolution of chemical states and defect structure in titanium during low energy nitrogen ion implantation by Plasma Immersion Ion Implantation (PIII) process is studied. The underlying process of chemical state evolution is investigated using secondary ion mass spectrometry and X-ray photoelectron spectroscopy. The implantation induced defect structure evolution as a function of dose is elucidated using variable energy positron annihilation Doppler broadening spectroscopy (PAS) and the results were corroborated with chemical state. Formation of 3 layers of defect state was modeled to fit PAS results.

Defect studies of Mg films deposited on various substrates

In the present work the structure of Mg films deposited by RF magnetron sputtering was characterized using variable energy positron annihilation spectroscopy combined with scanning electron microscopy and X-ray diffraction. The effect of deposition parameters, namely temperature, type of substrate and deposition rate, on the microstructure was examined. All Mg films studied grow with the basal (0001) plane parallel with the substrate and exhibit only negligible in-plane stress. Films deposited at room temperature are characterized by nanocrystalline structure with high volume fraction of grain boundaries. and positrons are preferentially trapped in open volume defects present at grain boundaries. In these films positrons are trapped predominantly in open-volume defects present at grain boundaries. With increasing deposition temperature the mean grain size increases and the volume fraction of grain boundaries decreases. Hence, in Mg films prepared at elevated temperatures positrons are trapped mainly at misfit dislocations compensating different atomic spacing in the films and the substrate. Moreover, it was found that slow deposition rate leads to higher density of defects compared to fast deposition rate. By annealing of Mg film with thin 20 nm Pd overlayer at 300°C for 1 hour Pd layer is mixed with Mg film forming a Mg-Pd compound. The Mg-Pd phase likely contains structural open-volume defects which trap positrons.

Metal-Semiconductor Interfaces Investigated by Positron Annihilation Spectroscopy

Variable-energy positron annihilation spectroscopy has been applied to study interfaces in Al/Si, Au/Si and Au/GaAs structures. Computational fittings of ROYPROF program were used to analyze Doppler broadening results in order to determine kinds of regions that positrons were likely to sample. The interfaces were found acting as a capturing thin layer with negligible positrons stopped in them and their characteristics came only from positrons diffusing to these interfaces, the positron work function of these materials were taken into consideration. In all fittings, the interfaces are found to have 1 nm thickness and act as an absorbing sink for all thermal positrons diffusing towards them, and this indicates either the existence of open volume defects or a weakness of known theoretical models for positron affinities. The result is supported by measurements obtained by applying external electric fields on Al/Si sample. Theoretical fittings have clearly demonstrated the sensitivity of interfaces in these attempts and their importance in data analyzing and in developing of fitting cods.

Positron annihilation lifetime spectroscopy study of Kapton thin foils

Variable energy positron annihilation lifetime spectroscopy (VE-PALS) experiments on polyimide material Kapton are reported. Thin Kapton foils are widely used in a variety of mechanical, electronic applications. PALS provides a sensitive probe of vacancy-related defects in a wide range of materials, including open volume in polymers. Varying the positron implantation energy enables direct measurement of thin foils. Thin Kapton foils are also commonly used to enclose the positron source material in conventional PALS measurements performed with unmoderated radionuclide sources. The results of depth-profiled positron lifetime measurements on 7.6 μm and 25 μm Kapton foils are reported and determine a dominant 385(1) ps lifetime component. The absence of significant nanosecond lifetime component due to positronium formation is confirmed.