Positron Annihilation Spectroscopy Research Articles

Bi-Deficiency Leading to High-Performance in Mg3 (Sb,Bi)2 -Based Thermoelectric Materials.

Mg3 (Sb,Bi)2 is a potential nearly-room temperature thermoelectric compound composed of earth-abundant elements. However, complex defect tuning and exceptional microstructural control are required. Prior studies have confirmed the detrimental effect of Mg vacancies in Mg3 (Sb,Bi)2 . This study proposes an approach to mitigating the negative scattering effect of Mg vacancies (VMg ) by Bi deficiency, synergistically modulating the electrical and thermal transport properties to enhance the thermoelectric performance. Positron annihilation spectrometry and Cs -corrected scanning transmission electron microscopy analyses indicated that the VMg tends to coalesce due to the introduced VBi . The defects created by Bi deficiency effectively weaken the scattering of electrons from the intrinsic VMg and enhance phonon scattering. A peak zT of 1.82 at 773 K and high conversion efficiency of 11.3% at ∆T = 473 K are achieved in the optimized composition of Mg3 (Sb,Bi)2 by tuning the defect combination. This work demonstrates a feasible and effective approach to improving the performance of Mg3 (Sb,Bi)2 as an emerging thermoelectric material. This article is protected by copyright. All rights reserved.

Positron annihilation spectroscopy as a tool for examining a microstructure in differently thick polymeric sample

Positron annihilation spectroscopy as a tool for examining a microstructure in differently thick polymeric sample

Evaluation of adsorption and mechanical strength of 13X zeolite mixtures with phyllosilicate binders using molecular dynamics simulation and positron annihilation spectroscopy

There is growing interest in developing zeolites with novel internal structures that have optimal adsorptive capacity and high mechanical strength, while offering advantages, such as being light weight. We integrate computational and experimental methods to explore the effect of binder/zeolite types, and weight percentages on the mechanical strength of 13X zeolite and adsorption capacities of N2, H2O, and CO2 for additive manufacturing (AM) applications with the goal of maximizing both adsorption and strength. Zeolite 13X mixtures and phyllosilicate binders (either bentonite or kaolin) are combined using molecular dynamics (MD) simulations to create structures with various binder/zeolite weight percentages. Adsorption capabilities and mechanical strength are assessed using the grand canonical Monte Carlo (GCMC) and ReaxFF modules, respectively. Our modeling shows that an optimized zeolite/binder ratio for N2 adsorption is around 15 wt% for kaolin and roughly 10 wt% for bentonite. The resulting parameters can be applied to facilitate macro-scale computational fluid dynamics (CFD) and finite element method (FEM) simulations of an AM zeolite structure. We also performed Positron Annihilation Lifetime Spectroscopy (PALS) measurements on zeolite samples to explore the effect of changes in the internal volume. The results show an inverse relationship between the free volume and the solid loading. Adding a binder changes the morphology of the zeolite-binder compound and decreases open-volume area significantly.

Multi–length scale characterization of point defects in thermally oxidized, proton irradiated iron oxides

A key for the success of safe nuclear power generation system is to consider structural materials that are economical, meet mechanical property needs, possess good corrosion resistance, and are radiation tolerant. Nevertheless, fundamental insights that elucidate the details of radiation damage on materials corrosion performance are lacking. This includes the behavior of surface oxides which often regulate corrosion. For example, it is unclear how non-equilibrium point defects, oxide structure, mass transport in oxides, and subsequent oxidation behavior are altered by the radiation. In this work, some of the effects of proton irradiation on the attributes of point defects, iron oxide microstructures, and the physical nature of the oxidation product were correlated with corrosion behavior. Iron oxides, fabricated by thermal oxidation in air at 400°C and 800°C for 1 h, were subjected to 200 keV, 0.03 dpa (displacements per atom) of proton irradiation, and subjected to corrosion reactivity assessment using AC and DC electrochemical methods. Experimental methods that target materials information at different length scales, such as positron annihilation spectroscopy (atomistic), transmission electron microscopy (mesoscopic), and electrochemical methods (macroscopic), were coupled to shed light on the impact of radiation-induced defect modifications and structural changes in oxides on corrosion reactivity which ultimately affects durability in harsh environments.

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.

Exploring the Sub-nanoscale Structure of Cobalt Molybdenum Sulfide and the Role of a Cobalt Promoter in Catalytic Hydrogen Evolution.

Cobalt-promoted molybdenum sulfide (CoMoS) is known as a promising catalyst for H2 evolution reaction and hydrogen desulfurization reaction. This material exhibits superior catalytic activity as compared to its pristine molybdenum sulfide counterpart. However, revealing the actual structure of cobalt-promoted molybdenum sulfide as well as the plausible contribution of a cobalt promoter is still challenging, especially when the material has an amorphous nature. Herein, we report, for the first time, on the use of positron annihilation spectroscopy (PAS), being a nondestructive nuclear radiation-based method, to visualize the position of a Co promoter within the structure of MoS at the atomic scale, which is inaccessible by conventional characterization tools. It is found that at low concentrations, a Co atom occupies preferably the Mo-vacancies, thus generating the ternary phase CoMoS whose structure is composed of a Co-S-Mo building block. Increasing the Co concentration, e.g., a Co/Mo molar ratio of higher than 1.12/1, leads to the occupation of both Mo-vacancies and S-vacancies by Co. In this case, secondary phases such as MoS and CoS are also produced together with the CoMoS one. Combining the PAS and electrochemical analyses, we highlight the important contribution of a Co promoter to enhancing the catalytic H2 evolution activity. Having more Co promoter in the Mo-vacancies promotes the H2 evolution rate, whereas having Co in the S-vacancies causes a drop in H2 evolution ability. Furthermore, the occupation of Co to the S-vacancies leads also to the destabilization of the CoMoS catalyst, resulting in a rapid degradation of catalytic activity.

Origin of Voids at the SiO2/SiO2 and SiCN/SiCN Bonding Interface Using Positron Annihilation Spectroscopy and Electron Spin Resonance

To obtain reliable 3D stacking, a void-free bonding interface should be obtained during wafer-to-wafer direct bonding. Historically, SiO2 is the most studied dielectric layer for direct bonding applications, and it is reported to form voids at the interface. Recently, SiCN has raised as a new candidate for bonding layer. Further understanding of the mechanism behind void formation at the interface would allow to avoid bonding voids on different dielectrics. In this study, the void formation at the bonding interface was studied for a wafer pair of SiO2 and SiCN deposited by plasma enhanced chemical vapor deposition (PECVD). The presence of voids for SiO2 was confirmed after the post-bond anneal (PBA) at 350 °C by Scanning Acoustic Microscopy. Alternatively, SiCN deposited by PECVD has demonstrated a void-free interface after post bond annealing. To better understand the mechanism of void formation at the SiO2 bonding interface, we used Positron Annihilation Spectroscopy (PAS) to inspect the atomic-level open spaces and Electron Spin Resonance (ESR) to evaluate the dangling bond formation by N2 plasma activation. By correlating these results with previous results, a model for void formation mechanism at the SiO2 and the absence of for SiCN bonding interface is proposed.

Charged particles: Unique tools to study irradiation resistance of concentrated solid solution alloys

• Both energetic ions and high-energy primary recoils induce defect processes in complex alloys that are consequences of the spatial and temporal coupling of atomic displacement processes and energy dissipation from ionization. • Chemical disorder does not monotonically increase with more alloying elements but can be tuned by specific alloying elements and the corresponding concentrations. • Differences between ions and neutrons need to be taken when relying on ion beam testing for reactor applications. Many multicomponent concentrated solid solution alloys (CSAs), including high-entropy alloys (HEAs), exhibit improved radiation resistance and enhanced structural stability in harsh environments. To study and assess irradiation resistance of nuclear materials, energetic ion and electron beams are commonly used to create displacement damage. Moreover, charged particles of ions, electrons, and positrons are unique tools to create and characterize radiation effects. Ion beam analysis (e.g., Rutherford backscattering spectrometry, nuclear reaction analysis, and time-of-flight elastic recoil detection analysis), electron microscopy techniques (e.g., transmission or scanning electron microscopy, and electron diffraction), and positron annihilation spectroscopy have been applied to characterize irradiated CSAs or HEAs to understand defect formation and evolution together with chemical and microstructural information. Their distinctive analyzing power and some perspectives in these techniques are reviewed. In developing structural alloys desirable for applications in advanced reactors, neutron exposure is a critical test but the limitation in achievable high damage levels is, however, a bottleneck. Ion irradiation is often used as a surrogate for neutron irradiation, and the associated reduced transmutations and higher displacements per atom (dpa) rates are desirable for materials research. Nevertheless, cautions need to be taken when relying on ion irradiation results for reactor evaluations. Literature on differences between ions and neutrons is briefly reviewed. In addition, the links to bridge the current advances on fundamental understandings to reactor applications are discussed to lay the groundwork between neutrons and ions for radiation effects studies.

Laser Powder Bed Fusion of Molybdenum and Mo-0.1SiC Studied by Positron Annihilation Lifetime Spectroscopy and Electron Backscatter Diffraction Methods.

Positron annihilation lifetime spectroscopy (PALS) has been used for the first time to investigate the microstructure of additively manufactured molybdenum. Despite the wide applicability of positron annihilation spectroscopy techniques to the defect analysis of metals, they have only been used sparingly to monitor the microstructural evolution of additively manufactured metals. Molybdenum and molybdenum with a dilute addition (0.1 wt%) of nano-sized silicon carbide, prepared via laser powder bed fusion (LPBF) at four different scan speeds: 100, 200, 400, and 800 mm/s, were studied by PALS and compared with electron backscatter diffraction analysis. The aim of this study was to clarify the extent to which PALS can be used to identify microstructural changes resulting from varying LPBF process parameters. Grain sizes and misorientation results do not correlate with positron lifetimes indicating the positrons are sampling regions within the grains. Positron annihilation spectroscopy identified the presence of dislocations and nano-voids not revealed through electron microscopy techniques and correlated with the findings of SiO2 nanoparticles in the samples prepared with silicon carbide. The comparison of results indicates the usefulness of positron techniques to characterize nano-structure in additively manufactured metals due to the significant increase in atomic-level information.

Positron annihilation studies of methylammonium lead bromide perovskite

Methylammonium lead halide-based perovskite has shown excellent optoelectronic properties. But their performances and stability are critically affected by the ionic defects present in the crystal lattice. In this article, we have investigated the presence of ionic vacancy mediated defects formation in ball mill ground methylammonium lead bromide (MAPbBr3) which has applications in tandem solar cell, light emitting diodes and laser devices. The evaluation of those point defects with temperature was analysed by employing the positron annihilation spectroscopic (PAS) studies. The phase transition from tetragonal to cubic phases around 260 K was exactly correlated with the temperature-dependent ‘S parameter’ determination from PAS analysis and with dc conductivity measurement. From coincidence Doppler broadening (CDB) spectroscopy significant proportion of defects arising from lead vacancy was observed whose magnitude reduces from the low-temperature tetragonal phase to higher temperature cubic phases.

Monovacancy-hydrogen interaction in pure aluminum: Experimental and ab-initio theoretical positron annihilation study

We report here on hydrogen-vacancy interactions in high purity aluminum by employing positron annihilation spectroscopy (PAS) analysis of hydrogen-loaded samples, aiming to study the mobility of vacancies. The samples were heat treated at 893 K in an atmosphere consisting of a mixture of H2 and Ar gas and, thus, loaded with hydrogen. The samples were then quenched to ice water and subsequently measured in-situ at different temperatures. In parallel we performed ab-initio density functional theory (DFT) calculations of lifetimes of positrons trapped in vacancies associated with 1–8 H atoms. Our experimental results suggest in comparison with the ab-initio calculations that complexes of vacancies with one hydrogen atom (V-H pairs) were formed in Al samples annealed in a mixture of H2 and Ar gas. Furthermore, hydrogen absorbed in aluminum immobilizes vacancies, i.e. the recovery of vacancies is delayed from 220 K up to around 280 K. At that temperature, V-H complexes start to dissociate, and hydrogen atoms previously bound to vacancies are released. In contrast, for Al samples not loaded with hydrogen isolated monovacancies become mobile around 220 K. In both cases mobile vacancies start to form vacancy clusters. From our experimental data we determined that the formation energy of monovacancies in Al is 0.62 ± 0.01 eV. This value is in very good agreement with 0.63 eV obtained by our ab-initio DFT calculations.

Gate Opening Induced High Pore Volume Expansion in Flexible Zeolitic Imidazole Frameworks during CO2 Adsorption: A Direct Observation Using Positron Annihilation Spectroscopy

Gate Opening Induced High Pore Volume Expansion in Flexible Zeolitic Imidazole Frameworks during CO₂ Adsorption: A Direct Observation Using Positron Annihilation Spectroscopy

Nanoscale mapping of point defect concentrations with 4D-STEM

Vacancies are missing atoms in a crystalline material, and occur both at equilibrium (varying with temperature) and out of equilibrium such as when crystalline materials are damaged with radiation or corrosion. While we know of their importance, particularly regarding diffusive mechanisms, it is not straightforward to experimentally measure their concentration or to visualize them directly. Traditionally, measurements such as positron annihilation spectroscopy and to some degree X-ray diffraction can measure average concentrations, but generally lack the ability to visualize or quantify a heterogenous concentration of vacancies that can occur at the level of individual defects and microstructural features. Here, we present a method to map vacancy concentrations and their distribution using local lattice parameter measurements with a high-resolution electron microscope. Our method utilizes a Au thin film as a model to demonstrate the method via four-dimensional scanning transmission electron microscopy (4D-STEM) by correlating the differences between changes in lattice parameter and the volumetric thermal expansion during in situ heating experiments. The vacancy mapping methodology is also applied to non-equilibrium defects accumulated in pure Al via knock-on electron beam irradiation. Our method demonstrates the ability to map point defect concentrations in heterogeneous systems in situ with nanometer spatial resolution. The result is a technique that can provide direct measurements of vacancy concentrations at the level of individual defects in studies of materials in and out of equilibrium.

Ionization-induced annealing of defects in 3C–SiC: Ion channeling and positron annihilation spectroscopy investigations

Ionization-induced annealing of defects in 3C–SiC: Ion channeling and positron annihilation spectroscopy investigations

Positron Annihilation Spectroscopy as a Diagnostic Tool for Probing the First‐Cycle Defect Evolution in Magnesium–Sulfur Battery Electrodes

Magnesium–sulfur batteries are elusive candidates for the post‐lithium‐ion battery. Their critical challenge for commercialization is rapid capacity fading due to polysulfide shuttle dissolution and slow kinetics during cycling. Insight into the free volumes, morphology, and structural evolution of the sulfur cathode in an Mg/S battery results in a deep understanding of the electrochemical reaction mechanism to further engineer an efficient electrode. In this work, a sulfur cathode with silicon carbide and graphene‐based material S_SiC_GNP is designed and characterized. The full cell based on the Mg anode and S_SiC cathode achieves a high initial discharge capacity of ≈600 mAh g−1 with short cycle life. Positron annihilation spectroscopy (PAL), X‐ray diffraction (XRD), and X‐ray photoelectron spectroscopy (XPS) combined with a scanning electron microscope are used to investigate defect states, free volume interconnectivity/morphology, and structure evolution of sulfur electrode at different electrochemical states. The results show growth in the free volumes and Mg2+ content upon discharge and shrinking upon recharge, while sulfur content is deficient upon demagnesiation. This work provides deep insight and an effective strategy helping to engineer an efficient cathodic material.

Radiation response of Y3Al5O12 and Nd3+-Y3Al5O12 to Swift heavy ions: insight into structural damage and defect dynamics.

Understanding the behavior of a material under irradiation is paramount to its application in the nuclear industry. The present work explores the radiation response of garnet Y3Al5O12 (YAG) and Nd3+-substituted Y3Al5O12 (Nd-YAG) under a 100 MeV Iodine beam at varying fluences to mimic the effect of fission fragments. This is relevant to the potential application of garnet as a host for minor actinide (MA) transmutation (Nd3+: surrogate for long-lived MA (Am3+, Np3+, Cm3+)). The un-irradiated and irradiated YAG and Nd-YAG samples were investigated by X-ray diffraction and Raman spectroscopy. Positron annihilation spectroscopy, thermal spike modelling and theoretical studies have been employed to understand the role of substitution and defect energetics in influencing this radiation response. Although both materials were not completely amorphized under the present irradiation conditions, a tremendous loss in crystallinity could be observed with increase in fluence, the damage being much more in Nd-YAG. Ion track radii of 2.17 nm and 2.91 nm were estimated for YAG and Nd-YAG respectively. Thermal-spike calculations show an increase in radiation-induced transient temperatures upon Nd-substitution that causes greater radiation damage in Nd-YAG. The enhancement in radiation-induced damage with increasing ion-fluence manifests in broadening and weakening of the Raman modes and XRD peaks. An increase in the average positron annihilation lifetime indicated the creation of oxygen vacancies. The defect formation energies of Y3Al5O12 have been theoretically estimated via density functional theory (DFT) and unfavorable energies required for creating cation pair anti-sites have been proposed as one of the possible reasons for the relatively poorer radiation response of YAG. The irradiation behavior of Y3Al5O12 has been compared with disordered fluorite (YSZ) and zirconate pyrochlores, which are well-researched ceramics for MA transmutation.

Observation of irradiation-induced defects in nuclear-related materials by using positron annihilation spectroscopy

Observation of irradiation-induced defects in nuclear-related materials by using positron annihilation spectroscopy

Phase separation and chemistry evolution in Fe-rich Sm(CobalFe0.31Cu0.07Zr0.025)7.7 magnets: The effect of initial defect

The intrinsic coercivity of Fe-rich Sm2Co17-type permanent magnets is closely associated with the unique cellular microstructures. Usually, the continuous distribution of cell boundaries is destroyed in Fe-rich Sm2Co17-type magnets. Herein, a relatively high maximum energy product of about 32.7 MGOe and a nearly 300% increase in intrinsic coercivity are observed for Fe-rich Sm2Co17-type permanent magnets via regulating the initial defects to introduce numerous 1:5H precipitates nucleation sites. Synchrotron XRD and HR-TEM results reveal that the solution-treated Fe-rich Sm2Co17-type magnets consist of supersaturated 1:7H phase and a partial 2:17R phase. Furthermore, the solution-treated magnet with a lower fraction of 2:17R phase was found to have a higher density of initial defects through positron annihilation spectroscopy measurement. In the magnet with a higher density of initial defects, high density of defects-aggregated cell boundaries and high internal stress promote the precipitation of 1:5H phase. Moreover, the ordering transformation of 2:17R phase was facilized during aging treatment, and elements segregation was promoted. These results present a novel way in designing high-performance Fe-rich Sm2Co17-type magnets.

Investigation of Nitrogen and Vacancy Defects in Synthetic Diamond Plates by Positron Annihilation Spectroscopy.

Currently, diamonds are widely used in science and technology. However, the properties of diamonds due to their defects are not fully understood. In addition to optical methods, positron annihilation spectroscopy (PAS) can be successfully used to study defects in diamonds. Positrons are capable of detecting vacancies, and small and large clusters of vacancies induced by irradiation, by providing information about their size, concentration, and chemical environment. By mapping in the infrared (IR) range, it is possible to consider the admixture composition of the main inclusions of the whole plate. This article presents the results of a study of defects in synthetic diamond plates, one of which was irradiated by electrons. It presents data about the distribution of the defect concentration obtained by Infrared spectroscopy. PAS with a monochromatic positron beam can be used as a non-destructive technique of detecting defects (vacancy) distribution over the depth of diamond plates.

Effect of Vacancy Behavior on Precipitate Formation in a Reduced-Activation V-Cr-Mn Medium-Entropy Alloy.

In this work, we studied the evolution of vacancy-like defects and the formation of brittle precipitates in a reduced-activation V-Cr-Mn medium-entropy alloy. The evolution of local electronic circumstances around Cr and Mn enrichments, the vacancy defects, and the CrMn3 precipitates were characterized by using scanning electron microscopy with energy-dispersive spectroscopy, X-ray diffraction, and positron annihilation spectroscopy. The microstructure measurements showed that the Mn and Cr enrichments in the as-cast sample significantly evolved with temperature, i.e., from 400 °C, the Cr/Mn-segregated regions gradually dissolved into the matrix and then disappeared, and from 900 °C to 1000 °C, they existed as CrMn3 precipitates. The crystallite size of the phase corresponding to CrMn3 precipitates was about 29.4 nm at 900 °C and 43.7 nm at 1000 °C. The positron annihilation lifetime results demonstrated that the vacancies mediated the migration of Cr and Mn, and Cr and Mn segregation finally led to the formation of CrMn3 precipitates. The coincidence Doppler broadening results showed that the characteristic peak moved to the low-momentum direction, due to an increase in the size of the vacancy defects at the interface and the formation of CrMn3 precipitates.