Defect Structure Research Articles

Defect Structure and Luminescence of κ‐Ga2O3 Micro‐Monocrystals

Wide bandgap orthorhombic polymorph of gallium oxide (κ‐Ga2O3) possessing a high spontaneous polarization grown on wurtzite‐type semiconducting substrates is considered to create a high mobility electron channel suitable for applications. Such κ‐Ga2O3 layers are composed of hexagon microprisms whose properties affect the lateral electric conductance. In this work, the structure and recombination properties of extended defects in individual “suspended” thin microprisms are investigated with transmission and scanning electron microscopy techniques (STEM, HR‐TEM) including cathodoluminescence (CL‐SEM). It is established that the microprism is composed of six equisized orthorhombic domains bounded by twin domain boundaries (TDBs) along the directions <110>. Twin domain contains a parallel array of antiphase boundaries (APB) of a high density stretched in the [010] direction. APBs possess steps or interruption and can form double oppositely shifted spatially separated layers (APB dipoles). TDBs on majority of their length are incoherent and serve as the border for the APB terminations. Panchromatic CL maps reveal either enhanced or reduced intensity of APB without noticeable spectral changes. CL intensity enhancement is proposed to be due to enhanced electron–hole generation caused by excess scattering of primary electron beam by APBs in thin films while, in fact, APB exhibits enhanced nonradiative recombination activity.

Defect crystal structure of α-Na0.5-xR0.5+xF2+2x (R = Dy-Lu, Y) on X-Ray and electron diffraction data. I. MethoD of Defect structure modelling on the α-Na0.35Dy0.65F2.30 example

For the first time, the crystal α-Na0.35Dy0.65F2.30 was studied using X-ray diffraction at 293 K and 85 K and electron diffraction at 293 K. A unified cluster model of the defective structure of nanostructured crystals with a fluorite-type structure, based on the polymorphism of ordered phases KR3F10 (R = Er, Yb), was expanded with a matrix part model based on the structure of the KYF4 compound. The unified cluster model was applied to construct the defective structure of α-Na0.35Dy0.65F2.30. It was found that the matrix part of the crystal contains Na+ и Dy3+ cations in a 1:1 ratio. Some of the anions in the matrix are displaced to the 32f positions (space group Fm3m). The excess Dy3+ forms octahedral-cubic clusters with Na+ [Na14–nDynF64+n] with cores in the form of distorted and regular cuboctahedrons {F12}. These are composed of interstitial anions in two 32f positions and one 48i position. The cluster component of the α-Na0.35Dy0.65F2.30 crystal contains octahedral-cubic clusters of f-, f–i- and i-types. Electron diffraction showed that α-Na0.35Dy0.65F2.30 is a nanostructured crystal. Its cluster component is in the form of plate-like inclusions about 5 nm thick with superstructural ordering and individual octahedral-cubic clusters. A model of their structure was proposed. Lowering the temperature to 85 K increases the number of interstitial F(32f)1 anions in the matrix component of the crystal.

Photoluminescence Spectra of Helium Ion-Implanted Diamond.

Ion implantation in diamond crystals is widely used both for producing conducting microstructures in the bulk of the material and for creating isolated photon emitters in quantum optics, photonics, cryptography, and biosensorics. The photoluminescence (PL) spectra of helium ion-implanted diamonds are dominated by two sharp emission lines, HR1 and HR2 (from Helium-Related), at ~536 and 560 nm. Here, we report on PL studies of helium-related optical centers in diamonds. Experiments have been carried out on a (110) plate of natural single-crystal type IIa diamonds. The uniform distribution of radiation defects in a 700 nm-thick layer was obtained by ten cycles of multiple-energy (from 24 to 350 kV) helium ion implantation with a total dose of 5 × 1016 cm-2. The diamonds were annealed in steps in a vacuum oven at temperatures from 200 to 1040 °C. It is demonstrated that helium ion implantation in diamonds followed by annealing gives rise to more than a dozen various centers that are observed in the PL spectra in the range of 530-630 nm. The transformations of the PL spectra due to annealing are investigated in detail. The spectral shapes of phonon sidebands are determined for the HR1, HR2, and HR3 bands with ZPLs at ~536, 560, and 577 nm, respectively, and it is shown that these bands are attributed to interstitial-related centers in diamonds. The reported results are important for understanding the structure and properties of helium-related defects in diamonds.

Anisotropy of radiation-induced defects in Yb-implanted β-Ga2O3

RE-doped β-Ga2O3 seems attractive for future high-power LEDs operating in high irradiation environments. In this work, we pay special attention to the issue of radiation-induced defect anisotropy in β-Ga2O3, which is crucial for device manufacturing. Using the RBS/c technique, we have carefully studied the structural changes caused by implantation and post-implantation annealing in two of the most commonly used crystallographic orientations of β-Ga2O3, namely the (-201) and (010). The analysis was supported by advanced computer simulations using the McChasy code. Our studies reveal a strong dependence of the structural damage induced by Yb-ion implantation on the crystal orientation, with a significantly higher level of extended defects observed in the (-201) direction than for the (010). In contrast, the concentration and behavior of simple defects seem similar for both oriented crystals, although their evolution suggests the co-existence of two different types of defects in the implanted zone with their different sensitivity to both, radiation and annealing. It has also been found that Yb ions mostly occupy the interstitial positions in β-Ga2O3 crystals that remain unchanged after annealing. The location is independent of the crystal orientations. We believe that these studies noticeably extend the knowledge of the radiation-induced defect structure, because they dispel doubts about the differences in the damage level depending on crystal orientation, and are important for further practical applications.

A novel millimetre‐wave 2D wide‐angle scanning phased array antenna based on decoupling surface

AbstractThis paper presents a novel millimetre‐wave (mmWave) 2D wide‐angle scanning (WAS) phased array antenna (PAA) based on decoupling surface (DS). The proposed element is a coaxial feeding stacked patch antenna structure that consists of an L‐shape coaxial probe, substrate integrated waveguide cavity, slot layer, radiating patch, DS and defective ground structure. The simulated impedance bandwidth for the element is 14.85% (26.18–30.34 GHz). The simulated result of the 2 × 2 array shows that the designed antenna based on DS achieves an isolation of ≥19 dB within the bandwidth. To validate the scanning capabilities of the proposed antenna, an 8 × 8 PAA prototype is fabricated and measured. The measured scanning range of the prototype achieves a 2D WAS range of ±56° at 27 GHz. The proposed antenna shows great potential in application scenarios, such as automotive radar and satellite communication due to its compact design and ability to achieve WAS in two dimensions.

Enhancing anti-adhesion properties by designing microstructure - the microscopy and spectroscopy study of the intercellular bacterial response.

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 Cu2O and CuO, and a thickness of 6nm. 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 Cu2O nanoparticles and the increased concentration of sulphur-rich compounds near these nanoparticles.

Hydrogen- assisted synthesis of defective triazine/heptazine homostructured nanosheets for efficient CO2photoreduction.

Homostructure construction has been demonstrated to be an effective way for boosting the photocatalytic activity of polymeric carbon nitride. However, the contribution of the intrinsic activity of molecular fragments in the catalytic performance of homostructured carbon nitride is yet to be explored. In this paper, a facile hydrogen-assisted strategy was used to synthesize triazine/heptazine intermolecular homojunctions (g-C3N4(MU-H)) with an ultrathin and defective structure, via the co-pyrolysis of melamine and urea precursors. Experimental characterizations and theoretical calculations revealed the copolymerization of triazine- and heptazine-based carbon nitride generated a homostructured interface with a large build-in electric field for efficient separation of photogenerated carriers. Due to the synergestic effect between the homostructured interface and nitrogen vacancies, as-synethesized g-C3N4(MU-H) exhibited an outstanding activity for photocatalytic CO2 reduction, with a CO yield rate of 14.45 μmol h-1, which was 23.5 and 3.64 times higher than those of bulk g-C3N4 and g-C3N4(M-H) synthesized from a single precursor, respectively. This study provides a new avenue for optimizing the charge separation efficiency of CO2 photoreduction catalysts by constructing intramolecular homojunction.

Control of Grain Boundary Formation in Atomically Resolved Nanocrystalline Carbon Monolayers: Dependence on Electron Energy

Abstract In this study, we explore the dynamics of grain boundaries in nanocrystalline carbon monolayers, focusing on their variation with electron beam energy and electron dose rate in a spherical and chromatic aberration-corrected transmission electron microscope. We demonstrate that a clean surface, a high-dose rate, and a 60 keV electron beam are essential for precise local control over the dynamics of grain boundaries. The structure of these linear defects has been evaluated using neural network-generated polygon mapping.

The Design and Analysis of circular Patch Antennas with Defective Ground Structures (DGS) for C and X-Band Applications

The Design and Analysis of circular Patch Antennas with Defective Ground Structures (DGS) for C and X-Band Applications

Defect Chemistry in High-Voltage Cathode Materials for Lithium-Ion Batteries.

High-voltage cathodes (HVCs) have emerged as a paramount role for the next-generation high-energy-density lithium-ion batteries (LIBs). However, the pursuit of HVCs comes with inherent challenges related to defective structures, which significantly impact the electrochemical performance of LIBs. The current obstacle lies in the lack of a comprehensive understanding of defects and their precise effects. This perspective aims to provide insights into defect chemistry for governing HVCs. The classifications, formation mechanisms, and evolution of defects are outlined to explore the intricate relationship between defects and electrochemical behavior. The pressing need for cutting-edge characterization techniques that comprehensively investigate defects across various temporal and spatial scales is emphasized. Building on these fundamental understandings, engineering strategies such as composition tailoring, morphology design, interface modification, and structural control to mitigate or utilize defects are thoroughly discussed for enhanced HVCs performance. These insights are expected to provide vital guidelines for developing high-performance HVCs for next-generation high-energy lithium-ion batteries.

Advancing Graphene Imaging for Clear Identification of Lattice Defects: The Application of Revolve Sphere Levelling to Scanning Tunnelling Microscopy Images.

Application of revolve sphere levelling (RSL) as a practical and effective image processing tool for enhancing scanning tunnelling microscopy (STM) images of graphene atomic lattices is presented. Low-cost, ambient, and non-invasive STM methods overcome limitations of traditional imaging methods like scanning transmission electron microscopy (STEM) and transmission electron microscopy (TEM) that can introduce or alter defects in graphene. Utilizing high-quality graphene synthesized via Paragraf's patented Metal-Organic Chemical Vapor Deposition (MOCVD) method, RSL, which is easily implemented via the Gwyddion software package, effectively highlights the hexagonal lattice structure and specific defect structures. This provides clarity of the atomic structure that traditional methods struggle to achieve. This research emphasizes the utility of RSL in materials science for defect identification in graphene, and points to future research in optimizing RSL for a broader range of defects and applications in other 2D materials.

Subtraction-based DNA Origami Cryptography by using Structural Defects for Information Encryption.

Conventional cryptographic methods rely on increased computational complexity to counteract the threat posed by growing computing power for sustainable protection. DNA cryptography circumvents this threat by leveraging complex DNA recognition to maintain information security. Specifically, DNA origami has been repurposed for cryptography, using programmable folding of the long scaffold strand carrying additional tagged strands for information encryption. Herein, a subtraction-based cryptographic strategy is presented that uses structural defects on DNA origami to contain encrypted information. Designated staple strands are removed from the staple pool with "hook" strands to create active defect sites on DNA origami for information encryption. These defects can be filled by incubating the structures with the intact pool of biotinylated staple strands, resulting in biotin patterns that can be used for protein-binding steganography. The yields of individual protein pixels reached over 91%, and self-correction codes are implemented to aid the information recovery. Furthermore, the encrypted organization of defective DNA origami structures is investigated to explore the potential of this method for scalable information storage. This method uses DNA origami to encrypt information in hidden structural features, utilizing subtraction for robust cryptography while ensuring the safety and recovery of data.

Bilateral chronic cavitary pulmonary aspergillomas in an adult patient with recurrent tuberculosis: a case report and literature review

BackgroundAspergillomas are globular growths of Aspergillus fumigatus, a benign aspergillosis of the lungs. It usually affects patients who are immunocompromised and have anatomically defective lung structures. The majority of aspergilloma cases are asymptomatic, despite the fact that 10% of cases spontaneously resolve. Most patients do not have any symptoms from their lesions. Direct serological or microbiological evidence of an Aspergillus species along with radiologic evidence is required for the diagnosis of an aspergilloma.CaseWe describe a 35-year-old adult Oromo male patient who had been experiencing night sweats, an intermittent productive cough with sparse whitish sputum, loss of appetite, and easy fatigability for 3 months. At 5 years prior, he received treatment for pulmonary tuberculosis that was smear-positive and was subsequently certified healed. Objectively, he was tachypneic and had intercostal, subcostal, and supraclavicular retractions with symmetric chest movement. A high-resolution computed tomography scan revealed bilateral apical cavitary lesions with core soft tissue attenuating spherical masses and an air crescentic sign suggestive of aspergillomas, which were confirmed by sputum light microscopic examination. The patient was managed with antibiotics and antifungals.ConclusionAspergilloma is a symptom of chronic pulmonary aspergillosis, a category of lung disorders caused by a persistent Aspergillus infection. Primary aspergillomas are uncommon and frequently occur in people with compromised immune systems. A prolonged cough, fever, chest pain, and hemoptysis are all symptoms of pulmonary aspergillomas. The majority of the time, pulmonary aspergillosis is difficult to identify. Despite high mortality and morbidity rates, surgery is still the most effective treatment for pulmonary aspergilloma.

Upconversion photoluminescence of Er-doped Bi$_{4}$Ti$_{3}$O$_{12}$ ceramics enhanced by vacancy clusters revealed by positron annihilation spectroscopy

Abstract Doping of rare earth elements into Bi$_{4}$Ti$_{3}$O$_{12}$ can significantly enhance the upconversion photoluminescence (UCPL) properties, but its structure-property relationship is still unclear. In this work, Er-doped bismuth titanate Bi$_{4-x}$Er$_{x}$Ti$_{3}$O$_{12}$ ($x$=0, 0.1, 0.2, 0.3, 0.4, 0.5) ceramics were synthesized via solid-state reaction method. The X-ray diffraction analysis confirmed the orthorhombic crystalline structure of the Bi$_{4-x}$Er$_{x}$Ti$_{3}$O$_{12}$ ceramics without any secondary phases. Experiments and calculations of positron annihilation spectroscopy were carried out to characterize their defect structure. The comparison between the experimental and calculated lifetime revealed that vacancy clusters were the main defects in the ceramics. The increase of the intensity of the second positron lifetime component (I$_{2}$) of Bi$_{3.5}$Er$_{0.5}$Ti$_{3}$O$_{12}$ ceramics indicated the presence of a high concentration of vacancy clusters. The UCPL spectra shown the sudden enhanced UCPL performance in Bi$_{3.7}$Er$_{0.3}$Ti$_{3}$O$_{12}$ and Bi$_{3.5}$Er$_{0.5}$Ti$_{3}$O$_{12}$ ceramics, which were consistent with the variation of the second positron lifetime component (I$_{2}$). These results indicate that the enhanced UCPL properties are influenced not only by the concentrations of rare earth ions but also by the concentration of vacancy clusters present within the ceramics.

Fatigue properties of a Ti–5Al–5Mo-5 V–3Cr alloy manufactured by electron beam powder bed fusion

AbstractAdditive manufacturing (AM) is a modern way of manufacturing structures, which tends to have fewer design limitations than those manufactured by conventional processes such as casting or forging. A combination of high-strength materials and small and complex structures opens up a wide range of potential applications, especially in the fields of medicine and aerospace. Titanium and its alloys show a very beneficial combination of density and mechanical properties. One of these alloys is the metastable β titanium alloy Ti– 5Al–5Mo–5 V–3Cr (Ti-5553), which is currently used mainly for large forged structures like landing gears of airplanes. In this study, for the first time the fatigue behavior of electron beam powder bed fused (PBF-EB) Ti-5553 was investigated with a focus on the defects created by the layer wise manufacturing. To understand the defect structure and its respective influence on the fatigue behavior, all specimens were scanned prior to fatigue testing using a state-of-the-art µ-focus CT. The specimens were subjected to two heat treatment procedures commonly used in technical applications, which were aiming for high strength (solution treated and aged—STA) as well as high ductility (beta annealed, slow cooled and aged—BASCA). Results indicate that the fatigue strength of PBF-EB manufactured Ti-5553 is significantly reduced compared to conventionally manufactured Ti-5553. The main reason for this are defects, which have varying critical effects depending on the heat treatment of the specimen and the defect size, shape, location and type.

Molecular dynamics simulations of nanoparticle sintering in additive nanomanufacturing: insights from sintering mechanisms

The sintering behavior of nanoparticles (NPs), which determines the quality of additively nanomanufactured products, differs from conventional understanding established for microparticles. As NPs have a high surface-to-volume ratio, they are subjected to a higher influence from surface tension and a lower melting point than microparticles, resulting in variations in both crystallographic defect-mediated and surface diffusion mechanisms. Meanwhile, the interplay between these controlling mechanisms in NPs has not been well understood, primarily because sintering occurs on the nanosecond timescale, making it an exceptionally transient process. In this work, sintering of both equal and unequal sized Ag and Cu NP doublets with and without misorientation (both tilt and twist) is modeled through molecular dynamics (MD) simulations. The formation and evolution of crystallographic defects, such as vacancies, dislocations, stacking faults, twin boundaries, and grain boundaries, during sintering are investigated. The influence of these defects on plastic deformation and diffusion mechanisms, such as volume diffusion and grain boundary (GB) diffusion, is discussed to elucidate the responsible sintering mechanisms. The surface diffusion mechanism is visualized by using detailed atomic trajectories generated during the sintering process. Finally, the overall effectiveness of all diffusion sintering mechanisms is quantified. This study provides first insights into the complexity and dynamics of NP sintering mechanisms which can aid in the development of accurate predictive models.

Bjerrum defects in s-II gas hydrate

The energy and structure of Bjerrum defects in structure II gas hydrates were investigated by using first-principle calculations for finite-size clusters and periodic 3D lattice systems. The formation energies of these defects were calculated for the first time when the cages of the structure II structure were completely empty and the large cage was filled with a THF molecule. Analogous to findings in ice structures, one of the hydrogen atoms forming the D defect was noted to orient toward the cage. If the excess proton resides in the large cage, it acts as an attraction center for the polar guest molecule, i.e., THF. Therefore, the large cage guest THF molecule stabilizes the D/L defect pair and isolated D/L defect formation energies by forming hydrogen bonds with the D defect. In such cases, the defect structure representing a D/L defect pair containing a THF molecule interacting with one of the hydrogen atoms of the D defect mirrors the guest-induced ones. Notably, the classical Bjerrum defect and the guest-induced Bjerrum defect exhibit a similar phenomenon in defective structures. Contrary to existing literature, it is evident that guest-induced Bjerrum defects involve both the L and D components. The insights gained from this study could potentially offer an alternative perspective to understand various experimental observations, such as those related to dielectric and NMR properties.

Electrospun carbon/iron–vanadium oxide nanofibers for high energy density supercapacitors

Highly flexible and conductive carbon nanofibers (CNFs) embedded with pseudocapacitive iron–vanadium oxide (FVO) nanoparticles were fabricated via electrospinning of a metal salt/polyacrylonitrile solution followed by high-temperature annealing (750 °C). CNFs have a graphitic structure with defects, which could accelerate electron mobility and the access of electrolytic ions to the multivalent FVO nanoparticles, respectively. Poly(methyl methacrylate) (PMMA) was introduced as a sacrificial polymer to alter the internal structure of the nanofibers and thus enhance the electrolytic ion transport pathways. Terephthalic acid was added to provide flexibility by increasing the cross-linking within the electrospun fibers. The flexible FVO/CNFs exhibited excellent electrochemical performance. The optimal sample had a high areal capacitance of 1058 mF·cm−2 at a current density of 2.5 mA·cm−2 and showed 100 % capacitance retention during long-term cycling (10,000 cycles). The capacitance at a high current density of 25 mA·cm−2 was 81.3 % of that at a current density of 2.5 mA·cm−2. Using a wider potential window of 0–1.6 V increased the energy density to 389 μW·h·cm−2. The optimal FVO/CNF sample maintained 90 % of its initial capacitance after 200 bending cycles.

Synergistic modulation of SrTiO3-TiO2 colossal permittivity system by internal lattice defects and phase composition: Experimental and theoretical investigations

The SrTiO3–TiO2 composite ceramics with different contents of La doping were fabricated by traditional solid-state sintering methods. The performance of the colossal permittivity ceramics was enhanced by the synergistic design of the internal defect structure and phase composition. When the doping content is 2%, SrTiO3–TiO2 composite ceramics possessed a colossal permittivity (ԑr ∼ 1.1 × 105), low dielectric loss (tanδ ∼ 0.050) and favorable thermal stability (−70 °C-150 °C, ΔC/C25°C ≤ ±15%). Phase structure analysis suggested that a TiO2 secondary phase was induced at the grain boundaries of SrTiO3 phase with the addition of La3+ ions. XPS and dielectric behavior analyses revealed that oxygen vacancies and lattice defects formed by inhomogeneous ion-doping act to modulate the dielectric behavior in ceramics. The IBLC interfacial effects in relation to semiconductor grains and insulation grain boundaries are the main contributors to the colossal permittivity (CP) properties of ceramics, and the contribution of the IBLC effects becomes more prominent with increasing doping content. On the basis of first-principles analysis, the ceramic lattice undergoes severe deformation when the La content is increased, and the gathering of electrons at oxygen vacancies and defects is evident. As a result, it leads to enhanced grain semiconducting properties and interfacial effects, which facilitate colossal permittivity and low dielectric loss for ceramics. The results are prospective in the application of CP ceramics.

Selective photocatalytic oxidative coupling of methane via directional activation of oxygen over Au-loaded ZnSn-LDH with defect structure

The selective photocatalytic oxidative coupling of methane (OCM) holds great potential in converting low-cost feedstock into C2 products. However, the challenge lies in improving the photocatalytic OCM activity through catalyst design and gaining a deeper understanding of reactant activation in the OCM process. Here, we synthesized Au-ZnSn-LDH with oxygen vacancies to achieve efficient selective oxidation of methane using O2. The optimal hybrid exhibits a C2H6 yield of 2666 μmol g−1 h−1 and 76.8 % selectivity. Our findings showed that the oxygen within the surface of ZnSn-LDH (possibly from adsorption at Ov vacancy sites) provides sites for the evolution of O2 to O2− with assistance from Au cocatalyst. More O2− could be generated from O2 provides a desired reactivity to selectively promote selective C−H activation of CH4 under photoexcitation. The Au cocatalyst plays crucial roles in facilitating the methyl transfer and promoting C−C coupling to produce C2H6 as the main product while avoiding undesirable overoxidation.