Nanoscale Defects Research Articles

Nitrogen-Anchored Boridene Enables Mg-CO2 Batteries with High Reversibility.

Nanoscale defect engineering plays a crucial role in incorporating extraordinary catalytic properties in two-dimensional materials by varying the surface groups or site interactions. Herein, we synthesized high-loaded nitrogen-doped Boridene (N-Boridene (Mo4/3(BnN1-n)2-mTz), N-doped concentration up to 26.78 at %) nanosheets by chemical exfoliation followed by cyanamide intercalation. Three different nitrogen sites are observed in N-Boridene, wherein the site of boron vacancy substitution mainly accounts for its high chemical activity. Attractively, as a cathode for Mg-CO2 batteries, it delivers a long-term lifetime (305 cycles), high-energy efficiency (93.6%), and ultralow overpotential (∼0.09 V) at a high current of 200 mA g-1, which overwhelms all Mg-CO2 batteries reported so far. Experimental and computational studies suggest that N-Boridene can remarkably change the adsorption energy of the reaction products and lower the energy barrier of the rate-determining step (*MgCO2 → *MgCO3·xH2O), resulting in the rapid reversible formation/decomposition of new MgCO3·5H2O products. The surging Boridene materials with defects provide substantial opportunities to develop other heterogeneous catalysts for efficient capture and converting of CO2.

On the role of defects in modelling approaches for thin film gas barrier coatings on polymer substrates: I. Model development

We present a method to model the gas permeation through silicon-oxide thin film coatings that are afflicted with nanoscale defects. With it, we are able to give an estimation of the diffusion coefficient in bulk by subtracting the influence of the defects. The model is based on data obtained from positron annihilation spectroscopy, which is processed to yield possible defect allocation patterns of the coatings. For a systematic evaluation of these patterns, a path through the coating is calculated and then subjected to in-depth analysis to evaluate the used approach as well as to interpret the results for insights on the permeation mechanisms. The model appears to function as intended and no unexpected behaviour is observed. The defect volume share is overestimated, which can be retraced to the underlying algorithm, and a correction method is applied to the resulting bulk diffusion coefficient. The model gives reasonable results both for oxygen and water vapor permeation. These results can be used in following works that build on the presented model.

Break the strength and ductility trade-off in novel NbC reinforced Fe40.5(CoCr)25Mn17.5Ni10Si5 high entropy alloy

In this study, a novel NbC reinforced Fe40.5(CoCr)25Mn17.5Ni10Si5 high entropy alloy (HEA) was designed, which exhibits high strength and ductility at room temperature. This alloy was prepared through hot forging and annealing treatments, which exhibited the FCC microstructure with NbC and discrete nano-sized M23C6 carbides precipitation. The studied HEA retained a tensile strength of 863 MPa, and an outstanding ductility of 58 %. The microstructure evolution and deformation mechanisms were further investigated. The deformation mechanism was mainly governed by nano-scale defect heterogeneity of stacking faults (SFs), deformation twins and dislocations. The improved strength-ductility synergy is attributed to the formation of multiple SFs, deformation twining, dislocation cells, and nano-sized NbC precipitation. Moreover, the TEM observation elucidates the presence of chemical short-range order (SRO) domain in the studied HEA, which also has a major contribution in strength and ductility increment. The present findings shed light on developing the HEAs through proper compositional design and heat treatments, resulting in the combine effect of precipitation strengthening, SFs mediated plasticity, twinning induced plasticity (TWIP), and SRO effect.

Molybdenum effects on the stability of passive films unraveled at the nanometer and atomic scales

Data recently obtained on model FeCrNi(Mo), 316 L stainless steel, and FeCrNiCo(Mo) passivated surfaces by advanced surface analysis and density functional theory modeling are comprehensively discussed to unravel the multiple effects that molybdenum might have at the nanometer and atomic scales to enhance the stability of passive films. The key role played on corrosion protection by the compositional and structural nanoscale defects of the passive film that originate from the pre-passivation mechanisms of the surface is considered. It is shown how Mo, enriched together with Cr in the nanometer-thick passive film, can combine several effects to enhance the resistance to Cl--induced passivity breakdown. Enriched as Mo(VI) species in the outer exchange layer of the passive film, Mo impedes the deep penetration of Cl- ions and limits their access to the inner barrier layer. Dispersed as Mo(IV) at the interface with the inner layer, Mo protects against the entry of Cl- ions into the defect sites of the Cr(III) oxide barrier. Present as Mo(IV + δ) in the Fe-rich compositional nanoscale defects self-generated by the local failure of Cr supply upon initial formation of the barrier layer, Mo enhances the selective dissolution of iron and its replacement by chromium and molybdenum. By impeding the formation of O vacancies, Mo also increases the resistance against chloride entry in the oxide matrix, thereby curing these the Fe-rich weak sites against Cl--induced passivity breakdown.

Structure-dependent CO2 reduction on molybdenite (MoS2) electrocatalysts.

Scanning electrochemical cell microscopy (SECCM) is employed to directly identify the structure-dependent electrochemical CO2 reduction reaction (eCO2RR) activity of molybdenite (MoS2) electrocatalysts in an aqueous imidazolium-based aprotic ionic liquid electrolyte. Nanoscale defects, where the edge plane (EP) is exposed, are directly targeted, revealing heightened overall activity (eCO2RR + the competing hydrogen evolution reaction, HER) over the relatively inactive basal plane (BP). In addition, certain types of defects (e.g., step edges) only exhibit heightened activity under a CO2 atmosphere (i.e., compared to N2), indirectly confirming higher selectivity at these surface sites. Overall, this work will guide the bottom-up design of earth-abundant electrocatalysts for use in large-scale CO2 electrolysis.

Gradual degradation in InAs quantum dot lasers on Si and GaAs.

Reliable quantum dot lasers on silicon are a key remaining challenge to successful integrated silicon photonics. In this work, quantum dot (QD) lasers on silicon with and without misfit dislocation trapping layers are aged for 12 000 hours and are compared to QD lasers on native GaAs aged for 8400 hours. The non-trapping-layer (TL) laser on silicon degrades heavily during this time, but much more modest gradual degradation is observed for the other two devices. Electroluminescence imaging reveals relatively uniform gradual dimming for the aged TL laser on silicon. At the same time, we find nanoscale dislocation loop defects throughout the quantum dot-based active region of all three aged lasers via electron microscopy. The Burgers vector of these loops is consistent with . We suggest that the primary source of degradation, however, is the generation and migration of point defects that substantially enhance non-radiative recombination in the active region, the visible symptom of which is the formation of dislocation loops. To prevent this, we propose that laser fabrication should be switched from deeply etched to shallow etch ridges where the active region remains intact near the mesa. Additionally, post-growth annealing and altered growth conditions in the active region should be explored to minimize the grown-in point defect density.

Tuning the water intrinsic permeability of PEGDA hydrogel membranes by adding free PEG chains of varying molar masses.

We explore the effect of poly(ethylene glycol) (PEG) molar mass on the intrinsic permeability and structural characteristics of poly(ethylene glycol) diacrylate PEGDA/PEG composite hydrogel membranes. We observe that by varying the PEG content and molar mass, we can finely adjust the water intrinsic permeability by several orders of magnitude. Notably, we show the existence of maximum water intrinsic permeability, already identified in a previous study to be located at the critical overlap concentration C* of PEG chains, for the highest PEG molar mass studied. Furthermore, we note that the maximum intrinsic permeability follows a non-monotonic evolution with respect to the PEG molar mass and reaches its peak at 35 000 g mol-1. Besides, our results show that a significant fraction of PEG chains is irreversibly trapped within the PEGDA matrix even for the lowest molar masses down to 600 g mol-1. This observation suggests the possibility of covalent grafting of the PEG chains onto the PEGDA matrix. CryoSEM and AFM measurements demonstrate the presence of large micron-sized cavities separated by PEGDA-rich walls whose nanometric structures strongly depend on the PEG content. By combining our permeability and structural measurements, we suggest that the PEG chains trapped inside the PEGDA-rich walls induce nanoscale defects in the crosslinking density, resulting in increased permeability below C*. Conversely, above C*, we speculate that partially trapped PEG chains may form a brush-like arrangement on the surface of the PEGDA-rich walls, leading to a reduction in permeability. These two opposing effects are anticipated to exhibit molar-mass-dependent trends, contributing to the non-monotonic variation of the maximum intrinsic permeability at C*. Overall, our results demonstrate the potential to fine-tune the properties of hydrogel membranes, offering new opportunities for separation applications.

Super-Resolution Exciton Imaging of Nanobubbles in 2D Semiconductors with Near-Field Nanophotoluminescence Microscopy.

Two-dimensional (2D) semiconductors, such as transition metal dichalcogenides, have emerged as important candidate materials for next-generation chip-scale optoelectronic devices with the development of large-scale production techniques, such as chemical vapor deposition (CVD). However, 2D materials need to be transferred to other target substrates after growth, during which various micro- and nanoscale defects, such as nanobubbles, are inevitably generated. These nanodefects not only influence the uniformity of 2D semiconductors but also may significantly alter the local optoelectronic properties of the composed devices. Hence, super-resolution discrimination and characterization of nanodefects are highly demanded. Here, we report a near-field nanophotoluminescence (nano-PL) microscope that can quickly screen nanobubbles and investigate their impact on local excitonic properties of 2D semiconductors by directly visualize the PL emission distribution with a very high spatial resolution of ∼10 nm, far below the optical diffraction limit, and a high speed of 10 ms/point under ambient conditions. By using nano-PL microscopy to map the exciton and trion emission intensity distributions in transferred CVD-grown monolayer tungsten disulfide (1L-WS2) flakes, it is found that the PL intensity decreases by 13.4% as the height of the nanobubble increases by every nanometer, which is mainly caused by the suppression of trion emission due to the strong doping effect from the substrate. In addition to the nanobubbles, other types of nanodefects, such as cracks, stacks, and grain boundaries, can also be characterized. The nano-PL method is proven to be a powerful tool for the nondestructive quality inspection of nanodefects as well as the super-resolution exploration of local optoelectronic properties of 2D materials.

Prediction of Nanoscale Water Meniscus Shape between Deliquescent KDP Crystal Optics and AFM Probe for Water-Dissolution Repairing.

KDP (KH2PO4) crystal optics are the key elements for megajoule laser facilities. Nanoscale surface defects would cause laser-induced damage when the optics are irradiated by a high-fluence laser (over 10 J/cm2). Dip-pen nanolithography (DPN) could be used to repair the nanoscale surface defects in the KDP optics by the water meniscus. The high humidity required for high-efficiency and soft KDP surfaces penetrated by the AFM probe brings challenges for accurately predicting the water meniscus shape to evaluate the effectiveness of the DPN water-dissolution repairing. The multisolutions of the Young-Laplace and Kelvin equations also lead to the wrong water meniscus shape. A theoretical model that takes the high humidity and the penetration of the AFM probes into account is developed. The parametrization Young-Laplace equations are adopted for the zero contact angle of the water films, and the AFM probe is treated as the combination of the cone and sphere for the water meniscus whose size is larger than the AFM tip radius under high humidity. The penetration of the AFM probe is modeled by Hertz theory. Both the water films (3.3 nm thickness at 99% relative humidity) and indentations (1.46 nm depth at 300 nN contact force) are non-negligible for the nanoscale water meniscus between the KDP surface and the AFM probe. Moreover, the rough-fine two-step method is proposed to lock the correct solution of the Young-Laplace and Kelvin equations. The effectiveness of the proposed model is verified by comparison with reported ESEM images and pull-off forces. In addition, the overgrowth dots on the KDP surface are compared with the water meniscus. The linear growth of the water meniscus would cause the linear growth of the overgrowth dot, which proves the proposed model could be used to guide the DPN water-dissolution repairing for the nanoscale surface defects in the KDP optics.

Discrete dislocation dynamics simulations of [formula omitted]-type prismatic loops in zirconium

Neutron irradiation of zirconium alloys in light water nuclear reactors generates nano-scale defects in the form of vacancy and interstitial 〈a〉-type prismatic loops which lie in prismatic planes of the sample. The dynamics of idealised conservative square 〈a〉-type prismatic loops have been investigated for a range of loop lengths in the framework of linear isotropic elasticity. Three-dimensional dislocation dynamics (DD) simulations of a dislocation-loop interaction have been performed to investigate the dislocation-loop interaction mechanism. For this purpose, a mobility law developed for hexagonally close-packed materials has been implemented and described in detail. Analytical and numerical calculations have been performed to obtain expressions for the restoring force and angular stability of prismatic loops. These analyses have been used to inform a 2.5D discrete dislocation plasticity (DDP) model in order to emulate realistic prismatic loop physics and improve irradiation hardening simulations. From the 2.5D DDP prismatic loop analyses, it has been observed that the stable angle of smaller sized loops is less sensitive to external stresses compared to that of larger loops, which may have implications for the mechanisms of irradiation hardening. Furthermore, initial 2.5D single-slip simulations predict that prismatic loops cause significantly elevated flow stress that increases with increasing loop density in accord with experimental observations, and that the restraining effect of the out-of-plane loop segments (the restoring force) plays an important role in the strengthening caused by loops.

Sieving and Clogging in PEG-PEGDA Hydrogel Membranes.

Hydrogels are promising systems for separation applications due to their structural characteristics (i.e., hydrophilicity and porosity). In our study, we investigate the permeation of suspensions of rigid latex particles of different sizes through free-standing hydrogel membranes prepared by photopolymerization of a mixture of poly(ethylene glycol) diacrylate (PEGDA) and large poly(ethylene glycol) (PEG) chains of 300,000 g·mol-1 in the presence of a photoinitiator. Atomic force microscopy and cryoscanning electron microscopy (cryoSEM) were employed to characterize the structures of the hydrogel membranes. We find that the 20 nm particle permeation depends on both the PEGDA/PEG composition and the pressure applied during filtration. In contrast, we do not measure a significant permeation of the 100 nm and 1 μm particles, despite the presence of large cavities of 1 μm evidenced by the cryoSEM images. We suggest that the PEG chains induce local nanoscale defects in the cross-linking of PEGDA-rich walls separating the micrometer-sized cavities, which control the permeation of particles and water. Moreover, we discuss the decline of the permeation flux observed in the presence of latex particles compared to that of pure water. We suggest that a thin layer of particles forms on the surface of the hydrogels.

Toward a Nanoscale‐Defect‐Free Ni‐Rich Layered Oxide Cathode Through Regulated Pore Evolution for Long‐Lifespan Li Rechargeable Batteries

AbstractNi‐rich layered oxides are envisioned as the most promising cathode materials for next‐generation lithium‐ion batteries; however, their practical adoption is plagued by fast capacity decay originating from chemo‐mechanical degradation. The intrinsic chemical–mechanical instability, inherited from atomic‐ and nanoscale defects generated during synthesis, is not yet resolved. Here, atomic‐ and nanoscale structural evolution during solid‐state synthesis of Ni‐rich layered cathode, Li[Ni0.92Co0.03Mn0.05]O2, is investigated using combined X‐ray/neutron scattering and electron/X‐ray microscopy. The multiscale analyses demonstrate the intertwined correlation between phase transition and microstructural evolution, with atomic‐scale defects derived from the decomposition of precursors leading to the creation of intra/inter‐granular pores. The nucleation and coalescence mechanism of pore defects during the synthesis of Ni‐rich layered cathodes are quantitatively revealed. Furthermore, a modified synthetic route is proposed to effectively circumvent the formation of nanoscale defects in Ni‐rich layered cathodes by facilitating uniform synthetic reactions, resulting in superior electrochemical and microstructural stability.

Assessing the quality of large-area monolayer graphene grown on liquid copper for size-selective ionic/molecular membrane separations

Monolayer graphene growth on liquid copper (Cu) has attracted attention due to advantages of a flat/smooth catalytic growth surface, high synthesis temperature (>1080 °C) as well as the possibility of forming graphene domains that are mobile on the liquid Cu with potential to minimize grain boundary defects and self-assemble into a continuous monolayer film. However, the quality of monolayer graphene grown on liquid copper and its suitability for size-selective ionic/molecular membrane separations has not been evaluated/studied. Here, we probe the quality of monolayer graphene grown on liquid Cu (via a metallurgical process, HSMG®) using Scanning Electron Microscope (SEM), High-resolution transmission electron microscope (HR-TEM), Raman spectroscopy and report on a facile approach to assess intrinsic sub-nanometer to nanometer-scale defects over centimeter-scale areas. We demonstrate high transfer yields of monolayer graphene (>93% coverage) from the growth substrate to polyimide track etched membrane (PITEM, pore diameter ∼200 nm) supports to form centimeter-scale atomically thin membranes. Next, we use pressure-driven transport of ethanol to probe defects > 60 nm and diffusion-driven transport of analytes (KCl ∼0.66 nm, L-Tryptophan ∼0.7–0.9 nm, Vitamin B12 ∼1–1.5 nm and Lysozyme ∼3.8–4 nm) to probe nanoscale and sub-nanometer scale defects. Diffusive transport confirms the presence of intrinsic sub-nanometer to nanometer scale defects in monolayer graphene grown on liquid Cu are no less than that in high-quality graphene synthesized via chemical vapor deposition (CVD) on solid Cu. Our work not only benchmarks quality of graphene grown on liquid copper for membrane applications but also provides fundamental insights into the origin of intrinsic defects in large-area graphene synthesized via bottom-up processes for membrane applications.

Investigation of Surface Defects in Optical Components Based on Reflection Mueller Matrix Spectroscopy

Nanoscale defects on the surface of ultra-precision optical elements seriously affect the beam quality in optical systems. In response to the challenge of detecting nanoscale defects on optical component surfaces, we propose a method for the detection and classification of various types of defects on optical component surfaces via reflection Mueller matrix spectroscopy (RMMS). Firstly, an electromagnetic scattering theoretical model for various types of defects on the surface of optical elements and the incident and scattered fields were established by combining the bidirectional reflection distribution function (BRDF) and the Rayleigh–Rice vector scattering theory. Then, the optimal conditions for RMMS measurements were determined by numerically simulating the BRDF. On this basis, the surface roughness and pockmarks of the optical test plate were simulated and analyzed via RMMS, and the results were verified experimentally; then, dirty particles and pockmarks above the surface of the optical element and subsurface bubble defects (SSBD) were simulated and analyzed via RMMS. The results showed that some elements of the Mueller matrix could significantly distinguish defects on the surface of the optical element with dimensions smaller than the visible wavelength, and the dimensions of various types of defects of the element could be inverted using the values of the Mueller matrix elements. This method provides a theoretical basis and reference for the detection and classification of various types of defects in precision optical components.

Low Energy Twist Defects in Pentatwinned Silver Nanowires

Transmission electron microscopy investigation of networks of pentatwinned silver nanowires has identified the presence of nanoscale defects within individual wires, showing narrow regions of banded contrast normal to the nanowire axis (bamboo faults). Structural analysis using machine learning decomposition of scanning precession electron diffraction data identifies these bamboo faults as a pair of twist boundaries normal to the wire axis creating low energy coincident site lattices between the faulted region and the parent nanowire. This leads to a conservation of the relative misorientation of the twinned structure within the faulted region, leading to an apparent local rotation of the nanowire. Their presence after spraying and nonthermal processing suggests that they may form during nanowire synthesis. However, examination of the networks before and after cyclic straining finds an increase in the density of the defects, indicating that they may also form as a result of mechanical deformation.

Engineer Nanoscale Defects into Selective Channels: MOF-Enhanced Li+ Separation by Porous Layered Double Hydroxide Membrane

Highlights The zeolitic imidazolate framework functionalized modified layered double hydroxide (ZIF-8@MLDH) composite membranes with superior structural stability and Li+ permeability are prepared by selectively growing ZIF-8 nanoparticles in the framework defects of the MLDH membrane.The tailor-made ZIF-8@MLDH membrane has a large Li+ permeability of up to 1.73 mol m-2 h-1 and a high Li+/Mg2+ selectivity of 31.9, which exceed most of the current 2D lamellar membranes.

Near‐Field Nano‐Optical Imaging of van der Waals Materials

Abstract2D van der Waals (vdW) materials are emerging as the next generation platform for optical and electronic devices with their wide coverage of the energy bandgaps. The strong light–matter interactions in 2D vdW layers allow for exploring novel optical and electronic phenomena such as 2D polaritons exhibiting ultrahigh field confinement, defects‐induced new quantum states, and strain‐modulated quantum confinement of 2D excitons. Far‐field optical imaging techniques are extensively used to characterize the 2D vdW materials so far, however, subdiffraction spatial resolution is required for comprehensive investigations of 2D vdW materials of which physical properties are greatly influenced by local defects and strain. This article aims to cover historical advances, fundamental principles, and distinct features of emerging near‐field optical imaging techniques: scattering‐type scanning near‐field optical microscopy, tip‐enhanced Raman spectroscopy, tip‐enhanced photoluminescence techniques, and photo‐induced force microscopy. The recent developments toward spectroscopic analysis of near‐field imaging and applications for unveiling unique properties of 2D polaritons, nanoscale defects, and mechanical strains in 2D vdW materials, are also discussed. This review article provides an understanding of emerging near‐field imaging techniques and suggests prospective applications for exploring 2D vdW materials.

Comprehensive review on thermal aspects of nonthermal irreversible electroporation

AbstractIrreversible electroporation (IRE) is an innovative cell ablation method based on the concept that the application of excessive electric pulses induces a lethal increase in the permeability of the cell membrane owing to nanoscale defects, resulting in a gentle form of necrotic cell death. Although the mechanism of cell death by IRE is primarily nonthermal, thermal effects are inevitable because electric pulses inherently generate Joule heat. The larger the applied voltage to treat a large target, the greater the Joule heating and the consequent temperature rise. Therefore, the temperature increase due to Joule heating during pulse application should be carefully controlled to minimize thermal damage. Research on IRE is an interdisciplinary endeavor incorporating health science for humanitarian relief and engineering. Therefore, this study provides a comprehensive review of the thermal aspects of IRE based on existing in vitro and in vivo experimental and numerical studies. The paper begins with an overview of IRE treatment covering the geometry and arrangement of electrodes, pulse parameters, and cell death mechanisms, followed by sections on thermal damage evaluation that summarize the significant work of experiments, analysis, and comparisons. Finally, thermal mitigation strategies, including electrode modification, lowering the IRE threshold, and modified pulsing protocols, are discussed.

Oxygen-defects evolution to stimulate continuous capacity increase in Co-free Li-rich layered oxides

Though oxygen defects are associated with deteriorated structures and aggravated cycling performance in traditional layered cathodes, the role of oxygen defects is still ambiguous in Li-rich layered oxides due to the involvement of oxygen redox. Herein, a Co-free Li-rich layered oxide Li1.286Ni0.071Mn0.643O2 has been prepared by a co-precipitation method to systematically investigate the undefined effects of the oxygen defects. A significant O2 release and the propagation of oxygen vacancies were detected by operando differential electrochemical mass spectroscopy (DEMS) and electron energy loss spectroscopy (EELS), respectively. Scanning transmission electron microscopy-high angle annular dark field (STEM-HAADF) reveals the oxygen vacancies fusing to nanovoids and monitors a stepwise electrochemical activation process of the large Li2MnO3 domain upon cycling. Combined with the quantitative analysis conducted by the energy dispersive spectrometer (EDS), existed nano-scale oxygen defects actually expose more surface to the electrolyte for facilitating the electrochemical activation and subsequently increasing available capacity. Overall, this work persuasively elucidates the function of oxygen defects on oxygen redox in Co-free Li-rich layered oxides.

MEMS Reliability: On-Chip Testing for the Characterization of the Out-of-Plane Polysilicon Strength

Polycrystalline silicon is a brittle material, and its strength results are stochastically linked to microscale (or even nanoscale) defects, possibly dependent on the grain size and morphology. In this paper, we focus on the out-of-plane tensile strength of columnar polysilicon. The investigation has been carried out through a combination of a newly proposed setup for on-chip testing and finite element analyses to properly interpret the collected data. The experiments have aimed to provide a static loading to a stopper, exploiting electrostatic actuation to move a massive shuttle against it, up to failure. The failure mechanism observed in the tested devices has been captured by the numerical simulations. The data have been then interpreted by the Weibull theory for three different stopper sizes, leading to an estimation of the reference out-of-plane strength of polysilicon on the order of 2.8-3.0 GPa, in line with other results available in the literature.