Lattice Defects Research Articles

Manganese oxides/graphene aerogels as lightweight microwave absorbers for extreme environment application

The development of microwave absorbing materials (MAMs) with photothermal and electrothermal properties can satisfy special requirements for MAMs used in extreme environment. Herein, manganese oxide/graphene aerogel (MnOx/GA) composites were successfully fabricated by uniformly growing MnOx on GA through combining the hydrothermal and freeze-drying methods. The MnOx/GA composite exhibits a distinctive three-dimensional network structure with heterogeneous interfaces and lattice defects that can optimize the impedance matching and enhance the interfacial polarization, resulting in improved microwave absorption (MA) performance, including absorption intensity and bandwidth. The MnOx/GA sample prepared in this study exhibits an outstanding MA intensity of −54.70 dB at a frequency of 9.92 GHz, accompanied by an effective absorption bandwidth (EAB) of 5.60 GHz with a sample thickness of 2.60 mm and a filling content of 8.0 wt%. Meanwhile, the simulation of the radar cross section (RCS) further confirms the excellent MA performance and practical application potential of the MnOx/GA material. Additionally, MnOx/GA possesses outstanding electrothermal and photothermal properties, rendering it suitable for application in extreme environments. This work provides an economical, environmentally friendly, and efficient method for preparing lightweight and broadband multi-functional MAMs.

Lattice defects distribution of H+ implanted 4H-SiC investigated by deep-ultraviolet Raman spectroscopy

Lattice defects distribution of H+ implanted 4H-SiC investigated by deep-ultraviolet Raman spectroscopy

Embedding Te4+ into Sn4+-Based Metal Halide To Passivate Structure Defects for High-Performance Light-Emitting Application.

Low-dimensional lead-halide hybrids are an emerging class of optical functional material but suffer the problems of toxicity and poor air stability. Among lead-free metal halides, tin(IV)-based metal halides are promising optoelectronic materials due to their robust structure and environmental friendliness. However, their photoluminescence (PL) properties are poor, and the underlying mechanisms are still elusive. Herein, a stable Sn4+-based halide hybrid, (C4H7N2)2SnCl6, was developed, which however exhibits poor PL properties at room temperature (RT) due to the lattice defects and the robust crystal structure. To enhance its PL efficiency, the Te4+ ion with a stereoactive 5s2 lone pair has been introduced into the lattice. As a result, Te4+-doped (C4H7N2)2SnCl6 displays broadband orange emission (∼640 nm) with a PL efficiency of ∼46% at RT. Interestingly, Te4+-doped (C4H7N2)2SnCl6 shows triple emission bands at 80 K, which could be due to the synergistic effect of the organic cations and the self-trapped state induced by Te4+. Additionally, high-performance white light-emitting diodes were prepared using Te4+-doped (C4H7N2)2SnCl6, revealing the potential of this material for lighting applications. This study provides new insight into the PL mechanism of Sn4+-based metal-halide hybrids and thus facilitates the design and development of eco-friendly light-emitting metal halides.

Free-form acoustic topological waveguides enabled by topological lattice defects

Free-form acoustic topological waveguides enabled by topological lattice defects

Imaging extended single crystal lattice distortion fields with multi-peak Bragg ptychography

Recent advances in phase-retrieval-based x-ray imaging methods have demonstrated the ability to reconstruct 3D distortion vector fields within a nanocrystal by using coherent diffraction information from multiple crystal Bragg reflections. However, these works do not provide a solution to the challenges encountered in imaging lattice distortions in crystals with significant defect content that result in phase wrapping. Moreover, these methods only apply to isolated crystals smaller than the x-ray illumination, and therefore cannot be used for imaging of distortions in extended crystals. We introduce multi-peak Bragg ptychography which addresses both challenges via an optimization framework that combines stochastic gradient descent and phase unwrapping methods for robust image reconstruction of lattice distortions and defects in extended crystals. Our work uses modern automatic differentiation toolsets so that the method is easy to extend to other settings and easy to implement in high-performance computers. This work is particularly timely given the broad interest in using the increased coherent flux in fourth-generation synchrotrons for innovative material research.

Effect of growth conditions on magnetization reversal and magnetic anisotropy in Co2Fe0.5Ti0.5Si quaternary Heusler alloy thin films

Ferromagnetic resonance and magneto-optic Kerr effect (MOKE) techniques are employed to unravel the nature of ‘in-plane’ (IP) magnetic anisotropy and magnetization reversal (MR) processes in magnetron-sputtered 100 nm Co2Fe0.5Ti0.5Si (CFTS) thin films, deposited (and subsequently annealed) at different substrate temperatures (Ts) ranging from 200 °C to 550 °C. By varying TS, the CFTS films are produced with different amounts of anti-site (AS) atomic disorder. Irrespective of the degree of AS disorder, the IP uniaxial magnetic anisotropy (UMA) is prevalent in all the CFTS films. The TS450 and TS500 films, deposited at T S = 450 °C and 500 °C, stand out as they have (i) the least AS disorder, (ii) lowest value (α = 0.0055) of the Gilbert damping constant, (iii) high saturation magnetization ( ≅770 G ) at 300 K, (iv) UMA energy density as high as ≅1.6×104erg/cc at 120 K dropping to ≅1.0×104erg/cc at 300 K, (v) spin-wave stiffness ( D ) at T = 0 K, D0≅175 meVÅ2 and, as in other CFTS films, the electron–magnon interaction is primarily responsible for the thermal renormalization of D . Furthermore, in the TS450 and TS500 films, MOKE hysteresis loops at various angles ( ψH ) that the field makes with the easy axis in the film plane, reveals two mutually exclusive UMAs, UMA1≫UMA2 , with easy axes perpendicular to each other. By contrast, only a single UMA is observed in all the remaining films. When ψH=0∘ , MOKE domain images reveal that, consistent with the uniaxial nature of magnetic anisotropy, an abrupt reversal of magnetization is accompanied by the formation of 180° domains. When ψH = 90°, due to the presence of two UMAs in TS450 and TS500 films, following the field reversal, first the reverse domains nucleate and then grow at the expense of the fundamental domains through field-induced domain wall motion.

Mesoporous hollow Fe4[Fe(CN)6)]3 hierarchical nanocrystal architecture for advanced sodium-ion batteries

Prussian blue (PB) has been broadly recognized as promising cathode materials for sodium-ion batteries (SIBs) due to its large interstitial space and robust frame structure, whereas their applications are impeded by unsatisfied long-term cyclability and poor rate capability due to its inherent lattice defects. Herein, we report to fabricate the mesoporous hollow Fe4(Fe(CN)6)3 (one kind of PB) hierarchical nanocrystal architecture by the hydrothermal crystallization and HCl etching of the mesoporous precursor Fe4[Fe(CN)6]3 cubic particles, leading to high crystallinity and large specific surface area. The resultant Fe4[Fe(CN)6]3 cathode for SIBs exhibits a good reversibility and cycling stability with a capacity retention of 75.6 % at 0.5 C after 200 cycles as well as superb rate capability featuring a stable discharge specific capacity of 30.2 mAh g−1 at as high as 10 C, demonstrating the fast kinetics and low polarization of electrochemical reaction, which might be ascribed to the unique architecture and high crystallinity. This offers a new route to designing PB cathode of for SIBs with high rate capabilities.

Generalized Kitaev spin liquid model and emergent twist defect

The Kitaev spin liquid model on a honeycomb lattice offers an intriguing feature that encapsulates both Abelian and non-Abelian phases (Alexei Kitaev, 2006). Recent studies suggest that the comprehensive phase diagram of the possible generalized Kitaev model largely depends on the specific details of the discrete lattice, which somewhat deviates from the traditional understanding of “topological” phases. In this paper, we propose an adapted version of the Kitaev spin liquid model on arbitrary planar lattices. Our revised model recovers the surface code model under certain parameter selections within the Hamiltonian terms. Changes in parameters can initiate the emergence of holes, domain walls, or twist defects. Notably, the twist defect, which presents as a lattice dislocation defect, exhibits non-Abelian braiding statistics upon tuning the coefficients of the Hamiltonian. Additionally, we illustrate that the creation, movement, and fusion of these defects can be accomplished through natural time evolution by linearly interpolating the static Hamiltonian. These defects demonstrate the Ising anyon fusion rule as anticipated. Our findings hint at possible implementation in actual physical materials owing to a more realistically achievable two-body interaction.

Experimental study and numerical simulation on porosity dependent direct reducibility of high-grade iron oxide pellets in hydrogen

The transition to more environmentally friendly steel production methods has intensified research into hydrogen-based direct reduction (HyDR) of iron oxide pellets. The aim of this study is to systematically investigate the kinetics of the reduction process, the evolution of porosity and the resulting microstructural changes on the reduction behavior of high-quality pellets during HyDR of iron ore at different temperatures. A modified mathematical model is developed based on the shrinkage kernel model, taking into account both mass and heat transport in a hydrogen atmosphere. The effects of temperature, particle size and time on the reduction behavior of the pellets are investigated. The simulated results are validated and discussed by the results of a batch of iron oxide pellets consisting of ten almost spherical pellets subjected to the direct reduction process with pure hydrogen. The results show that the total energy input to the HyDR process is a complex balance of factors, including chemical reaction rates, diffusion dynamics and entropy generation. The increase in free volume and simultaneous decrease in pore diameter reflect the dynamic nature of the microstructure, which includes additional free volume and defects due to the volume discrepancies and associated stresses between the reactant and product phases. Furthermore, the data show that higher temperatures accelerate the reduction reactions, especially the transformation of wustite into metallic iron. This phase transition is characterized by a significant volume change that cannot be accommodated by elastic deformation alone, leading to the development of lattice defects such as cracks, creep pores and dislocations that serve as stress relief mechanisms. The trends for porosity change at 950 °C and 1000 °C observed in the experimental results are correct and in good agreement with the numerical and simulated results.

Integrating Sulfur Doping with a Multi-Heterointerface Fe7S8/NiS@C Composite for Wideband Microwave Absorption.

Heterointerface engineering is presently considered a valuable strategy for enhancing the microwave absorption (MA) properties of materials via compositional modification and structural design. In this study, a sulfur-doped multi-interfacial composite (Fe7S8/NiS@C) coated with NiFe-layered double hydroxides (LDHs) is successfully prepared using a hydrothermal method and post-high-temperature vulcanization. When assembled into twisted surfaces, the NiFe-LDH nanosheets exhibit porous morphologies, improving impedance matching, and microwave scattering. Sulfur doping in composites generates heterointerfaces, numerous sulfur vacancies, and lattice defects, which facilitate the polarization process to enhance MA. Owing to the controllable heterointerface design, the unique porous structure induced multiple heterointerfaces, numerous vacancies, and defects, endowing the Fe7S8/NiS@C composite with an enhanced MA capability. In particular, the minimum reflection loss (RLmin) value reached -58.1dB at 15.8GHz at a thickness of 2.1mm, and a broad effective absorption bandwidth (EAB) value of 7.3GHz is achieved at 2.5mm. Therefore, the Fe7S8/NiS@C composite exhibits remarkable potential as a high-efficiency MA material owing to the synergistic effects of the polarization processes, multiple scatterings, porous structures, and impedance matching.

Deformation mechanism and minimum energy path in Silicon–graphite composites with lattice defects

Edge-on atomic layers in layered solids undergo buckling, which creates a structure referred to as a “ripplocation.” A collective set of multiple ripplocations is referred to as a “ripplocation boundary.” In this study, in order to investigate the impact of lattice defects on ripplocation, we investigate the buckling deformation of graphene with lattice defects under confinement. To this end, we conducted confined uniaxial compression simulations by placing graphene sheets with various lattice defects between silicon atomic layers. Different types of lattice defects affect the mechanical properties of graphene, the results show that Young's modulus of graphene with the (1,0)_5 dislocation pair was the maximum at 494.6 GPa, whereas the Young's modulus of the (1,2)_10 dislocation pair was the minimum at 309.5 GPa. In addition, we employed a differential geometry method to study the out-of-plane deformation of a single-layer graphene system. Further, we used the nudged elastic band method for various types of lattice defects in graphene to uncover the minimum transition pathways, activation energy required to move from the (1, 0) dislocation pair to the (1, 1) pair is 44.916 eV. In particular, the results indicate that graphene with lattice defects exhibit kink deformation after buckling compared to that of perfect graphene. Our study not only explores the deformation of ripplocations and kink boundaries in layered solids but also provides a more comprehensive description influencing lattice defects on the nucleation mechanism and mechanical changes of ripplocations in graphene.

Influence of Lattice Defects on Trans-Oligoene Substructure Formation in Graphene.

The photochemical reaction of iodine and graphene induces strong new Raman modes due to the formation of trans-oligoene substructures in graphene domains. This unique reactivity was demonstrated before on defect-free graphene, however leaving the influence of e. g. carbon vacancies, unexplored. Here, we investigate the photochemical reaction applied on graphene with varying average distances of lattice defects and statistically analyze the characteristic Raman modes which develop with the iodination reaction. We show that the iodination reaction does not lead to Raman-active defects and thus, the newly formed trans-oligoene substructures do not contribute to the D-mode of graphene. A statistical analysis reveals the correlation between the average distance of lattice defects and the intensity of the v1-mode. For defective graphene with average defect distances below ~1 nm no new Raman modes evolve, which is the lower limit of the substructure size probed at 532 nm and explains why this observation was not possible before using common graphene oxide as graphene source.

Behavior of Microstrain in Nd3+-Sensitized Near-Infrared Upconverting Core-Shell Nanocrystals for Defect-Induced Tailoring of Luminescence Intensity.

In an attempt to optimize the upconversion luminescence (UCL) output of a Nd3+-sensitized near-infrared (808 nm) upconverting core-shell (CS) nanocrystal through deliberate incorporation of lattice defects, a comprehensive analysis of microstrain both at the CS interface and within the core layer was performed using integral breadth calculation of high-energy synchrotron X-ray (λ = 0.568551 Å) diffraction. An atomic level interpretation of such microstrain was performed using pair distribution function analysis of the high-energy total scattering. The core NC developed compressive microstrain, which gradually transformed into tensile microstrain with the growth of the epitaxial shell. Such a reversal was rationalized in terms of a consistent negative lattice mismatch. Upon introduction of lattice defects into the CS systems upon incorporation of Li+, the corresponding UCL intensity was maximized at some specific Li+ incorporation, where the tensile microstrain of CS, compressive microstrain of the core, and atomic level disorders exhibited their respective extreme values irrespective of the activator ions.

Enhanced chalcopyrite leaching by mechanical activation: New insights from microstructure

Bioleaching is an effective technique for treating low-grade copper sulfide ore, but low leaching rate limit its industrial application of chalcopyrite bioleaching. Many passivation film compositions have been hypothesized to explain the difficulty of chalcopyrite leaching, but the essential reason remain unclear. Mechanical activation can not only reduce the solid particle size, but also result in lattice defects and induce redox reactions, and even affect the electronic structure of the solid. Therefore, the mechanical activation enhanced chalcopyrite leaching and its influence mechanism was investigated. The main conclusions are as follows: mechanical activation can significantly reduce chalcopyrite particle size, simultaneously, microscopic strain and cell volume increased; the mechanical activation changed the energy band structure of chalcopyrite—the positions of the conduction band and the valence band were positively shifted, implying that Fe3+ could more easily capture electrons from the chalcopyrite surface to be reduced, thus the leaching rate of chalcopyrite increased significantly in in Fe3+ solution. The results show that the passivation film may affect the leaching of chalcopyrite, but the structural characteristics of chalcopyrite is the essential reason for the difficulty of chalcopyrite leaching.

Theoretical modeling of defect diffusion in wide bandgap semiconductors

Since the 1940s, it has been known that diffusion in crystalline solids occurs due to lattice defects. The diffusion of defects can have a great impact on the processing and heat treatment of materials as the microstructural changes caused by diffusion can influence the material qualities and properties. It is, therefore, vital to be able to control the diffusion. This implies that we need a deep understanding of the interactions between impurities, matrix atoms, and intrinsic defects. The role of density functional theory (DFT) calculations in solid-state diffusion studies has become considerable. The main parameters to obtain in defect diffusion studies with DFT are formation energies, binding energies, and migration barriers. In particular, the utilization of the nudged elastic band and the dimer methods has improved the accuracy of these parameters. In systematic diffusion studies, the combination of experimentally obtained results and theoretical predictions can reveal information about the atomic diffusion processes. The combination of the theoretical predictions and the experimental results gives a unique opportunity to compare parameters found from the different methods and gain knowledge about atomic migration. In this Perspective paper, we present case studies on defect diffusion in wide bandgap semiconductors. The case studies cover examples from the three diffusion models: free diffusion, trap-limited diffusion, and reaction diffusion. We focus on the role of DFT in these studies combined with results obtained with the experimental techniques secondary ion mass spectrometry and deep-level transient spectroscopy combined with diffusion simulations.

Unraveling two yellow fluorescence emission mechanisms and color-changing afterglow characteristics of Dy-doped Mg2SnO4 luminescent materials

In this work, Dy ion doped Mg2SnO4 (Mg2SnO4:Dy3+) with monochromatic yellow fluorescence and color-changing long afterglow properties are prepared by the high-temperature solid-phase method. Mg2SnO4:Dy3+ shows the best luminescence performance under the preparation conditions of 1550 °C and 0.02 Dy3+ concentration. The samples are able to achieve yellow fluorescence emission (λem = 575 nm) under 350 nm and 291 nm excitation, and the emission intensity of the samples under 350 nm excitation is much higher than that of 291 nm excitation. Under 254 nm excitation, the sample not only emits bright white fluorescence but also has the ability of obvious afterglow after excitation. Moreover, the afterglow also has the color change function of transition from bright white to yellow. The luminescence mechanism study shows that Mg2SnO4:Dy3+ contains two emission centers, Dy3+ and lattice defects. Combining the results of spectroscopic measurements with the Dy3+ energy level distribution data, two different fluorescence emission processes under 291 and 350 nm excitation as well as the afterglow discoloration mechanism due to 254 nm excitation are discussed in detail.

TiO2 modified limonite for selective catalytic reduction of NO from cement kiln flue gas with NH3

Limonite was used as a precursor and TiO2 as a modifier to synthesize TiO2/Limonite composites through the wet impregnation method. The influences of the TiO2 doping amount, the calcination temperature on the denitration efficiency and the structure and properties of composites were systematically studied. The results showed that the modified catalyst over the Ti/Fe mass ratio was 0.07 and the calcination temperature was 300°C exhibited excellent catalytic activity, good stability, and remarkable resistance to water and sulfur dioxide within reaction temperature of 100 ∼ 240°C. When NO initial concentration was 0.05 % and gas hourly space velocity (GHSV) was 36,000 h−1 and the reaction temperature was 130°C, the NO conversion efficiency reached 100 %, and the N2 selectivity was 99.6 %. When the catalyst was exposed to 10 %H2O at 150°C, it maintained a 100 % NO conversion efficiency. In the presence of 10 %H2O and 50 ppm SO2 at 200°C, the NO conversion efficiency remained at 100 %. The TiO2/Limonite catalyst possessed improved performance due to the introduction of the anatase TiO2, which led to more lattice defects, weak Lewis acid sites, and higher adsorbed oxygen mobility.

In situ synthesis of three-dimensional flower-like TiO2/WO3 heterojunction: Enhanced visible photocatalytic properties and theoretical calculations

The construction of heterojunction photocatalysts is an excellent strategy for treating wastewater. Herein, a three-dimensional nanoflower-like TiO2/WO3 heterojunction photocatalyst was synthesized in situ on the surface of pure Ti substrate by plasma electrolyte oxidation (PEO) combined with a subsequent process, and the abundant network topology and lattice defects improved the adsorption performance of the photocatalyst. The construction of Z-scheme heterojunction not only promotes the separation of photogenerated carriers, but also enhances the light absorption ability and greatly improves the photocatalytic performance of photocatalysts. Under the synergistic effect of adsorption and photocatalysis, the degradation rate of MB reached 86.2 % in 2 h, which was significantly higher than that of the single-component photocatalyst. Finally, the synthesis of TiO2/WO3 heterojunction photocatalysts by this process and the reaction mechanism of heterojunction photocatalysts for the degradation of organic dyes were illustrated by combining experiments and DFT calculations. In conclusion, this study opens up a new process for synthesizing Z-scheme heterojunction photocatalysts, which brings new insights for photocatalytic treatment of water pollution.

Nanostructuring and oxygen-vacancy tuning to repress thermal transport and activate thermoelectric properties of green-synthesized ZnO

We introduce eco-friendly synthesized ZnO nanoparticles by using orange peel extract for thermoelectric applications. Orange peel extract plays a crucial role as a reducing and surface-stabilizing agent in the synthesis process. It significantly affects the microstructure and lattice defects governing transport properties and thermoelectric performance of polycrystalline ZnO. A comparison of the structural and thermoelectric properties between the green-synthesized ZnO (ZnO OPE) and commercial ZnO (ZnO com) is conducted. The outcomes indicate that the ZnO OPE sample exhibits a 3.5-time higher electrical conductivity than the commercial ZnO at 1073 K, which is thermally activated at more than 673 K by oxygen vacancies. Moreover, the highly porous nanostructure of the ZnO OPE sample substantially reduces thermal conductivity from 14.5 W/mK to 5.5 W/mK with increasing temperature from 300 to 1073 K. The combination of nanostructure and defect modification paves the way for thermoelectric ZnO-based materials synthesized using environmentally friendly processes.

Effect of Ball Milling Conditions on the Microstructure and Dehydrogenation Behavior of TiH2 Powder

This study investigated the effects of revolution speed and ball size in planetary milling on the microstructure and dehydrogenation behavior of TiH2 powder. The particle size analysis showed that the large particles present in the raw powder were effectively refined as the revolution speed increased, and when milled at 500 rpm, the median particle size was 1.47 m. Milling with a mixture of balls of two or three sizes was more effective in refining the raw powder than milling with balls of a single size. A mixture of 3-mm and 5-mm-diameter balls was the optimal condition for particle refinement, and the measured median particle size was 0.71 m. The dependence of particle size on revolution speed and ball size was explained by changes in input energy and the number of contact points of the balls. In the milled powder, the endothermic peak measured using differential thermal analysis was observed at a relatively low temperature. This finding was interpreted as the activation of a dehydrogenation reaction, mainly due to the increase in the specific surface area and the concentration of lattice defects.