Twinning and 9R Phase Transition Mediated Extraordinary Cold-drawn Deformability in NiCoCrFeMo High-Entropy Alloy.

The production and application of materials are evolving towards the low-dimensional micro-nano scale. Nevertheless, the fabrication of micron-scale alloy fibers remains a challenge. Herein, a novel Ni-Co-Cr-Fe-Mo high-entropy alloy (HEA) fiber with a cold-drawn reduction rate of 99.9995% and a strain (ɛ) of 12.19 is presented without requiring intermediate annealing. The exceptional deformation strain of 11.62 within the fiber leads to extraordinary tensile strengths of 2.8 GPa at room temperature and 3.6 GPa at 123 K. The in-depth investigation of the microstructure of fibers has revealed the cold drawing deformation mechanisms mediated by the synergistic effects of plane defects. Specifically, various geometrically necessary dislocation interfaces, such as dislocation walls and microbands, along with deformation twins and long-period 9R structures, form in response to external stress when ɛ≤2.7. As the strain increases, the saturated layered structure emerges and progressively evolves into a 3D equiaxed crystal. Moreover, the formation and evolution of the 9R structure (i.e., the migration of incoherent twin boundaries), coupled with the interaction of partial dislocations and the role of deformation twins, are crucial factors determining the fiber's plastic response. This work provides a novel approach to discovering new high-strength metallic fibers with excellent deformability through plane defects engineering.

Substantial Energy Band Modulation of Semiconducting Hexagonal GaTe Quantum Wells by Layer Thickness and Mirror Twin Boundaries.

Exploring emerging two-dimensional (2D) van der Waals (vdW) semiconducting materials and precisely tuning their electronic properties at the atomic level have long been recognized as crucial issues for developing their high-end electronic and optoelectronic applications. As a III-VI semiconductor, ultrathin layered hexagonal GaTe (h-GaTe) remains unexplored in terms of its intrinsic electronic properties and band engineering strategies. Herein, we report the successful synthesis of ultrathin h-GaTe layers on a selected graphene/SiC(0001) substrate, via molecular beam epitaxy (MBE). The widely tunable quasiparticle band gaps (∼2.60-1.55 eV), as well as the vdW quantum well states (QWSs) that can be strictly counted by the layer numbers, are well characterized by onsite scanning tunneling microscopy/spectroscopy (STM/STS), and their origins are clearly addressed by density functional theory (DFT) calculations. More intriguingly, distinctive 8|8E and 4|4P (Ga) mirror twin boundaries (MTBs) are identified in the ultrathin h-GaTe flakes, which can induce decreased band gaps and prominent p-doping effects. This work should deepen our understanding on the electronic tunability of 2D III-VI semiconductors by thickness control and line defect engineering, which may hold promise for fabricating atomic-scale vertical and lateral homojunctions toward ultrascaled electronics and optoelectronics.

Unraveling Mechanism for Microstructure Engineering toward High-Capacity Nickel-Rich Cathode Materials.

Microstructural engineering on nickel-rich layered oxide (NRLO) cathode materials is considered a promising approach to increase both the capacity and lifespan of lithium-ion batteries by introducing high valence-state elements. However, rational regulation on NRLO microstructures based on a deep understanding of its capacity enhancement mechanism remains challenging. Herein for the first time, it is demonstrated that an increase of 14 mAh g-1 in reversible capacity at the first cycle can be achieved via tailoring the micro and nano structure of NRLO through introducing tungsten. Aberration-corrected scanning transmission electron microscopy (STEM) characterization reveals that the formation of a modified microstructure featured as coherent spinel twin boundaries. Theoretical modeling and electrochemical investigations further demonstrate that the capacity increase mechanism is related to such coherent spinel twin boundaries, which can lower the Li+ diffusion barrier and thus allow more Li+ to participate in deeper phase transitions. Meanwhile, the surface and grain boundaries of NRLOs are found to be modified by generating a dense and uniform LiWxOy phase, which further extends its cycle life by reducing side reactions with electrolytes. This work enables a comprehensive understanding of the capacity-increased mechanism and endows the remarkable potential of microstructural engineering for capacity- and lifespan-increased NRLOs.

Characterizing Local Electronic States of Twin Boundaries in Copper.

Grain boundaries (GBs) and twin boundaries (TBs) in copper (Cu) are two major planar defects that influence electrical conductivity due to their complex electron transport characteristics, involving electron scattering and electron concentration. Understanding their local electronic states is crucial for the design of future conductor materials. In this study, we characterized electron behaviors at TBs and GBs within one Cu grain using atomic force microscopy. Our findings revealed that, compared with GBs, TBs exhibit better current transport capability (direct-current mode) and larger electromagnetic loss (high-frequency microwave mode). Both kelvin probe force microscopy and theoretical analysis suggested that TBs with smaller lattice disorder possess lower density of states at the Fermi level. The reduced density of states may result in decreased electron scattering and a lower electron concentration at TBs. The latter can be highlighted by the high-frequency skinning effect, manifested as larger electromagnetic loss and weaker high-frequency conductivity.

The Electrical Behaviors of Grain Boundaries in Polycrystalline Optoelectronic Materials.

Polycrystalline optoelectronic materials are widely used for photoelectric signal conversion and energy harvesting and play an irreplaceable role in the semiconductor field. As an important factor in determining the optoelectronic properties of polycrystalline materials, grain boundaries (GBs) are the focus of research. Particular emphases are placed on the generation and height of GB barriers, how carriers move at GBs, whether GBs act as carrier transport channels or recombination sites, and how to change the device performance by altering the electrical behaviors of GBs. This review introduces the evolution of GB theory and experimental observation history, classifies GB electrical behaviors from the perspective of carrier dynamics, and summarizes carrier transport state under external conditions such as bias and illumination and the related band bending. Then the carrier scattering at GBs and the electrical differences between GBs and twin boundaries are discussed. Last, the review describes how the electrical behaviors of GBs can be influenced and modified by treatments such as passivation or by consciously adjusting the distribution of grain boundary elements. By studying the carrier dynamics and the relevant electrical behaviors of GBs in polycrystalline materials, researchers can develop optoelectronics with higher performance.

In Situ Observation of Fracture along Twin Boundaries in Boron Carbide.

The observation of fracture behaviors in perfect and twinned B4 C crystals via in situ transmission electron microscopy (TEM) mechanical testing is reported. The crystal structure of the synthesized B4 C, composed of B11 C icosahedra connected by boron-deficient C-▫-C chains in a chemical formula of B11 C3 , is determined by state-of-the-art aberration-corrected scanning TEM. The in situ TEM observations reveal that cracking is preferentially initiated at the twin boundaries (TBs) in B4 C under both indentation and tension loading. The cracks then propagate along the TBs, thus resulting in the fracture of B4 C. These results are consistent with the theoretical calculations that show that TBs have a softening effect on B4 C with amorphous bands preferentially nucleated at the TBs. These findings elucidate the atomic arrangement and the role of planar defects in the failure of B4 C. Furthermore, they can guide the design of advanced superhard materials via planar defect control.

Exploration of Twin-Modified Grain Boundary Engineering in Metallic Copper Predominated Electromagnetic Wave Absorber.

High density and skin effect restrict the research progress of metal predominated electromagnetic wave absorbing (EMA) materials. Although some works try to solve it, they do not focus on the metal itself and do not involve the optimization of the active site of the inherent defects of the metal. In this work, the modulation of morphology, composition, interface, defects, and conductivity is achieved by adjusting the ratio of copper salt to reducing agent chitosan. Uniquely, the appearance of twin boundaries (TBs) accelerates the ability of the homogeneous interfaces to transfer charges, resists the oxidation of metal Cu0 , keeps the high electric conductivity of Cu0 nanoparticles, and enhances the conduction loss, which provides a boost for electromagnetic wave dissipation. As a result, the metal Cu0 predominated absorber (Cu-NC (N-doped carbon)-10,) exhibits an ultra-width effective absorption band of 8.28 GHz (9.72-18.00 GHz) at a thickness of 2.47 mm and the minimum reflection loss (RL) value of -63.8 dB with a thickness of 2.01 mm. In short, this work explores the EM regulation mechanism of TBs compared with grain boundaries (GBs), which provides a new insight for the rational design of metal predominated EMA materials.

Controlling the Thermoelectric Properties of Nb-Doped TiO2 Ceramics through Engineering Defect Structures.

Donor-doped TiO2 ceramics are promising high-temperature oxide thermoelectrics. Highly dense (1 - x)TiO2-xNb2O5 (0.005 ≤ x ≤ 0.06) ceramics were prepared by a single-step, mixed-oxide route under reducing conditions. The microstructures contained polygonal-shaped grains with uniform grain size distributions. Subgrain structures were formed in samples with low Nb contents by the interlacing of rutile and higher-order Magnéli phases, reflecting the high density of shear planes and oxygen vacancies. Samples prepared with a higher Nb content showed no subgrain structures but high densities of planar defects and lower concentrations of oxygen vacancies. Through optimizing the concentration of point defects and line defects, the carrier concentration and electrical conductivity were enhanced, yielding a much improved power factor of 5.3 × 10-4 W m-1 K-2 at 823 K; lattice thermal conductivity was significantly reduced by enhanced phonon scattering. A low, temperature-stable thermal conductivity of 2.6 W m-1 K-1 was achieved, leading to a ZT value of 0.17 at 873 K for compositions with x = 0.06, the highest ZT value reported for single Nb-doped TiO2 ceramics without the use of spark plasma sintering (SPS). We demonstrate the control of the thermoelectric properties of Nb-doped TiO2 ceramics through the development of balanced defect structures, which could guide the development of future oxide thermoelectric materials.

Evaluation of Dihedral Angle Twin Boundaries in Cu10 wt%Zn Alloy Using Atomic Force Microscopy.

Atomic force microscopy (AFM) measurements of dihedral angles are conducted for the first time to characterize the ratio of the twin-boundary energy (γΤ) to the surface free energy (γS). In plane, twin morphology is measured with AFM, verified by scanning electron microscopy, optical microscopy, and found to be consistent. The chemical composition and homogeneity of annealed Cu10 wt%Zn sample are confirmed by energy-dispersive spectroscopy. AFM data indicate that the average depth and height of the grooves and peaks are 118 ± 45 and 158 ± 45 nm, respectively. Surface roughness parameters, Sq and Sa, are measured by a factor of two to four less than the depth and height of the twin boundaries. Both surface roughness parameters are less with no planar defects present compared with selected areas containing twin boundaries. The average dihedral angle is found to be 167 ± 5° for the grooves and 193 ± 4° for the peaks. The twin to surface interfacial free energy ratio, γT/γS, is 0.0018. The comparison of AFM-based results to the other method-based results obtained on pure metals is discussed.

Twinning-Detwinning in Pre-Compressed and Thermally Treated ZX10 and ZN10 Alloys.

The deformation behavior of extruded Mg alloys with a Ca or Nd addition (up to 0.5 wt.%) is addressed with respect to a specified thermo-mechanical treatment, realized by pre-compression and subsequent heat treatment at intermediate temperature. The twinning-detwinning process is discussed with respect to the initial texture and applied heat treatment. Isothermal aging leads to precipitation and segregation along twin boundaries and dislocations in the pre-compressed Mg alloys, and, thus, variation in the mobility of twin boundaries (TB) is observed in the investigated alloys. Despite individual scenarios of TB mobility in particular grains, in general, the same TB mobility modes are observed in the alloys independently on Ca or Nd alloying. The microstructure development, particularly the twin volume fraction and the mobility of tensile {10-12} twin boundaries, is tracked using scanning electron microscopy, including backscattered electron (BSE) imaging and electron backscatter diffraction (EBSD) mapping.

Direct Observation of One-Dimensional Peierls-type Charge Density Wave in Twin Boundaries of Monolayer MoTe2.

One-dimensional (1D) metallic mirror-twin boundaries (MTBs) in monolayer transition-metal dichalcogenides exhibit a periodic charge modulation and provide an ideal platform for exploring collective electron behavior in the confined system. The underlying mechanism of the charge modulation and how the electrons travel in 1D structures remain controversial. Here, for the first time, we observed atomic-scale structures of the charge distribution within one period in MTB of monolayer MoTe2 by using scanning tunneling microscopy/spectroscopy. The coexisting apparent periodic lattice distortions and U-shaped energy gap clearly demonstrate a Peierls-type charge density wave (CDW). Equidistant quantized energy levels with varied periodicity are further discovered outside the CDW gap along the metallic MTB. Density functional theory calculations are in good agreement with the gapped electronic structures and reveal that they originate mainly from a Mo 4d orbital. Our work presents hallmark evidence of the 1D Peierls-type CDW on the metallic MTBs and offers opportunities to study the underlying physics of 1D charge modulation.

Twisted palladium-copper nanochains toward efficient electrocatalytic oxidation of formic acid.

Twisted PdCu nanochains are synthesized successfully via a staged thermal treatment route, offering rich twin boundaries as catalytic "active sites" and modified electronic effects. Toward formic acid oxidation, the twisted PdCu nanochains hold the highest catalytic peak current density (1108.2 mA mg-1Pd) over previous reported PdCu alloy catalysts, and also much higher catalytic activity and durability comparing with Pd nanochains and commercial Pd/C. The catalytic enhancement mechanism to PdCu nanochains is proposed and discussed. Additionally, we found that the formation of PdCu nanochains follows a typical anisotropic growth approach, and the multiple steps of staged thermal treatment route displays a vital role in fabricating the unique PdCu nanochains while the introduced Cu precursors might affect the reduction rate of Pd species and act as deposition or nucleation sites for twisted structure in terms of rich twin boundaries. This work describes an efficient, low-Pd loading catalyst for electrooxidation of formic acid, and also demonstrates a universal method to fabricate other defect-rich catalysts for broad applications in energy conversion and storage systems and sensing devices.

Microscale 3D Printing of Nanotwinned Copper.

Nanotwinned (nt)-metals exhibit superior mechanical and electrical properties compared to their coarse-grained and nanograined counterparts. nt-metals in film and bulk forms are obtained using physical and chemical processes including pulsed electrodeposition (PED), plastic deformation, recrystallization, phase transformation, and sputter deposition. However, currently, there is no process for 3D printing (additive manufacturing) of nt-metals. Microscale 3D printing of nt-Cu is demonstrated with high density of coherent twin boundaries using a new room temperature process based on localized PED (L-PED). The 3D printed nt-Cu is fully dense, with low to none impurities, and low microstructural defects, and without obvious interface between printed layers, which overall result in good mechanical and electrical properties, without any postprocessing steps. The L-PED process enables direct 3D printing of layer-by-layer and complex 3D microscale nt-Cu structures, which may find applications for fabrication of metamaterials, sensors, plasmonics, and micro/nanoelectromechanical systems.

Helical Growth of Ultrathin Gold-Copper Nanowires.

In this work, we report the synthesis and detailed structural characterization of novel helical gold-copper nanowires. The nanowires possess the Boerdijk-Coxeter-Bernal structure, based on the pile up of octahedral, icosahedral, and/or decahedral seeds. They are self-assembled into a coiled manner as individual wires or into a parallel-ordering way as groups of wires. The helical nanowires are ultrathin with a diameter of less than 10 nm and variable length of several micrometers, presenting a high density of twin boundaries and stacking faults. To the best of our knowledge, such gold-copper nanowires have never been reported previously.

A Shear Strain Route Dependency of Martensite Formation in 316L Stainless Steel.

In this study, the effect of simple shearing on microstructure evolution and mechanical properties of 316L austenitic stainless steel were investigated. Two different shear strain routes were obtained by twisting cylindrical specimens in the forward and backward directions. The strain-induced martensite phase was effectively obtained by alteration of the routes. Formation of the martensite phase clearly resulted in significant hardening of the steel. Grain-size reduction and strain-induced martensitic transformation within the deformed structures of the strained specimens were characterized by scanning electron microscopy - electron back-scattered diffraction, X-ray diffraction, and the TEM-ASTAR (transmission electron microscopy - analytical scanning transmission atomic resolution, automatic crystal orientation/phase mapping for TEM) system. Significant numbers of twin networks were formed by alteration of the shear strain routes, and the martensite phases were nucleated at the twin interfaces.

Impact of twin boundaries on bulk elastic constants: Density-functional theory data for Young׳s modulus of Ag.

Experimental and theoretical studies on nanowires have reported a size-dependence of the Young׳s modulus in the axial direction, which has been attributed to the increasing influence of surface stresses with decreasing wire diameter. Internal interfaces and their associated interface stresses could lead to similar changes in the elastic properties. In Kobler et al. [1], however, we reported results from atomistic calculations which showed for Ag that twin boundaries have a negligible effect on the Young׳s modulus. Here, we present data of density-functional theory calculations of elastic constants and Young׳s modulus for defect-free bulk Ag as well as for bulk Ag containing dense arrays of twin boundaries. It is shown that rigorous convergence tests are required in order to be able to deduce changes in the elastic properties due to bulk defects in a reliable way.

Tunable Dirac Electron and Hole Self-Doping of Topological Insulators Induced by Stacking Defects.

Via density functional theory based calculations we show that self-doping of the surface Dirac cones in three-dimensional Bi2X3 (X = Se, Te) topological insulators can be tuned by controlling the sequence of stacking defects in the crystal. Twin boundaries inside the Bi2X3 bulk drive either n- or p-type self-doping of the (0001) topological surface states, depending on the precise orientation of the twin. The surface doping may achieve values up to 300 meV and can be controlled by the number of defects and their relative position with respect to the surface. Its origin relies on the spontaneous polarization generated by the dipole moments associated with the lattice defects. Our findings open the route to the fabrication of Bi2X3 surfaces with tailored surface charge and spin densities in the absence of external electric fields. In addition, in a thin film geometry two-dimensional electron and hole Dirac gases with the same spin-helicity coexist at opposite surfaces.

Dislocation-Governed Plastic Deformation and Fracture Toughness of Nanotwinned Magnesium.

In this work, the plastic deformation mechanisms responsible for mechanical properties and fracture toughness in nanotwinned (NT) magnesium is studied by molecular dynamics (MD) simulation. The influence of twin boundary (TBs) spacing and crack position on deformation behaviors are investigated. The microstructure evolution at the crack tip are not exactly the same for the left edge crack (LEC) and the right edge crack (REC) models according to calculations of the energy release rate for dislocation nucleation at the crack tip. The LEC growth initiates in a ductile pattern and then turns into a brittle cleavage. In the REC model, the atomic decohesion occurs at the crack tip to create a new free surface which directly induces a brittle cleavage. A ductile to brittle transition is observed which mainly depends on the competition between dislocation motion and crack growth. This competition mechanism is found to be correlated with the TB spacing. The critical values are 10 nm and 13.5 nm for this transition in LEC and REC models, respectively. Essentially, the dislocation densities affected by the TB spacing play a crucial role in the ductile to brittle transition.