Lattice Distortion Promotes Incipient Plasticity in Multiprincipal Element Alloys.

Multiprincipal element alloys usually exhibit earlier pop-in events than pure metals and dilute solid solutions during nanoindentation experiments. To understand the origin of this phenomenon, large-scale atomic simulations of nanoindentation were performed on a series of metallic materials to investigate the underlying physics of incipient plasticity at the nanoscale. Statistical result shows that lattice distortion δ and normalized critical pressure pc/Es follow a power-law relationship. Via quantitative analysis on the relative positions of the atoms within the nearest neighbor shell, the physical origin of premature incipient plasticity is revealed as severe lattice distortion induces large relative atomic displacement, so only a small indentation strain is required to meet the critical displacement threshold that triggers incipient plasticity. Therefore, for perfect crystals, lattice distortion is an intrinsic and determinative factor that affects the first pop-in event.

Efficient Tin Perovskite Solar Cells via Suppressing Autoxidation in Inert Atmosphere.

The unsatisfactory power conversion efficiency (PCE) and long-term stability of tin perovskite solar cells (TPSCs) restrict its further development as alternatives to lead perovskite solar cells (LPSCs). Considerable research has focused on the negative impacts of O2 and H2 O, while discussions about degradation mechanism in an inert atmosphere remains insufficient. Herein, the light-induced autoxidation of tin perovskite in nitrogen atmosphere is revealed for the first time and the elastic lattice distortion is demonstrated as the crucial role of rapid degradation. The continuous injection of photons induces energy transfer from excited A-site cations to vibrating Sn-I framework, leading to the elastic deformation of perovskite lattice. Consequently, the over distorted Sn-I framework releases free iodine and further oxidizes Sn2+ in the form of molecular iodine. Through an appropriately designed light-dark cyclic test, a remarkable PCE of 14.41% is achieved based on (Cs0.025 (MA0.25 FA0.75 )0.975 ) 0.98 EDA0.01 SnI3 solar cells, which is the record of hybrid triple TPSCs so far. The findings unveil autoxidation as the crux of TPSCs' degradation in an inert atmosphere and suggest the possibility of reinforcing the tin perovskite lattice towards highly efficient and stable TPSCs.

Unraveling Lattice-Distortion Hardening Mechanisms in High-Entropy Carbides.

Uncovering the hardening mechanisms is of great importance to accelerate the design of superhard high-entropy carbides (HECs). Herein, the hardening mechanisms of HECs by a combination of experiments and first-principles calculations are systematically explored. The equiatomic single-phase 4- to 8-cation HECs (4-8HECs) are successfully fabricated by the two-step approach involving ultrafast high-temperature synthesis and hot-press sintering techniques. The as-fabricated 4-8HEC samples possess fully dense microstructures (relative densities of up to ≈99%), similar grain sizes, clean grain boundaries, and uniform compositions. With the elimination of these morphological properties, the monotonic enhancement of Vickers hardness and nanohardness of the as-fabricated 4-8HEC samples is found to be driven by the aggravation of lattice distortion. Further studies show no evident association between the enhanced hardness of the as-fabricated 4-8HEC samples and other potential indicators, including bond strength, valence electron concentration, electronegativity mismatch, and metallic states. The work unveils the underlying hardening mechanisms of HECs and offers an effective strategy for designing superhard HECs.

Enhanced Spin-Polarized Electric Field Modulating p-Band Center on Ni-Doped CdS for Boosting Photocatalytic Hydrogen Evolution.

It is a challenge to regulate charge separation dynamics and redox reaction kinetics at the atomic level to synergistically boost photocatalytic hydrogen (H2) evolution. Herein, a robust Ni-doped CdS (Ni-CdS) photocatalyst is synthesized by incorporating highly dispersed Ni atoms into the CdS lattice in substitution for Cd atoms. Combined characterizations with theoretical analysis indicate that local lattice distortion and S-vacancy of Ni-CdS induced by Ni incorporation lead to an increased dipole moment and enhanced spin-polarized electric field, which promotes the separation and transfer of photoinduced carriers. In this contribution, charge redistribution caused by enhanced internal electric field results in the downshift of the S p-band center, which is conducive to the desorption of intermediate H* for boosting the H2 evolution reaction. Accordingly, the Ni-CdS photocatalyst shows a remarkably improved photocatalytic performance with an H2 evolution rate of 20.28 mmol g-1 h-1 under visible-light irradiation, which is 5.58 times higher than that of pristine CdS. This work supplied an insightful understanding that the enhanced polarization electric field governs the p-band center for efficient photocatalytic H2 evolution activity.

Influence of Light Atoms on Quantification of Atomic Column Positions in Distorted Perovskites with HAADF-STEM.

Measurement of picometer-scale atomic displacements by aberration-corrected STEM has become invaluable in the study of crystalline materials, where it can elucidate ordering mechanisms and local heterogeneities. HAADF-STEM imaging, often used for such measurements due to its atomic number contrast, is generally considered insensitive to light atoms such as oxygen. Light atoms, however, still affect the propagation of the electron beam in the sample and, therefore, the collected signal. Here, we demonstrate experimentally and through simulations that cation sites in distorted perovskites can appear to be displaced by several picometers from their true positions in shared cation-anion columns. The effect can be decreased through careful choice of sample thickness and beam voltage or can be entirely avoided if the experiment allows reorientation of the crystal along a more favorable zone axis. Therefore, it is crucial to consider the possible effects of light atoms and crystal symmetry and orientation when measuring atomic positions.

Observations of Charge-Density-Wave States in W6Te6 Wires.

Determining the electronic ground state of a one-dimensional system is crucial to understanding the underlying physics of electronic behavior. Here, we demonstrate the discovery of charge-density wave states in few-wire W6Te6 arrays using scanning tunneling microscopy/spectroscopy. We directly visualize incommensurate charge orders, energy gaps with prominent coherence peaks, and the picometer-scale lattice distortion in nearly disorder-free double-wire systems, thereby demonstrating the existence of Peierls-type charge density waves. In the presence of disorder-induced charge order fluctuations, the coherence peaks resulting from phase correlation disappear and gradually transform the system into the pseudogap states. The power-law zero-bias anomaly and quasi-particle interference analysis further suggest the Tomonaga-Luttinger liquid behavior in such pseudogap region. In addition, we explicitly determined the evolution of the CDW energy gap as a function of stacking-wire numbers. The present study demonstrates the existence of electron-phonon interactions in few-wire W6Te6 that can be tuned by disorders and van der Waals stacking.

Concentrated Formic Acid from CO2 Electrolysis for Directly Driving Fuel Cell.

The production of formic acid via electrochemical CO2 reduction may serve as a key link for the carbon cycle in the formic acid economy, yet its practical feasibility is largely limited by the quantity and concentration of the product. Here we demonstrate continuous electrochemical CO2 reduction for formic acid production at 2 M at an industrial-level current densities (i.e., 200 mA cm-2 ) for 300 h on membrane electrode assembly using scalable lattice-distorted bismuth catalysts. The optimized catalysts also enable a Faradaic efficiency for formate of 94.2 % and a highest partial formate current density of 1.16 A cm-2 , reaching a production rate of 21.7 mmol cm-2 h-1 . To assess the practicality of this system, we perform a comprehensive techno-economic analysis and life cycle assessment, showing that our approach can potentially substitute conventional methyl formate hydrolysis for industrial formic acid production. Furthermore, the resultant formic acid serves as direct fuel for air-breathing formic acid fuel cells, boasting a power density of 55 mW cm-2 and an exceptional thermal efficiency of 20.1 %.

Electronic Structure Engineered Heteroatom Doped All Transition Metal Sulfide Carbon Confined Heterostructure for Extrinsic Pseudocapacitor.

Ultra-high energy density battery-type materials are promising candidates for supercapacitors (SCs); however, slow ion kinetics and significant volume expansion remain major barriers to their practical applications. To address these issues, hierarchical lattice distorted α-/γ-MnS@Cox Sy core-shell heterostructure constrained in the sulphur (S), nitrogen (N) co-doped carbon (C) metal-organic frameworks (MOFs) derived nanosheets (α-/γ-MnS@Cox Sy @N, SC) have been developed. The coordination bonding among Cox Sy , and α-/γ-MnS nanoparticles at the interfaces and the π-π stacking interactions developed across α-/γ-MnS@Cox Sy and N, SC restrict volume expansion during cycling. Furthermore, the porous lattice distorted heteroatom-enriched nanosheets contain a sufficient number of active sites to allow for efficient electron transportation. Density functional theory (DFT) confirms the significant change in electronic states caused by heteroatom doping and the formation of core-shell structures, which provide more accessible species with excellent interlayer and interparticle conductivity, resulting in increased electrical conductivity. . The α-/γ-MnS@Cox Sy @N, SC electrode exhibits an excellent specific capacity of 277 mA hg-1 and cycling stability over 23 600 cycles. A quasi-solid-state flexible extrinsic pseudocapacitor (QFEPs) assembled using layer-by-layer deposited multi-walled carbon nanotube/Ti3 C2 TX nanocomposite negative electrode. QFEPs deliver specific energy of 64.8 Wh kg-1 (1.62 mWh cm-3 ) at a power of 933 W kg-1 and 92% capacitance retention over 5000 cycles.

Physicochemical Properties of High-Entropy Oxides.

The development of industry has triggered an increasingly severe demand for new functional materials. In recent years, researches on high-entropy oxides (HEOs) are more comprehensive and in-depth, and their fascinating properties are gradually known to the public. The unique elemental synergistic effect and lattice distortion endow the high-entropy family with various untapped potential, and wide application fields and outstanding performance of HEOs make them candidates for future materials. In this review, the concept, structure, and synthesis of HEOs are firstly highlighted. Secondly, a variety of excellent properties and applications in the fields of mechanics, electrics, thermotics, optics and magnetics are summarized. This work provides a comprehensive overview about HEOs, facilitating the development of modern functionalities of the high-entropy family.

Long-Range Cationic Disordering Induces two Distinct Degradation Pathways in Co-Free Ni-Rich Layered Cathodes.

Ni-rich layered oxides are one of the most attractive cathode materials in high-energy-density lithium-ion batteries, their degradation mechanisms are still not completely elucidated. Herein, we report a strong dependence of degradation pathways on the long-range cationic disordering of Co-free Ni-rich Li1-m (Ni0.94 Al0.06 )1+m O2 (NA). Interestingly, a disordered layered phase with lattice mismatch can be easily formed in the near-surface region of NA particles with very low cation disorder (NA-LCD, m≤0.06) over electrochemical cycling, while the layered structure is basically maintained in the core of particles forming a "core-shell" structure. Such surface reconstruction triggers a rapid capacity decay during the first 100 cycles between 2.7 and 4.3 V at 1 C or 3 C. On the contrary, the local lattice distortions are gradually accumulated throughout the whole NA particles with higher degrees of cation disorder (NA-HCD, 0.06≤m≤0.15) that lead to a slow capacity decay upon cycling.

Lattice Distortion and H-passivation in Pure Carbon Electrocatalysts for Efficient and Stable Two-electron Oxygen Reduction to H2 O2.

The exploration of inexpensive and efficient catalysts for oxygen reduction reaction (ORR) is crucial for chemical and energy industries. Carbon materials have been proved promising with different catalysts enabling 2 and 4e- ORR. Nevertheless, their ORR activity and selectivity is still complex and under debate in many cases. Many structures of these active carbon materials are also chemically unstable for practical implementations. Unlike the well-discussed structures, this work presents a strategy to promote efficient and stable 2e- ORR of carbon materials through the synergistic effect of lattice distortion and H-passivation (on the distorted structure). We show how these structures can be formed on carbon cloth, and how the reproducible chemical adsorption can be realized on these structures for efficient and stable H2 O2 production. The work here gives not only new understandings on the 2e- ORR catalysis, but also the robust catalyst which can be directly used in industry.

Random Occupation of Multimetal Sites in Transition Metal-Organic Frameworks for Boosting the Oxygen Evolution Reaction.

Developing robust oxygen evolution reaction (OER) electrocatalysts with excellent performance is essential for the conversion of renewable electricity to clean fuel. Herein, we present a facile concept for the synthesis of efficient high-entropy metal-organic frameworks (HEMOFs) as electrocatalysts in a one-step solvothermal synthesis. This strategy allows control of the microstructure and corresponding lattice distortion by tuning the metal ion composition. As a result, the OER activity was improved by optimizing the coordination environment of the metal catalytic center. The optimized Co-rich HEMOFs exhibited a low overpotential of 310 mV at a current density of 10 mA cm-2 , better than a RuO2 catalyst tested under the same conditions. The finding of lattice distortion of the HEMOFs provides a new strategy for developing high-performance electrocatalysts for energy conversion.

Zinc Substitution-Induced Subtle Lattice Distortion Mediates the Active Center of Cobalt Diselenide Electrocatalysts for Enhanced Oxygen Evolution.

Doping engineering has been an important approach to boost oxygen evolution reaction (OER) activity, while investigation on the dopant-induced modification of active sites and reaction kinetics remains incomplete. Herein, taking the cubic CoSe2 as an example, a universal strategy to synergistically achieve active sites and dynamic regulation is developed by incorporating low-valence Zn. It is revealed that regulation by Zn can facilitate reconstruction of the surface to form active Co oxyhydroxides under OER conditions. By combining theoretical calculations and characterization by various techniques, it is shown that the incorporation of Zn into CoSe2 can cause subtle lattice distortion and strong electronic interactions, thereby contributing to increased active site exposure and improved OER kinetics. Density functional theory simulations demonstrate that Zn incorporation synergistically optimizes the kinetic energy barrier by promoting co-adsorption of OER intermediates on a Co site and its adjacent Zn site. As a result, the modified CoSe2 NAs electrode shows optimized catalytic activity and excellent stability with the low overpotential of only 286 mV required to drive a current density of 10 mA cm-2 in an alkaline electrolyte.

Diffusion Barrier Performance of AlCrTaTiZr/AlCrTaTiZr-N High-Entropy Alloy Films for Cu/Si Connect System.

In this study, high-entropy alloy films, namely, AlCrTaTiZr/AlCrTaTiZr-N, were deposited on the n-type (100) silicon substrate. Then, a copper film was deposited on the high-entropy alloy films. The diffusion barrier performance of AlCrTaTiZr/AlCrTaTiZr-N for Cu/Si connect system was investigated after thermal annealing for an hour at 600 °C, 700 °C, 800 °C, and 900 °C. There were no Cu-Si intermetallic compounds generated in the Cu/AlCrTaTiZr/AlCrTaTiZr-N/Si film stacks after annealing even at 900 °C through transmission electron microscopy (TEM) and atomic probe tomography (APT) analysis. The results indicated that AlCrTaTiZr/AlCrTaTiZr-N alloy films can prevent copper diffusion at 900 °C. The reason was investigated in this work. The amorphous structure of the AlCrTaTiZr layer has lower driving force to form intermetallic compounds; the lattice mismatch between the AlCrTaTiZr and AlCrTaTiZ-rN layers increased the diffusion distance of the Cu atoms and the difficulty of the Cu atom diffusion to the Si substrate.

Lattice Distortion in Hollow Multi-Shelled Structures for Efficient Visible-Light CO2 Reduction with a SnS2 /SnO2 Junction.

Precise control of the micro-/nanostructures of nanomaterials, such as hollow multi-shelled structures (HoMSs), has shown its great advantages in various applications. Now, the crystal structure of building blocks of HoMSs are controlled by introducing the lattice distortion in HoMSs, for the first time. The lattice distortion located at the nanoscale interface of SnS2 /SnO2 can provide additional active sites, which not only provide the catalytic activity under visible light but also improve the separation of photoexcited electron-hole pairs. Combined with the efficient light utilization, the natural advantage of HoMSs, a record catalytic activity was achieved in solid-gas system for CO2 reduction, with an excellent stability and 100 % CO selectivity without using any sensitizers or noble metals.

Local Lattice Distortion Activate Metastable Metal Sulfide as Catalyst with Stable Full Discharge-Charge Capability for Li-O2 Batteries.

The direct lattice strain, either distortion, compressive, or tensile, can efficiently alter the intrinsic electrocatalytic property of the catalysts. In this work, we report a novel and effective strategy to distort the lattice structure by constructing a metastable MoSSe solid solution and thus, tune its catalytic activity for the Li-O2 batteries. The lattice distortion structure with inequivalent interplanar spacing between the same crystals plane were directly observed in individual MoSSe nanosheets with transmission electron microscopy and aberration-corrected transmission electron microscopy. In addition, in situ transmission electron microscopy analysis revealed the fast Li+ diffusion across the whole metastable structure. As expected, when evaluated as oxygen electrode for deep-cycle Li-O2 batteries, the metastable MoSSe solid solution deliver a high specific capacity of ∼730 mA h g-1 with stable discharge-charge overpotentials (0.17/0.49 V) over 30 cycles.

Lattice Distortion and Phase Stability of Pd-Doped NiCoFeCr Solid-Solution Alloys.

In the present study, we have revealed that (NiCoFeCr)100-xPdx (x= 1, 3, 5, 20 atom%) high-entropy alloys (HEAs) have both local- and long-range lattice distortions by utilizing X-ray total scattering, X-ray diffraction, and extended X-ray absorption fine structure methods. The local lattice distortion determined by the lattice constant difference between the local and average structures was found to be proportional to the Pd content. A small amount of Pd-doping (1 atom%) yields long-range lattice distortion, which is demonstrated by a larger (200) lattice plane spacing than the expected value from an average structure, however, the degree of long-range lattice distortion is not sensitive to the Pd concentration. The structural stability of these distorted HEAs under high-pressure was also examined. The experimental results indicate that doping with a small amount of Pd significantly enhances the stability of the fcc phase by increasing the fcc-to-hcp transformation pressure from ~13.0 GPa in NiCoFeCr to 20-26 GPa in the Pd-doped HEAs and NiCoFeCrPd maintains its fcc lattice up to 74 GPa, the maximum pressure that the current experiments have reached.

Analysis of traction-free assumption in high-resolution EBSD measurements.

The effects of using a traction-free (plane-stress) assumption to obtain the full distortion tensor from high-resolution EBSD measurements are analyzed. Equations are derived which bound the traction-free error arising from angular misorientation of the sample surface; the error in recovered distortion is shown to be quadratic with respect to that misorientation, and the maximum 'safe' angular misorientation is shown to be 2.7 degrees. The effects of localized stress fields on the traction-free assumption are then examined by a numerical case study, which uses the Boussinesq formalism to model stress fields near a free surface. Except in cases where localized stress field sources occur very close to sample points, the traction-free assumption appears to be admirably robust.

Bandgap tuning with thermal residual stresses induced in a quantum dot.

Lattice distortion induced by residual stresses can alter electronic and mechanical properties of materials significantly. Herein, a novel way of the bandgap tuning in a quantum dot (QD) by lattice distortion is presented using 4-nm-sized CdS QDs grown on a TiO2 particle as an application example. The bandgap tuning (from 2.74 eV to 2.49 eV) of a CdS QD is achieved by suitably adjusting the degree of lattice distortion in a QD via the tensile residual stresses which arise from the difference in thermal expansion coefficients between CdS and TiO2. The idea of bandgap tuning is then applied to QD-sensitized solar cells, achieving ≈60% increase in the power conversion efficiency by controlling the degree of thermal residual stress. Since the present methodology is not limited to a specific QD system, it will potentially pave a way to unexplored quantum effects in various QD-based applications.

Constructing Bipolar Dual-Active Sites through High-Entropy-Induced Electric Dipole Transition for Decoupling Oxygen Redox.

It remains a significant challenge to construct active sites to break the trade-off between oxidation and reduction processes occurring in battery cathodes with conversion mechanism, especially for the oxygen reduction and evolution reactions (ORR/OER) involved in the zinc-air batteries (ZABs). Here, using a high-entropy-driven electric dipole transition strategy to activate and stabilize the tetrahedral sites is proposed, while enhancing the activity of octahedral sites through orbital hybridization in a FeCoNiMnCrO spinel oxide, thus constructing bipolar dual-active sites with high-low valence states, which can effectively decouple ORR/OER. The FeCoNiMnCrO high-entropy spinel oxide with severe lattice distortion, exhibits a strong 1s→4s electric dipole transition and intense t2g(Co)/eg(Ni)-2p(OL) orbital hybridization that regulates the electronic descriptors, eg and t2g, which leads to the formation of low-valence Co tetrahedral sites (Coth) and high-valence Ni octahedral sites (Nioh), resulting in a higher half-wave potential of 0.87 V on Coth sites and a lower overpotential of 0.26 V at 10 mA cm-2 on Nioh sites as well as a superior performance of ZABs compared to low/mild entropy spinel oxides. Therefore, entropy engineering presents a distinctive approach for designing catalytic sites by inducing novel electromagnetic properties in materials across various electrocatalytic reactions, particularly for decoupling systems.