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At least 19 records

Mesoscale interplay among composition heterogeneity, lattice deformation, and redox stratification in single-crystalline layered oxide cathode

Single-crystalline layered oxide materials for lithium-ion batteries are featured by their excellent capacity retention over their polycrystalline counterparts, making them sought-after cathode candidates. Their capacity degradation, however, becomes more severe under high-voltage cycling, hindering many high-energy applications. It has long been speculated that the interplay among composition heterogeneity, lattice deformation, and redox stratification could be a driving force for the performance decay. The underlying mechanism, however, is not well-understood. In this study, we use X-ray microscopy to systematically examine single-crystalline NMC particles at the mesoscale. This technique allows us to capture detailed signals of diffraction, spectroscopy, and fluorescence, offering spatially resolved multimodal insights. Focusing on early high-voltage charging cycles, we uncover heterogeneities in valence states and lattice structures that are inherent rather than caused by electrochemical abuse. These heterogeneities are closely associated with compositional variations within individual particles. Our findings provide useful insights for refining material synthesis and processing for enhanced battery longevity and efficiency.

36 MATERIALS SCIENCE↗

Speckle correlation as a monitor of X-ray free-electron laser induced crystal lattice deformation

X-ray free-electron lasers (X-FELs) present new opportunities to study ultrafast lattice dynamics in complex materials. While the unprecedented source brilliance enables high fidelity measurement of structural dynamics, it also raises experimental challenges related to the understanding and control of beam-induced irreversible structural changes in samples that can ultimately impact the interpretation of experimental results. This is also important for designing reliable high performance X-ray optical components. In this work, X-FEL beam-induced lattice alterations are investigated by measuring the shot-to-shot evolution of near-Bragg coherent scattering from a single crystalline germanium sample. It is shown that X-ray photon correlation analysis of sequential speckle patterns measurements can be used to monitor the nature and extent of lattice rearrangements. Additionally, abrupt, irreversible changes are observed following intermittent high-fluence monochromatic X-ray pulses, thus revealing the existence of a threshold response to X-FEL pulse intensity.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Local Lattice Deformation of Tellurene Grain Boundaries by Four-Dimensional Electron Microscopy

Two-dimensional (2D) tellurene is a promising competitor for the fabrication of ultrathin optoelectronic devices belonging to a new family of monoelemental 2D materials. Furthermore, the precise fabrication and characterization of tellurene and its lattice defects is of utmost importance to determine device reliability and predict functionality, yet it remains experimentally challenging. The rapid growth of the four-dimensional scanning transmission electron microscopy (4D-STEM) technique as well as postprocessing tools now allows for structural analysis with nanometer-scale resolution over a broad range of length scales. Here, we use 4D-STEM to reveal the three-dimensional (3D) atomic structure of the characteristic grain boundary in 2D tellurium formed through a new microwave-enabled chemical self-assembly. Strain and lattice parameter maps permit the reconstruction of the roughness of the grain boundary and suggest that its formation is promoted by a wedge of helical atomic chains along the [0001] crystallographic direction. The observation of wrinkles at the grain boundary is found to be the dominant relaxation mechanism. Insights into the formation mechanism are elucidated by mapping the lattice parameters as the first demonstration of local in-plane and out-of-plane unit cell variation in a nanometer-by-nanometer real-space array.

36 MATERIALS SCIENCE↗

Transient X-ray Diffraction Reveals Nonequilibrium Phase Transition in Thin Films of CH 3 NH 3 PbI 3 Perovskite

Advantageous optoelectronic properties of methylammonium lead triiodide likely arise from coupling between photogenerated charge-carriers and the soft, deformable lattice. We investigate structural dynamics of MAPbI 3 films using time-resolved X-ray diffraction versus pump-probe time delay and pump intensity. During the first nanosecond, the lattice anisotropically distorts from tetragonal to cubic at excitation intensities that are insufficient to thermally induce the first-order thermodynamic phase transition at 330K. Further, the high-symmetry structure then relaxes back to the starting phase with 11 and 236-ns time constants via a different transition pathway than observed either in the first nanosecond or in previous reports for MAPbI 3 . Early-time dynamics are consistent with polaron formation and lattice strain stabilization while the slower recovery dynamics outlive radiative recombination and relates metastability. Fluence-independence of these lattice deformations in the low-power regime conveys relevance to optoelectronics including photovoltaics and highlights sustained involvement of non-equilibrium, photoinduced lattice reorganization in MAPbI 3 under functional conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Simulation and Emulation of X-Ray Diffraction from Dynamic Compression Experiments

Many important aspects of the dynamic thermo-mechanical response of materials occur at the mesoscale, i.e. a physical scale of interactions smaller than what can be adequately described by homogenous behaviors, yet larger than the scale of the atomic lattice. Concurrent advancements in computational power, continuum theory, and experimental diagnostics are enabling unprecedented understanding of such interactions. However, we cannot develop a sufficient level of confidence in such mesoscale capability until the constitutive description of the underlying constituents is reliably representative of their actual physical behavior. Therefore, there is a strong need to combine experimental, modeling, and data-science techniques to validate models of the thermomechanical response of individual single crystals. One experimental diagnostic with high potential impact to shock physics and materials science is in-situ x-ray diffraction. This paper is primarily focused on simulation of x-ray diffraction in shock physics, but with an aim toward quantifying parametric uncertainty of simulation models. Here, we develop and demonstrate a data-science and model-driven approach to constrain the parameterization of continuum models of crystal lattice deformation associated with the shock response of crystalline materials. The framework is built around the connection between continuum hydrodynamic simulations of lattice deformation and a new Bragg diffraction simulation code, BarberShop. The dynamic deformation of a crystal lattice is modeled using the DiscoFlux model within an arbitrary Lagrangian-Eulerian hydrodynamic code, FLAG. These detailed continuum simulations of lattice deformation can be computationally slow, thus a statistical model is used to emulate the evolution of lattice deformation fields in time and across the considered model parameter space. Emulated lattice deformation fields can then be generated rapidly for any combination of physics model parameters. In turn, these fields can be fed into BarberShop to realize a rapid prediction of Bragg diffraction patterns associated with particular values of physics model parameters. The framework enables parameterization of the single crystal model to obtain Bragg diffraction patterns that most closely resemble a corresponding measurement. Furthermore, the framework naturally provides sensitivities of the lattice deformation to the physics parameters. We highlight the utility of this framework through the application to a synthetic closed-loop inverse problem leading to the parameterization of a single crystal material model. As a model problem, we consider the dynamic response of the energetic molecular crystal, cyclotrimethylenetrinitramine (or RDX), under dynamic compression induced by simulated flyer plate impact experiments.

36 MATERIALS SCIENCE↗

Multiwavelength anomalous X-ray diffraction for combined imaging of atomic displacement and strain

The X-ray Bragg coherent diffractive imaging (CDI) technique assumes that the structure factor holds constant over the measured crystal. This approximation breaks down for materials exhibiting variations in the unit-cell configuration, such as piezo- and ferroelectrics. In that case, the strain field cannot be reliably determined from the reconstruction because the lattice deformation and the structure factor contribute concomitantly. Proposed here is a solution to this problem achieved by combining Bragg CDI and the multiwavelength anomalous diffraction approach that measures a Friedel pair of reflections at two different photon energies near an absorption edge. Comparing the obtained reconstructions with a parametric model that includes calculating the scattering amplitude as a function of wavelength and the unit-cell configuration, the contributions of the lattice deformation and the structure factor are separated. Simulations of the ferroelectric material BaTiO 3 demonstrate the possibility of simultaneous probing of the strain and displacement of the Ti atoms. The proposed method opens up an opportunity to apply coherent X-ray diffraction for nanoscale-resolved 3D mapping of polarization domains in micro- and nanocrystals.

lattice deformation↗

Relationship among the Crystal Structure, Texture, and Macroscopic Properties of Tetragonal (Pb,La)(Zr,Ti)O 3 Ferroelectrics Investigated by In Situ High-Energy Synchrotron Diffraction

In situ diffraction investigations have played an important role in experimentally revealing the mechanism of piezoelectric and ferroelectric properties. In this study, a pure tetragonal ferroelectric ceramic of La-doped PbZr 0.5 Ti 0.5 O 3 (LaPZT50) was investigated to eliminate the complex influence of phase coexistence. The electric field evolutions of the crystal structure, domain switching, and lattice deformation of the tetragonal phase have been revealed by in situ high-energy synchrotron X-ray diffraction. Furthermore, we found that the crystal structure of LaPZT50 is quite stable, showing a negligible change in the Pb–O bond length, unit cell volume, and spontaneous polarization upon application of an in situ external electric field. Importantly, the maximum macroscopic polarization of tetragonal LaPZT50 is defined by the 111-oriented grains. As determined by the intensity difference, the switching of non-180° domains plays a more significant role in contributing to the macroscopic strain than lattice deformation. These results further imply that the phase coexistence around the morphotropic phase boundary facilitates domain wall motion in the tetragonal phase and improves the ferroelectric and piezoelectric properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cyclic deformation and lattice strain distribution of high Nb containing TiAl alloy

Low cycle fatigue of lamellar TiAl with 8.5 at.-%Nb was studied with a total strain amplitude of 0.28% at three temperatures: room temperature, 750°C and 900°C. At room temperature, the material exhibited cyclic hardening and the fracture mode was mainly interlamellar. At 750°C and 900°C, the material showed cyclic softening and the fracture mode was translamellar. The lattice strain in γ phase was almost tensile and larger tensile lattice strain in γ phase seems detrimental. Besides, the opposite direction of {201} γ and {100} α2 lead to crack propagation along α 2 /γ interfaces. B2/β o phase always suffered compressive lattice strain in the tests. Finally, the destruction of lamellar microstructure was the reason for colony refinement at 750°C and 900°C.

phase transformation↗

Ballistic-Electron-Emission Microscopy of Strained Si l-x Ge x Layers

Ballistic-electron-emission microscopy has been used to investigate the effects of strain on Si l-x Ge x alloys. Lifting of the degeneracy of the conduction-band minimum of SiGe due to lattice deformation has been directly measured by application of BEEM spectroscopy to Ag/Si structures.

lattice↗

Dislocation‐Driven Formation of Oriented Macroperiodic Metastructures of Curved Single Crystal Lattices in Glass

Abstract Single crystals fabricated in glass by localized heating can develop uniquely deformed lattices stabilized by the surrounding amorphous medium. The development of lattice curvature appears to be intrinsic to the crystal growth process in some systems, while the result of the locally changing crystallography in others. In this work, a model laser‐fabricated rotating lattice Sb 2 S 3 crystal grown in stoichiometric glass is used to demonstrate fabrication of novel macroperiodic metastructures that utilize intrinsic lattice curvature superimposed with subtle crystallographic influences. The limited availability of slip systems drives the lattice curvature magnitude to vary with crystal growth direction, maximizing for lattices aligned with the predominant Burgers vector along with corresponding increases in dislocation density. Misaligned lattice orientations form smaller secondary lattice curvatures arising from misaligned Burgers vectors with further elastic contributions. Over extended crystal growth, these secondary components align the lattice to rotate about either the <001> or <010> crystal axes forming repeating metastructures of lattice orientation with periodicity 20–160 microns in length. The mechanistic approach used in this work may be expanded to other systems with known slip systems to better understand and design macroperiodic metastructures.

36 MATERIALS SCIENCE↗

Liquid Between Macromolecules in Protein Crystals: Static Versus Dynamics

Protein crystals are so fragile that they often can not be handled by tweezers. Indeed, measurements of the Young modulus, E, of lysozyme crystals resulted in E approx. equals 0.1 - 1 GPa, the lower figures, 0.1 - 0.5 GPa, being obtained from triple point bending of as-grown and not cross-linked crystals sitting in solution. The bending strength was found to be approx.10(exp -2) E. On the other hand, ultrasound speed and Mandelstam-Raman-Brilloin light scattering experiments led to much higher figures, E approx. equals 2.7 GPa. The lower figures for E were found from static or low frequency crystal deformations measurements, while the higher moduli are based on high frequency lattice vibrations, 10(exp 7) - 10(exp 10) 1/s. The physical reason for the about an order of magnitude discrepancy is in different behavior of water filling space between protein molecules. At slow lattice deformation, the not-bound intermolecular water has enough time to flow from the compressed to expanded regions of the deformed crystal. At high deformation frequencies in the ultra- and hypersound waves, the water is confined in the intermolecular space and, on that scale, behaves like a solid, thus contributing to the elastic crystal moduli. In this case, the reciprocal crystal modulus is expected to be an average of the water protein and water compressibilities (reciprocal compressibilities): the bulk modulus for lysozyme is 26 GPa, for water it is 7 GPa. Anisotropy of the crystal moduli comes from intermolecular contacts within the lattice while the high frequency hardness comes from the bulk of protein molecules and water bulk moduli. These conclusions are based on the analysis of liquid flow in porous medium to be presented.

Chernov, A. A.↗

Stressing Halide Perovskites with Light and Electric Fields

Understanding the light and electric field-induced effects underlying the local changes in optoelectronic properties in lead halide perovskites is crucial to establish a detailed structure–function relationship. Here, in this study, we use single-molecule absorption scanning tunneling microscopy (SMA-STM) to probe the local surface inhomogeneity of a mixed A-site cation/mixed halide perovskite under pulsed 532 nm photoexcitation to gain insight into the varying grain-to-grain absorption behavior at the nanoscale and reduction in the electronic bandgap under illumination. To correlate the observed changes in the absorption signal to structural ones, we utilize synchrotron X-ray STM (SX-STM) where we find that photoexcitation induces changes in the X-ray absorption spectral signatures. Lastly, using pump–probe time-resolved wide-angle X-ray scattering, we show the presence of nonthermal lattice deformations upon photoexcitation which indicate that the excited photocarriers distort the perovskite lattice, corroborating the local electronic changes observed by our STM measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Morphology, Deformations, and Photocatalytic Activity of Thermally Treated Brookite Titanium Dioxide Thin Films

Metastable states, in which the coupling between long-range lattice deformations and electronic properties can be controlled, provide a pathway to tailoring the behavior of photocatalytic materials by directing the flow of photoinduced charge carriers. Brookite is a metastable polymorph of earth-abundant TiO 2 that exhibits photocatalytic function and, due to its high energy relative to the anatase and rutile polymorphs, may serve as a precursor for the formation of transitional metastable structures. In this work, facile thermal annealing is employed to promote the formation of predominantly brookite-phase films, regulate the brookite lattice distortions, and determine the effect of these distortions on charge separation, ultimately directed at enhancing photocatalytic activity. Profile fitting of X-ray diffraction patterns and peak shifts in Raman spectra revealed structural distortions of the brookite lattice. Structural defects, including lattice gliding, dislocations, stacking faults, and twin boundaries, were observed using scanning transmission electron microscopy. First-principles simulations reveal how the lattice distortions associated with stacking faults induce band bending, thus increasing the photocatalytic activity of brookite. In conclusion, this study provides insight into the microstructural tuning of metastable phases to enhance their unique functionalities.

band bending↗

Thermal-healing of lattice defects for high-energy single-crystalline battery cathodes

Abstract Single-crystalline nickel-rich cathodes are a rising candidate with great potential for high-energy lithium-ion batteries due to their superior structural and chemical robustness in comparison with polycrystalline counterparts. Within the single-crystalline cathode materials, the lattice strain and defects have significant impacts on the intercalation chemistry and, therefore, play a key role in determining the macroscopic electrochemical performance. Guided by our predictive theoretical model, we have systematically evaluated the effectiveness of regaining lost capacity by modulating the lattice deformation via an energy-efficient thermal treatment at different chemical states. We demonstrate that the lattice structure recoverability is highly dependent on both the cathode composition and the state of charge, providing clues to relieving the fatigued cathode crystal for sustainable lithium-ion batteries.

36 MATERIALS SCIENCE↗

Geometric frustration of Jahn–Teller order in the infinite-layer lattice

The Jahn–Teller effect, in which electronic configurations with energetically degenerate orbitals induce lattice distortions to lift this degeneracy, has a key role in many symmetry-lowering crystal deformations. Lattices of Jahn–Teller ions can induce a cooperative distortion, as exemplified by LaMnO 3 . Although many examples occur in octahedrally or tetrahedrally coordinated transition metal oxides due to their high orbital degeneracy, this effect has yet to be manifested for square-planar anion coordination, as found in infinite-layer copper, nickel, iron and manganese oxides. Here, for this work, we synthesize single-crystal CaCoO 2 thin films by topotactic reduction of the brownmillerite CaCoO 2.5 phase. We observe a markedly distorted infinite-layer structure, with ångström-scale displacements of the cations from their high-symmetry positions. This can be understood to originate from the Jahn–Teller degeneracy of the d xz and d yz orbitals in the d 7 electronic configuration along with substantial ligand–transition metal mixing. A complex pattern of distortions arises in a $2\sqrt2$ x $2\sqrt2$ x $1$ tetragonal supercell, reflecting the competition between an ordered Jahn–Teller effect on the CoO 2 sublattice and the geometric frustration of the associated displacements of the Ca sublattice, which are strongly coupled in the absence of apical oxygen. As a result of this competition, the CaCoO 2 structure forms an extended two-in–two-out type of Co distortion following ‘ice rules’.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Low Temperature Dynamic Polaron Liquid in a Manganite Exhibiting Colossal Magnetoresistance

Polarons - fermionic charge carriers bearing a strong companion lattice deformation - exhibit a natural tendency for self-localization due to the recursive interaction between electrons and the lattice. While polarons are ubiquitous in insulators, how they evolve in transitions to metallic and superconducting states in quantum materials remains an open question. Here, we use resonant inelastic x-ray scattering to track the electron-lattice coupling in the colossal magneto-resistive bi-layer manganite La 1.2 Sr 1.8 Mn 2 O 7 across its metal-to-insulator transition. The response in the insulating high-temperature state features harmonic emissions of a dispersionless oxygen phonon at small energy transfer. Additionally, upon cooling into the metallic state, we observe a drastic redistribution of spectral weight from the region of these harmonic emissions to a broad high energy continuum. In concert with theoretical calculations, we show that this evolution implies a shift in electron-lattice coupling from static to dynamic lattice distortions that leads to a distinct polaronic ground state in the low temperature metallic phase - a dynamic polaron liquid.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗