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At least 109 records · Page 6

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↗

Local strain-dependent electronic structure and perpendicular magnetic anisotropy of a MnGaN 2D magnetic monolayer

Local strain-dependent spin-polarized electronic structure of a two-dimensional (2D) magnetic layer is an exciting property for practical applications. For example, it holds the promise for advanced ultrathin spintronic nanodevices with customized electronic and magnetic properties by local strain engineering. Here, we demonstrate that the spin-polarized electronic structure of a 2D manganese gallium nitride (MnGaN-2D) magnetic monolayer is sensitive to intrinsic local lattice strain, as proven by first-principles calculations and indicated by scanning tunneling spectroscopy measurements. Atomic resolution images reveal a highly non-Gaussian lattice spacing/strain distribution, while the spectroscopy reveals variations in the electronic density of states. Simulations of the MnGaN-2D monolayer based on first-principles calculations, including both isotropic and anisotropic strains, confirm a highly strain-dependent manganese partial density of states. Spin-orbit coupling is included which indicates either out-of-plane perpendicular magnetic anisotropy (PMA) or in-plane magnetic anisotropy, dependent on the type of strain whether compressive or tensile, suggesting that MnGaN-2D is magnetoelastic. The MnGaN-2D PMA is further supported by superconducting quantum interference device magnetometry measurements which reveal a high spin polarization of ~ 79 % at room temperature.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Effect of Annealing Conditions on Recovery of Lattice Damage in a High-Energy-Implanted 4H-SiC Superjunction PIN Diode

A high energy ion implantation system has been recently developed at the Tandem Van de Graaff facility at Brookhaven National Laboratory with tunable energy to 150 MeV capable of multi-step, deep implantation in 4H-SiC wafers with dopant atoms, such as B, P, Al, and N. Medium and high voltage devices with deep junctions can be fabricated using this system. Lattice strain introduced by the implantation process needs to be recovered and dopant atoms activated by appropriate annealing process as the device performance is strongly associated with the extent of recovery of the lattice. Using Synchrotron X-ray Rocking Curve Topography (SXRCT) and Reciprocal Space Mapping (RSM), the strain induced by high energy implantation of Al and N in 4H-SiC in different patterns are measured and mapped. It is observed that the strain levels correlate with the total fluence levels. PiN diodes fabricated on these implanted wafers were then annealed at temperatures ranging from 1700 °C to 2000 °C for 60 min. The SXRCT and RSM analysis of the annealed samples suggests that for the same annealing duration, higher temperature leads to better lattice recovery.

43 PARTICLE ACCELERATORS↗

Factors Affecting the Electron Conductivity in Single Crystal Li 7 La 3 Zr 2 O 12 and Li 7 P 3 S 11

One of the serious challenges in all solid-state Li ion batteries is neutral Li intrusion into the solid-state electrolyte that can ultimately cause catastrophic failure. One possibility for this is due to n-type electron conductivity that induces the reaction Li + + e – → Li 0 at sites where the potential is less than the Li + /Li potential. This paper reports hybrid density functional theory calculations of the electronic conductivity in two prototype single crystalline solid-state electrolytes, cubic Li 7 La 3 Zr 2 O 12 (c-LLZO) and Li 7 P 3 S 11 (LPS). The formation energies of important point defects that can affect electron conductivity are determined, and we find that the mechanism of n-type electron conductivity for both solid-state electrolytes is via “small” electron polaron hopping, where the quotes signify that substantial Li ion rearrangement is associated with the polaron formation and its migration. In both electrolytes, the formation energies for the small polarons at the Fermi energy are too high to generate measurable electron conductivity at room temperature. For c-LLZO, the concentration of electron polarons necessary to ensure charge neutrality from positively charged oxygen vacancies formed in synthesis can be significantly higher. Hence, the electron conductivity could be significant when measured with ion-blocking metal electrodes, and we discuss how the synthesis conditions could affect this magnitude. However, in the solid-state battery, these polarons are replaced by negatively charged Li vacancies so that the electron conductivity should remain minimal. For LPS single crystals, the inherent minimal electron conductivity is independent of synthesis conditions. Here we also show that the cost of forming Li 0 in bulk c-LLZO is enormous due to strain effects so that it could only potentially form at voids, grain boundaries, or around vacancy defects which relax the lattice strain.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Exploring the hardness and high-pressure behavior of osmium and ruthenium-doped rhenium diboride solid solutions

Rhenium diboride (ReB 2 ) exhibits high differential strain due to its puckered boron sheets that impede shear deformation. Here, we demonstrate the use of solid solution formation to enhance the Vickers hardness and differential strain of ReB 2 . ReB 2 -structured solid solutions (Re 0.98 Os 0.02 B 2 and Re 0.98 Ru 0.02 B 2 , noted as “ReOsB 2 ” and “ReRuB 2 ”) were synthesized via arc-melting from the pure elements. In-situ high-pressure radial x-ray diffraction was performed in the diamond anvil cell to study the incompressibility and lattice strain of ReOsB 2 and ReRuB 2 up to ~56 GPa. Both solid solutions exhibit higher incompressibility and differential strain than pure ReB 2 . However, while all lattice planes are strengthened by doping osmium (Os) into the ReB 2 structure, only the weakest ReB 2 lattice plane is enhanced with ruthenium (Ru). These results are in agreement with the Vickers hardness measurements of the two systems, where higher hardness was observed in ReOsB 2 . The combination of high-pressure studies with experimentally observed hardness data provides lattice specific information about the strengthening mechanisms behind the intrinsic hardness enhancement of the ReB 2 system.

36 MATERIALS SCIENCE↗

Intralattice-bonded phase-engineered ultrahigh-Ni single-crystalline cathodes suppress strain evolution

Single crystallization remains a debated strategy for advancing Ni-rich cathode materials. While it mitigates particle cracking and improves tap density by eliminating particle boundaries, extended diffusion pathways introduce volumetric and lattice distortions, compromising electrochemical and structural stability. These challenges hinder the commercialization of high-Ni single-crystal cathodes, calling for a reassessment of their viability. Here, in this study, we report a structural design: intralattice-bonded phase single-crystal LiNi 0.92 Co 0.03 Mn 0.05 O 2 (IBP-SC92). This architecture maintains structural integrity while shortening diffusion pathways, resulting in almost zero electrochemical degradation during cycling. The robust structure and fast ion transport mitigate lattice strain, as confirmed by multiscale high-resolution diffraction and imaging techniques, preventing intragranular cracks and irreversible phase transitions. As a result, IBP-SC92 shows outstanding cycling stability, with nearly 100% capacity retention after 100 cycles in half cells and 94.5% retention after 1,000 cycles in full cells. This redefined single-crystal cathode represents a significant step towards the industrial adoption of high-energy-density materials.

36 MATERIALS SCIENCE↗

Emergent interlayer magnetic order via strain-induced orthorhombic distortion in the 5 d Mott insulator Sr 2 IrO 4

In this letter, we report a La 2 CuO 4 -like interlayer antiferromagnetic order in Sr2IrO4 films with large orthorhombic distortion (>1.5%). The biaxial lattice strain in epitaxial heterostructures of Sr 2 IrO 4 /Ca 3 Ru 2 O 7 lowers the crystal symmetry of Sr 2 IrO 4 from tetragonal ($C_4$) to orthorhombic ($C_2$), guiding the Ir $5d J_{text{eff}}$ = 1/2 pseudospin moment parallel to the elongated b axis via magnetic anisotropy. From resonant x-ray scattering experiments, we observed an antiferromagnetic order in the orthorhombic Sr 2 IrO 4 film whose interlayer stacking pattern is inverted from that of the tetragonal Sr 2 IrO 4 crystal. This interlayer stacking is similar to that of the orthorhombic La 2 CuO 4 , implying that the asymmetric interlayer exchange interactions between $\textit{a}$ and $\textit{b}$ directions exceed the anisotropic interlayer pseudodipolar interaction. Our result suggests that strain-induced distortion can provide a delicate knob for tuning the long-range magnetic order in quasi-two-dimensional systems by evoking the competition between the interlayer exchange coupling and the pseudodipolar interaction.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Adaptive sampling for accelerating neutron diffraction-based strain mapping *

Abstract Neutron diffraction is a useful technique for mapping residual strains in dense metal objects. The technique works by placing an object in the path of a neutron beam, measuring the diffracted signals and inferring the local lattice strain values from the measurement. In order to map the strains across the entire object, the object is stepped one position at a time in the path of the neutron beam, typically in raster order, and at each position a strain value is estimated. Typical dwell times at neutron diffraction instruments result in an overall measurement that can take several hours to map an object that is several tens of centimeters in each dimension at a resolution of a few millimeters, during which the end users do not have an estimate of the global strain features and are at risk of incomplete information in case of instruments outages. In this paper, we propose an object adaptive sampling strategy to measure the significant points first. We start with a small initial uniform set of measurement points across the object to be mapped, compute the strain in those positions and use a machine learning technique to predict the next position to measure in the object. Specifically, we use a Bayesian optimization based on a Gaussian process regression method to infer the underlying strain field from a sparse set of measurements and predict the next most informative positions to measure based on estimates of the mean and variance in the strain fields estimated from the previously measured points. We demonstrate our real-time measure-infer-predict workflow on additively manufactured steel parts—demonstrating that we can get an accurate strain estimate even with 30%–40% of the typical number of measurements—leading the path to faster strain mapping with useful real-time feedback. We emphasize that the proposed method is general and can be used for fast mapping of other material properties such as phase fractions from time-consuming point-wise neutron measurements.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

In situ deformation of antigorite-olivine two-phase mixtures: Implications for dynamics and seismic anisotropy in the mantle wedge

Water released from hydrous minerals in subducting slabs reacts with the overlying plate, resulting in widespread serpentinization in the mantle wedge. Deformation of serpentinized peridotites has been invoked to explain forearc seismic anisotropy, yet studies of the mechanical properties and deformation behaviors of serpentine-bearing multiphase aggregates remain limited. Here we deformed olivine-antigorite mixtures containing 70, 50, and 20 vol.% of antigorite at 2.5 – 7.6 GPa, 673 K and strain rates of ∼10 –5 –10 –4 s –1 . Elasto-viscoplastic self-consistent simulations, constrained by synchrotron X-ray diffraction (XRD) data, were used to estimate lattice strain, stress–strain partitioning, crystallographic preferred orientations (CPO) development, and aggregate strength. Selected run products were also analyzed by electron backscatter diffraction for comparison with the CPO results obtained from XRD experiments. We found olivine transitions from A- or B-type to C-type when antigorite fraction drops to 20 vol.%, coinciding with a microstructural change from interconnected weak layers to a load-bearing framework (LBF). An additional run on a sample Atg50/Ol50 with preexisting microstructures suggested the formation of LBF was promoted by these microstructures, although the preexisting antigorite CPO has been overprinted at 20.8 % strain and could be erased completely by subsequent deformation in nature. Estimated viscosity of the two-phase mixtures suggests that low-degree serpentinization (≤20 %) in the mantle wedge may increase the strength of olivine-rich peridotite and hinder slab-mantle decoupling, whereas high-degree serpentinization (≥50–70 %) weakens the peridotite and favors decoupling if sufficient viscosity contrast (>10) develops. Seismic anisotropy shows a nonlinear dependence on antigorite fraction: antigorite CPO governs the anisotropy of the mixtures with ≥50 vol.% antigorite, whereas olivine CPO dominates at low fractions (∼20 vol.%). The presence of pre-existing microstructures reduces seismic anisotropy of the deformed mixtures, however the persistence of pre-existing CPO in actively subducting slabs remains uncertain, making their significance over geological timescales questionable.

Crystallographic preferred orientation↗

Buffer Layer Effects on Tandem InGaAs TPV Devices

Single junction indium gallium arsenide (InGaAs) based TPV devices have demonstrated efficiencies in excess of 20% at radiator temperatures of 1058 C. Modeling suggests that efficiency improvements in single bandgap devices should continue although they will eventually plateau. One approach for extending efficiencies beyond the single bandgap limit is to follow the technique taken in the solar cell field, namely tandem TPV cells. Tandem photovoltaic devices are traditionally composed of cells of decreasing bandgap, connected electrically and optically in series. The incident light impinges upon the highest bandgap first. This device acts as a sieve, absorbing the high-energy photons, while allowing the remainder to pass through to the underlying cell(s), and so on. Tandem devices reduce the energy lost to overexcitation as well as reducing the current density (Jsc). Reduced Jsc results in lower resistive losses and enables the use of thinner and lower doped lateral current conducting layers as well as a higher pitch grid design. Fabricating TPV tandem devices utilizing InGaAs for all of the component cells in a two cell tandem necessitates the inclusion of a buffer layer in-between the high bandgap device (In0.53 Ga0.47As - 0.74eV) and the low bandgap device (In0.66Ga0.34As - 0.63eV) to accommodate the approximately 1% lattice strain generated due to the change in InGaAs composition. To incorporate only a single buffer layer structure, we have investigated the use of the indium phosphide (InP) substrate as a superstrate. Thus the high-bandgap, lattice- matched device is deposited first, followed by the buffer structure and the low-bandgap cell. The near perfect transparency of the high bandgap (1.35eV) iron-doped InP permits the device to be oriented such that the light enters through the substrate. In this paper we examine the impact of the buffer layer on the underlying lattice-matched InGaAs device. 0.74eV InGaAs devices were produced in a variety of configurations both with and without buffer layers. All structures were characterized by reciprocal space x-ray diffraction to determine epilayer composition and residual strain. Electrical characterization of the devices was performed to examine the effect of the buffer on the device performance. The effect of the buffer structure depends upon where it is positioned. When near the emitter region, a 2.6x increase in dark current was measured, whereas no change in dark current was observed when it was near the base region.

Wilt, David M.↗

Facile Tensile Testing Platform for In Situ Transmission Electron Microscopy of Nanomaterials

In situ tensile testing using transmission electron microscopy (TEM) is a powerful technique to probe structure-property relationships of materials at the atomic scale. In this work, a facile tensile testing platform for in situ characterization of materials inside a transmission electron microscope is demonstrated. The platform consists of: 1) a commercially available, flexible, electron-transparent substrate (e.g., TEM grid) integrated with a conventional tensile testing holder, and 2) a finite element simulation providing quantification of specimen-applied strain. The flexible substrate (carbon support film of the TEM grid) mitigates strain concentrations usually found in free-standing films and enables in situ straining experiments to be performed on materials that cannot undergo localized thinning or focused ion beam lift-out. The finite element simulation enables direct correlation of holder displacement with sample strain, providing upper and lower bounds of expected strain across the substrate. The tensile testing platform is validated for three disparate material systems: sputtered gold-palladium, few-layer transferred tungsten disulfide, and electrodeposited lithium, by measuring lattice strain from experimentally recorded electron diffraction data. The results show good agreement between experiment and simulation, providing confidence in the ability to transfer strain from holder to sample and relate TEM crystal structural observations with material mechanical properties.

2D materials↗

High-resolution 3D strain and orientation mapping within a grain of a directed energy deposition laser additively manufactured superalloy

The industrialization of Laser Additive Manufacturing (LAM) is challenged by the undesirable microstructures and high residual stresses originating from the fast and complex solidification process. Non-destructive assessment of the mechanical performance controlling deformation patterning is therefore critical. Here, we use Dark Field X-ray Microscopy (DFXM) to map the 3D subsurface intragranular orientation and strain variations throughout a surface-breaking grain within a directed energy deposition nickel superalloy. DFXM results reveal a highly heterogenous 3D microstructure in terms of the local orientation and lattice strain. The grain comprises ≈ 5 μm-sized cells with alternating strain states, as high as 5 x10 -3 , and orientation differences <0.5°. The DFXM results are compared to Electron Backscatter Diffraction measurements of the same grain from its cut-off surface. Here, we discuss the microstructure developments during LAM, rationalising the development of the deformation patterning from the extreme thermal gradients during processing and the susceptibility for solute segregation.

36 MATERIALS SCIENCE↗

Assessment of Shape Memory Alloys - From Atoms To Actuators - Via In Situ Neutron Diffraction

As shape memory alloys (SMAs) become an established actuator technology, it is important to identify the fundamental mechanisms responsible for their performance by understanding microstructure performance relationships from processing to final form. Yet, microstructural examination of SMAs at stress and temperature is often a challenge since structural changes occur with stress and temperature and microstructures cannot be preserved through quenching or after stress removal, as would be the case for conventional materials. One solution to this dilemma is in situ neutron diffraction, which has been applied to the investigation of SMAs and has offered a unique approach to reveal the fundamental micromechanics and microstructural aspects of bulk SMAs in a non-destructive setting. Through this technique, it is possible to directly correlate the micromechanical responses (e.g., internal residual stresses, lattice strains), microstructural evolutions (e.g., texture, defects) and phase transformation properties (e.g., phase fractions, kinetics) to the macroscopic actuator behavior. In this work, in situ neutron diffraction was systematically employed to evaluate the deformation and transformation behavior of SMAs under typical actuator conditions. Austenite and martensite phases, yield behavior, variant selection and transformation temperatures were characterized for a polycrystalline NiTi (49.9 at. Ni). As the alloy transforms under thermomechanical loading, the measured textures and lattice plane-level variations were directly related to the cyclic actuation-strain characteristics and the dimensional instability (strain ratcheting) commonly observed in this alloy. The effect of training on the shape memory characteristics of the alloy and the development of two-way shape memory effect (TWSME) were also assessed. The final conversion from a material to a useful actuator, typically termed shape setting, was also investigated in situ during constrained heatingcooling and subsequent shape recovery experiments. Neutron diffraction techniques are also being applied to the investigation of novel high temperature SMAs with the objective of designing alloys with better stability, higher transition temperatures and ultimately superior durability.

Shape Memory Alloys↗

Strain-Modulated Platinum–Palladium Nanowires for Oxygen Reduction Reaction

Electrocatalytic activity of alloy nanocatalytsts can be manipulated effectively by tuning their physical properties (ensemble, geometric, and ligand effects) to afford optimal surface structure and compositions for proton exchange membrane fuel cell (PEMFC) application. Herein, highly catalytic platinum-palladium nanowires (Pt n Pd 100-n NWs) with a subtle lattice strain and Boerdijk-Coxeter helix type morphology are synthesized through a surfactant-free, thermal single phase solvent method. X-ray diffraction results show that Pt n Pd 100-n NWs are exposed through the (111) facets and their shrinking or expanding lattice parameters can be modulated by the alloy compositions. Electrochemical results reveal that their high catalytic activity correlates with the lattice shrinking, facets, and bimetallic compositions, showing higher activity when the ratio of Pt and Pd is similar to ~78:22, which is further supported by DFT results. Compared to the nanoparticle type platinum-palladium alloyed catalysts with similar metal compositions (Pt n Pd 100-n NPs), the Pt n Pd 100-n NWs exhibit significantly improved electrocatalytic activity and stability for the oxygen reduction reaction. Our findings open new strategies to design the highly active and stable alloy nanocatalysts with controllable compositions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Laboratory multiple-crystal X-ray topography and reciprocal-space mapping of protein crystals: influence of impurities on crystal perfection

Double-axis multiple-crystal X-ray topography, rocking-curve measurements and triple-axis reciprocal-space mapping have been combined to characterize protein crystals using a laboratory source. Crystals of lysozyme and lysozyme crystals doped with acetylated lysozyme impurities were examined. It was shown that the incorporation of acetylated lysozyme into crystals of lysozyme induces mosaic domains that are responsible for the broadening and/or splitting of rocking curves and diffraction-space maps along the direction normal to the reciprocal-lattice vector, while the overall elastic lattice strain of the impurity-doped crystals does not appear to be appreciable in high angular resolution reciprocal-space maps. Multiple-crystal monochromatic X-ray topography, which is highly sensitive to lattice distortions, was used to reveal the spatial distribution of mosaic domains in crystals which correlates with the diffraction features in reciprocal space. Discussions of the influence of acetylated lysozyme on crystal perfection are given in terms of our observations.

Muramidase/chemistry↗

Layer number dependent ferroelasticity in 2D Ruddlesden–Popper organic-inorganic hybrid perovskites

Ferroelasticity represents material domains possessing spontaneous strain that can be switched by external stress. Three-dimensional perovskites like methylammonium lead iodide are determined to be ferroelastic. Layered perovskites have been applied in optoelectronic devices with outstanding performance. However, the understanding of lattice strain and ferroelasticity in layered perovskites is still lacking. Here, using the in-situ observation of switching domains in layered perovskite single crystals under external strain, we discover the evidence of ferroelasticity in layered perovskites with layer number more than one, while the perovskites with single octahedra layer do not show ferroelasticity. Density functional theory calculation shows that ferroelasticity in layered perovskites originates from the distortion of inorganic octahedra resulting from the rotation of aspherical methylammonium cations. The absence of methylammonium cations in single layer perovskite accounts for the lack of ferroelasticity. These ferroelastic domains do not induce non-radiative recombination or reduce the photoluminescence quantum yield.

36 MATERIALS SCIENCE↗

Understanding the asymmetric orientations and stress states in polycrystalline NiTi SMA by in-situ synchrotron-based high-energy X-ray diffraction

The stress-induced martensite transformations (SIMTs) dramatically affect the recoverable strain and mechanical response of polycrystalline NiTi. An in-depth understanding of the propagation manner and orientation preference of SIMTs is therefore crucial. Here, in this work, we present a unique asymmetric anisotropy of SIMTs and lattice strains induced by Lüders-type deformation in polycrystalline NiTi, achieved through a combination of in-situ synchrotron X-ray diffraction and uniaxial tensile loading and unloading experiments. Our experimental findings reveal that in polycrystalline NiTi under uniaxial deformation, the asymmetry of SIMTs is attributed to the inhomogeneous strain field caused by the Lüders-type mechanism. The asymmetrical SIMT starts with the forward Lüder band and disappears along with the backward Lüder band. The austenite with the favored orientation of $\langle$110$\rangle$ A //loading direction (LD) transformed and recovered back at a higher rate compared to other orientations during both loading and unloading.

36 MATERIALS SCIENCE↗

Residual stresses in continuous graphite fiber Al metal matrix composites

The residual stresses in graphite fiber reinforced aluminum (Gr/Al) composites with various thermal histories are measured using X-ray diffraction (XRD) methods. The XRD stress analysis is based on the determination of lattice strains by precise measurements of the interplanar spacings in different directions of the sample. The sample is a plate consisting of two-ply P 100 Gr/Al 6061 precursor wires and Al 6061 overlayers. Prior to XRD measurement, the 6061 overlayers are electrochemically removed. In order to calibrate the relationship between stress magnitude and lattice spacing shift, samples of Al 6061 are loaded at varying stress levels in a three-point bend fixture, while the stresses are simultaneously determined by XRD and surface-attached strain gages. The stresses determined by XRD closely match those determined by the strain gages. Using these calibrations, the longitudinal residual stresses of P 100 Gr/Al 6061 composites are measured for various heat treatments, and the results are presented.

Park, Hun Sub↗