Time-resolved X-ray Diffraction Research Articles

Direct Monitoring of Conical Intersection Passage via Electronic Coherences in Twisted X-Ray Diffraction.

Quantum coherences in electronic motions play a critical role in determining the pathways and outcomes of virtually all photophysical and photochemical molecular processes. However, the direct observation of electronic coherences in the vicinity of conical intersections remains a formidable challenge. We propose a novel time-resolved twisted x-ray diffraction technique that can directly monitor the electronic coherences created as the molecule passes through a conical intersection. We show that the contribution of electronic populations to this signal is canceled out when using twisted x-ray beams that carry a light orbital angular momentum, providing a direct measurement of transient electronic coherences in gas-phase molecules.

Activation of the myosin motors in fast-twitch muscle of the mouse is controlled by mechano-sensing in the myosin filaments.

Myosin motors in resting muscle are inactivated by folding against the backbone of the myosin filament in an ordered helical array and must be released from that conformation to engage in force generation. Time‐resolved X‐ray diffraction from single fibres of amphibian muscle showed that myosin filament activation could be inhibited by imposing unloaded shortening at the start of stimulation, suggesting that filaments were activated by mechanical stress. Here we improved the signal‐to‐noise ratio of that approach using whole extensor digitorum longus muscles of the mouse contracting tetanically at 28°C. Changes in X‐ray signals associated with myosin filament activation, including the decrease in the first‐order myosin layer line associated with the helical motor array, increase in the spacing of a myosin‐based reflection associated with packing of myosin tails in the filament backbone, and increase in the ratio of the 1,1 and 1,0 equatorial reflections associated with movement of motors away from the backbone, were delayed by imposing 10‐ms unloaded shortening at the start of stimulation. These results show that myosin filaments are predominantly activated by filament stress, as in amphibian muscle. However, a small component of filament activation at zero load was detected, implying an independent mechanism of partial filament activation. X‐ray interference measurements indicated a switch‐like change in myosin motor conformation at the start of force development, accompanied by transient disordering of motors in the regions of the myosin filament near its midpoint, suggesting that filament zonal dynamics also play a role in its activation. Key points Activation of myosin filaments in extensor digitorum longus muscles of the mouse is delayed by imposing rapid shortening from the start of stimulation.Stress is the major mechanism of myosin filament activation in these muscles, but there is a small component of filament activation during electrical stimulation at zero stress.Myosin motors switch rapidly from the folded inhibited conformation to the actin‐attached force‐generating conformation early in force development.

Synthesis, structure and properties of MAB phase MoAlB ceramics produced by combination of SHS and HP techniques

The kinetics and stages of phase formation in the combustion wave of the MoAlB mixture are studied. The phase diagrams in the Mo-Al-B system were built using the AFLOW and Materials Project databases. The time-resolved X-ray diffraction analysis demonstrate that the MoAlB phase crystallizes from the melt without formation of any intermediate compounds. The structure of the synthesized ceramics was MoAlB lamellar grains 0.4 µm thick and ~2–10 µm long. Compact samples characterized by homogeneous structure and low residual porosity were obtained by hot pressing of SHS powders. The ceramic MoAlB has a layered structure, which is consistent with the morphology of the synthesis products. Mechanical and thermophysical properties are measured for samples obtained under optimal HP conditions at 1300 °C. The calculated value of the oxidation rate for MoAlB at 1200 °C for 30 h was 2.21∙10−5 mg/(cm2∙s). Oxide layer ~14 µm thick consists of elongated polygonal Al2O3 grains.

Evidence for superionic H2O and diffusive He–H2O at high temperature and high pressure

We present the evidence of superionic phase formed in H2O and, for the first time, diffusive H2O–He phase, based on time-resolved x-ray diffraction experiments performed on ramp-laser-heated samples in diamond anvil cells. The diffraction results signify a similar bcc-like structure of superionic H2O and diffusive He–H2O, while following different transition dynamics. Based on time and temperature evolution of the lattice parameter, the superionic H2O phase forms gradually in pure H2O over the temperature range of 1350–1400 K at 23 GPa, but the diffusive He–H2O phase forms abruptly at 1300 K at 26 GPa. We suggest that the faster dynamics and lower transition temperature in He–H2O are due to a larger diffusion coefficient of interstitial-filled He than that of more strongly bound H atoms. This conjecture is then consistent with He disordered diffusive phase predicted at lower temperatures, rather than H-disordered superionic phase in He–H2O.

Low-temperature nanoscale heat transport in a gadolinium iron garnet heterostructure probed by ultrafast x-ray diffraction.

Time-resolved x-ray diffraction has been used to measure the low-temperature thermal transport properties of a Pt/Gd3Fe5O12//Gd3Ga5O12 metal/oxide heterostructure relevant to applications in spin caloritronics. A pulsed femtosecond optical signal produces a rapid temperature rise in the Pt layer, followed by heat transport into the Gd3Fe5O12 (GdIG) thin film and the Gd3Ga5O12 (GGG) substrate. The time dependence of x-ray diffraction from the GdIG layer was tracked using an accelerator-based femtosecond x-ray source. The ultrafast diffraction measurements probed the intensity of the GdIG (1 −1 2) x-ray reflection in a grazing-incidence x-ray diffraction geometry. The comparison of the variation of the diffracted x-ray intensity with a model including heat transport and the temperature dependence of the GdIG lattice parameter allows the thermal conductance of the Pt/GdIG and GdIG//GGG interfaces to be determined. Complementary synchrotron x-ray diffraction studies of the low-temperature thermal expansion properties of the GdIG layer provide a precise calibration of the temperature dependence of the GdIG lattice parameter. The interfacial thermal conductance of the Pt/GdIG and GdIG//GGG interfaces determined from the time-resolved diffraction study is of the same order of magnitude as previous reports for metal/oxide and epitaxial dielectric interfaces. The thermal parameters of the Pt/GdIG//GGG heterostructure will aid in the design and implementation of thermal transport devices and nanostructures.

Understanding of the Mechanism and Kinetics of the Fast Solid-State Reaction between NaF and VPO4 to Form Na3V2(PO4)2F3.

The solid-state reaction between NaF and VPO4 is widely used to produce Na3V2(PO4)2F3, a promising cathode material for sodium-ion batteries. In the present work, the mechanism and kinetics of the reaction between NaF and VPO4 were investigated, and the effect of preliminary high-energy ball milling (HEBM) was studied using in situ time-resolved synchrotron powder X-ray diffraction, in situ transmission electron microscopy, differential scanning calorimetry, etc. The reaction was attributed to a "dimensional reduction" formalism; it proceeds quickly with the unilateral diffusion of Na+ and F- ions into VPO4 particles as a limiting stage. The use of HEBM leads to the mechanism corresponding to the third-order reaction model and accelerates the interaction. The rate constant k increases from 3.5 × 10-5 to 3.4 × 10-3 s-1, and diffusion coefficient D increases from 2 × 10-14 to 4 × 10-13 cm2 s-1 when HEBM is used. The calculated apparent activation energy is ∼290 kJ mol-1. The electrochemical properties of the as-prepared Na3V2(PO4)2F3 are not inferior to the properties of the materials prepared by conventional solid-state synthesis.

Hematite-goethite ratios at pH 2–13 and 25–170 °C: A time-resolved synchrotron X-ray diffraction study

Iron (oxyhydr)oxides are sensitive indicators of pH, Eh, temperature, microbial activity, and climate conditions in the Critical Zone. The most ubiquitous and environmentally significant iron oxides in most soils are two-line ferrihydrite, goethite, and hematite. Here we present a comprehensive study of the transformation of two-line ferrihydrite to hematite and goethite over a wide range of temperature (25–170 °C) and initial pH (2−13) conditions through ex situ batch and in situ synchrotron X-ray diffraction (XRD) experiments.Within the high time resolution of our experiments, goethite and hematite nucleated nearly simultaneously from ferrihydrite in nearly equal concentrations by mass. Hematite increased in abundance relative to goethite until a steady-state ratio was achieved, and both phases ceased growth on the depletion of ferrihydrite. Higher temperatures and lower water activities favored hematite formation at all pH values studied. In both our batch and our time-resolved, angle-dispersive synchrotron X-ray diffraction experiments, hematite was favored relative to goethite at an initial pH of 3 to 5. In contrast, goethite preferentially formed in neutral (initial pH 7–8) and highly alkaline conditions (initial pH ≥ 11). Surprisingly, mildly alkaline conditions (initial pH 9–11) induced the precipitation of a highly Fe-deficient (Feocc = ~0.80–0.90) variety of hematite known as “hydrohematite” in greater concentrations than goethite. Our results are useful for the application of hematite-goethite ratios as paleoclimate proxies for soil and sediment systems with low pH buffering capacities.

Synchrotron X-Ray-Driven Nitrogen Reduction on an AgCu Thin Film.

Nitrogen (N2 ) is an essential element for life, but kinetically stable N2 in the atmosphere needs to be reduced to biologically available forms as a nutrient for organisms. Abiotic nitrogen fixation is critical to the origin of life on the early Earth, which is due to lightning or mineral-based reduction. Here, synchrotron X-ray-induced silver nitrate formation on a silver copper (AgCu) thin-film is reported. Time-resolved X-ray diffraction measurements show that under intense X-ray exposure, initially formed silver oxides (AgOx) are quickly converted to silver nitrate (AgNO3 ). Interestingly, AgNO3 is first formed in its high-temperature phase with a space group of R3cH, which gradually transforms to the room temperature phase with a space group of Pbca under continuous X-ray irradiation. The result not only provides a new clue about the abiotic nitrogen reduction prior to life but also demonstrates a novel strategy of materials synthesis using synchrotron X-rays.

A multipurpose laboratory diffractometer for operando powder X-ray diffraction investigations of energy materials.

Laboratory X-ray diffractometers are among the most widespread instruments in research laboratories around the world and are commercially available in different configurations and setups from various manufacturers. Advances in detector technology and X-ray sources push the data quality of in-house diffractometers and enable the collection of time-resolved scattering data during operando experiments. Here, the design and installation of a custom-built multipurpose laboratory diffractometer for the crystallographic characterization of battery materials are reported. The instrument is based on a Huber six-circle diffractometer equipped with a molybdenum microfocus rotating anode with 2D collimated parallel-beam X-ray optics and an optional two-bounce crystal monochromator. Scattered X-rays are detected with a hybrid single-photon-counting area detector (PILATUS 300K-W). An overview of the different diffraction setups together with the main features of the beam characteristics is given. Example case studies illustrate the flexibility of the research instrument for time-resolved operando powder X-ray diffraction experiments as well as the possibility to collect higher-resolution data suitable for diffraction line-profile analysis.

Melting of magnetic order in NaOsO3 by femtosecond laser pulses

${\mathrm{NaOsO}}_{3}$ has recently attracted significant attention for the strong coupling between its electronic band structure and magnetic ordering. Here, we used time-resolved magnetic x-ray diffraction to determine the timescale of the photoinduced antiferromagnetic dynamics in ${\mathrm{NaOsO}}_{3}$. Our measurements are consistent with a sub-100 fs melting of the antiferromagnetic long-range order that occurs significantly faster than the lattice dynamics as monitored by the transient change in intensity of selected Bragg structural reflections, which instead show a decrease of intensity on a timescale of several ps.

Direct Observation of Coherent Longitudinal and Shear Acoustic Phonons in TaAs Using Ultrafast X-Ray Diffraction.

Using femtosecond time-resolved x-ray diffraction, we investigated optically excited coherent acoustic phonons in the Weyl semimetal TaAs. The low symmetry of the (112) surface probed in our experiment enables the simultaneous excitation of longitudinal and shear acoustic modes, whose dispersion closely matches our simulations. We observed an asymmetry in the spectral line shape of the longitudinal mode that is notably absent from the shear mode, suggesting a time-dependent frequency chirp that is likely driven by photoinduced carrier diffusion. We argue on the basis of symmetry that these acoustic deformations can transiently alter the electronic structure near the Weyl points and support this with model calculations. Our study underscores the benefit of using off-axis crystal orientations when optically exciting acoustic deformations in topological semimetals, allowing one to transiently change their crystal and electronic structures.

Optical excitation of electromagnons in hexaferrite

Understanding ultrafast magnetization dynamics on the microscopic level is of strong current interest due to the potential for applications in information storage. In recent years, spin-lattice coupling has been recognized as essential for ultrafast magnetization dynamics. Magnetoelectric multiferroics of type II possess intrinsic correlations among magnetic sublattices and electric polarization $(P)$ through spin-lattice coupling, enabling fundamentally coupled dynamics between spins and lattice. Here, we report on ultrafast magnetization dynamics in a room-temperature multiferroic hexaferrite possessing ferrimagnetic (FM) and antiferromagnetic sublattices, revealed by time-resolved resonant x-ray diffraction. A femtosecond above-bandgap excitation triggers a coherent magnon in which the two magnetic sublattices entangle and give rise to a transient modulation of $P$. A microscopic mechanism for triggering the coherent magnon in this FM insulator based on the spin-lattice coupling is proposed. Our finding opens a general pathway for ultrafast control of magnetism.

Nonequilibrium sub-10 nm spin-wave soliton formation in FePt nanoparticles.

Magnetic nanoparticles such as FePt in the L10 phase are the bedrock of our current data storage technology. As the grains become smaller to keep up with technological demands, the superparamagnetic limit calls for materials with higher magnetocrystalline anisotropy. This, in turn, reduces the magnetic exchange length to just a few nanometers, enabling magnetic structures to be induced within the nanoparticles. Here, we describe the existence of spin-wave solitons, dynamic localized bound states of spin-wave excitations, in FePt nanoparticles. We show with time-resolved x-ray diffraction and micromagnetic modeling that spin-wave solitons of sub-10 nm sizes form out of the demagnetized state following femtosecond laser excitation. The measured soliton spin precession frequency of 0.1 THz positions this system as a platform to develop novel miniature devices.

Nucleation Kinetics and Structure Evolution of Quasi-Two-Dimensional ZnO at the Air-Water Interface: An In Situ Time-Resolved Grazing Incidence X-ray Scattering Study.

The design and synthesis of high-quality two-dimensional (2D) materials with desired morphology are essential for property control. One critical challenge that impedes the understanding and control of 2D crystal nucleation and growth is the inability of direct observation of the nanocrystal evolution process with high enough time resolution. Here, we demonstrated an in situ X-ray scattering approach that directly reveals 2D wurtzite ZnO nanosheet growth at the air-water interface. The time-resolved grazing incidence X-ray diffraction (GID) and grazing incidence X-ray off-specular scattering (GIXOS) results uncovered a lateral to vertical growth kinetics switch phenomenon in the ZnO nanosheet growth. This switch represents the 2D to three-dimensional (3D) crystal structure evolution, which governs the size and thickness of nanosheets, respectively. This phenomenon can guide 2D nanocrystal synthesis with rationally controlled size and thickness. Our work opens a new pathway toward the understanding of 2D nanomaterial growth kinetics based on time-resolved liquid surface grazing incidence X-ray techniques.

Visualizing Light-Induced Microstrain and Phase Transition in Lead-Free Perovskites Using Time-Resolved X-Ray Diffraction.

Metal halide perovskites have emerged as promising materials for optoelectronic applications in the last decade. A large amount of effort has been made to investigate the interplay between the crystalline lattice and photoexcited charge carriers as it is vital to their optoelectronic performance. Among them, ultrafast laser spectroscopy has been intensively utilized to explore the charge carrier dynamics of perovskites, from which the local structural information can only be extracted indirectly. Here, we have applied a time-resolved X-ray diffraction technique to investigate the structural dynamics of prototypical two-dimensional lead-free halide perovskite Cs3Bi2Br9 nanoparticles across temporal scales from 80 ps to microseconds. We observed a quick recoverable (a few ns) photoinduced microstrain up to 0.15% and a long existing lattice expansion (∼a few hundred nanoseconds) at mild laser fluence. Once the laser flux exceeds 1.4 mJ/cm2, the microstrain saturates and the crystalline phase partially transfers into a disordered phase. This photoinduced transient structural change can recover within the nanosecond time scale. These results indicate that photoexcitation of charge carriers couples with lattice distortion, which fundamentally affects the dielectric environment and charge carrier transport.

RT-XAMF and TR-XRD studies of solid-state synthesis and thermal stability of NaNiO2 as cathode material for sodium-ion batteries

Room-temperature sodium storage technology has been attracting considerable attention, and its potential as a alternative technology to lithium-ion batteries for electrical energy storage has been studied owing to the abundance of sodium resources and its inexpensiveness. In situ X-ray diffraction (XRD) techniques, such as real-time X-ray analytical micro-furnace (RT-XAMF) and time-resolved X-ray diffraction (TR-XRD), are utilized to identify the synthesis process and thermal stability of the NaNiO2 cathode material for Na-ion batteries. Using the RT-XAMF technique, the solid-state reaction of Na2O2 and NiO was investigated in real-time to verify the phase transition from rhombohedral NaNiO2 at temperatures above 243 °C to monoclinic NaNiO2 at temperatures below 243 °C during heat treatment. In addition, the structural instability of the monoclinic NaNiO2 phase changes to the Na-deficient Na0.91NiO2 phase. The TR-XRD technique was used to investigate the thermal stability of the desodiated Na1−xNiO2 (x = 0.09, 0.5) cathodes in the presence of an electrolyte. It was confirmed that the structural changes of desodiated Na1−xNiO2 were relatively simple compared to those of the Ni-based cathode material in Li-ion batteries. First, the layered structure of Na1−xNiO2 at room temperature turns into an MO-type rock salt phase (NiO) and subsequently into a metallic phase (Ni) without the appearance of spinel-type (Li1−xM2O4 and M3O4) intermediates, which are typically observed in lithium nickel-based oxides. In addition, it was concluded that desodiated Na1−xNiO2 materials have higher thermal stability than delithiated Li1−xNiO2 (x = 0.5, below ∼200 °C) based on its high decomposition temperature (∼300 °C for Na0.91NiO2 and ∼280 °C for Na0.5NiO2). From these results, we believe that our in-situ XRD findings on the real-time solid-state synthesis process and thermal stability can be used as a fundamental guide for the development of Ni-based NaMO2 (M = Ni, Co, Mn, etc.) oxides for next-generation advanced Na-ion batteries.

Manipulating Crystallization Kinetics in High-Performance Blade-Coated Perovskite Solar Cells via Cosolvent-Assisted Phase Transition.

Manipulating the perovskite solidification process, including nucleation and crystal growth, plays a critical role in controlling film morphology and thus affects the resultant device performance. In this work, a facile and effective ethyl alcohol (EtOH) cosolvent strategy is demonstrated with the incorporation of EtOH into perovskite ink for high-performance room-temperature blade-coated perovskite solar cells (PSCs) and modules. Systematic real-time perovskite crystallization studies uncover the delicate perovskite structural evolutions and phase-transition pathway. Time-resolved X-ray diffraction and density functional theory calculations both demonstrate that EtOH in the mixed-solvent system significantly promotes the formation of an FA-based precursor solvate (FA2 PbBr4 ·DMSO) during the trace-solvent-assisted transition process, which finely regulates the balance between nucleation and crystal growth to guarantee high-quality perovskite films. This strategy efficiently suppresses nonradiative recombination and improves efficiencies in both 1.54 (23.19%) and 1.60eV (22.51%) perovskite systems, which represents one of the highest records for blade-coated PSCs in both small-area devices and minimodules. An excellent VOC deficit as low as 335mV in the 1.54eV perovskite system, coincident with the measured nonradiative recombination loss of only 77mV, is achieved. More importantly, significantly enhanced device stability is another signature of this approach.

LixFePO4 -ийн фазын салалтын кинетик болон соронзон шинж чанарын судалгаа

Time-resolved X-ray diffraction was used to investigate the kinetics of phase separation in polycrystalline LixFePO4 samples which were quenched from the homogeneous phase to lower temperatures. On quenching from 380°C (homogeneous phase) to ageing various temperatures, we observed that the structural features of the formation of the two product phases LiFePO4 and orthorhombic FePO4, i.e. the splitting of selected Bragg reflections, appear on a time-scale of hours. The kinetic behaviour seems to vary strongly with the ageing temperatures. In the case of quenching to temperatures lower than 50°C, no significant splitting of Bragg reflections is observed. Hence, the homogeneous phase may be stabilised by quenching to sufficiently low temperatures. We have studied the magnetic properties of the samples by SQUID-magnetometry. The partially delithiated samples show the known temperature dependence of the magnetic susceptibility with ordering temperatures of about 122K (FePO4) and 50K (LiFePO4). In order to create a single phase, the samples were quenched from the homogeneous phase to room temperature. Obviously, Néel temperatures of these samples were observed in between the values of pure compounds and depend on the overall composition.

Exchange scaling of ultrafast angular momentum transfer in 4f antiferromagnets

Ultrafast manipulation of magnetism bears great potential for future information technologies. While demagnetization in ferromagnets is governed by the dissipation of angular momentum1–3, materials with multiple spin sublattices, for example antiferromagnets, can allow direct angular momentum transfer between opposing spins, promising faster functionality. In lanthanides, 4f magnetic exchange is mediated indirectly through the conduction electrons4 (the Ruderman–Kittel–Kasuya–Yosida (RKKY) interaction), and the effect of such conditions on direct spin transfer processes is largely unexplored. Here, we investigate ultrafast magnetization dynamics in 4f antiferromagnets and systematically vary the 4f occupation, thereby altering the magnitude of the RKKY coupling energy. By combining time-resolved soft X-ray diffraction with ab initio calculations, we find that the rate of direct transfer between opposing moments is directly determined by this coupling. Given the high sensitivity of RKKY to the conduction electrons, our results offer a useful approach for fine tuning the speed of magnetic devices.

Revealing complex microstructure formation mechanisms in the Al[formula omitted]Cr[formula omitted]Fe[formula omitted]Ni[formula omitted]Ti[formula omitted] compositionally complex alloy

The complex phase evolution sequence of a promising new high temperature structural alloy with composition Al20Cr20Fe35Ni20Ti5 (at.%) has been studied in situ using an electromagnetic levitation (EML) setup combined with time-resolved high energy X-ray diffraction (XRD), as well by scanning transmission electron microscopy (STEM) observations during in situ heating. These experiments were supplemented by both scanning electron microscopy (SEM) and high resolution STEM observations of the as-cast alloy microstructure, as well as by energy dispersive X-ray spectroscopy (EDS) composition measurements. Differential scanning calorimetry (DSC) was used to identify liquidus, solidus, A2 ↔ B2, and B2 ↔ L21 transition temperatures. The results obtained by these complementary techniques indicate that the alloy forms primary dendrites of A2-structured body-centered cubic (bcc) phase initially from the melt, followed by ordered bcc of B2-structure in interdendritic regions once compositional segregation has sufficiently enriched the remaining liquid. Ordered B2 precipitates form within the primary A2-structured dendrites and the interdendritic B2 regions undergo a continuous decomposition reaction into a maze-like arrangement of A2 and B2/L21 phases below the solidus. Below approximately 1380 K, the B2 domains in both dendritic and interdendritic regions likely undergo a continuous ordering transition to the L21 phase. The experimental observations of Al20Cr20Fe35Ni20Ti5 are found to be in good agreement with CALPHAD predictions but suggest that the solubility limits of the L21-Heusler phase in the database should be relaxed to include greater Fe solubility for the Ni sublattice and to consider deviations in order parameter from stoichiometric ordering.