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At least 595 records · Page 33

Non-resonant Bragg scattering four-wave mixing at near-visible wavelengths in low-confinement silicon nitride waveguides

Quantum state coherent frequency conversion processes—such as Bragg-scattering four-wave mixing (BSFWM)—hold promise as a flexible technique for networking heterogeneous and distant quantum systems. In this Letter, we demonstrate BSFWM within an extended (1.2-m) low-confinement silicon nitride waveguide and show that this system has the potential for near-unity frequency conversion in visible and near-visible wavelength ranges. Using sensitive classical heterodyne laser spectroscopy at low optical powers, we characterize the Kerr coefficient (∼1.55 W −1 m −1 ) and linear propagation loss (∼0.0175 dB/cm) of this non-resonant waveguide system, revealing a record-high nonlinear figure of merit (NFM = γ / α ≈ 3.85 W −1 ) for BSFWM of near-visible light in non-resonant silicon nitride waveguides. We predict how, at high yet achievable on-chip optical powers, this NFM would yield a comparatively large frequency conversion efficiency, opening the door to near-unity flexible frequency conversion without cavity enhancement and resulting bandwidth constraints.

Jaber, Nicholas (ORCID:000900070106809X)↗

Synchrotron-based techniques for characterizing STCH water-splitting materials

Understanding the role of oxygen vacancy–induced atomic and electronic structural changes to complex metal oxides during water-splitting processes is paramount to advancing the field of solar thermochemical hydrogen production (STCH). The formulation and confirmation of a mechanism for these types of chemical reactions necessitate a multifaceted experimental approach, featuring advanced structural characterization methods. Synchrotron X-ray techniques are essential to the rapidly advancing field of STCH in part due to properties such as high brilliance, high coherence, and variable energy that provide sensitivity, resolution, and rapid data acquisition times required for the characterization of complex metal oxides during water-splitting cycles. X-ray diffraction (XRD) is commonly used for determining the structures and phase purity of new materials synthesized by solid-state techniques and monitoring the structural integrity of oxides during water-splitting processes (e.g., oxygen vacancy–induced lattice expansion). X-ray absorption spectroscopy (XAS) is an element-specific technique and is sensitive to local atomic and electronic changes encountered around metal coordination centers during redox. While in operando measurements are desirable, the experimental conditions required for such measurements (high temperatures, controlled oxygen partial pressures, and H 2 O) practically necessitate in situ measurements that do not meet all operating conditions or ex situ measurements. Here, we highlight the application of synchrotron X-ray scattering and spectroscopic techniques using both in situ and ex situ measurements, emphasizing the advantages and limitations of each method as they relate to water-splitting processes. The best practices are discussed for preparing quenched states of reduction and performing synchrotron measurements, which focus on XRD and XAS at soft (e.g., oxygen K-edge, transition metal L-edges, and lanthanide M-edges) and hard (e.g., transition metal K-edges and lanthanide L-edges) X-ray energies. The X-ray absorption spectra of these complex oxides are a convolution of multiple contributions with accurate interpretation being contingent on computational methods. The state-of-the-art methods are discussed that enable peak positions and intensities to be related to material electronic and structural properties. Through careful experimental design, these studies can elucidate complex structure–property relationships as they pertain to nonstoichiometric water splitting. A survey of modern approaches for the evaluation of water-splitting materials at synchrotron sources under various experimental conditions is provided, and available software for data analysis is discussed.

08 HYDROGEN↗

Chirality manipulation of ultrafast phase switches in a correlated CDW-Weyl semimetal

Light engineering of correlated states in topological materials provides a new avenue of achieving exotic topological phases inaccessible by conventional tuning methods. Here we demonstrate a light control of correlation gaps in a model charge-density-wave (CDW) and polaron insulator (TaSe 4 ) 2 I recently predicted to be an axion insulator. Our ultrafast terahertz photocurrent spectroscopy reveals a two-step, non-thermal melting of polarons and electronic CDW gap via the fluence dependence of a longitudinal circular photogalvanic current. This helicity-dependent photocurrent reveals continuous ultrafast phase switches from the polaronic state to the CDW (axion) phase, and finally to a hidden Weyl phase as the pump fluence increases. Additional distinctive attributes aligning with the light-induced switches include: the mode-selective coupling of coherent phonons to the polaron and CDW modulation, and the emergence of a non-thermal chiral photocurrent above the pump threshold of CDW-related phonons. The demonstrated ultrafast chirality control of correlated topological states here holds large potentials for realizing axion electrodynamics and advancing quantum-computing applications.

36 MATERIALS SCIENCE↗

Quasiparticle excitations in a one-dimensional interacting topological insulator: Application for dopant-based quantum simulation

Here, we study the effects of electron-electron interactions on the charge excitation spectrum of the spinful Su-Schrieffer-Heeger (SSH) model, a prototype of a one-dimensional bulk obstructed topological insulator. In view of recent progress in the fabrication of dopant-based quantum simulators we focus on experimentally detectable signatures of interacting topology in finite lattices. To this end we use Lanczos-based exact diagonalization to calculate the single-particle spectral function in real space which generalizes the local density of states to interacting systems. Its spatial and spectral resolution allows for the direct investigation and identification of edge states. By studying the noninteracting limit, we demonstrate that the topological in-gap states on the boundary are robust against both finite-size effects as well as random bond and onsite disorder which suggests the feasibility of simulating the SSH model in engineered dopant arrays in silicon. While edge excitations become zero-energy spinlike for any finite interaction strength, our analysis of the spectral function shows that the single-particle charge excitations are gapped out on the boundary. Despite the loss of topological protection, we find that these edge excitations are quasiparticlelike as long as they remain within the bulk gap. Above a critical interaction strength of U c ≈5t these quasiparticles on the boundary lose their coherence which is explained by the merging of edge and bulk states. This is in contrast to the many-body edge excitations which survive the limit of strong coupling, as established in the literature. Our findings show that for moderate repulsive interactions the nontrivial phase of the interacting SSH model can be detected through remnant signatures of topological single-particle states using single-particle local measurement techniques such as scanning tunneling spectroscopy.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Two-tooth bosonic quantum comb for temporal-correlation sensing

We introduce a two-tooth bosonic quantum comb that captures the sequential interactions between a thermal absorber and a long-lived coherent probe. The comb provides a causal, multi-time description of coherence transport, tracking how the probe records both instantaneous fluctuations and their temporal correlations. Using a process-tensor formulation, we derive closed form expressions showing that interference between the two interaction windows generates a non-monotonic memory response that reflects a fundamental competition between the absorbers thermal population and its dynamical correlations. By sweeping the temporal separation between the interaction windows, the probe directly samples the absorbers population correlator, enabling bosonic noise spectroscopy that discriminates Markovian temperature noise from slow or spectrally structured fluctuations. The approach is readily compatible with circuit-QED platforms and offers a general method for probing fluctuating bosonic environments.

Zhu, Shaojiang [Fermilab]↗

Electron Energy-Loss Spectroscopy and Differential Phase Contrast Imaging with Active Decision in Multimodal Electron Microscopy: Isotopic detection at the atomic scale

Isotopic engineering provides a powerful route to control phonon behavior in crystalline solids, enabling fundamental studies of lattice dynamics and heat transport at the atomic scale. Here, we directly visualize isotope-dependent phonon propagation in epitaxial Cr 2 O 3 using aberration-corrected scanning transmission electron microscopy (STEM) combined with monochromated, high-energy-resolution electron energy-loss spectroscopy (EELS). Guided by ab initio phonon calculations, we demonstrate that optical phonon modes above 70 meV are predominantly oxygen-derived and exhibit measurable redshifts upon substitution of natural 16 O by enriched 18 O. Spatially resolved vibrational spectrum imaging reveals isotope-enriched tracer layers within Cr 2 O 3 thin films, correlating isotope concentration with phonon intensity variations and vibrational energy shifts. At the nanometer and atomic scales, vibrational EELS mapping uncovers coherent phonon propagation across isotopic interfaces, consistent with theoretical phonon density of states and dispersion relations. These results establish vibrational EELS as a quantitative probe for isotope-dependent phonon transport in materials, opening new possibilities for studying energy dissipation and lattice dynamics.

36 MATERIALS SCIENCE↗

Intermittent Defect Fluctuations in Oxide Heterostructures

Abstract The heterogeneous nature, local presence, and dynamic evolution of defects typically govern the ionic and electronic properties of a wide variety of functional materials. While the last 50 years have seen considerable efforts into development of new methods to identify the nature of defects in complex materials, such as the perovskite oxides, very little is known about defect dynamics and their influence on the functionality of a material. Here, the discovery of the intermittent behavior of point defects (oxygen vacancies) in oxide heterostructures employing X‐ray photon correlation spectroscopy is reported. Local fluctuations between two ordered phases in strained SrCoO x with different degrees of stability of the oxygen vacancies are observed. Ab‐initio‐informed phase‐field modeling reveals that fluctuations between the competing ordered phases are modulated by the oxygen ion/vacancy interaction energy and epitaxial strain. The results demonstrate how defect dynamics, evidenced by measurement and modeling of their temporal fluctuations, give rise to stochastic properties that now can be fully characterized using coherent X‐rays, coupled for the first time to multiscale modeling in functional complex oxide heterostructures. The study and its findings open new avenues for engineering the dynamical response of functional materials used in neuromorphic and electrochemical applications.

36 MATERIALS SCIENCE↗

A Compact, Tunable Near-UV Source for Quantitative Microgravity Combustion Diagnostics

There is a need for improved optical diagnostic methods for use in microgravity combustion research. Spectroscopic methods with fast time response that can provide absolute concentrations and concentration profiles of important chemical species in flames are needed to facilitate the understanding of combustion kinetics in microgravity. Although a variety of sophisticated laser-based diagnostics (such as planar laser induced fluorescence, degenerate four wave mixing and coherent Raman methods) have been applied to the study of combustion in laboratory flames, the instrumentation associated with these methods is not well suited to microgravity drop tower or space station platforms. Important attributes of diagnostic systems for such applications include compact size, low power consumption, ruggedness, and reliability. We describe a diode laser-based near-UV source designed with the constraints of microgravity research in mind. Coherent light near 420 nm is generated by frequency doubling in a nonlinear crystal. This light source is single mode with a very narrow bandwidth suitable for gas phase diagnostics, can be tuned over several 1/cm and can be wavelength modulated at up to MHz frequencies. We demonstrate the usefulness of this source for combustion diagnostics by measuring CH radical concentration profiles in an atmospheric pressure laboratory flame. The radical concentrations are measured using wavelength modulation spectroscopy (WMS) to obtain the line-of-sight integrated absorption for different paths through the flame. Laser induced fluorescence (LIF) measurements are also demonstrated with this instrument, showing the feasibility of simultaneous WMS absorption and LIF measurements with the same light source. LIF detection perpendicular to the laser beam can be used to map relative species densities along the line-of-sight while the integrated absorption available through WMS provides a mathematical constraint on the extraction of quantitative information from the LIF data. Combining absorption with LIF - especially if the measurements are made simultaneously with the same excitation beam - may allow elimination of geometrical factors and effects of intensity fluctuations (common difficulties with the analysis of LIF data) from the analysis.

Peterson, K. A.↗

Asymmetric nanoparticle oxidation observed in-situ by the evolution of diffraction contrast

Abstract The use of transmission electron microscopy (TEM) to observe real-time structural and compositional changes has proven to be a valuable tool for understanding the dynamic behavior of nanomaterials. However, identifying the nanoparticles of interest typically require an obvious change in position, size, or structure, as compositional changes may not be noticeable during the experiment. Oxidation or reduction can often result in subtle volume changes only, so elucidating mechanisms in real-time requires atomic-scale resolution or in-situ electron energy loss spectroscopy, which may not be widely accessible. Here, by monitoring the evolution of diffraction contrast, we can observe both structural and compositional changes in iron oxide nanoparticles, specifically the oxidation from a wüstite-magnetite (FeO@Fe 3 O 4 ) core – shell nanoparticle to single crystalline magnetite, Fe 3 O 4 nanoparticle. The in-situ TEM images reveal a distinctive light and dark contrast known as the ‘Ashby-Brown contrast’, which is a result of coherent strain across the core – shell interface. As the nanoparticles fully oxidize to Fe 3 O 4 , the diffraction contrast evolves and then disappears completely, which is then confirmed by modeling and simulation of TEM images. This represents a new, simplified approach to tracking the oxidation or reduction mechanisms of nanoparticles using in-situ TEM experiments.

36 MATERIALS SCIENCE↗

Origin of spin-driven ferroelectricity and effect of external pressure on the complex magnetism of the 6⁢ H perovskite Ba 3 ⁢Ho⁢Ru 2⁢ O 9

The compound Ba 3 HoRu 2 O 9 magnetically orders at 50 K (T N1 ), followed by another complex magnetic ordering at 10.2 K (T N2 ). The second magnetic phase transition was characterized by the coexistence of two competing magnetic ground states associated with two different magnetic wave vectors (K 1 = 0.5 0 0 and K 2 = 0.25 0.25 0). The multiferroicity and magnetoelectric coupling were predicted below T N2 in these 4d-based materials. Here, in this work, we have discussed the origin of spin-driven ferroelectricity, which is not known yet, and the nature of magnetoelectric domains. We have investigated the compound through time-of-flight neutron diffraction, synchrotron x-ray diffraction (XRD), ac susceptibility, frequency-dependent complex dielectric spectroscopy, and dc magnetization under external pressure. We have demonstrated that the noncollinear structure involving two different magnetic ions, Ru (4d) and Ho (4f), breaks the spatial inversion symmetry via inverse Dzyaloshinskii-Moriya (DM) interaction through strong 4d-4f magnetic correlation, which shifts the oxygen atoms and results in nonzero polarization. Such an observation of inverse DM interaction from two different magnetic ions which cause ferroelectricity is rarely observed. The stronger spin-orbit coupling of 4d orbital might play a major role in creating DM interaction of noncollinear spins. We have systematically studied the spin and dipolar dynamics, which exhibit intriguing behavior with shorter coherence lengths of second magnetic phase associated with the k 2 wave vector. The results manifest the development of finite-size magnetoelectric domains instead of true long-range ordering, which justifies the experimentally obtained low value of ferroelectric polarization. The lattice parameters and volume show a sharp anomaly at T N2 obtained by analyzing the temperature-dependence XRD, which is consistent with the ferroelectric transition, predicting a noncentrosymmetric space group, $P\bar{6}2c$, for this compound. Furthermore, we have investigated the effect of external pressure on this complex magnetism. The result reveals an enhancement of ordering temperature by the application of external pressure (~1.6 K/GPa). The external pressure might favor stabilizing the magnetic ground state associated with second magnetic phase. Our study shows an unconventional mechanism of spin-driven ferroelectricity involving inverse DM interaction between Ru (4d) and Ho (4f) magnetic ions due to strong 4d-4f cross coupling.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Symmetry-mediated quantum coherence of W 5+ spins in an oxygen-deficient double perovskite

Elucidating the factors limiting quantum coherence in real materials is essential to the development of quantum technologies. Here we report a strategic approach to determine the effect of lattice dynamics on spin coherence lifetimes using oxygen deficient double perovskites as host materials. In addition to obtaining millisecond T 1 spin-lattice lifetimes at T ~ 10 K, measurable quantum superpositions were observed up to room temperature. We determine that T 2 enhancement in Sr 2 CaWO 6-δ over previously studied Ba 2 CaWO 6-δ is caused by a dynamically-driven increase in effective site symmetry around the dominant paramagnetic site, assigned as W 5+ via electron paramagnetic resonance spectroscopy. Further, a combination of experimental and computational techniques enabled quantification of the relative strength of spin-phonon coupling of each phonon mode. This analysis demonstrates the effect of thermodynamics and site symmetry on the spin lifetimes of W 5+ paramagnetic defects, an important step in the process of reducing decoherence to produce longer-lived qubits.

36 MATERIALS SCIENCE↗

Overcoming energy limitation in post-compression of picosecond pulses by free beam propagation in air and temporal pulse splitting and recombining

Cryogenically cooled diode-pumped Yb:YAG has been demonstrated to efficiently generate pulses of >1 J energy and several picoseconds duration at a kilohertz repetition rate. Pulse broadening and post-compression techniques capable of operating at these high pulse energies will expand the use of these lasers in applications requiring shorter pulses. Towards this goal, we demonstrate the post-compression of 5.5 ps pulses with energy in the 0.1 J range by spectral broadening of self-collimated large area beams in air. In proof-of-principle experiments, pulses of 65 mJ energy from a cryogenically cooled Yb:YAG laser were compressed to 1.1 ps after 65 m propagation in a compact setup in which the beam was folded using flat mirrors. Further energy scaling was demonstrated by combining this spectral broadening technique with temporal pulse splitting and recombining. 120 mJ pulses were split into two pulses and coherently recombined with 85% efficiency after 50 m of propagation in air to yield 1.4 ps pulses.

High Energy Laser↗

Laser Measurements and Modeling of Shock Tunnel Freestream Velocity and Multispecies Thermal Nonequilibrium

Coherent anti-Stokes Raman scattering (CARS) and nitric oxide molecular tagging velocimetry (NO-MTV) were used to characterize the freestream in Sandia’s Hypersonic Shock Tunnel (HST) using a burst-mode laser operated at 100 kHz. Experiments were performed at nominal freestream velocities of 3 and 4 km/s using both air and N 2 test gas. The CARS diagnostic provides nonequilibrium characterization of the flow by measuring vibrational and rotational temperatures of N 2 and O 2 , which are compared to NO temperatures from separate laser absorption experiments. Simultaneous, collinear freestream velocities were measured using NO MTV along with pitot pressure measurements. Furthermore, this extensive freestream dataset is compared to nonequilibrium CFD that is capable of modeling species-specific, vibrational temperatures throughout the nozzle expansion. Significant nonequilibrium between vibrational and rotational temperatures was measured at each flow condition. N 2 exhibits the most nonequilibrium, followed by O 2 and NO. The CFD model captures this trend, although it consistently overpredicts N 2 and O 2 vibrational temperatures. At 3 km/s, the modeled NO nonequilibrium is underpredicted, whereas it is overpredicted at 4 km/s. Good agreement is seen between CFD and the velocity and rotational temperature measurements. Experiments with water added to the test gas yielded no discernable difference in vibrational relaxation.

Aerodynamics↗

Photoisomerization transition state manipulation by entangled two-photon absorption

Significance Entangled two-photon absorption has attracted considerable interest due to its potential applications for low–photon flux spectroscopy and microscopy. The entanglement parameters in the twin-photon state can be exploited to control two-photon excitation processes. Here we demonstrate that photon entanglement provides a powerful novel control knob for the nuclear wave packets in an optically dark electronic state. We show that the transition states in the trans–cis photoisomerization of azobenzene, initiated by an entangled two-photon absorption process, can be manipulated significantly by entangled light. These effects can be monitored experimentally by coherent stimulated X-ray Raman signals which reveal electronic coherences during the passage through conical intersections.

54 ENVIRONMENTAL SCIENCES↗

Imaging Nanoscale Energy Transport and Conversion with Ultrafast Electron Microscopy (Final Technical Report)

Light-matter interactions are ubiquitous in nature and reside at the heart of innumerable technologies. The cascade of processes that occur when a material absorbs a photon of light are exceedingly complex and are interwoven in both space and time, rendering precise determination of the atomic-scale and ultrafast mechanisms immensely challenging. The advent of methods for generating short pulses of light several decades ago led to major advances in understanding the initial moments of light absorption and the resultant effects, though directly interrogating the response of the atoms within the material continued to prove challenging. More recently, methods for generating ultrashort pulses of X-rays and fast electrons have opened the way to probing photoinduced structural dynamics of a wide range of matter in multiple phases. An especially promising laboratory-scale method is ultrafast electron microscopy (UEM), wherein the modalities of conventional transmission electron microscopes (imaging, diffraction, spectroscopy) are extended into the femtosecond temporal regime. Here, the ultrafast imaging and diffraction modalities of UEM were used to study the transient structural aspects of photoexcitation of semiconducting materials (e.g., spatially-resolved electron-phonon coupling, excitation and emission of acoustic phonons, and discrete nanoscale scattering processes). The project had three main objectives: (1) determination of the excitation mechanisms of dense, hypersonic charge-carrier waves and the spatially mediated means by which they couple to the lattice via coherent phonon emission, especially with UEM imaging, wherein effects of nanoscale structural and morphological features on the coupling and relaxation dynamics are expected to dictate nucleation sites and preferred wave vectors, (2) elucidation of photoinduced acoustic-phonon seeding, emergence, propagation, and decay over nanoscale crystal regions and especially with respect to local strain fields and atomic-scale disruptions in lattice order, and (3) interwoven with the first two were efforts aimed at realizing combined angstrom-femtosecond spatiotemporal imaging with UEM. The outcomes and impacts of this project were the generation of new knowledge with respect to fundamental light-matter interactions and, especially, the spatially-mediated excitation and evolution of the structural response of materials following coherent photoexcitation. Importantly, the spatial and temporal resolutions of the UEM imaging modalities used are well-suited for such studies and enable spatially-resolved mechanisms to be determined as a function of atomic order, structural features, and morphology. In addition, ultrafast crystallographic measurements were used to correlate real- and reciprocal-space dynamics in order to determine atomic-scale preferential wave vectors and ultrafast scattering mechanisms, especially as dictated by specimen boundary conditions. The obtained results, as detailed in peer-reviewed publications and presentations, illustrate the importance of ultrafast, angstrom-scale real-space imaging for developing a comprehensive understanding of energy transport and conversion in materials.

47 OTHER INSTRUMENTATION↗

Layer-dependent spin-resolved electronic structure of ferromagnetic triple-layered ruthenate Sr4Ru3O10

High-resolution angle- and spin-resolved photoemission spectroscopy (ARPES) of the triple-layered ruthenate Sr4Ru3O10 reveals features of the electronic structure that extend our understanding of the layered strontium ruthenates. The spectra near the Fermi energy are very different from the nonmagnetic analogues Sr2RuO4 and Sr3Ru2O7 with distinct Fermi surfaces for wide electronlike minority spin bands around the zone center and narrow holelike majority spin Fermi surface contours around the zone corners. The most dramatic results are two narrow spectral peaks ∼30 meV below the Fermi level, a spin-minority holelike band at the Brillouin zone center, and a spin-majority saddle-band van Hove singularity at the zone edge, which exhibits almost 100% spin polarization at low temperature, and a strong temperature dependent coherence-incoherence crossover attributed to Hund metal correlations. Quantitative comparison of the ARPES to spin-polarized density functional theory (DFT) calculations identify the specific antibonding and nonbonding orbital origins of the narrow bands, with a prediction of different spatial localization in the central and outer layers. This is shown to be consistent with experimental ARPES multizone matrix element intensity variations, and implicates outer-layer-specific control of the in-plane metamagnetism. The renormalization of the bands relative to the mean-field DFT, the demonstration of spin-polarized oxygen bands, and of spin-minority and spin-majority band-crossing hybridization provide a more complete picture of the magnetism which displays aspects of both delocalized and local moment behavior.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Two-dimensional spin systems in PECVD-grown diamond with tunable density and long coherence for enhanced quantum sensing and simulation

Systems of spins engineered with tunable density and reduced dimensionality enable a number of advancements in quantum sensing and simulation. Defects in diamond, such as nitrogen-vacancy (NV) centers and substitutional nitrogen (P1 centers), are particularly promising solid-state platforms to explore. However, the ability to controllably create coherent, two-dimensional spin systems and characterize their properties, such as density, depth confinement, and coherence, is an outstanding materials challenge. We present a refined approach to engineer dense (≳1 ppm ∙ nm), 2D nitrogen, and NV layers in diamond using delta-doping during plasma-enhanced chemical vapor deposition epitaxial growth. We employ both traditional materials techniques, e.g., secondary ion mass spectrometry, alongside NV spin decoherence-based measurements to characterize the density and dimensionality of the P1 and NV layers. We find P1 densities of 5–10 ppm ∙ nm, NV densities between 1 and 3.5 ppm ∙ nm tuned via electron irradiation dosage, and depth confinement of the spin layer down to 1.6 nm. We also observe high (up to 0.74) ratios of NV to P1 centers and reproducibly long NV coherence times, dominated by dipolar interactions with the engineered P1 and NV spin baths.

36 MATERIALS SCIENCE↗