Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “nonlinear optic”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 487 records · Page 27
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Hydrogen-Bond-Driven Chemical Separations: Elucidating the Interfacial Steps of Self-Assembly in Solvent Extraction

Chemical separations, particularly liquid extractions, are pervasive in academic and industrial laboratories, yet a mechanistic understanding of the events governing their function are obscured by interfacial phenomena that are notoriously difficult to measure. In this work, we investigate the fundamental steps of ligand self-assembly as driven by changes in the interfacial H-bonding network using vibrational sum frequency generation. Our results show how the bulk pH modulates the interfacial structure of extractants at the buried oil/aqueous interface via the formation of unique H-bonding networks that order and bridge ligands to produce self-assembled aggregates. These extended H-bonded structures are key to the subsequent extraction of Co2+ from the aqueous phase in promoting micelle formation and subsequent ejection of the said micelle into the oil phase. The combination of static and time-resolved measurements reveals the events underlying complexities of liquid extractions at high [Co2+]:[ligand] ratios by showing an evolution of interfacially assembled structures that are readily tuned on a chemical basis by altering the compositions of the aqueous phase. The results of this work point to new principles to design-applied separations through the manipulation of surface charge, electrostatic screening, and the associated H-bonding networks that arise at the interface to facilitate organization and subsequent extraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Millimeter-Scale Exfoliation of hBN with Tunable Flake Thickness for Scalable Encapsulation

As a two-dimensional (2D) dielectric material, hexagonal boron nitride (hBN) is in high demand for applications in photonics, nonlinear optics, and nanoelectronics. Unfortunately, the high-throughput preparation of macroscopic-scale, high-quality hBN flakes with controlled thickness is an ongoing challenge, limiting device fabrication and technological integration. In this report we present a metal thin-film exfoliation method to prepare hBN flakes with millimeter-scale dimension, near-unity yields, and tunable flake thickness distribution from 1-7 layers, a substantial improvement over scotch tape exfoliation. The single crystallinity and high quality of the exfoliated hBN are demonstrated with optical microscopy, atomic force microscopy, Raman spectroscopy, and second harmonic generation. We further explore a possible mechanism for the effectiveness and selectivity based on thin-film residual stress measurements, density functional theory calculations, and transmission electron microscopy imaging of the deposited metal films. We find that the magnitude of the residual tensile stress induced by thin film deposition plays a key role in determining exfoliated flake thickness in a manner which closely resembles 3D semiconductor spalling. Lastly, we demonstrate that our exfoliated, large-area hBN flakes can be readily incorporated as encapsulating layers for other 2D monolayers. Altogether, this method brings us one step closer to the high throughput, mass production of hBN-based 2D photonic, optoelectronic, and quantum devices.

2D materials↗
DOE OSTI2023

Dual Emission Bands of a 2D Perovskite Single Crystal with Charge Transfer State Characteristics

Several hybrid halide 2D-perovskite species emit light with an emergent and controversial broadband emission Stokes-shifted down from the narrow band emission. This work uncovers the sub- and above-bandgap emission and absorption characteristics of PEA 2 PbI 4 prepared with gap states introduced during single crystal growth. Here, gap states led to coexistent intrinsic and heterostructured electronic frameworks that are selectively accessible with ultraviolet (UV) and infrared (IR) light, respectively, resulting in the phenomenon of photoluminescence (PL) switching from narrowband green to broadband red. Electron-energy dependent cathodoluminescence shows a relative increase in the broadband red PL intensity as the electron penetration depth increases from 30 nm to 2 μm, confirming the heterostructured framework is formed in the bulk of the crystal. Excitation–emission power slope of 2.5 and up-conversion pump transient absorption (TA) spectra suggest that the IR up-conversion excitation with red photoluminescence, peaked at 655 nm, is a multiphoton process occurring in the heterostructured framework through a nonlinear optical response. The energetic pathways toward the dual emission bands are revealed by pump–probe transient absorption spectroscopy, showing energetically broad gap states with high sensitivity to an IR pump are upconverted and subsequently quickly relax from high to low energy levels within 4 ps. Furthermore, the up-conversion red PL demonstrates a linear polarization with magnetic field effects, thus affirming that the band-like heterostructured framework is crystallographically aligned with characteristics of spatially extended charge-transfer states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Manipulating Excitonic Quantum Droplets in Two-Dimensional CdSe Nanoplatelets via Thickness and Core/Shell Morphology

Recently, photoexcitation of high-density 4 or 5 monolayer (ML) thick CdSe nanoplatelet films at temperatures below ~200K was observed to produce pump-intensitydependent, superlinear, progressively red-shifted light output due to amplified spontaneous emission (ASE) from polyexcitonic species, distinct from biexcitonic ASE. These polyexcitonic species comprise Coulombically bound multiexciton states, termed “quantum droplets”, that form when multiexciton binding energy exceeds thermal energy fluctuations. In this work, we investigate thinner samples as well as core/shell nanoplatelet films and find that the 3 ML sample supports quantum droplet ASE up to higher temperatures than the 4 or 5 ML whereas core/shell structures suppress this form of ASE even at very low sample temperatures despite observable biexcitonic ASE, suggesting that the reduced or repulsive Coulomb binding energy of multiple excitons suppresses quantum droplets. These findings help to add understanding of routes to harness quantum droplet optical nonlinearities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Optomechanical Tuning of Second Harmonic Generation Anisotropy in Janus MoSSe/MoS 2 Heterostructures

Symmetry breaking in van der Waals materials enables the realization of quantum states and advanced device functionalities. Janus transition-metal dichalcogenides (TMDs) exhibit distinctive nonlinear optical properties due to their broken out-of-plane mirror symmetry. However, the dynamic control of second harmonic generation (SHG) anisotropy and resonance behavior via optical excitation remains elusive. Here, in this work, we investigate the SHG response of Janus MoSSe/MoS 2 heterostructures with 2H and 3R stackings. We can tune the SHG response by varying the incident photon wavelength from 800 to 1000 nm, which shows a resonance-dependent enhancement in intensity and a deviation from 6-fold symmetry, indicating wavelength-dependent anisotropy. The ratio between maximum and minimum intensity in the armchair directions, associated with the SHG anisotropy, reaches a value of 1.73 at the excitation wavelength of 1000 nm. Group theory analysis and first-principles calculations reveal that the observed anisotropy arises from optically induced strain. Our findings highlight the role of symmetry breaking and optical resonance contributing to the optomechanical tuning of SHG anisotropy, offering opportunities for developing Janus TMD-based photonic devices for frequency conversion, light generation, and optical switching.

Janus transition metal dichalcogenides↗
DOE OSTI2024

Circularly Polarized Attosecond Pulses Enabled by an Azimuthal Phase and Polarization Grating

High-harmonic generation (HHG) is an extreme nonlinear optical process that can map the properties of an infrared driving laser beam onto short wavelength attosecond pulse trains. However, current techniques for generating circularly polarized high harmonics for probing magnetic materials and chiral systems have limitations: two-color collinear counter-rotating driving lasers result in a low cutoff photon energy, while single-color non-collinear counter-rotating schemes suffer from low conversion efficiency. In this work, we generate circularly polarized attosecond pulse trains by using a structured laser driver which has a rotating polarization and phase grating along the azimuthal coordinate. Furthermore, our experimental and numerical results demonstrate the production of left and right circularly polarized harmonics, which naturally separate upon propagation. Our approach uses a single laser color in a collinear geometry, that can be scaled for high efficiency. Simulations show this scheme can extend into the soft x-ray region when driven by mid-infrared driving lasers, while preserving the same high phase-matching cutoff photon energy as for linearly-polarized high harmonics.

attosecond science↗
DOE OSTI2020

Machine-Learning-Assisted Synthesis of Polar Racemates

Racemates have recently received attention as nonlinear optical and piezoelectric materials. We report a machine-learning-assisted composition space approach was applied to synthesize the missing M = Ti, Zr members of the Δ,Λ-[Cu(bpy) 2 (H 2 O)] 2 [MF 6 ] 2·3 H 2 O (M = Ti, Zr, Hf; bpy = 2,2'-bipyridine) family (space group: Pna2 1 ). In each (CuO, MO 2 )/bpy/HF(aq) (M = Ti, Zr, Hf) system, the polar noncentrosymmetric racemate (M-NCS) forms in competition with a centrosymmetric one-dimensional chain compound (M-CS) based on alternating Cu(bpy)(H 2 O) 2 2+ and MF 6 2– basic building units (space groups: Ti-CS (Pnma), Zr-CS (P1̅), Hf-CS (P2/n)). Machine learning models were trained on reaction parameters to gain unbiased insight into the underlying statistical trends in each composition space. A human-interpretable decision tree shows that phase selection is driven primarily by the bpy:CuO molar ratio for reactions containing Zr or Hf, and predicts that formation of the Ti-NCS compound requires that the amount of HF present be decreased to raise the pH, which we verified experimentally. Predictive leave-one-metal-out (LOO) models further confirm that behavior in the Ti system is distinct from that of the Zr and Hf systems. The chemical origin of this distinction was probed via fluorine K-edge X-ray absorption spectroscopy. Pre-edge features in the F1s X-ray absorption spectra reveal the strong ligand-to-metal π bonding between Ti(3d – t 2g ) and F(2p) states that distinguishes the TiF 6 2– anion from the ZrF 6 2– and HfF 6 2– anions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Unprecedented lattice volume expansion on doping stereochemically active Pb 2+ into uniaxially strained structure of CaBa 1- x Pb x Zn 2 Ga 2 O 7

Lone pair cations like Pb 2+ are extensively utilized to modify and tune physical properties, such as nonlinear optical property and ferroelectricity, of some specific structures owing to their preference to adopt a local distorted coordination environment. Here we report that the incorporation of Pb 2+ into the polar “114”-type structure of CaBaZn 2 Ga 2 O 7 leads to an unexpected cell volume expansion of CaBa 1- x Pb x Zn 2 Ga 2 O 7 (0 ≤ x ≤ 1), which is a unique structural phenomenon in solid state chemistry. Structure refinements against neutron diffraction and total scattering data and theoretical calculations demonstrate that the unusual evolution of the unit cell for CaBa 1- x Pb x Zn 2 Ga 2 O 7 is due to the combination of the high stereochemical activity of Pb 2+ with the extremely strained [Zn 2 Ga 2 O 7 ] 4- framework along the c -axis. The unprecedented cell volume expansion of the CaBa 1- x Pb x Zn 2 Ga 2 O 7 solid solution in fact is a macroscopic performance of the release of uniaxial strain along c -axis when Ba 2+ is replaced with smaller Pb 2+ .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Topological solitonic macromolecules

Being ubiquitous, solitons have particle-like properties, exhibiting behaviour often associated with atoms. Bound solitons emulate dynamics of molecules, though solitonic analogues of polymeric materials have not been considered yet. Here we experimentally create and model soliton polymers, which we call “polyskyrmionomers”, built of atom-like individual solitons characterized by the topological invariant representing the skyrmion number. With the help of nonlinear optical imaging and numerical modelling based on minimizing the free energy, we reveal how topological point defects bind the solitonic quasi-atoms into polyskyrmionomers, featuring linear, branched, and other macromolecule-resembling architectures, as well as allowing for encoding data by spatial distributions of the skyrmion number. Application of oscillating electric fields activates diverse modes of locomotion and internal vibrations of these self-assembled soliton structures, which depend on symmetry of the solitonic macromolecules. Our findings suggest new designs of soliton meta matter, with a potential for the use in fundamental research and technology.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Domain-dependent strain and stacking in two-dimensional van der Waals ferroelectrics

Van der Waals (vdW) ferroelectrics have attracted significant attention for their potential in next-generation nano-electronics. Two-dimensional (2D) group-IV monochalcogenides have emerged as a promising candidate due to their strong room temperature in-plane polarization down to a monolayer limit. However, their polarization is strongly coupled with the lattice strain and stacking orders, which impact their electronic properties. Here, we utilize four-dimensional scanning transmission electron microscopy (4D-STEM) to simultaneously probe the in-plane strain and out-of-plane stacking in vdW SnSe. Specifically, we observe large lattice strain up to 4% with a gradient across ~50 nm to compensate lattice mismatch at domain walls, mitigating defects initiation. Additionally, we discover the unusual ferroelectric-to-antiferroelectric domain walls stabilized by vdW force and may lead to anisotropic nonlinear optical responses. Our findings provide a comprehensive understanding of in-plane and out-of-plane structures affecting domain properties in vdW SnSe, laying the foundation for domain wall engineering in vdW ferroelectrics.

42 ENGINEERING↗
DOE OSTI2025

Vibronic coupling-driven symmetry breaking and solvation in the photoexcited dynamics of quadrupolar dyes

Quadrupolar dyes, such as acceptor–donor–acceptor molecules, are highly relevant for applications in nonlinear optics and photovoltaics. They are also versatile models for exploring photoinduced charge-transfer dynamics. The interplay between electronic and vibronic couplings in these molecules may break excited-state symmetry, resulting in intramolecular charge separation and pronounced solvatochromism. Experimentally, distinguishing the roles of intramolecular vibronic coupling and solvent reorganization for the initial charge-transfer dynamics has been challenging so far. Here we investigate a prototypical quadrupolar dye in polar and non-polar solvents using ultrafast pump–probe and two-dimensional electronic spectroscopy. Our results reveal that vibronic couplings initiate excited-state symmetry breaking during the first ~50 fs of the photoinduced charge transfer, whereas solvent-induced charge localization sets in at later times. Quantum dynamics and electronic structure simulations support our experimental findings. Our results reveal the details of solvation dynamics in photoexcited molecules and suggest strategies for their manipulation through vibronic couplings.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Supramolecular assembly of molecular wires alternating crown ethers and metal–halide complexes

Metal–halide complexes serve as key emissive centres in halide perovskites; however, precise control over their spatial organization through bottom-up assembly is challenging. Here we show that a crown-ether-assisted supramolecular assembly strategy can alternatingly connect metal–halide complexes and (crown ether@A) 2+ (where ‘A’ is an alkaline earth metal cation) complexes into a one-dimensional molecular wire, which can then be packed into a hexagonal crystal structure. This process resulted in the creation of an (18C6@Ba)MnBr 4 single crystal with green emission, achieving over 80% photoluminescence quantum yield and a narrow full width at half maximum. In addition, the non-centrosymmetric crystal structure gave rise to strong nonlinear optical responses, including second-harmonic generation. This versatile supramolecular assembly approach could be generalized to create various [M(I)X 2 ] − , [M(I)X 3 ] 2− , [M(II)X 4 ] 2− and [M(III)X 5 ] 2− molecular wires, broadening the potential for diverse emission colours and distinct optical properties. This strategy provides a general design principle for constructing supramolecular metal–halide building blocks with diverse optical functionalities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Coherence and superradiance from a plasma-based quasiparticle accelerator

Coherent light sources, such as free electron lasers, provide bright beams for biology, chemistry, physics, and advanced technological applications. Increasing the brightness of these sources requires progressively larger devices, with the largest being several km long (e.g., LCLS). Can we reverse this trend, and bring these sources to the many thousands of labs spanning universities, hospitals, and industry? Here we address this long-standing question by rethinking the basic principles of radiation physics. At the core of our work is the introduction of quasiparticle-based light sources that rely on the collective and macroscopic motion of an ensemble of light-emitting charges to evolve and radiate in ways that would be unphysical when considering single charges. The underlying concept allows for temporal coherence and superradiance in new configurations, such as in plasma accelerators, providing radiation with intriguing properties and clear experimental signatures spanning nearly 10 octaves, from THz to the extreme ultra-violet. The concept extends well beyond this case, such as to nonlinear optical configurations. Furthermore, the simplicity of the quasiparticle approach makes it suitable for experimental demonstrations at existing laser and accelerator facilities.

43 PARTICLE ACCELERATORS↗
DOE OSTI2023

Visualization of bulk and edge photocurrent flow in anisotropic Weyl semimetals

Materials that rectify light into current in their bulk are desired for optoelectronic applications. In Weyl semimetals that break inversion symmetry, bulk photocurrents may arise due to nonlinear optical processes that are enhanced near the Weyl nodes. However, the photoresponse of these materials is commonly studied by scanning photocurrent microscopy, which convolves the effects of photocurrent generation and collection. Here we directly image the photocurrent flow inside the type-II Weyl semimetals WTe 2 and TaIrTe 4 using high-sensitivity quantum magnetometry with nitrogen-vacancy centre spins. We elucidate a mechanism for bulk photocurrent generation, which we call the anisotropic photothermoelectric effect, where unequal thermopowers along different crystal axes drive intricate circulations of photocurrent around the photoexcitation. Using overlapping scanning photocurrent microscopy and magnetic imaging at the interior and edges of the sample, we visualize how the anisotropic photothermoelectric effect stimulates the long-range photocurrent collected in our WTe 2 and TaIrTe 4 devices through the Shockley–Ramo mechanism. Furthermore, our results highlight a widely relevant source of current flow and will inspire photodetectors that utilize bulk materials with thermoelectric anisotropy.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Controllable skyrmion chirality in ferroelectrics

Chirality, an intrinsic handedness, is one of the most intriguing fundamental phenomena in nature. Materials composed of chiral molecules find broad applications in areas ranging from nonlinear optics and spintronics to biology and pharmaceuticals. However, chirality is usually an invariable inherent property of a given material that cannot be easily changed at will. Here, we demonstrate that ferroelectric nanodots support skyrmions the chirality of which can be controlled and switched. We devise protocols for realizing control and efficient manipulations of the different types of skyrmions. Our findings open the route for controlled chirality with potential applications in ferroelectric-based information technologies.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2023

Performance characterization of freeform finished surfaces of potassium dihydrogen phosphate using fluid jet polishing with a nonaqueous slurry

Abstract Potassium dihydrogen phosphate (KDP) and its deuterated analog (DKDP) are unique nonlinear optical materials for high power laser systems. They are used widely for frequency conversion and polarization control by virtue of the ability to grow optical-quality crystals at apertures suitable for fusion-class laser systems. Existing methods for freeform figuring of KDP/DKDP optics do not produce surfaces with sufficient laser-induced–damage thresholds (LIDT’s) for operation in the ultraviolet portion of high-peak-power laser systems. In this work, we investigate fluid jet polishing (FJP) using a nonaqueous slurry as a sub-aperture finishing method for producing freeform KDP surfaces. This method was used to selectively polish surface areas to different depths on the same substrate with removals ranging from 0.16 μm to 5.13 μm. The finished surfaces demonstrated a slight increase in roughness as the removal depth increased along with a small number of fracture pits. Laser damage testing with 351 nm, 1 ns pulses demonstrated excellent surface damage thresholds, with the highest values in areas devoid of fracture pits. This work demonstrates, for the first time, a method that enables fabrication of a waveplate that provides tailored polarization randomization that can be scaled to meter-sized optics. Furthermore, this method is based on FJP technology that incorporates a nonaqueous slurry specially designed for use with KDP. This novel nonaqueous FJP process can be also used for figuring other types of materials that exhibit similar challenging inherent properties such as softness, brittleness, water-solubility, and temperature sensitivity.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Gradient-based optimization of complex nanoparticle heterostructures enabled by deep learning on heterogeneous graphs

Applications of deep learning (DL) to design nanomaterials are hampered by a lack of suitable data representations and training data. Here, in this study, we report efforts to overcome these limitations and leverage DL to optimize the nonlinear optical properties of core–shell upconverting nanoparticles (UCNPs). UCNPs, which have applications in fields such as biosensing, super-resolution microscopy and three-dimensional printing, can emit visible and ultraviolet light from near-infrared excitations. We report a large-scale dataset of UCNP emission spectra based on accurate but expensive kinetic Monte Carlo simulations (N > 6,000) and use these data to train a heterogeneous graph neural network using a physically motivated representation of UCNP nanostructure. Applying gradient-based optimization on the trained graph neural network, we identify structures with 6.5× higher predicted emission under 800-nm illumination than any UCNP in our training set. Our work reveals design principles for UCNP heterostructures and presents a roadmap for DL-based inverse design of nanomaterials.

Sivonxay, Eric [Lawrence Berkeley National Laborat↗