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At least 991 records · Page 55

Optical conductivity and vibrational spectra of the narrow-gap semiconductor FeGa 3

Intermetallic narrow-gap semiconductors have been intensively explored due to their large thermoelectric power at low temperatures and a possible role of strong electronic correlations in their unusual thermodynamic and transport properties. Here we study the optical spectra and vibrational properties of FeGa 3 . The optical conductivity indicates that FeGa 3 has a direct band gap of ≈ 0.7 eV, consistent with density functional theory (DFT) calculations. Most importantly, we find a substantial spectral weight also below 0.4 eV, which is the energy of the indirect (charge) gap found in resistivity measurements and ab initio calculations. We find that the spectral weight below the gap decreases with increasing temperature, which indicates that it originates from the impurity states and not from the electronic correlations. Interestingly, we did not find any signatures of the impurity states in vibrational spectra. The infrared and Raman vibrational lines are narrow and weakly temperature dependent. The vibrational frequencies are in excellent agreement with our DFT calculations, implying a modest role of electronic correlations. Narrow Mössbauer spectral lines also indicate high crystallinity of the sample.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

O 2 -Oxidation of Individual Graphite and Graphene Nanoparticles in the 1200 – 2200 K Range: Particle-to-Particle Variations and the Evolution of the Reaction Rates and Optical Properties

The kinetics for O 2 oxidation of individual graphite and graphene platelet nanoparticles (NPs) were studied as a function of temperature (1200 to 2200 K) at varying oxygen partial pressures, using a single nanoparticle mass spectrometry method. NP temperature (TNP) was measured by measuring the NP thermal emission spectra during the kinetics studies. The initial oxidation efficiency is found to peak in the 1200 to 1500 K range, dropping by an order of magnitude as TNP was increased above 2000 K. There were large NP-to-NP variations in the oxidation rates, attributed to variations in the NP surface structure. In addition, the oxidation efficiencies evolved, non-monotonically, as the NPs reacted, decreasing by factors of between 10 and 300. This evolution of reactivity is attributed to changes in the NP surface structure due to the combination of oxidation and annealing. In conclusion, the optical properties, including wavelength dependence of the emissivity and the absorption cross section for the 532 nm heating laser, also tended to evolve as the NPs oxidized, but differently for each individual NP, presumably reflecting differences in the initial structures and their evolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluating Brightness and Stability of Cathodoluminescence from Colloidal Semiconductor Nanocrystals

Cathodoluminescence offers promise as a technique for correlation of atomic structure with electronic structure at the level of individual nanoparticles or even defects, with the ability to analyze complex nanostructures at length-scales far below those typically available to optical spectroscopy. Unlike other forms of electron microscopy, cathodoluminescence offers direct insights into the electronic structure of the visualized sample. Despite reports more than 10 years ago of individual nanoparticle cathodoluminescence, effective cathodoluminescence collection from colloidal semiconductor materials is relatively rare and remains challenging due to the instability of materials under the conditions of electron beam irradiation. In this work, to clarify the roadblocks for cathodoluminescence analysis of colloidal nanocrystals, we attempt a comprehensive study of the cathodoluminescence properties of semiconductor quantum shells, which have a thin concentric CdSe shell surrounding CdS nanoparticles, then surrounded by a further concentric CdS shell. These same materials were recently demonstrated to show promising scintillation performance in radioluminescence measurements, including high brightness (up to 100 ph/keV) and excellent durability. Comparative quantum yield measurements are designed to assess the brightness of semiconductor nanocrystal films, which show that the quantum shells are much less bright under electron irradiation compared to X-ray photons. Instability of CL emission is assigned to charging effects on the samples—and not thermal effects—through a series of voltage, current, dwell time, and atmospheric pressure experiments.

cathodoluminescence↗

3D Bacterial flagella as both synthetic biotemplates and ultrathin spacers for enhanced inter-particle coupling and solar energy harvesting

Linear light-absorbing nanomaterials are ideal for film-based solar harvesting applications as they form porous structures that can maximize the absorption and minimize the reflection of the solar light. Conventional 1D nanochains of plasmonic nanoparticle assemblies can achieve significantly broadened optical absorption through surface plasmon coupling, but their optical bands are still not broad enough to absorb through the solar spectrum and thus are not efficient solar absorbers. Here we discovered first by simulation that 3D structured nanochains of plasmonic nanoparticles presented a remarkably increased optical broadening effect and much longer redshift of the optical peaks due to the enhanced inter-particle coupling effect. Then we fabricated 3D nanochains by assembling gold nanoparticles (AuNPs) around 14 nm ultrathin bionanofibers, the bacterial flagella. Additionally, the ultrathin biotemplates enabled the 3D arrangement of 50 nm AuNPs along the nanofiber with a very small inter-particle gap, allowing the strong coupling of surface plasmons in a 3D manner. Consistent with the theoretical prediction, the 3D nanochains, when assembled into films, could effectively convert nearly the full spectrum of solar energy into heat, which was further efficiently converted into electricity through a thermoelectric generation unit. Our work represents a nanobiomaterial approach to highly efficient solar thermal power generation.

36 MATERIALS SCIENCE↗

Low-energy excitations in type-II Weyl semimetal T d - MoTe 2 evidenced through optical conductivity

Molybdenum ditelluride, MoTe 2 , is a versatile material where the topological phase can be readily tuned by manipulating the associated structural phase transition. The fine details of the band structure of MoTe 2 , key to understanding its topological properties, have proven difficult to disentangle experientially due to the multiband character of the material. Through experimental optical conductivity spectra, we detect two strong low-energy interband transitions. Both are linked to excitations between spin-orbit split bands. The lowest interband transition shows a strong thermal shift, pointing to a chemical potential that dramatically decreases with temperature. Finally, with the help of ab initio calculations and a simple two-band model, we give qualitative and quantitative explanations of the main features in the temperature-dependent optical spectra up to 400 meV.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Copper-nickel electroplating of 3D-printed acrylonitrile butadiene styrene for interference and radiation shielding applications

Here, in this study, electromagnetic and radiation shielding structures were fabricated by 3D printing acrylonitrile butadiene styrene (ABS) structures via fused filament fabrication and electroplating with copper (Cu) and nickel (Ni) metals. Prior to electroplating, the printed ABS materials were made conductive by surface electrodeposition of polypyrrole (PPy). ABS adsorbs the pyrrole monomer, which subsequently polymerizes via oxidation forming conductive PPy layer on the printed structures. The successful anchoring of PPy layer can be attributed to its hydrogen bonding and electrostatic interactions with ABS. Thermal analysis, optical, and electron microscopy equipped with energy dispersive X-ray were employed to characterize the printed shielding structures, while the interference and radiation shielding effectiveness were evaluated using a spectrum analyzer and dosimeter, respectively. The interference shielding was found to be effective at 60 ± 5 dB over relatively small frequency range. Shielding was also apparent against gamma and X-ray ionizing rays, but more significantly effective against beta rays. Furthermore, the Cu/Ni coating was able to reduce any heat-induced dimensional changes for the 3D printed ABS substrate without compromising the mechanical integrity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Efficient generation and amplification of intense vortex and vector laser pulses via strongly-coupled stimulated Brillouin scattering in plasmas

The past decade has seen tremendous progress in the production and utilization of vortex and vector laser pulses. Although both are considered as structured light beams, the vortex lasers have helical phase fronts and phase singularities, while the vector lasers have spatially variable polarization states and polarization singularities. In contrast to the vortex pulses that carry orbital angular momentum (OAM), the vector laser pulses have a complex spin angular momentum (SAM) and OAM coupling. Despite many potential applications enabled by such pulses, the generation of high-power/-intensity vortex and vector beams remains challenging. Here, we demonstrate using theory and three-dimensional simulations that the strongly-coupled stimulated Brillouin scattering (SC-SBS) process in plasmas can be used as a promising amplification technique with up to 65% energy transfer efficiency from the pump beam to the seed beam for both vortex and vector pulses. We also show that SC-SBS is strongly polarization-dependent in plasmas, enabling an all-optical polarization control of the amplified seed beam. Additionally, the interaction of such structured lasers with plasmas leads to various angular momentum couplings and decouplings that produce intense new light structures with controllable OAM and SAM. This scheme paves the way for novel optical devices such as plasma-based amplifiers and light field manipulators.

Physics↗

III-nitride m-plane violet narrow ridge edge-emitting laser diodes with sidewall passivation using atomic layer deposition

A novel deep-ridge laser structure with atomic-layer deposition (ALD) sidewall passivation was proposed that enhances the optical characteristics of 8-µm ridge width III-nitride violet lasers on freestanding m -plane GaN substrates. The internal loss was determined using the variable stripe length method, where the laser structure with ALD sidewall passivation showed lower internal loss compared to the conventional shallow-ridge laser design. ALD sidewall passivation plays a critical role in device improvements; compared to the lasers without ALD sidewall passivation, the lasers with ALD sidewall passivation yield improved optoelectrical performance and longer lifetime under continuous-wave operation at high current density. This work demonstrates the importance of ALD sidewall passivation to laser performance, which enables high energy efficiency.

Wong, Matthew S.↗

Summary of Working Group 3: Laser and High-Gradient Structure-Based Acceleration

Accelerating particles at high gradients with high efficiencies is essential for reduction of size and cost of future accelerators for science and industry. This includes a future multi-TeV e+e- collider for particle, free-electron lasers for basic energy sciences and national security, industrial accelerators for energy and environmental applications, and accelerators for other applications. One way to achieve this is to use advanced externally-powered structures, both laser and RF driven. Working Group 3 (WG3) discussed novel accelerating structures with new geometries, new materials, frequencies from microwave to THz and optical spectrum, and operating conditions from room temperature to cryogenic. Presentations included recent advances in understanding RF breakdown and multipactor phenomena at different frequencies and materials, and other physics limitations to the accelerating gradient. Other relevant topics, such as developing high-gradient photoinjectors, high-efficiency RF power sources, and RF structures for a potential muon collider were discussed also. More details on each of the WG3 topics can be found in the articles published in these proceedings.

43 PARTICLE ACCELERATORS↗

Strain mapping of three-dimensionally structured two-dimensional materials

Strain plays a crucial role in tuning materials’ properties, influencing their optical, electrical, and chemical performances. In two-dimensional (2D) materials, applied stress often induces out-of-plane deformation, resulting in a more intricate three-dimensional (3D) topography, where mapping the strain remains a challenge due to the limitations of conventional characterization techniques. In this work, we introduce BRIGHT (Bragg-Rod Informed, Gradient-based Height-mapping Technique), an integrated method for reconstructing both the topography and planar strain profile of 3D-structured 2D materials using nanobeam four-dimensional scanning transmission electron microscopy (4D-STEM). We apply BRIGHT to a MoS2-MoSe2 transition metal dichalcogenide (TMD) lateral heterojunctions exhibiting built-in strain and out-of-plane ripples and show that varying heterojunction widths lead to distinct surface morphologies and corresponding changes in the planar strain distribution. These results establish a foundation for more effective strain engineering in 2D materials by accounting for out-of-plane structural features, thereby enabling more precise control of strain-dependent properties.

Mireles, Adan [Rice Univ., Houston, TX (United Sta↗

Filament-induced breakdown spectroscopy with structured beams

Filament-induced ablation represents an attractive scheme for long-range material identification via optical spectroscopy. However, the delivery of laser energy to the target can be severely hindered by the stochastic nature of multiple-filamentation, ionization of ambient gas, and atmospheric turbulence. In order to mitigate some of these adverse effects, we examine the utility of beam shaping for femtosecond filament-induced breakdown spectroscopy with Gaussian and structured (Laguerre-Gaussian, Airy, and Bessel-Gaussian) beams in the nonlinear regime. Interaction of filaments with copper, zinc, and brass targets was studied by recording axially-resolved broadband emission from the filament-induced plasma. The laser-solid coupling efficacy was assessed by inferring thermodynamic parameters such as excitation temperature and electron density. While under our experimental conditions the ablation rate with Gaussian- and Laguerre-Gaussian beams is found to be similar, the Airy and Bessel-Gaussian beams offer the advantage of longitudinally extended working zones. These results provide insights into potential benefits of structuring ultrafast laser beams for standoff sensing applications.

47 OTHER INSTRUMENTATION↗

High-Pressure Investigation of 2,4,6-Trinitro-3-bromoanisole (TNBA): Structural Determination and Piezochromism

Understanding phase transitions in energetic materials is crucial for developing predictive models of detonation. 2,4,6-Trinitro-3-bromoanisole (TNBA), an energetic material, was studied in its single-crystal form up to pressures of 45 GPa in a diamond anvil cell. The material was characterized by using X-ray, Raman, and optical transmission measurements. From single-crystal X-ray diffraction, the ambient structure of TNBA was determined which crystallizes in the P2 1 /c space group having four molecular units per unit cell. The X-ray data up to 9.2 GPa were fitted to a third-order Birch–Murnaghan equation of state by using the parameters K o = 13.2(2.4) GPa and K p = 5.1(1.4). Between 6.8 and 7.3 GPa, a phase transition was inferred in TNBA from concurrent fading of X-ray diffraction, disappearance of Raman peaks, increase in sample fluorescence, and discontinuous color change. The new phase was consistent with an amorphous state of at least partially intact molecules judging from the presence of higher-order Raman modes and irreversibility of the Raman spectra upon release. Piezochromism was observed with the translucent yellow TNBA gradually darkening and becoming opaque black at ~25 GPa. This correlated to the absorption edge gradually shifting to the red in the visible spectrum. Signs of two possible additional structural transitions were detected in the 32.4–41.0 GPa range as suggested by a jump in the absorption edge, the irreversible changes in the absorption spectrum upon release to ambient pressure, and by the lack of Raman modes in recovered samples. Here, the crystal and electronic structures of TNBA were also investigated up to 10 GPa by using DFT calculations and crystal structure prediction (CSP) simulations. In agreement with the experimentally observed transition at 7 GPa, the simulations at 10 GPa found a bevy of polymorphs lower in enthalpy and higher in density than P2 1 /c. The lowest calculated enthalpy structure was determined to be P2 1 2 1 2 1 , being in a different space group than the ambient experimental result.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Combining Organic Cations of Different Sizes Grants Improved Control over Perovskitoid Dimensionality and Bandgap

Because mixed-halide wide-bandgap (1.6-2.0 eV) perovskite solar cells suffer from operating instability related to light-induced halide segregation, it is of interest to study alternative means of bandgap widening. Perovskitoids combine wide bandgaps and structural stability resulting from face- or edge-sharing octahedral connections in their crystal structures. Unfortunately, there existed no prior reports of three-dimensional (3D) perovskitoids having direct bandgaps with optical absorption edges less than 2.2 eV. As the most significant predictor of perovskitoid bandgaps is the fraction of corner-sharing in their crystal structures, we hypothesized that increasing the amount of corner-sharing would access lower bandgaps than previously reported. Here, we accomplished this by mixing a spacer cation within the size range for 3D perovskitoid formation with a smaller perovskite-forming cation. We explored three spacer cations of different sizes: ethylammonium (EA), cyclopropylammonium (c-C3A), and cyclobutylammonium (c-C4A), combining these with methylammonium (MA), and found that the middle cation, c-C3A, pairs with MA to form a 3D perovskitoid with the formula (c-C3A) 3 (MA) 3 Pb 5 I 16 and a direct bandgap with an optical absorption edge at 2.0 eV. Solution-processed films of this perovskitoid showed improved light stability over mixed-halide perovskites, and solar cells based on these films exhibit increased maximum power point operating stability compared to reference mixed-halide devices.

Gilley, Isaiah W. [Northwestern University, Evanst↗

Ba 6 (Cu x Z y )Sn 4 S 16 (Z = Mg, Mn, Zn, Cd, In, Bi, Sn): High Chemical Flexibility Resulting in Good Nonlinear-Optical Properties

Seven acentric sulfides Ba 6 (Cu x Z y )Sn 4 S 16 (Z = Mg, Mn, Zn, Cd, In, Bi, Sn) were grown by a high-temperature salt flux method. The crystal structures of the Ba 6 (Cu x Z y )Sn 4 S 16 (Z = Mg, Mn, Zn, Cd, In, Bi, Sn) compounds were determined by single-crystal X-ray diffraction with the aid of solid-state NMR spectroscopy. The Ba 6 (Cu x Z y )Sn 4 S 16 (Z = Mg, Mn, Zn, Cd, In, Bi) compounds are isostructural and crystallize in the Ba 6 Ag 4 Sn 4 S 16 structure type. The Sn-containing compound exhibits high structural similarity to Ba 6 (Cu x Z y )Sn 4 S 16 (Z = Mg, Mn, Zn, Cd, In, Bi) with the presence of an interstitial atomic position partially occupied by Sn atoms. The chemical bonding characteristics of Ba 6 (Cu 2.9 Sn 0.4 )Sn 4 S 16 were understood with electron localization function calculations coupled with crystal orbital Hamilton population calculations. The Ba–S and Cu–S interactions are dominantly ionic, but the Sn–S interactions consist of strong covalent bonding characteristics in Ba 6 (Cu 2.9 Sn 0.4 )Sn 4 S 16 . The monovalent Cu atoms, mixed with certain metals with various oxidation states, significantly shift the optical properties of the Ba 6 (Cu x Z y )Sn 4 S 16 (Z = Mg, Mn, Zn, Cd, In, Bi) compounds. This results in a good balance between the second-harmonic-generation (SHG) response and laser damage threshold (LDT). Ba 6 (Cu 1.9 Zn 1.1 )Sn 4 S 16 possesses a high SHG response and a high LDT of 2.8 × AGS and 3 × AGS, respectively. Here, a density functional theory calculation revealed that CuS 4 and SnS 4 tetrahedra significantly contribute to the SHG response in Ba 6 (Cu 2 Mg)Sn 4 S 16 , which also confirmed that CuS 4 tetrahedra are crucial for the stability and optical properties of the Ba 6 (Cu x Z y )Sn 4 S 16 (Z = Mg, Mn, Zn, Cd, In, Bi, Sn) compounds revealed by electronic structure analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tunable band gaps and optical absorption properties of bent MoS2 nanoribbons

Abstract The large tunability of band gaps and optical absorptions of armchair MoS 2 nanoribbons of different widths under bending is studied using density functional theory and many-body perturbation GW and Bethe–Salpeter equation approaches. We find that there are three critical bending curvatures, and the non-edge and edge band gaps generally show a non-monotonic trend with bending. The non-degenerate edge gap splits show an oscillating feature with ribbon width n , with a period $$\Delta n=3$$ Δ n = 3 , due to quantum confinement effects. The complex strain patterns on the bent nanoribbons control the varying features of band structures and band gaps that result in varying exciton formations and optical properties. The binding energy and the spin singlet–triplet split of the exciton forming the lowest absorption peak generally decrease with bending curvatures. The large tunability of optical properties of bent MoS 2 nanoribbons is promising and will find applications in tunable optoelectronic nanodevices.

36 MATERIALS SCIENCE↗

Near-field imaging of optical resonances in silicon metasurfaces using photoelectron microscopy

Precise control of light–matter interactions at the nanoscale lies at the heart of nanophotonics. However, experimental examination at this length scale is challenging since the corresponding electromagnetic near-field is often confined within volumes below the resolution of conventional optical microscopy. In semiconductor nanophotonics, electromagnetic fields are further restricted within the confines of individual subwavelength resonators, limiting access to critical light–matter interactions in these structures. In this work, we demonstrate that photoelectron emission microscopy (PEEM) can be used for polarization-resolved near-field spectroscopy and imaging of electromagnetic resonances supported by broken-symmetry silicon metasurfaces. We find that the photoemission results, enabled through an in situ potassium surface layer, are consistent with full-wave simulations and far-field reflectance measurements across visible and near-infrared wavelengths. In addition, we uncover a polarization-dependent evolution of collective resonances near the metasurface array edge taking advantage of the far-field excitation and full-field imaging of PEEM. Here, we deduce that coupling between eight resonators or more establishes the collective excitations of this metasurface. All told, we demonstrate that the high-spatial resolution hyperspectral imaging and far-field illumination of PEEM can be leveraged for the metrology of collective, non-local, optical resonances in semiconductor nanophotonic structures.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Complex Relationship between Side-Chain Polarity, Conductivity, and Thermal Stability in Molecularly Doped Conjugated Polymers

Molecularly doped conjugated polymers with polar side chains are an emerging class of conducting materials exhibiting enhanced and thermally stable conductivity. In this work, we study the electronic conductivity (σ) and the corresponding thermal stability of two polythiophene derivatives comprising oligoethylene glycol side chains: one having oxygen attached to the thiophene ring (poly(3-(methoxyethoxyethoxy)thiophene) (P3MEET)) and the other having a methylene spacer between the oxygen and the thiophene ring (poly(3-(methoxyethoxyethoxymethyl)thiophene) (P3MEEMT)). Thin films were vapor-doped with fluorinated derivatives of tetracyanoquinodimethane (FnTCNQ, n = 4, 2, 1) to determine the role of dopant strength (electron affinity) in maximum achievable σ. Specifically, when vapor doping with F 4 TCNQ, P3MEET achieved a substantially higher σ of 37.1 ± 10.1 S/cm compared to a σ of 0.82 ± 0.06 S/cm for P3MEEMT. Structural characterization using a combination of X-ray and optical spectroscopy reveals that the higher degree of conformational order of polymer chains in the amorphous domain upon doping with F 4 TCNQ in P3MEET is a major contributing factor for the higher σ of P3MEET. Additionally, vapor-doped P3MEET exhibited superior thermal stability compared to P3MEEMT, highlighting that the presence of polar side chains alone does not ensure higher thermal stability. Molecular dynamics simulations indicate that the dopant–side-chain nonbond energy is lower in the P3MEET:F 4 TCNQ mixture, suggesting more favorable dopant–side-chain interaction, which is a factor in improving the thermal stability of a polymer/dopant pair. Our results reveal that additional factors such as polymer ionization energy and side-chain–dopant interaction should be taken into account for the design of thermally stable, highly conductive polymers.

36 MATERIALS SCIENCE↗