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At least 55 records · Page 3

Properties of V-defect injectors in long wavelength GaN LEDs studied by near-field electro- and photoluminescence

The efficiency of multiple quantum well (QW) light emitting diodes (LEDs) to a large degree depends on uniformity of hole distribution between the QWs. Typically, transport between the QWs takes place via carrier capture into and thermionic emission out of the QWs. In InGaN/GaN QWs, the thermionic hole transport is hindered by the high quantum confinement and polarization barriers. To overcome this drawback, hole injection through semipolar QWs located at sidewalls of V-defects had been proposed. However, in the case of the V-defect injection, strong lateral emission variations take place. In this work, we explore the nature of these variations and the impact of the V-defects on the emission spectra and carrier dynamics. The study was performed by mapping electroluminescence (EL) and photoluminescence (PL) with a scanning near-field optical microscope in LEDs that contain a deeper well that can only be populated by holes through the V-defects. Applying different excitation schemes (electrical injection and optical excitation in the far- and near-field), we have shown that the EL intensity variations are caused by the lateral nonuniformity of the hole injection. We have also found that, in biased structures, the PL intensity and decay time in the V-defect regions are only moderately lower that in the V-defect-free regions thus showing no evidence of an efficient Shockley-–Read–Hall recombination. In the V-defect regions, the emission spectra experience a red shift and increased broadening, which suggests an increase of the In content and well width in the polar QWs close to the V-defects.

Electroluminescence↗

Satellites, core hole excitations, and spin-resolved electronic structure in the spectroscopy of half-metallic CrO 2

Photoelectron satellites—the structures appearing on the low kinetic or high binding-energy side of the “main” or “elastic” photopeak—betray the complex many-body interactions set in motion by the sudden creation of the core hole. In this work, we demonstrate, using the technologically important ferromagnetic half-metal CrO 2 , how such satellites can manifest themselves in other core-level spectroscopies of the material and how they can reveal important details pertinent to its electronic structure. Specifically, we identify a fluorescence satellite in the Cr 𝐿 3 resonant x-ray-emission spectra that radiates at a constant emission energy across the Cr 𝐿 3 x-ray edge with energy ≈1.3 eV above the ordinary valence fluorescence. Here, we provide evidence that this feature arises from the valence recombination of the Cr 2⁢𝑝 core hole “dressed” by the same shakeup charge-transfer process present in both the Cr x-ray photoelectron and the Cr x-ray absorption spectra with its energy uniquely measuring the exchange splitting of the Cr 3⁢𝑑 level. Further analysis of the x-ray emission data reveals three additional features that radiate at constant loss energy that are attributed to combinations of Cr 3⁢𝑑⁢(𝑡 2⁢𝑔 ) → Cr 3⁢𝑑⁢(𝑡 2⁢𝑔 ), charge-transfer O 2⁢𝑝→Cr 3⁢𝑑, and crystal-field Cr⁢ 3⁢𝑑⁡(𝑡 2⁢𝑔 )→Cr⁢ 3⁢𝑑⁡(𝑒 𝑔 ) excitations. These assignments and their energies are supported by density-functional theory calculations, the accuracy of which we demonstrate by hard x-ray valence-photoemission measurements. Atomic multiplet calculations, which include crystal-field effects, help interpret x-ray photoelectron and x-ray absorption spectra of the covalently mixed Cr ion. Resonant Cr K-𝐿 2,3 ⁢𝐿 2,3 Auger-electron emission spectra support a ligand-to-metal nature of the charge-transfer process while highlighting the charge sensitivity differences between photon-in/electron-out and photon-in/photon-out spectroscopies.

36 MATERIALS SCIENCE↗

Evaluation of analytical performance of double pulse laser-induced breakdown spectroscopy for the detection of rare earth elements

Double pulse laser-induced breakdown spectroscopy (DP-LIBS) in collinear configuration was demonstrated to enhance the signal intensity of three rare earth elements (REEs), Eu, Gd, Pr, and Y (Yttrium is included because of its similar chemical properties and occurrence in similar deposits as REE). Significant enhancement in spectral signals of all elements was observed with an aid of second laser. Two laser pulses of 1064 nm wavelength were employed in collinear geometry on the Pr 2 O 3 , Eu 2 O 3 , Gd 2 O 3 , and Y 2 O 3 pellets to obtain emission spectra. For selected strong emission lines of Eu and Gd signal enhancement was found to be 3 to 7-fold and that for Y and Pr lines was observed to be 3 to 13-fold compared to single-pulse laser-induced breakdown spectroscopy (SP-LIBS). Role of inter-pulse delay between two pulses in DP-LIBS was found to be very crucial. Furthermore, while comparing selected ionic and neutral lines, ionic lines were found to have larger signal enhancement in DP-LIBS at the experimental conditions used in this study.

47 OTHER INSTRUMENTATION↗

Characterization of the ALSEP Process at Equilibrium: Speciation and Stoichiometry of the Extracted Complex

We have determined the identity of the complexes extracted into the ALSEP process solvent from solutions of nitric acid. The ALSEP process is a new solvent extraction separation designed to separate americium and curium from trivalent lanthanides in irradiated nuclear fuel. ALSEP employs a mixture of two extractants, 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) and N,N,N',N'-tetra(2-ethylhexyl)diglycolamide (TEHDGA) in n-dodecane, which makes it difficult to ascertain the nature of the extracted metal complexes. It is often asserted that the weak acid extractant HEH[EHP] does not participate in the extracted complex under ALSEP extraction conditions (2–4 M HNO 3 ). However, the analysis of the Am extraction equilibria, Nd absorption spectra, and Eu fluorescence emission spectra of metal-loaded organic phases argues for the participation of HEH[EHP] in the extracted complex despite the high acidity of the aqueous phases. The extracted complex was determined to contain fully protonated molecules of HEH[EHP] with an overall stoichiometry of M(TEHDGA) 2 (HEH[EHP]) 2 ·3NO 3 . Computations also demonstrate that replacing one TEHDGA molecule with one (HEH[EHP]) 2 dimer is likely energetically favorable compared to Eu(TEHDGA) 3 ·3NO 3 , whether the HEH[EHP] dimer is monodentate or bidentate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tumor‐pH‐value responsive non‐peripheral substituted phthalocyanines: Synthesis, investigation of photophysical and photochemical properties

Cancer is one of the diseases with the highest mortality rate worldwide. Although PDT has recently produced encouraging outcomes, there are still many areas that need to be improved. The first of these is the negative consequences faced by patients treated with the PDT method when exposed to sunlight. For this reason, a new PDT method has been developed in recent years, and it is aimed at using photosensitizer molecules that can be active in acidic conditions. Since the pH values of tumor tissues are more acidic than normal tissues, preparing molecules that act effectively in acidic conditions will allow for more effective results in treating cancer with PDT. In this context, within the scope of this study, 3‐(4‐propionylphenoxy)phthalonitrile ( 1 ) and its non‐peripheral tetra‐substituted phthalocyanine derivatives [( 2 ), ( 3 ), and ( 4 )] were prepared. With these phthalocyanine derivatives, the novel compounds ( 5 ), ( 6 ), and ( 7 ) were synthesized for the first time. The aggregation tendencies of newly synthesized phthalocyanines ( 5–7 ) were investigated in solvent media. The effects of pH changes upon UV–Vis and fluorescence spectra were performed. The electronic and emission spectra of synthesized phthalocyanine derivatives are highly sensitive to pH changes. Formation constant (Log K) values of mono‐ and di‐protonated phthalocyanine forms were calculated by the Henderson–Hasselback equation. The mono‐ and di‐protonated species' equilibrium constants (logK 1 and logK 2 ) were calculated as ~5.0. This value may be promising for pH‐sensitizing photosensitizers. Also, the photophysical and photochemical properties of synthesized metallophthalocyanine derivatives ( 2 ) and ( 5 ) were studied at different pH values. The singlet oxygen quantum yield of ( 2 ) and ( 5 ) was calculated to be 0.78 and 0.81 in DMSO, respectively. When pH = 6.4, that is, tumor‐pH‐values, this value for ( 5 ) has increased to 0.92. The newly synthesized phthalocyanines are suitable photosensitizers for PDT applications, especially with high singlet oxygen quantum yield at pH 6.4.

Genc Bilgicli, Hayriye↗

Lasing efficiency of krypton ions in the (8 – 14)-nm band upon pulsed laser excitation

The emission spectra of krypton plasma in the range of 8 – 14 nm upon excitation of a pulsed gas jet by 1.06-mm Nd : YAG laser radiation with a pulse energy of 0.85 J, pulse duration of 5.2 ns, and repetition rate of 10 Hz are investigated. The krypton emission spectrum is a wide (8 – 14 nm) band, peaking at 10.3 nm, which is formed by a series of much narrower lines. The observed lines are identified, and the fraction of laser pulse energy converted into the (8 – 14)-nm emission band and emitted into half-space (2π sr) is determined. The maximum conversion efficiency is found to be 21 %. The expected throughputs of lithographic systems with sources based on Sn, Xe, and Kr ions for different wavelengths, corresponding to the emission peaks of ions of these materials, are compared. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

High-resolution Spectra of Earth-like Planets Orbiting Red Giant Host Stars

In the near future we will have ground- and space-based telescopes that are designed to observe and characterize Earth-like planets. While attention is focused on exoplanets orbiting main-sequence stars, more than 150 exoplanets have already been detected orbiting red giants, opening the intriguing question of what rocky worlds orbiting in the habitable zone (HZ) of red giants would be like and how to characterize them. We present a high-resolution spectral database of reflection and emission spectra for nominal Earth-like planets orbiting in the red giant HZ from the visible to infrared (0.4–20 μm) for planets orbiting at the Earth-equivalent distance. We also show the change of such planetary spectra through the evolution of their red giant hosts. While the luminosity of the host increases the contrast ratio between star and planet, the increased orbital distance of the HZ for red giant hosts relaxes the light suppression requirements close to the star, which could make such planets interesting targets to characterize and search for signs of life, if new coronagraph designs with higher suppression at larger orbital separations could be developed. We assess the feasibility of characterizing atmospheric features including biosignatures for such planets with the proposed mission concept Large UV/Optical/IR Surveyor (LUVOIR).

79 ASTRONOMY AND ASTROPHYSICS↗

3D Printable Polymers for Radiological Applications

Additive manufacturing of polymers is a widely used and growing technology throughout the DOE complex. Composite filaments for Fused Deposition Modeling (FDM) printers are commonly used to enhance material properties such as mechanical strength, operating temperature and chemical resistance. Radio luminescent properties were added to 3D filaments by impregnating clear poly(ethylene terephthalate)-glycol (PETG) with X-ray scintillator powder. X-ray scintillators have unique, narrow emission spectra which can be imaged with low light DSLR cameras, photomultiplier tubes, or spectrometers. Filament Production: 1. Pellets are loaded into the hopper. 2. Temperature and extrusion speed are set on extruder. 3. Extruder turned on and filament is pulled from nozzle along air path to cool. 4. Spooler drive speeds set. 5. Filament is inserted through Filameasure then guided along drive wheels and into traverse. 6. Parameters adjusted to obtain 1.75 mm diameter 7. Filament is inserted into spooler wheel. Traverse speed set and slip nut adjusted to make tight and even roll. From Raw Materials to Printed Part: Clear PETG pellets were dipped in ZnS:Cu scintillator powder to coat pellets. Coated and uncoated pellets were mixed together before inserting into hopper. Filament showed trace amounts of powder and luminesced under UV light. Powder distribution is random and not reproducible thus providing a unique identification marker potentially useful for national security applications. Multiple X-ray scintillators can be arranged in a panel to discriminate incident X-ray photon energies. Variable panel arrangement: pixelated, layered, solid from homogenous filament. Ratio of emission intensities. Response varies with incident photon energy. Spectrally separate scintillators. Scintillators: Yttrium Oxide Europium Doped - Red, Gadolinium Oxysulfide Terbium Doped - Green, Barium Magnesium Aluminate Europium Doped - Blue, Zinc Sulfide Copper Doped - Green. Powder concentrations will need to be increased in the filament for use in the energy discriminating panel. Homogeneity in the filament will be a challenge that can be solved by turning the pellets into a powder and mixing it with scintillator powder prior to extrusion. The panels will be tested using x-ray booths and button sources such as Am-241, Cs-137, and Co-60.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Detecting Atmospheric Molecules of Nontransiting Temperate Terrestrial Exoplanets Using High-resolution Spectroscopy in the Mid-infrared Domain

Motivated by the development of high-dispersion spectrographs in the mid-infrared (MIR) range, we study their application to the atmospheric characterization of nearby nontransiting temperate terrestrial planets around M-type stars. We examine the detectability of CO{sub 2}, H{sub 2}O, N{sub 2}O, and O{sub 3 }features in high-resolution planetary thermal emission spectra at 12–18 μm assuming an Earth-like profile and a simplified thermal structure. The molecular line width of such planets can be comparable to or broader than the Doppler shift due to the planetary orbital motion. Given the likely difficulty in knowing the high-resolution MIR spectrum of the host star with sufficient accuracy, we propose observing the target system at two quadrature phases and extracting the differential spectra as the planetary signal. In this case, the signals can be substantially suppressed compared with the case where the host star spectrum is perfectly known, as some parts of the spectral features do not remain in the differential spectra. Despite this self-subtraction, the CO{sub 2} and H{sub 2}O features of nearby (≲5 pc) systems with mid-/late-M host stars would be feasible with a 6.5 m class cryogenic space telescope, and orbital inclination could also be constrained for some of them. For CO{sub 2} and N{sub 2}O in a 1 bar Earth-like atmosphere, this method would be sensitive when the mixing ratio is 1–10{sup 3} ppm. The detectability of molecules except O{sub 3} is not significantly improved when the spectral resolution is higher than R≳10,000, although the constraint on the orbital inclination is improved. This study provides some benchmark cases useful for assessing the value of MIR high-resolution spectroscopy in terms of characterization of potentially habitable planets.

47 OTHER INSTRUMENTATION↗

JWST Noise Floor. I. Random Error Sources in JWST NIRCam Time Series

James Webb Space Telescope (JWST) transmission and emission spectra will provide invaluable glimpses of transiting exoplanet atmospheres, including possible biosignatures. This promising science from JWST, however, will require exquisite precision and understanding of systematic errors that can impact the time series of planets crossing in front of and behind their host stars. Here, we provide estimates of the random noise sources affecting JWST Near-Infrared Camera (NIRCam) time-series data on the integration-to-integration level. We find that 1/f noise can limit the precision of grism time series for two groups (230–1000 ppm depending on the extraction method and extraction parameters), but will average down like the square root of N frames/reads. The current NIRCam grism time-series mode is especially affected by 1/f noise because its GRISMR dispersion direction is parallel to the detector fast-read direction, but could be alleviated in the GRISMC direction. Care should be taken to include as many frames as possible per visit to reduce this 1/f noise source: thus, we recommend the smallest detector subarray sizes one can tolerate, four output channels, and readout modes that minimize the number of skipped frames (RAPID or BRIGHT2). We also describe a covariance-weighting scheme that can significantly lower the contributions from 1/f noise as compared to sum extraction. We evaluate the noise introduced by pre-amplifier offsets, random telegraph noise, and high dark current resistor capacitor (RC) pixels and find that these are correctable below 10 ppm once background subtraction and pixel masking are performed. We explore systematic error sources in a companion paper.

79 ASTRONOMY AND ASTROPHYSICS↗

Emission Lines of Fe xiv, Fe xv, and Fe xvi in the Extreme Ultraviolet Region 40–100 Å

We report on emission spectra of iron in the extreme ultraviolet recorded at an electron density of ~10 11 cm -3 on the Lawrence Livermore electron beam ion trap facility. We present a summary of the observed emission lines, including wavelengths and emission intensities, and present spectra of pure Fe xiv through Fe xvi emission derived from our measurements in the 40–100 Å wavelength range. We show that spectral models, especially the current version of CHIANTI v10.0, describe the M-shell emission from these three charge states of iron reasonably well, and we are able to verify several transitions in CHIANTI for the first time.

74 ATOMIC AND MOLECULAR PHYSICS↗

First-principles theory of direct-gap optical emission in hexagonal Ge and its enhancement via strain engineering

The emergence of hexagonal Ge (2H-Ge) as a candidate direct-gap group-IV semiconductor for Si photonics mandates a rigorous understanding of its optoelectronic properties. Theoretical predictions of a “pseudodirect” band gap, characterized by weak oscillator strength, contrast with a claimed high radiative recombination coefficient 𝐵 comparable to conventional (cubic) InAs. We compute 𝐵 in 2H-Ge from first principles and quantify its dependence on temperature, carrier density, and strain. For unstrained 2H-Ge, our calculated spontaneous emission spectra corroborate that measured photoluminescence corresponds to direct-gap emission, but with 𝐵 being approximately three orders of magnitude lower than in InAs. We confirm a pseudodirect-to-direct-gap transition under ∼2% [0001] uniaxial tension, which can enhance 𝐵 by up to 3 orders of magnitude, making it comparable to that of InAs. Beyond quantifying the strong enhancement of 𝐵 via strain engineering, our analysis suggests the dominance of additional, as-yet unquantified recombination mechanisms in this nascent material.

36 MATERIALS SCIENCE↗

Modeling Aerial Gamma-Ray Backgrounds Using Non-negative Matrix Factorization

Airborne gamma-ray surveys are useful for many applications, ranging from geology and mining to public health and nuclear security. In all these contexts, the ability to decompose a measured spectrum into a linear combination of background source terms can provide useful insights into the data and lead to improvements in the techniques that use spectral energy windows. Multiple methods for the linear decomposition of spectra exist but are subject to various drawbacks, such as allowing negative photon fluxes or requiring detailed Monte Carlo modeling. In this work, we propose using non-negative matrix factorization (NMF) as a data-driven approach to spectral decomposition. Using aerial surveys that include flights over water, we demonstrate that the mathematical approach of NMF finds physically relevant structure in the aerial gamma-ray background, namely, that measured spectra can be expressed as the sum of nearby terrestrial emission, distant terrestrial emission, and radon and cosmic emission. Furthermore, these NMF background components are compared with the background components obtained by noise-adjusted singular value decomposition (NASVD), which contain negative photon fluxes and, thus, do not represent the emission spectra in as straightforward a way. Finally, we comment on the potential areas of research that are enabled by NMF decompositions, such as new approaches to spectral anomaly detection and data fusion.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Laser-Plasma Spectroscopy of Hydroxyl with Applications

This article discusses laser-induced laboratory-air plasma measurements and analysis of hydroxyl (OH) ultraviolet spectra. The computations of the OH spectra utilize line strength data that were developed previously and that are now communicated for the first time. The line strengths have been utilized extensively in interpretation of recorded molecular emission spectra and have been well-tested in laser-induced fluorescence applications for the purpose of temperature inferences from recorded data. Moreover, new experiments with Q-switched laser pulses illustrate occurrence of molecular recombination spectra for time delays of the order of several dozen of microseconds after plasma initiation. The OH signals occur due to the natural humidity in laboratory air. Centrifugal stretching of the Franck-Condon factors and r-centroids are included in the process of determining the line strengths that are communicated as a Supplementary File. Laser spectroscopy applications of detailed OH computations include laser-induced plasma and combustion analyses, to name but two applications. This work also includes literature references that address various diagnosis applications.

47 OTHER INSTRUMENTATION↗

Radiation transfer in the spectra of short-pulse laser-heated targets

The conditions in laser-produced plasmas are frequently determined with x-ray spectroscopy by comparing calculated to measured spectra. Line spectra from K-shell transitions of low- to mid-atomic number elements are most often used since the important physical processes are well understood and reliable spectra can be readily measured and calculated. Radiation transfer effects due to large optical depths of strong lines can influence the spectra. In this work, the effects of radiation transfer on the emission spectra of short-laser pulse-heated targets are studied. The possible errors made in inferring electron temperature by not including radiation transfer are quantified. The inclusion of radiative transfer in spectral calculations improves the accuracy of typical temperature diagnostics and allows the use of strong lines for diagnostics.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Long-Lived Photoluminescence of Molecular Group 14 Compounds through Thermally Activated Delayed Fluorescence

Photoluminescent molecules exploiting the sizable spin-orbit coupling constants of main group metals and metalloids to access long-lived triplet excited states are relatively rare compared to phosphorescent transition metal complexes. Here we report the synthesis of three air- and moisture-stable group 14 compounds E( Me PDP Ph ) 2 , where E = Si, Ge, or Sn and [ Me PDP Ph] 2- is the doubly deprotonated form of 2,6-bis(5- methyl-3-phenyl-1H-pyrrol-2-yl)pyridine. In solution, all three molecules exhibit exceptionally long-lived triplet excited states with lifetimes in the millisecond range and show highly efficient photoluminescence (Φ ≤ 0.49) due to competing prompt fluorescence and thermally activated delayed fluorescence at and around room temperature. Temperature-dependent steady-state emission spectra and photoluminescent lifetime measurements provided conclusive evidence for the two distinct emission pathways. Picosecond transient absorption spectroscopy allowed further analysis of the intersystem crossing (ISC) between singlet and triplet manifolds (τ ISC = 0.25-3.1 ns) and confirmed the expected trend of increased ISC rates for the heavier elements in otherwise isostructural compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dual-Emitting Cyclometalated Platinum Compounds with Isocyanide Ligands

Cyclometalated platinum(II) compounds with both C^N chelating iminic ligands and isocyanide ligands were synthesized. Two sets of compounds from the reaction of two separate HC^N ligands (derived from thiophene or benzene) with [Pt2Me4(μ-SMe 2 ) 2 ] were obtained, resulting in square planar compounds with an anionic C^N ligand, a methyl ligand, and a dimethyl sulfide (dms) ligand completing the coordination sphere. Subsequently, the dms ligand was easily substituted by several isocyanide ligands (2-naphthyl, adamantyl, 2,6-dimethylphenyl, ptoluenesulfonylmethyl). The compounds were characterized by multinuclear NMR spectroscopy, IR spectroscopy, and singlecrystal X-ray diffraction (SCXRD). Their photophysical properties were explored using UV/vis, emission, and transient absorption (TA) spectroscopy. The emission spectra for the thiophene-derived compounds showed well-defined dual emission peaks, while the benzene-derived compounds’ bands appeared less resolved. DFT and TDDFT calculations were performed, and results were compared to the observed spectroscopic properties of the newly synthesized complexes.

Inorganic carbon compounds↗

Amplified Spontaneous Emission from Electron–Hole Quantum Droplets in Colloidal CdSe Nanoplatelets

Two-dimensional cadmium selenide nanoplatelets (NPLs) exhibit large absorption cross sections and homogeneously broadened band-edge transitions that offer utility in wide-ranging optoelectronic applications. Here, we examine the temperature-dependence of amplified spontaneous emission (ASE) in 4- and 5-monolayer thick NPLs and show that the threshold for close-packed (neat) films decreases with decreasing temperature by a factor of 2-10 relative to ambient temperature owing to extrinsic (trapping) and intrinsic (phonon-derived line width) factors. Interestingly, for pump intensities that exceed the ASE threshold, we find development of intense emission to lower energy in particular provided that the film temperature is <= 200 K. For NPLs diluted in an inert polymer, both biexcitonic ASE and low-energy emission are suppressed, suggesting that described neat-film observables rely upon high chromophore density and rapid, collective processes. Transient emission spectra reveal ultrafast red-shifting with the time of the lower energy emission. Taken together, these findings indicate a previously unreported process of amplified stimulated emission from polyexciton states that is consistent with quantum droplets and constitutes a form of exciton condensate. For studied samples, quantum droplets form provided that roughly 17 meV or less of thermal energy is available, which we hypothesize relates to polyexciton binding energy. Polyexciton ASE can produce pump-fluence-tunable red-shifted ASE even 120 meV lower in energy than biexciton ASE. Finally, our findings convey the importance of biexciton and polyexciton populations in nanoplatelets and show that quantum droplets can exhibit light amplification at significantly lower photon energies than biexcitonic ASE.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗