Two Regimes of Bandgap Red Shift and Partial Ambient Retention in Pressure-Treated Two-Dimensional Perovskites
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36 MATERIALS SCIENCE↗
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Crystal Chemistry, Band-Gap Red Shift, and Electrocatalytic Activity of Iron-Doped Gallium Oxide Ceramics
This work for the first time unfurls the fundamental mechanisms and set the stage for an approach to derive electrocatalytic activity, which is otherwise not possible, in a traditionally known wide band gap oxide material. Specifically, we report on the tunable optical properties, in terms of wide spectral selectivity and red-shifted band gap, and electrocatalytic behavior of iron (Fe) doped gallium oxide (ß-Ga 2 O 3 ) model system. X-ray diffraction (XRD) studies of sintered Ga 2-x Fe x O 3 (GFO) (0.0 ≤ x ≤ 0.3) compounds provide evidence for the Fe 3+ substitution at Ga 3+ site without any secondary phase formation. Rietveld refinement of XRD patterns reveal that the GFO compounds crystallize in monoclinic crystal symmetry with C2/m space group. The electronic structure of the GFO compounds probed using X-ray photoelectron spectroscopy data reveals that, at lower concentrations of Fe exhibits mixed chemical valence states (Fe 3+ , Fe 2+ ), whereas single chemical valence state (Fe 3+ ) is evident for higher Fe content (x = 0.20-0.30). The optical absorption spectra reveal a significant red shift in the optical band gap with Fe doping. The origin of the significant red shift even at low concentrations of Fe (x = 0.05) is attributed to the strong sp-d exchange interaction originated from the 3 d 5 electrons of Fe 3+ . The optical absorption edge observed at ˜450 nm with lower intensity is the characteristic of Fe doped compounds associated with Fe 3+ - Fe 3+ double excitation process. Coupled with optical band gap red shift, electrocatalytic studies of GFO compounds reveals that, interestingly, Fe doped Ga 2 O 3 compound exhibits electrocatalytic activity in contrast to intrinsic Ga 2 O 3 . Fe doped samples (GFO) demonstrated appreciable electrocatalytic activity towards the generation of H 2 through electrocatalytic water splitting. An onset potential and tafel slope of GFO compounds includes: ~900 mV, ~210 mVdec -1 (x = 0.15) and ~1036 mV, ~290 mVdec-1 (x = 0.30). The electrocatalytic activity of Fe doped Ga-oxide compounds is attributed to cumulative effect of different mechanisms such as; doping resulted new catalytic centers, enhanced conductivity and electron mobility. Hence, in this report, for the first time, we explored a new pathway; electrocatalytic behavior of Fe doped Ga 2 O 3 resulted due to Fe chemical states, red shift in optical band gap. The implications derived from this work may be applicable to a large class of compounds and further options may be available to design functional materials for electrocatalytic energy production.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Infrared Multiphoton Dissociation Spectroscopy of a Gas-Phase Complex of Uranyl and 3-Oxa-Glutaramide: An Extreme Red-Shift of the [O=U=O]²⁺ Asymmetric Stretch
The gas-phase complex UO₂(TMOGA)₂²⁺ (TMOGA = tetramethyl-3-oxa-glutaramide) prepared by electrospray ionization was characterized by infrared multiphoton dissociation (IRMPD) spectroscopy. The IRMPD spectrum from 700–1800 cm⁻¹ was interpreted using a computational study based on density functional theory. The predicted vibrational frequencies are in good agreement with the measured values, with an average deviation of only 8 cm⁻¹ (<1%) and a maximum deviation of 21 cm⁻¹ (<2%). The only IR peak assigned to the linear uranyl moiety was the asymmetric ν₃ mode, which appeared at 965 cm⁻¹ and was predicted by DFT as 953 cm⁻¹. This ν₃ frequency is red-shifted relative to bare uranyl, UO₂²⁺, by ca. 150 cm⁻¹ due to electron donation from the TMOGA ligands. Based on the degree of red-shifting, it is inferred that two TMOGA oxygen-donor ligands have a greater effective gas basicity than the four monodentate acetone ligands in UO₂(acetone)₄²⁺. The uranyl ν₃ frequency was also computed for uranyl coordinated by two TMGA ligands, in which the central Oether of TMOGA has been replaced by CH₂. The computed ν₃ for UO₂(TMGA)₂²⁺, 950 cm⁻¹, is essentially the same as that for UO₂(TMOGA)₂²⁺, suggesting that electron donation to uranyl from the Oether of TMOGA is minor. The computed ν₃ asymmetric stretching frequencies for the three actinyl complexes, UO₂(TMOGA)₂²⁺, NpO₂(TMOGA)₂²⁺ and PuO₂(TMOGA)₂²⁺, are comparable. This similarity is discussed in the context of the relationship between ν₃ and intrinsic actinide-oxygen bond energies in actinyl complexes.
Environmental Molecular Sciences Laboratory↗
Red-Shifted Absorptions of Cation-Defective and Surface-Functionalized Anatase with Enhanced Photoelectrochemical Properties
Manipulating the atomic structure of semiconductors is a fine way to tune their properties. The rationalization of their modified properties is, however, particularly challenging as defects locally disrupt the long-range structural ordering, and a deeper effort is required to fully describe their structure. In this work, we investigated the photoelectrochemical properties of an anatase-type structure featuring a high content of titanium vacancies stabilized by dual-oxide substitution by fluoride and hydroxide anions. Such atomic modification induces a slight red-shift band gap energy of 0.08 eV as compared to pure TiO 2 , which was assigned to changes in titanium–anion ionocovalent bonding. Under illumination, electron paramagnetic resonance spectroscopy revealed the formation of Ti III and O 2 – radicals which were not detected in defect-free TiO 2 . Consequently, the modified anatase shows higher ability to oxidize water with lower electron–hole recombination rate. To further increase the photoelectrochemical properties, we subsequently modified the compound by a surface functionalization with N-methyl-2-pyrrolidone (NMP). This treatment further modifies the chemical composition, which results in a red shift of the band gap energy to 3.03 eV. Moreover, the interaction of the NMP electron-donating molecules with the surface induces an absorption band in the visible region with an estimated band gap energy of 2.25–2.50 eV. Under illumination, the resulting core–shell structure produces a high concentration of reduced Ti III and O 2 – , suggesting an effective charge carrier separation which is confirmed by high photoelectrochemical properties. This work provides new opportunities to better understand the structural features that affect the photogenerated charge carriers.
74 ATOMIC AND MOLECULAR PHYSICS↗
100 MeV O{sup 7+} irradiation induced red shift in the band gaps of 3 wt% 'Li' doped Nb{sub 2}O{sub 5} thin film
Nb{sub 2}O{sub 5}:Li (3 wt%) thin film of thickness 353 nm spray deposited onto ITO coated glass substrate at 350 °C is irradiated with 100 MeV O{sup 7+} ion at a fluence of 5×10{sup 12} ions/cm{sup 2}. X-ray diffraction shows that the pristine and irradiated films are polycrystalline with a tetragonal phase. Raman peaks suppressed upon irradiation imply large surface degradation which is also seen as a decrement in transparency in visible region to one half of the pristine film. Large red shift is observed in direct and indirect band gaps upon irradiation. Hall effect reveals slight increase in carrier concentration due to irradiation induced defects.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Surface plasmon polariton assisted red shift in excitonic emission of semiconductor microflowers
We report on the study of metal nanoparticle-semiconductor hybrid system composed of β-indium sulfide (β-In{sub 2}S{sub 3}) and gold (Au) nanoparticles. β-In{sub 2}S{sub 3} micron sized flower like structures (∼1 μm) and Au nanoparticles (∼10 nm) were synthesized by chemical route. These Au nanoparticles have surface plasmon resonance at ∼ 520 nm. We study the influence of Au surface plasmon polaritons on the radiative properties of the β-In{sub 2}S{sub 3} microflowers. As a result of the coupling between the surface plasmon polaritons and the excitons there is a red shift ∼ 50 nm in emission spectrum of hybrid β-In{sub 2}S{sub 3}-Au system. Such hybrid systems provide scope for a control on the optical properties of semiconductor microstructures, thus rendering them suitable for specific device applications in optoelectronics and photovoltaics.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Red shift in the photoluminescence of colloidal carbon quantum dots induced by photon reabsorption
We synthesize the colloidal carbon/graphene quantum dots 1–9 nm in diameter and study their photoluminescence properties. Surprisingly, the luminescence properties of a fixed collection of colloidal carbon quantum dots can be systematically changed as the concentration varies. A model based on photon reabsorption is proposed which explains well the experiment. Infrared spectral study indicates that the surfaces of the carbon quantum dots are substantially terminated by oxygen atoms, which causes their ultra-high hydrophilicity. Our result clarifies the mystery of distinct emission colors in carbon quantum dots and indicates that photon reabsorption can strongly affect the luminescence properties of colloidal nanocrystals.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Highly coherent red-shifted dispersive wave generation around 1.3 μm for efficient wavelength conversion
This research investigates the mechanism of the optical dispersive wave (DW) and proposes a scheme that can realize an efficient wavelength conversion. In an elaborately designed photonic crystal fiber, a readily available ytterbium laser operating at ∼1 μm can be transferred to the valuable 1.3 μm wavelength range. A low-order soliton is produced to concentrate the energy of the DW into the target wavelength range and improve the degree of coherence. The input chirp is demonstrated to be a factor that enhances the wavelength conversion efficiency. With a positive initial chirp, 76.6% of the pump energy in the fiber can be transferred into a spectral range between 1.24 and 1.4 μm. With the use of a grating compressor, it is possible to compress the generated coherent DW of several picoseconds into less than 90 fs.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Engineering of a calcium-ion binding site into the RC-LH1-PufX complex of Rhodobacter sphaeroides to enable ion-dependent spectral red-shifting
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Communication: Towards the binding energy and vibrational red shift of the simplest organic hydrogen bond: Harmonic constraints for methanol dimer
The discrepancy between experimental and harmonically predicted shifts of the OH stretching fundamental of methanol upon hydrogen bonding to a second methanol unit is too large to be blamed mostly on diagonal and off-diagonal anharmonicity corrections. It is shown that a decisive contribution comes from post-MP2 electron correlation effects, which appear not to be captured by any of the popular density functionals. We also identify that the major deficiency is in the description of the donor OH bond. Together with estimates for the electronic and harmonically zero-point corrected dimer binding energies, this work provides essential constraints for a quantitative description of this simple hydrogen bond. The spectroscopic dissociation energy is predicted to be larger than 18 kJ/mol and the harmonic OH-stretching fundamental shifts by about −121 cm{sup −1} upon dimerization, somewhat more than in the anharmonic experiment (−111 cm{sup −1})
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Crystal structure, electronic structure, and photoluminescent properties of SrMoO{sub 4}:Tb{sup 3+} phosphors
Highlights: • SrMoO{sub 4}:Tb{sup 3+} phosphor samples were synthesized at different temperatures. • The crystal and electronic structures, and luminescence properties were studied. • The excitation peak shifts to red with increasing the sintering temperature. • The luminescence mechanism of SrMoO{sub 4}:Tb{sup 3+} was suggested. - Abstract: The experimental and theoretical studies of the optical properties of SrMoO{sub 4}:Tb{sup 3+} phosphors were carried out. The structural, optical, and electronical properties of the phosphors were systematically studied. The phosphor samples were crystallized at different temperatures via a sol–gel method. Excitation spectra of SrMoO{sub 4}:Tb{sup 3+} powder samples exhibited gradual red shift and luminescent intensity changed with increasing the sintering temperature. Such spectral changes depend strongly on the crystallographic properties such as lattice parameters and crystallinity. The shift of the excitation spectra is mainly ascribed to the covalent bond interaction between Mo−O bonds. An energy band model was demonstrated to describe the luminescence mechanism in the material.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Understanding and controlling chromaticity shift in LED devices
Chromaticity shift in light-emitting diode (LED) devices arises from multiple mechanisms, and at least five different chromaticity shift modes (CSMs) have been identified to date. This paper focuses on the impacts of irreversible phosphor degradation as a cause of chromaticity shifts in LED devices. The nitride phosphors used to produce warm white LEDs are especially vulnerable to degradation due to thermal and chemical effects such as reactions with oxygen and water. As a result, LED devices utilizing these phosphors were found to undergo either a green shift or, less commonly, a red shift depending on the phosphor mix in the LED devices. These types of chromaticity shifts are classified as CSM-2 (green shift) and CSM-5 (red shift). This paper provides an overview of the kinetic processes responsible for green and red chromaticity shifts along with examples from accelerated stress testing of 6” downlights. Both CSMs appear to proceed through analogous mechanisms that are initiated at the surface of the phosphor. A green shift is produced by the surface oxidation of the nitride phosphor that changes the emission profile to lower wavelengths. As the surface oxidation reaction proceeds, reactant limitations slow the rate and bulk oxidation processes become more prevalent. We found that a red chromaticity shift arises from quenching of the green phosphor, also possibly due to surface reactions of oxygen, which shift the emission chromaticity in the red direction. In conclusion, we discuss the implications of these findings on projecting chromaticity.
Davis, Lynn↗
Equatorial coordination of uranyl: Correlating ligand charge donation with the O yl -U-O yl asymmetric stretch frequency
In uranyl coordination complexes, UO 2 (L) n 2+ , uranium in the formally dipositive [O=U=O] 2+ moiety is coordinated by n neutral organic electron donor ligands, L. The extent of ligand electron donation, which results in partial reduction of uranyl and weakening of the U=O bonds, is revealed by the magnitude of the red-shift of the uranyl asymmetric stretch frequency, ν 3 . This phenomenon appears in gas-phase complexes in which uranyl is coordinated by electron donor ligands: the ν 3 red-shift increases as the number of ligands and their proton affinity (PA) increases. Because PA is a measure of the enthalpy change associated with a proton-ligand interaction, which is much stronger and of a different nature than metal ion-ligand bonding, it is not necessarily expected that ligand PAs should reliably predict uranyl-ligand bonding and the resulting ν 3 red-shift. In this study, ν 3 was measured for uranyl coordinated by ligands with a relatively broad range of PAs, revealing a surprisingly good correlation between PA and ν 3 frequency. From computed ν 3 frequencies for bare UO 2 cations and neutrals, it is inferred that the effective charge of uranyl in UO 2 (L) n 2+ complexes can be reduced to near zero upon ligation by sufficiently strong charge-donor ligands. The basis for the correlation between ν 3 and ligand PAs, as well as limitations and deviations from it, are considered. It is demonstrated that the correlation evidently extends to a ligand that exhibits polydentate metal ion coordination.
Gibson, John K.↗
When the universe expands too fast: relentless dark matter
Here we consider a modification to the standard cosmological history consisting of introducing a new species φ whose energy density red-shifts with the scale factor a like ρ φ ∝ a -(4+n) . For 0n>, such a red-shift is faster than radiation, hence the new species dominates the energy budget of the universe at early times while it is completely negligible at late times. If equality with the radiation energy density is achieved at low enough temperatures, dark matter can be produced as a thermal relic during the new cosmological phase. Dark matter freeze-out then occurs at higher temperatures compared to the standard case, implying that reproducing the observed abundance requires significantly larger annihilation rates. Here, we point out a completely new phenomenon, which we refer to as relentless dark matter: for large enough n, unlike the standard case where annihilation ends shortly after the departure from thermal equilibrium, dark matter particles keep annihilating long after leaving chemical equilibrium, with a significant depletion of the final relic abundance. Relentless annihilation occurs for n ≥ 2 and n ≥ 4 for s-wave and p-wave annihilation, respectively, and it thus occurs in well motivated scenarios such as a quintessence with a kination phase. We discuss a few microscopic realizations for the new cosmological component and highlight the phenomenological consequences of our calculations for dark matter searches.
79 ASTRONOMY AND ASTROPHYSICS↗
Interplay between Electrostatic Properties of Molecular Adducts and Their Positions at Carbon Nanotubes
Formation of the sp 3 -defect due to covalent functionalization of a single-walled carbon nanotube (SWCNT) results in a new red-shifted emissive excitons. Here, using density functional theory, we study the impact of the intrinsic molecular dipole moments and the local charges induced by various molecular adducts on the energy and localization properties of the optically active defect-based exciton in a (10,5) SWCNT. The interplay of two effects plays a role in the localization of the exciton and, therefore, its red shift, but at different scales: The source of the leading order contribution is the defect conformation, resulting in the red shift of the defect-associated exciton with respect to the E 11 band of the pristine SWCNT on the order of ~100 meV, while the individual dipoles and polarization properties of molecular adducts lead to significantly smaller red shifts on the order of ~10 meV. While the species-dependent trends in defect-induced charges do not directly correlate to the exciton red shift, the charge at the sp 3 -defect exhibits a distinct behavior between ortho- and para-defect configurations and is relevant to the chemical reactivity of the defect position depending on the adduct type. Overall, our computational results may be helpful for diverse synthetic strategies to fine-tune emission of SWCNTs toward desired applications.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Widely tunable alloy composition and crystal structure in catalyst-free InGaAs nanowire arrays grown by selective area molecular beam epitaxy
We delineate the optimized growth parameter space for high-uniformity catalyst-free InGaAs nanowire (NW) arrays on Si over nearly the entire alloy compositional range using selective area molecular beam epitaxy. Under the required high group-V fluxes and V/III ratios, the respective growth windows shift to higher growth temperatures as the Ga-content x(Ga) is tuned from In-rich to Ga-rich InGaAs NWs. Using correlated x-ray diffraction, transmission electron microscopy, and micro-photoluminescence spectroscopy, we identify structural defects to govern luminescence linewidths in In-rich (x(Ga) < 0.4) and Ga-rich (x(Ga) > 0.6) NWs, whereas limitations at intermediate Ga-content (0.4 < x(Ga) < 0.6) are mainly due to compositional inhomogeneities. Most remarkably, the catalyst-free InGaAs NWs exhibit a characteristic transition in crystal structure from wurtzite to zincblende (ZB) dominated phase near x(Ga) ∼ 0.4 that is further reflected in a cross-over from blue-shifted to red-shifted photoluminescence emission relative to the band edge emission of the bulk ZB InGaAs phase.
36 MATERIALS SCIENCE↗
Tunable trimers: Using temperature and pressure to control luminescent emission in gold(I) pyrazolate-based trimers
A systematic investigation into the relationship between the solid-state luminescence and the intermolecular Au∙∙∙Au interactions in a series of pyrazolate-based gold(I) trimers; tris(μ 2 -pyrazolato-N,N')-tri-gold(I) (1), tris(μ 2 -3,4,5-trimethylpyrazolato-N,N')-tri-gold(I) (2), tris(μ 2 -3-methyl-5-phenylpyrazolato-N,N')-tri-gold(I) (3) and tris(μ 2 -3,5-diphenylpyrazolato-N,N')-tri-gold(I) (4) has been carried out using variable temperature and high pressure X-ray crystallography, solid-state emission spectroscopy, Raman spectroscopy and computational techniques. Single-crystal X-ray studies show that there is a significant reduction in the intertrimer Au∙∙∙Au distances both with decreasing temperature and increasing pressure. In the four complexes, the reduction in temperature from 293 to 100 K is accompanied by a reduction in the shortest intermolecular Au∙∙∙Au contacts of between 0.04 and 0.08 Å. The solid-state luminescent emission spectra of 1 and 2 display a red shift with decreasing temperature or increasing pressure. Compound 3 does not emit under ambient conditions but displays increasingly red-shifted luminescence upon cooling or compression. Compound 4 remains emissionless, consistent with the absence of intermolecular Au∙∙∙Au interactions. The largest pressure induced shift in emission is observed in 2 with a red shift of approximately 630 cm -1 per GPa between ambient and 3.80 GPa. The shifts in all the complexes can be correlated with changes in Au∙∙∙Au distance observed by diffraction.
74 ATOMIC AND MOLECULAR PHYSICS↗