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Biomass burning emissions often contain brown carbon (BrC), which represents a large family of light-absorbing organics that are chemically complex, thus making it difficult to estimate their absorption of incoming solar radiation, resulting in large uncertainties in the estimation of the global direct radiative effect of aerosols. Here we investigate the contribution of BrC to the total light absorption of biomass burning aerosols over the South-East Atlantic Ocean with different optical models, utilizing a suite of airborne measurements from the ORACLES 2018 campaign. An effective refractive index of black carbon (BC), meBC=1.95+ikeBC, that characterizes the absorptivity of all absorbing components at 660 nm wavelength was introduced to facilitate the attribution of absorption at shorter wavelengths, i.e. 470 nm. Most values of the imaginary part of the effective refractive index, keBC, were larger than those commonly used for BC from biomass burning emissions, suggesting contributions from absorbers besides BC at 660 nm. The TEM-EDX single-particle analysis further suggests that these long-wavelength absorbers might include iron oxides, as iron is found to be present only when large values of keBC are derived. Using this effective BC refractive index, we find that the contribution of BrC to the total absorption at 470 nm (RBrC,470) ranges from ∼8 %–22 %, with the organic aerosol mass absorption coefficient (MACOA,470) at this wavelength ranging from 0.30±0.27 to 0.68±0.08 m2 g−1. The core–shell model yielded much higher estimates of MACOA,470 and RBrC,470 than homogeneous mixing models, underscoring the importance of model treatment. Absorption attribution using the Bruggeman mixing Mie model suggests a minor BrC contribution of 4 % at 530 nm, while its removal would triple the BrC contribution to the total absorption at 470 nm obtained using the AAE (absorption Ångström exponent) attribution method. Thus, it is recommended that the application of any optical properties-based attribution method use absorption coefficients at the longest possible wavelength to minimize the influence of BrC and to account for potential contributions from other absorbing materials.

In this work, a facile method to prepare Bi2O3 decorated activated carbon (Bi2O3@AC) composites with high pseudocapacitive properties was presented. The inorganic-organic composites synthesized using commercial Bi2O3 and active carbon with different weight ratio. The composites were assessed using spectroscopic, microscopic, and diffractive techniques. Our assessments confirmed that active carbons were successfully doped with commercial Bi2O3 nanoparticles with different dopant rates. The electrochemical performance of as-prepared materials was researched by cyclic voltammetry, chronopotentiometry, and electrochemical impedance spectroscopy in 6 M KOH electrolyte. Higher specific capacitance was achieved for increased Bi2O3 nanoparticle in composites. The 20%-Bi2O3@AC had a maximum specific capacitance of 565 F/g at a current density of 1 A/g. In addition, the symmetrically assembled supercapacitor delivers a high energy density (23.0 Wh kg(-1)). Moreover, 67% of the initial capacitance is maintained after 1500 cycles at 200 mV/s, suggesting good cycling stability. Due to the synergistic effect of compositing a promising electrochemical performance was observed that was not obtained by bare AC or Bi2O3. As a result, the electrochemical properties of 20%-Bi2O3@AC composite is promising and it may be used as potential electrode for supercapacitor. Kirklareli University Scientific Research Coordination Office [KLUBAP 207]; Krklareli University, Turkey [KLUBAP-139] Part of the project was supported Kirklareli University Scientific Research Coordination Office with project number KLUBAP 207. This study was partly supported by the Krklareli University, Turkey (Grant No. KLUBAP-139).

In this study, CdO films were successfully obtained by using a homemade chemical spray pyrolysis technique. The crystal structures of the CdO thin films improved due to an increase in the substrate temperature when the spray time was kept constant. Additionally, CdO film deposited at 250 degrees C exhibited amorphous crystal structure. The surface morphology of the samples was evaluated by scanning electron microscope (SEM) and it was observed that well-defined granules started to be clearly seen when the substrate temperature increased. Optical properties of CdO films were also investigated by using an ultraviolet-visible (UV-Vis) spectrophotometer, and the optical band gap of CdO varied from 2.57 eV to 2.73 eV with increasing substrate temperature. The electrical performance of the CdO films in the Au/CdO/p-Si device were determined by I-V measurements. According to the results, it was found that diode parameters depend on the changing properties of CdO in terms of the substrate temperature.

Al/n-Si/Ti1-xO2CdxO/Al photodiodes were produced using sol-gel and spin coating methods where CdO dopant was applied on different concentrations (x = 0.0; x = 0.01; x = 0.05; x = 0.10). Cd dopant effect upon structural, optical, photodiode and electrical properties was assessed. Scanning electron microscope and energy-dispersive spectra were used in the structural investigation. Optic properties were assessed using UV-Vis spectroscopy and bandgap energies of the photodiodes were calculated which were found to be between 3.25 and 3.36 eV. Increased bandgap energy was observed with increased CdO doping rate. Photodiode properties were assessed under varying daylight illuminations. Barrier height, ideality factor, dark current, linear dynamic rate, photosensitivity, photoresponsivity of the photodiodes were calculated. Electrical properties of the Al/n-Si/Ti1-xO2CdxO/Al photodiodes were calculated where conductance-voltage and capacitance-voltage plots were obtained. Corrective conductance-voltage and corrective capacitance-voltage graphs confirm that the electrical properties of the photodiodes depend on AC signal frequency. Frequency-dependent electrical characteristics were attributed to the density of interface states which were found to be between 10(11) and 10(12). Decreased density of interface state was found for increased AC signal frequency.

Mesocrystals are superstructures of crystallographically aligned nanoparticles and are a rapidly emerging class of crystalline materials displaying sophisticated morphologies and properties, beyond those originating from size and shape of nanoparticles alone. This study reports the first synthesis of Cu3N mesocrystals employing structure-directing agents with a subtle tuning of the reaction parameters. Detailed structural characterizations carried out with a combination of transmission electron microscopy techniques (HRTEM, HAADF-STEM-EXDS) reveal that Cu3N mesocrystals form by non-classical crystallization, and variations in their sizes and morphologies are traced back to distinct attachment scenarios of corresponding mesocrystal subunits. In the presence of oleylamine, the mesocrystal subunits in the early reaction stages prealign in a crystallographic fashion and afterwards grow into the final mesocrystals, while in the presence of hexadecylamine the subunits come into contact through misaligned attachment, and subsequently, to some degree, realign in crystallographic register. Upon prolonged heating both types of mesocrystals undergo chemical conversion processes resulting in structural and morphological changes. A two-step mechanism of chemical conversion is proposed, involving Cu3N decomposition and anion exchange driven by the nanoscale Kirkendall effect, resulting first in multicomponent/heterostructured Cu3N–Cu2O mesocrystals, which subsequently convert into Cu2O nanocages. It is anticipated that combining nanostructured Cu3N and Cu2O in a mesocrystalline and hollow morphology will provide a platform to expand their application potential.

Conveniently modified polycyclic aromatic hydrocarbon (PAH) fluorophores are obtained by a bromination–borylation sequence. The bis-borylated dyes show red-shifted absorption (λabs,max > 450 nm) and emission (λf,max > 500 nm; Φf: 0.3–0.5) properties as compared to the parent PAHs. Their centrosymmetric A–π-A (A: acceptor) structures led to the observation of two-photon absorption (up to 60 GM) in the near-infrared spectral region (>800 nm). The rigid structure shuts down non-radiative deactivation by limiting rotational or vibrational freedom. Thus, the excited-state pathways originating from the excited singlet state are resumed to fluorescence and excited triplet-state formation. The latter is involved in the energy-transfer sensitization of singlet oxygen (ΦΔ: 0.50–0.66). This bipartition provides the setting for the concomitant observation of fluorescence and photosensitization, making these dyes ideal bimodal chromophores., We are grateful for financial support from the Spanish Ministerio de Ciencia e Innovación (grant PID2020-119992GB-I00 for U. P., PID2019-106358GB-C21 and PID2019-106358GB-C22 for A. R., PID2019-110441RB-C33 for F. B., PID2019-104293GB-I00 for F. N and E. P.-I, and doctoral fellowship PRE2020-092646 for P. V.-D.), the European Research and Development Fund (ERDF), the Consejo Superior de Investigaciones Científicas (grant 202080I005 for A. R.), the Junta de Andalucía/University of Malaga (grant UMA18-FEDERJA-007 for F. N. and E. P.-I.), and the Junta de Andalucía/University of Huelva (grant UHU-202070 for U. P.). Dr Z. Domínguez (University of Huelva) is acknowledged for technical assistance in the early phase of this work.

Zeolite confined silver clusters (AgCLs) have attracted extensive attention due to their remarkable luminescent properties, but the elucidation of the underlying photophysical processes and especially the excited-state dynamics remains a challenge. Herein, we investigate the bright photoluminescence of AgCLs confined in Linde Type A zeolites (LTA) by systematically varying the temperature (298-77 K) and co-cation composition (Li/Na) and examining their respective influence on the steady-state and time-resolved photoluminescence. The observed polychromatic emission of the tetrahedral Ag4(H2O) n 2+ clusters ranges from orange to violet and three distinct emitting species are identified, corresponding to three long-lived triplet states populated consecutively and separated by a small energy barrier. These long-lived species are at the origin of the polychromatic luminescence with high photoluminescence quantum yields. Furthermore, the Li-content dependence of decay times points to the importance of guest-host-guest interactions in tuning the luminescent properties with a 43% decrease of the dominating decay time by increasing Li content. Based on our findings, a simplified model for the photophysical kinetics is proposed that identifies the excited-state processes. The results outlined here pave the way for a rational design of confined metal clusters in various frames and inspire the specified applications of Ag-zeolites. ispartof: CHEMICAL SCIENCE vol:13 issue:39 pages:11560-11569 ispartof: location:England status: published

Funder: Helmholtz Young Investigator Group Frontrunner, Over the past few years, lead‐halide perovskites (LHPs), both in the form of bulk thin films and colloidal nanocrystals (NCs), have revolutionized the field of optoelectronics, emerging at the forefront of next‐generation optoelectronics. The power conversion efficiency (PCE) of halide perovskite solar cells has increased from 3.8% to over 25.7% over a short period of time and is very close to the theoretical limit (33.7%). At the same time, the external quantum efficiency (EQE) of perovskite LEDs has surpassed 23% and 20% for green and red emitters, respectively. Despite great progress in device efficiencies, the photoactive phase instability of perovskites is one of the major concerns for the long‐term stability of the devices and is limiting their transition to commercialization. In this regard, researchers have found that the phase stability of LHPs and the reproducibility of the device performance can be improved by A‐site cation alloying with two or more species, these are named mixed cation (double, triple, or quadruple) perovskites. This review provides a state‐of‐the‐art overview of different types of mixed A‐site cation bulk perovskite thin films and colloidal NCs reported in the literature, along with a discussion of their synthesis, properties, and progress in solar cells and LEDs.

In this study, cinnamic acid derivatives were synthesized from the reaction of benzaldehyde derivatives with malonic acid in the presence of pyridine and piperidine. These compounds were then respectively reacted with glycine and L-alanine methyl ester hydrochloride based on triazine methodology to obtain novel cinnamoyl-amino acid ester derivatives. The structure of these compounds were established via H-1, C-13 APT, FT-IR, MS and elemental analysis. The synthesized novel compounds were studied in terms of structure-activity relationship based on dielectric, thermal stability, and theoretical analysis. Dielectric analysis was carried out in terms of amino acid type and aromatic substituted group (electron-withdrawing or releasing group factor). Amino acid side chain differences make alanine conjugates have higher epsilon \" values compared to glycine conjugates. Thermal stability analysis was performed for the compounds (10 and 16) with the highest dielectric constants. Thermal decomposition activation energies were calculated as 95 kJ mol(-1) and 100 kJ mol(-1) for 10 and 16, respectively. HOMO-LUMO energy levels and other related properties of the target compounds were analyzed and a correlation was observed between HOMO-LUMO energy band gap and dielectric constant.

Implementing nonlinear optical components in nanoscale photonic devices is challenged by phase-matching conditions requiring thicknesses in the order of hundreds of wavelengths, and is disadvantaged by the short optical interaction depth of nanometre-scale materials and weak photon–photon interactions. Here we report that ferroelectric NbOI2 nanosheets exhibit giant second-harmonic generation with conversion efficiencies that are orders of magnitude higher than commonly reported nonlinear crystals. The nonlinear response scales with layer thickness and is strain- and electrical-tunable; a record >0.2% absolute SHG conversion efficiency and an effective nonlinear susceptibility χ(2)eff in the order of 10−9 m V−1 are demonstrated at an average pump intensity of 8 kW cm–2. Due to the interplay between anisotropic polarization and excitonic resonance in NbOI2, the spatial profile of the polarized SHG response can be tuned by the excitation wavelength. Our results represent a new paradigm for ultrathin, efficient nonlinear optical components.

Combining liquid crystals (LCs) with well-designed anchoring patterns at the substrates offers tremendous potential for the development of functional electro-optic devices or stimuli-responsive actuators. Photo-alignment techniques nowadays allow an almost arbitrary control over the surface anchoring and this flexibility is used to design highly efficient flat optical LC components with different functionalities. Part of this research, dealing with nematic and chiral nematic LC between substrates with patterned azimuthal anchoring, is reviewed here. The focus is on understanding the self-assembly of complex structures, steered by an interplay between surface anchoring and LC elasticity. Additional insight into the LC bulk behaviour is obtained by comparing experimental results with numerical simulations of the director configuration. Periodic anchoring patterns with azimuthal rotation at the top and bottom substrate are studied, as well as ring-shaped alignment patterns with a 180 degrees or 360 degrees azimuthal rotation in a confined region in space. Different combinations of anchoring patterns at the top and bottom substrates are investigated and in addition to nematic liquid crystal (NLC), also short and long-pitch chiral nematic liquid crystal (CLC) is considered.

“Glow-in-the-dark” materials are known to practically everyone who has ever traveled by airplane or cruise ship, since they are commonly used for self-lit emergency exit signs. The green afterglow, persistent luminescence (PeL), is obtained from divalent europium doped to a synthetic strontium aluminate, but there are also some natural minerals capable of afterglow. One such mineral is hackmanite, the afterglow of which has never been thoroughly investigated, even if its synthetic versions can compete with some of the best commercially available synthetic PeL materials. Here we combine experimental and computational data to show that the white PeL of natural hackmanite is generated and controlled by a very delicate interplay between the natural impurities present. The results obtained shed light on the PeL phenomenon itself thus giving insight into improving the performance of synthetic materials. peerReviewed

Spectral albedo and light transmittance through snow, ice, and water were measured in Lake Wuliangsuhai (40 degrees 36 '-41 degrees 30 ' N, 108 degrees 43 '-108 degrees 70 ' E), Inner Mongolia, China, during winter 2016. Data on the weather, structure of lake ice, and geochemistry of water were also collected during the 60-day field program. The study lake is shallow (mean depth 1.0-1.5 m) with a large wetland area. Compared with polar lakes, solar elevation is higher, snow accumulation is much lower, and the ice has more sediment. The ice was all congelation ice with a mean thickness of 36.6 cm, corresponding to a mean air temperature of -9.6 degrees C. The mean daily broadband albedo and photosynthetically active radiation (PAR) band transmittance were 0.54 and 0.08 (bare ice), 0.74 and 0.04 (new snow), and 0.30 and 0.12 (melting period), respectively. The level of light allowed photosynthesis to occur to the bottom of the lake. The ice acted as a grey filter for the sunlight with a mean attenuation coefficient of 2.1 m(-1). These results expand our knowledge of the evolution of light transfer through ice and snow cover and its role in the ecology of lakes in temperate and arid areas.

Size-dependent optical properties of germanium (Ge) nanocrystals (NCs) make them a desirable material for optoelectronic applications. So far, the synthesis of ligand-free and tunable-size Ge NCs by inert gas condensation has been scarcely reported. In this work, we introduce a gas-phase approach to synthesize quantum-confined Ge NCs by inert gas condensation, where the size of the Ge NCs can be readily tuned by controlling the thickness of a Cu plate supporting the Ge target. As explained by simulations using the finite element method, the magnetic field configuration above the target can be manipulated by varying the thickness of the Cu backing plate. In-depth analysis based on transmission electron microscopy (TEM) results reveals the morphology and crystalline structure of Ge NCs. X-ray photoelectron spectroscopy has proven the formation of a substoichiometric Ge oxide shell for the as-deposited Ge NCs. In addition, Raman spectroscopy indicated peak shifts according to the phonon confinement model that yielded nanoparticle sizes in a good agreement with the TEM results. Furthermore, the quantum confinement effect for Ge NCs was demonstrated by analysis of the absorption (UV-vis-NIR) spectrum, which indicated that the band gap of the Ge NCs was increased from ∼0.8 to 1.1 eV with decreasing size of Ge NCs. Comparison with theory shows that the quantum confinement effect on the band gap energy for different-sized Ge NCs follows the tight-binding model rather well.

Control over the bottom up synthesis of metal nanoparticles (NP) depends on many experimental factors, including the choice of stabilising and reducing agents. By selectively manipulating these species, it is possible to control NP characteristics through solution-phase synthesis strategies. It is not known, however, whether NPs produced from mechanochemical syntheses are governed by the same rules. Using the Au NPs mechanosynthesis as a model system, we investigate how a series of common reducing agents affect both the reduction kinetics and size of Au NPs. It is shown that the relative effects of reducing agents on mechanochemical NP synthesis differ significantly from their role in analogous solution-phase reactions. Hence, strategies developed for control over NP growth in solution are not directly transferrable to environmentally benign mechanochemical approaches. This work demonstrates a clear need for dedicated, systematic studies on NP mechanosynthesis.

Antimony sulfide (Sb2S3) and selenide (Sb2Se3) have emerged as promising earth-abundant alternatives among thin-film photovoltaic compounds. A distinguishing feature of these materials is their anisotropic crystal structures, which are composed of quasi-one-dimensional (1D) [Sb4X6]n ribbons. The interaction between ribbons has been reported to be van der Waals (vdW) in nature and Sb2X3 are thus commonly classified in the literature as 1D semiconductors. However, based on first-principles calculations, here we show that inter-ribbon interactions are present in Sb2X3 beyond the vdW regime. The origin of the anisotropic structures is related to the stereochemical activity of the Sb 5s lone pair according to electronic structure analysis. The impacts of structural anisotropy on the electronic, dielectric and optical properties relevant to solar cells are further examined, including the presence of higher dimensional Fermi surfaces for charge carrier transport. Our study provides guidelines for optimising the performance of Sb2X3-based photovoltaics via device structuring based on the underlying crystal anisotropy.

The material and exact shape of a nanostructure determine its optical response, which is especially strong for plasmonic metals. Unfortunately, only a few plasmonic metals are available, which limits the spectral range where these strong optical effects can be utilized. Alloying different plasmonic metals can overcome this limitation, at the expense of using a high-temperature alloying process, which adversely destroys the nanostructure shape. Here, a low-temperature alloying process is developed where the sample is heated at only 300 degrees C for 8 h followed by 30 min at 450 degrees C and Au-Ag nanostructures with a broad diversity of shapes, aspect ratios, and stoichiometries are fabricated. Energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy analyses confirm the homogeneous alloying through the entire sample. Varying the alloy stoichiometry tunes the optical response and controls spectral features, such as Fano resonances. Binary metasurfaces that combine nanostructures with different stoichiometries are fabricated using multiple-step electron-beam lithography, and their optical function as a hologram or a Fresnel zone plate is demonstrated at the visible wavelength of lambda = 532 nm. This low-temperature annealing technique provides a versatile and cost-effective way of fabricating complex Au-Ag nanostructures with arbitrary stoichiometry.

Angle-resolved photoelectron spectroscopy is an extremely powerful probe of materials to access the occupied electronic structure with energy and momentum resolution. However, it remains blind to those dynamic states above the Fermi level that determine technologically relevant transport properties. In this work we extend band structure mapping into the unoccupied states and across the entire Brillouin zone by using a state-of-the-art high repetition rate, extreme ultraviolet femtosecond light source to probe optically excited samples. The wide-ranging applicability and power of this approach are demonstrated by measurements on the two-dimensional semiconductor WSe2, where the energy-momentum dispersion of valence and conduction bands are observed in a single experiment. This provides a direct momentum-resolved view, not only on the complete out-of-equilibrium band gap but also on its renormalization induced by electronic screening. Our work establishes a benchmark for measuring the band structure of materials, with direct access to the energy-momentum dispersion of the excited-state spectral function., This work was funded by the Max-Planck-Gesellschaft, by the German Research Foundation (DFG), with in the Emmy Noether Program (GrantNo.RE3977/1), and Grants No.FOR1700(ProjectE5), No.SPP2244(ProjectNo. 443366970), and from the European Research Council, Grant No. ERC-2015-CoG-682843. M.P. acknowledges financial support from the Swiss National Science Foundation (SNSF) through Grant No. CRSK-2_196756. C.W.N. and C.M. acknowledge financial support by Swiss National Science Foundation (SNSF) Grant No. P00P2_170597. A.R. and H.H. acknowledge financial support from the European Research Council (Grant No. ERC-2015-AdG-694097) and the Cluster of Excellence “CUI: Advanced Imaging of Matter” of the Deutsche Forschungsgemeinschaft (Grant EXC 2056, Project No. 390715994).

Publisher Copyright: © Since the 1960s, many indoor and outdoor smog chambers have been developed worldwide. However, most of them are made of Teflon films, which have relatively high background contaminations due to the wall effect. We developed the world's first medium-size quartz chamber (10 m(3)), which is jointed with 32 pieces of 5 mm thick polished quartz glasses and a stainless-steel frame. Characterizations show that this chamber exhibits excellent performance in terms of relative humidity (RH) (2-80%) and temperature (15-30 +/- 1 degrees C) control, mixing efficiency of the reactants (6-8 min), light transmittance (>90% above 290 nm), and wall loss of pollutants. The wall loss rates of the gas-phase pollutants are on the order of 10(-4) min(-1) at 298 K under dry conditions. It is 0.08 h(-1) for 100-500 nm particles, significantly lower than those of Teflon chambers. The photolysis rate of NO2 (J(NO2)) is automatically adjustable to simulate the diurnal variation of solar irradiation from 0 to 0.40 min(-1). The inner surface of the chamber can be repeatedly washed with deionized water, resulting in low background contaminations. Both experiments (toluene-NOx and alpha-pinene-ozone systems) and box model demonstrate that this new quartz chamber can provide high-quality data for investigating SOA and O-3 formation in the atmosphere.

We present temperature-dependent (from room temperature to 80 degrees C) absorption spectra of Au/SiO2 core-shell nanoparticles (NPs) (core diameter: similar to 25 nm) in water in the range from 1.5 to 4.5 eV, which spans the localized surface plasmon resonance (LSPR) and the interband transitions. A decrease in absorption with temperature over the entire spectral range is observed, which is more prominent at the LSPR. These changes are well reproduced by theoretical calculations of the absorption spectra, based on the experimentally measured temperature-dependent real (epsilon(1)) and imaginary (epsilon(2)) parts of the dielectric constant of Au NPs and of the surrounding medium. In addition, we model the photoinduced response of the NPs over the entire spectral range. The experimental and theoretical results of the thermal heating and the simulations of the photoinduced heating are compared with the ultrafast photoinduced transient absorption (TA) spectra upon excitation of the LSPR. These show that while the latter is a reliable monitor of heating of the NP and its environment, the interband region mildly responds to heating but predominantly to the population evolution of charge carriers.

The effect of sintering temperature on the structural and spectroscopic (CL, PL, decay) properties was investigated using 2.5 mol% Sm3+ doped BaTa2O6 samples, which were fabricated by solid state reaction at temperatures of 1150, 1250, 1350, 1425 degrees C. In XRD analysis of Sm3+ doped BaTa2O6 samples, orthorhombic phase appeared at temperatures of 1150 and 1250 degrees C, later the impurity phases disappeared at 1350 degrees C where orthorhombic polymorph completely transformed into a tetragonal tungsten bronze (TTB) structure. SEM analysis revealed the increase of grain size of Sm3+ doped BaTa2O6 with increasing sintering temperature. PL emissions were observed due to (4)G(5/2) -> H-6(J) (J = 5/2, 7/2, 9/2, 11/2, 13/2) transitions of Sm3+ where the emissions increased with the effect of increasing temperature and reached maximum at 1425 degrees C. The increase of PL emissions can be attributed to the developing of the tetragonal phase crystallinity which led to the decrease of non-radiative centers. CL emission of the undoped sample sintered at 1425 degrees C was monitored by the broad blue peak at about 495 nm which is related with the intrinsic emission of BaTa2O6. CL emissions of the doped samples sintered between 1150 and 1425 degrees C showed the host emissions and characteristic emissions of Sm3+ corresponding to (4)G(5/2) -> H-6(5/2), (4)G(5/2) -> H-6(7/2), (4)G(5/2) -> H-6(9/2), (4)G(5/2) -> H-6(11/2) transitions. The Sm3+ concentration led to a decrease in the decay time and an increase in the energy transfer, while the sintering temperature effect showed a different process where the decay time and energy transfer slightly increased.

Metal complexes with ligands that coordinate via the nitrogen atom of azo (N=N) or imino (C=N) groups are of interest due to their pi-acceptor properties and redox-active nature, which leads to interesting (opto)electronic properties and reactivity. Here, we describe the synthesis and characterization of rhenium(I) tricarbonyl complexes with neutral N,N-bidentate formazans, which possess both N=N and C=N fragments within the ligand backbone (Ar-1-NH-N=C(R-3)-N=N-Ar-5). The compounds were synthesized by reacting equimolar amounts of [ReBr(CO)(5)] and the corresponding neutral formazan. X-ray crystallographic and spectroscopic (IR, NMR) characterization confirmed the generation of formazan-type species with the structure fac-[ReBr(CO)(3)(kappa(2)-N-2,N-4(Ar-1-(NH)-H-1-N-2= C(R-3)-N-3=N-4-Ar-5))]. The formazan ligand coordinates the metal center in the 'open' form, generating a five-membered chelate ring with a pendant NH arm. The electronic absorption and emission properties of these complexes are governed by the presence of low-lying pi*-orbitals on the ligand as shown by DFT calculations. The high orbital mixing between the metal and ligand results in photophysical properties that contrast to those observed in fac-[ReBr(CO)(3)(L,L)] species with alpha-diimine ligands.

Tip-enhanced photoluminescence (TEPL) experiments have recently reached the ability to investigate single molecules exploiting resolution at the submolecular level. Localized surface plasmon resonances of metallic nanostructures have the capability of enhancing an impinging electromagnetic radiation in the proximity of their surface, with evident consequences both on absorption and emission of molecules placed in the same region. We propose a theoretical analysis of these phenomena in order to interpret TEPL experiments on single molecules, including a quantum mechanical description of the target molecule equilibrated with the presence of two nanostructures representative of the nanocavity usually employed in STMs. The approach has been applied to the zinc phthalocyanine molecule, previously considered in recent TEPL experiments [Yang et al., Nat. Photonics 14, 693-699 (2020)]. This work has the aim of providing a comprehensive theoretical understanding of the experimental results, particularly focusing on the investigation of the tip features that majorly influence the excitation and fluorescence processes of the molecule, such as the geometry, the dielectric function, and the tip-molecule distance. Published under an exclusive license by AIP Publishing.

The mechanical, electronic and thermoelectric calculations of the KMgP half-Heusler compound and its [111] thin films have been done in the framework of density functional theory. The KMgP bulk has mechanical stability in the static and dynamic viewpoints, and it has the p-type semiconductor behavior with the 1.1-eV energy gap. The KMgP in the bulk phase is a relatively good thermoelectric compound with a figure of merit of 0.7 above the room temperature. The KMgP [111] film has three K-, Mg- and P-terminations. The last one has 100% spin polarization at the Fermi level, which is referred to as the fully half-metallic behavior. The thermoelectric efficiency of the P-termination case in the up spin is more than that of the bulk structure. The figure of merit for this termination is about one at room temperature, which made it the right candidate for thermoelectric applications.

Methylammonium (MA) lead halide perovskites have been widely studied as active materials for advanced optoelectronics. As crystalline semiconductor materials, their properties are strongly affected by their crystal structure. Depending on their applications, the size of MA lead halide perovskite crystals varies by several orders of magnitude. The particle size can lead to different structural phase transitions and optoelectronic properties. Herein, we investigate the size effect for phase transition of MA lead bromide (MAPbBr3) by comparing the temperature-dependent neutron powder diffraction patterns of microcrystals and nanocrystals. The orthorhombic-to-tetragonal phase transition occurs in MAPbBr3microcrystals within the temperature range from 100 to 310 K. However, the phase transition is absent in nanocrystals in this temperature range. In this work, we offer a persuasive and direct evidence of the relationship between the particle size and the phase transition in perovskite crystals.

Colloidal CdSe nanoplatelets (NPLs) are unique systems to study two-dimensional excitons and excitonic complexes. However, while absorption and emission of photons through exciton formation and recombination have been extensively quantified, few studies have addressed the exciton-biexciton transition. Here, we use cross-polarized pump- probe spectroscopy to measure the absorption coefficient spectrum of this transition and determine the biexciton oscillator strength (fBX). We show that fBX is independent of the NPL area and that the concomitant biexciton area (SBX) agrees with predictions of a short-range interaction model. Moreover, we show that fBX is comparable to the oscillator strength of forming localized excitons at room temperature while being unaffected itself by center-of-mass localization. These results confirm the relevance of biexcitons for light-matter interaction in NPLs. Moreover, the quantification of the exciton-biexciton transition introduced here will enable researchers to rank 2D materials by the strength of this transition and to compare experimental results with theoretical predictions.

Context: Properly modelling scattering by interstellar dust grains requires a good characterisation of the scattering phase function. The Henyey-Greenstein phase function has become the standard for describing anisotropic scattering by dust grains, but it is a poor representation of the real scattering phase function outside the optical range. Aims: We investigate alternatives for the Henyey-Greenstein phase function that would allow the scattering properties of dust grains to be described. Our goal is to find a balance between realism and complexity: the scattering phase function should be flexible enough to provide an accurate fit to the scattering properties of dust grains over a wide wavelength range, and it should be simple enough to be easy to handle, especially in the context of radiative transfer calculations. Methods: We fit various analytical phase functions to the scattering phase function corresponding to the BARE-GR-S model, one of the most popular and commonly adopted models for interstellar dust. We weigh the accuracy of the fit against the number of free parameters in the analytical phase functions. Results: We confirm that the Henyey-Greenstein phase functions poorly describe scattering by dust grains, particularly at ultraviolet (UV) wavelengths, with relative differences of up to 50%. The Draine phase function alleviates this problem at near-infrared (NIR) wavelengths, but not in the UV. The two-term Reynolds-McCormick phase function, recently advocated in the context of light scattering in nanoscale materials and aquatic media, describes the BARE-GR-S data very well, but its five free parameters are degenerate. We propose a simpler phase function, the two-term ultraspherical-2 (TTU2) phase function, that also provides an excellent fit to the BARE-GR-S phase function over the entire UV-NIR wavelength range. (Abridged), Comment: 12 pages, 7 figures, accepted for publication in A&A

Undoped and Cr-doped zinc oxide (ZnO) thin films were deposited on the glass and p-Si substrates by the chemical spray pyrolysis technique. The films were characterized by x-ray diffractometry (XRD) and UV-visible spectrometry, and electrical characterization was achieved by using the films as an interfacial layer between the Au and p-Si. The XRD results confirmed the undoped and Cr-doped ZnO thin film crystalline structures. UV-visible spectra provided the transmittance plots and band gap energy values. I-V measurements were performed on the fabricated Au/ZnO/p-Si and Au/ZnO:Cr/p-Si devices to determine the effect of the ZnO interfacial layer on their performance. Various junction parameters, such as the ideality factor, barrier height, and series resistance, were calculated from the I-V measurements by various techniques, and have been discussed in detail. A 100-mW/cm(2) power intensity light was exposed on the Au/ZnO:Cr/p-Si device to see the photodiode behavior as well as to determine light sensitivity parameters such as photosensitivity and detectivity. The results highlight that the Au/ZnO:Cr/p-Si device can be thought of for optoelectronic applications., Sirnak University Research fund [2021], The authors would like to thanks Dr. Hatice Kacus for her technical support in this research. This study was supported by Sirnak University Research fund with Project Number 2021.FNAP.06.02.01.

In the study, by using 5-amino-4-arylazo-3-methyl-1H-pyrazole derivatives and 2-hydroxy-5(phenyldiazenyl) benzaldehyde; eight novel heterocyclic disperse disazo-azomethine dyes were synthesized, their chemical structures were characterized via FT-IR and 1 H NMR studies. Synthesized compounds were also investigated computationally by performing various techniques. In the computational part of the study, geometry optimizations, frequency analyses, frontier molecular orbital (FMO) calculations, molecular electrostatic potential (MEP) map calculations, FT-IR and NMR spectral analyses were performed on the compounds. Additionally, to reveal their potentials against SARS-CoV-2 main protease (SARS-CoV-2 M-pro), acetylcholine esterase (AChE), heat shock protein (HSP90 alpha) and nicotinamide N-methyl transferase (NNMT), molecular docking calculations were also performed on the synthesized compounds. Molecular dynamics (MD) simulations were carried out on the top-scoring ligand-receptor complexes to evaluate the stability of the complexes and the interactions between ligands and receptors in more detail. Results showed that synthesized compounds can interact with all these four receptors effectively and can be promising structures for further studies. (C) 2021 Elsevier B.V. All rights reserved.

Determining the concentration of carbonaceous particles in ambient air is important for climate modelling, source attribution and air quality management. This study presents the difficulties associated with the interpretation of apparent long-term changes in the mass absorption cross section (MAC) of carbonaceous particles in London and south-east England based on equivalent black carbon (eBC) and elemental carbon (EC) measurements between 2014 and 2019. Although these two measurement techniques were used to determine the concentration of carbonaceous aerosols, the concentrations of eBC and EC changed at different rates at all sites, and exhibited different long-term trends. eBC measurements obtained using aethalometer instruments for traffic and urban background sites demonstrated consistent trends, showing decreases in concentrations of up to −12.5% y−1. The EC concentrations showed no change at the urban background location, a similar change to eBC at the traffic site and a significant upward trend of +10% y−1 was observed at the rural site. Despite these differences, the trends in the MAC values decreased at all sites in a similar way, with rates of change from −5.5% y−1 to −10.1% y−1. The different trends and magnitudes of change for the eBC and EC concentrations could lead to uncertainty in quantifying the efficacy of intervention measures and to different conclusions for policy making. This paper provides possible explanations of the observed decrease in MAC values over time.

Lead-free halides with perovskite-related structures, such as the vacancy-ordered perovskite Cs3Bi2Br9, are of interest for photovoltaic and optoelectronic applications. We find that addition of SnBr2 to the solution-phase synthesis of Cs3Bi2Br9 leads to substitution of up to 7% of the Bi(III) ions by equal quantities of Sn(II) and Sn(IV). The nature of the substitutional defects was studied by X-ray diffraction, 133Cs and 119Sn solid state NMR, X-ray photoelectron spectroscopy and density functional theory calculations. The resulting mixed-valence compounds show intense visible and near infrared absorption due to intervalence charge transfer, as well as electronic transitions to and from localised Sn-based states within the band gap. Sn(II) and Sn(IV) defects preferentially occupy neighbouring B-cation sites, forming a double-substitution complex. Unusually for a Sn(II) compound, the material shows minimal changes in optical and structural properties after 12 months storage in air. Our calculations suggest the stabilisation of Sn(II) within the double substitution complex contributes to this unusual stability. These results expand upon research on inorganic mixed-valent halides to a new, layered structure, and offer insights into the tuning, doping mechanisms, and structure–property relationships of lead-free vacancy-ordered perovskite structures.