Nanocrystallization and optical properties of CsPbBr3−xIx perovskites in chalcogenide glasses

The confinement of CsPbX₃ (X = Cl, Br, and I) perovskite nanocrystals (NCs) in a stabilized inorganic glass matrix is a new strategy for improving their long-term stability and promoting their applications in the optoelectronic field. Here, in situ nanocrystallization strategy is developed to precipitate CsPbBr_3?xI_x NCs with arbitrary I/Br ratio among an elaborately designed GeS₂–Sb₂S₃-based chalcogenide glass matrix. Spherical CsPbBr_3?xI_x NCs are homogeneously distributed in the glass matrix after thermal treatment. The photoluminescence (PL) spectra show that the emission peaks of CsPbBr_3?xI_x NCs can be tuned from 570 nm to 722 nm with the replacement of Br by I. The fs transient absorption (TA) spectra reveal that there exists some structural defects in the NCs, leading to short PL decay life. This work would shed light on confining CsPbX₃ NCs into glassy matrices, facilitating their future applications in photoelectronic fields.     

Crystal-field engineering of ultrabroadband mid-infrared emission in Co2+-doped nano-chalcogenide glass composites

Tunable and ultrabroadband mid-infrared (MIR) emissions in the range of 2.5–4.5 μm are firstly reported from Co²⁺-doped nano-chalcogenide (ChG) glass composites. The composites embedded with a variety of binary (ZnS, CdS, ZnSe) and ternary (ZnCdS, ZnSSe) ChG nanocrystals (NCs) can be readily obtained by a simple one-step thermal annealing method. They are highly transparent in the near- and mid-infrared wavelength region. Low-cost and commercially available Er³⁺-doped fiber lasers can be used as the excitation source. By crystal-field engineering of the embedded NCs through cation- or anion-substitution, the emission properties of Co²⁺ including its emission peak wavelength and bandwidth can be tailored in a broad spectral range. The phenomena can be accounted for by crystal-field theory. Such nano-ChG composites, perfectly filling the 3–4 μm spectral gap between the oscillations of Cr²⁺ and Fe²⁺ doped IIVI ChG crystals, may find important MIR photonic applications (e.g., gas sensing), or can be used directly as an efficient pump source for Fe²⁺: IIVI crystals which are suffering from lack of pump sources.     

Nature of heterophase inclusions in high-purity optical fiber materials as studied with 3D laser ultramicroscopy

3D laser ultramicroscopy (3D LUM) is intended specially for determining the concentration and size distribution of submicron inclusions in the bulk samples of high-purity materials for visible and IR fiber optics. In this work the 3D LUM technique is shown to be able to identify the nature of individual inclusions detected. The measurement of the light scattered by an inclusion at a varied probe beam wavelength and polarization and at a varied scattered light collection angle makes it possible to determine the inclusion refractive index. The 3D LUM possibilities are illustrated by the example of studying the inclusion nature in the As₂S₃ glass samples prepared by the direct synthesis from elements in a quartz container at elevated temperatures.     

Gap modulation in MCu[Q1−xQ′x]F (M=Ba, Sr; Q, Q′=S, Se, Te) and related materials

BaCuQF (Q=S, Se, Te) materials exhibit band gaps that allow transmission of much of the visible spectrum. BaCuSF is transparent in thin-film form with a band gap of 3.1 eV. Band gap estimates for powders of the solid solution series BaCuS_1−xSe_xF were obtained from wavelength-dependent diffuse-reflectance measurements using an integrating sphere. The band gap can be tuned by the substitution of Se for S to 2.9 eV for BaCuSeF. The decrease scales almost linearly with the increase in the volume of the tetragonal unit cell, which is determined primarily by the expansion of the a lattice parameter; the overall volume increase is 7.0% from x=0 to 1. Further reduction of the band gap is observed in BaCuSe_1−xTe_xF solid solutions, where a unit cell volume increase of 5.5% produces a band gap of 2.7 eV in BaCuSe_0.5Te_0.5F. Powders and films of BaCuSF exhibit strong red luminescence under ultraviolet excitation, which is suppressed by K doping. Additional tuning of band gap and electrical properties (the materials are p-type conductors) can be achieved by replacing Ba with Sr.     

A novel methanol-tolerant Ir-Se chalcogenide electrocatalyst for oyxgen reduction

A novel methanol-tolerant oxygen-reduction catalyst, Iridium-selenium (Ir-Se) chalcogenide, was synthesized by chemical precipitation in an organic solvent. Auger electron spectroscopy (AES) analysis confirmed that the synthesized Ir-Se chalcogenide had a chemical formula of Ir₄Se. This chalcogenide showed strong catalytic activity towards the oxygen reduction reaction (ORR) and a high methanol tolerance. It was found that most of the oxygen could be directly reduced to water through a four-electron pathway with less than 10% hydrogen peroxide (H₂O₂) being produced during the ORR. The improvement in catalytic activity of the Ir-Se chalcogenide in comparison with that of pure Ir might be attributed to the effect of a bimetallic interaction.     

高纯硫系玻璃和光纤的制备技术

高纯度硫系玻璃如As-A,As-Se和Ge-As-Se系统都是很有希望作为中红外低损耗的光纤材料，本文主要回顾了制备高纯度的硫系玻璃和光纤材料的一些问题，并对这些问题进行了讨论，最后举例说明了这种光纤的一些实际应用。     

Stress formation in evaporated amorphous Ge-Se and Ge-Se-Ga(Tl, B) thin films

Thin amorphous chalcogenide films from the GeSe_x (x = 1-5), (GeSe₄)_100−yGa_y and (GeSe₅)_100−y Ga(Tl, B)_y (y = 5, 10, 15, 20) systems have been prepared by thermal evaporation and characterized with respect to their internal stress using a cantilever technique. The correlations between the stress, the composition and the structure of the films were investigated. The obtained results were related with some structural and mechanical parameters of the glasses like mean coordination number, number of constrains per atom, density, compactness, microhardness and Young's modulus. For all investigated chalcogenide films a stress relaxation with the time was observed as a result of spontaneous structural rearrangements.     

High aspect ratio CdS nanowires synthesized in microemulsion system

CdS nanowires with typical length more than 8 μm and width of 30 nm on average have been successfully synthesized through Cd(NO₃)₂ reacting with CS₂ and ethylenediamine in microemulsion system of sodium dodecylbenzene sulfonate (SBDS). The microstructures of the as-synthesized CdS nanowires were characterized using XRD, transmission electron microscopy (TEM) and HRTEM. The possible formation mechanism was discussed. The morphologies of CdS sample strongly depend on the concentration of surfactant in solutions.     

Kilogram-scale production of highly active chalcogenide photocatalyst for solar hydrogen generation

Solar photocatalytic hydrogen production from water has been regarded as an ideal way addressing world energy and environmental crises. The technology has long relied on the development of an efficient photocatalyst. In addition to its photocatalytic performance, the large-scale production of certain photocatalyst from the viewpoint of particle application remains a challenge yet has received insufficient focus. Herein, we report an efficient and practical batch preparation system based upon hydrothermal method to the scalable production of chalcogenide nanoparticle photocatalyst. Taking the synthesis of Cd_0.5Zn_0.5S (CZS) twinned photocatalyst as an example, the outcome of CZS photocatalyst could reach ～0.8 kg in this batched synthesis, which is about 390 times of the lab-scale production in mass amount. It was found that the twinned structure and visible-light absorption property were well maintained. Although further measurements toward the photocatalytic activity indicate slight decrement on solar H₂ generation compared to the lab-scale synthesized CZS photocatalyst, a high quantum efficiency of about 40.5% at 425 nm remained. The photocatalytic reaction could also stably proceed for 200 h without notable decay of H₂-evolution rate. This work thus provides a powerful means for facile scaling up the chalcogenide nanoparticle photocatalyst at the kilogram level with both high quality and good reproducibility.     

Dependence of activation energy and pre-exponential factor on electric field in amorphous thin films of Se70Te30−xZnx

The present paper reports the effect of electric field on the electrical parameters (activation energy and pre-exponential factor) in amorphous thin films of Se₇₀Te_30−xZn_x (x = 0, 6, 8). It is observed that, in a particular composition, at low electric field up to 10³ V/cm neither activation energy nor pre-exponential factor depend on electric field as expected in case of ohmic region. However, at higher electric fields where non ohmic region is observed, activation energy and pre-exponential factor both vary with electric field. Similar behavior is observed in all the compositions used in this study. A correlation between activation energy and pre-exponential factor is also observed in these alloys, which is known as Meyer-Neldel rule (MN rule). Further MN rule is also observed in the present case which is explained by the model suggested by Yelon and Movaghar responsible for MN rule in chalcogenide glasses.