Nanocrystallization of α-CsPbI3 perovskite nanocrystals in GeS2-Sb2S3 based chalcogenide glass

Black α-phase CsPbI₃ of cubic perovskite structure receives intense attentions recently for its unique combination of high photoluminescence quantum yield, suitable bandgap, and long lifetime. However, α-CsPbI₃ presents poor chemical and thermodynamic stability under atmosphere condition. Here, we report a strategy for confining the α-CsPbI₃ perovskite into chalcogenide glassy matrix through controllable glass nanocrystallization. In the chalcogenide glass with an elaborately designed composition of 80GeS₂·16Sb₂S₃·4CsPbI₃, spherical α-CsPbI₃ nanocrystals were formed and observed clearly, which present good red photoluminescence centered at 701 nm. With the increasing heat-treated temperature, the size of α-CsPbI₃ nanospheres increases, while the crystal quantity decreases. It is found that the nanocrystallization of α-CsPbI₃ nanospheres in chalcogenide glass is controlled by Ostwald-ripening process.     

Modification of crystallization behavior,mechanical strength and optical property of Ge–S binary chalcogenide glass ceramics by trace CsCl incorporation

In present work, we discovered that nano-crystallization behavior of Ge–S binary chalcogenide glass can be remarkably improved by incorporating trace amount of CsCl as nucleating agent. After implementing an annealing process, the resultant Ge-S-CsCl chalcogenide glass ceramics (GSC ChGCs) possess fine distribution of crystallites belonging to GeS₂ and GeS mixture phase which could enhance mechanical strength and narrow bandgap energy of the original glass. By utilizing femtosecond Z-scan method, nonlinear optical properties of the GSC ChGCs were investigated in a spectral range from 750 to 900 nm. The results showed that the nonlinear absorption attribute of the GSC ChGCs can be enhanced by the crystallinity increase which led to the maximum two-photon absorption coefficient of 19.57 cm/GW at excitation wavelength of 750 nm, increased by 78% as compared to the original glass. This indicates the current GSC ChGCs a promising candidate for the optical limiting devices.     

Study on third-order optical nonlinear properties of transparent chalcogenide glass ceramics within Ge–S binary system

transparent chalcogenide glass ceramics (ChGCs) based on a binary germanium-sulfur (Ge–S, GS) chalcogenide system were synthesized by heat treatment method. Compared with the precursor glass, the GS ChGCs embedded with GeS₂ nanocrystals have the same infrared transparency, but smaller optical bandgap energy and higher mechanical strength. Z-scan measurements show that third-order optical nonlinearity in the GS ChGCs was remarkably enhanced, and this material would be suitable for applications in optical limiting.     

CsCl对GeS2-Sb2S3硫系玻璃光学及析晶特性的影响

通过熔融-淬冷法制备了(100-x)(0.9GeS2-0.1Sb2S3.)-xCsCl(x=5,10,15,20,以摩尔计)系列硫卤玻璃.测试了样品的折射率和吸收光谱.根据Tauc方程计算了间接允许光学带隙和直接允许光学带隙.通过差热分析对微晶玻璃析晶动力学进行了研究.利用析晶活化能(E)和频率因子(v),并结合动力学因素和热力学因素分析了玻璃的稳定性.结果表明:随着CsCl含鼍的增加,样品的线性折射率变小,短波截止波长蓝移,光学带隙逐渐增大,玻璃稳定性变差:85(0.9GeS2-0.1Sb2S3)15CsCl玻璃样品较适合制备透明的微晶玻璃,可用于研究硫系基质玻璃与微晶玻璃之间的三阶非线性效应.     

Preparation and properties of Ge–Ga–La–S–AgI chalcogenide glass

Chalcogenide glasses of 65GeS₂–(25–x)Ga₂S₃–10AgI–xLa₂S₃ (x=0, 1, 3, and 5 mol%) were fabricated through the traditional melt-quenching method. The effects of addition of La₂S₃ on physical, thermal and optical properties of the glass system were investigated. The results showed that the fabricated glasses possess considerably high glass transition temperature, exhibit improved mechanical property and excellent infrared transmission. A redshift at the visible absorbing cut-off edge is observed with increasing of La₂S₃ content. The direct and indirect optical band gap values are also calculated. Raman spectra analysis indicated that the band at 265 cm⁻¹ decreased in amplitude and a new peak at 230 cm⁻¹ was detected manifesting the formation of La-S bond in the network. In addition, the mid-infrared emission at 3.74 µm of the glasses doped with Tm³⁺ ions was achieved. The results indicated that the glasses are promising materials for mid-infrared applications such as imaging, remote sensing and lasers.     

Glass Formation and Luminescence of Glasses in the Ga2S3–GeS2–Nd2S3System

The results of spectral measurements and the differential thermal analysis (DTA) data for glasses in the Ga₂S₃–GeS₂–Nd₂S₃system are presented. The boundaries of the glass formation region in the Ga₂S₃–GeS₂–Nd₂S₃system are determined. It is shown that the luminescence efficiency increases with an increase in the gallium sulfide content due to the displacement of the concentration quenching boundary of Nd³⁺luminescence with a change in the glass matrix composition.     

Mandelshtam–Brillouin Scattering in As2S3 and GeS2 Chalcogenide Glasses

Mandelshtam–Brillouin and Rayleigh scattering in As₂S₃ and GeS₂ chalcogenide glasses is investigated. Longitudinal hypersonic velocities, adiabatic elastooptical constants (p ₁₂) _ad at frequencies 15 GHz, extinction coefficients, and scattering losses are determined.     

Effective ionic transport in AgI-based Ge(Ga)–Sb–S chalcogenide glasses

AgI-based Ge–Sb–S, Ga–Sb–S, and Ge–Ga–Sb–S chalcogenide glasses were designed and prepared by melt-quenching, thereafter their thermal properties and conductive performance were comparatively investigated on the basis of their composition-induced network structures. Glass transition in each sample was examined by DSC measurements. Results showed that the samples containing Ge had a higher thermal stability than the Ga–Sb–S–AgI sample, and the Ge–Sb–S–AgI sample obtained had the highest conductivity ion. Raman spectrum analysis was performed, and the results indicated that the [GeS_4-xI_x] structural units and [SbS_3−xI_x] pyramids in the matrix produced effective ion transport channel for dissolved conductive Ag⁺ ions. In the matrix containing Ga, the [Ga(Ge)S_4-xI_x] structure was consumed by part of [S₃Ga–GaS₃] ethane-like units, which had no contribution to the ion transition framework. The study provided the directions for composition and structure configuration control in effective conductive chalcogenide glasses.     

Design and magneto-optical characteristics of Ge–Sb–S–PbI2 chalcogenide glasses with a high Verdet constant

To develop high-performance magneto-optical chalcogenide glasses and clarify the mechanisms of the Verdet constant, a series of GeS₂–Sb₂S₃–PbI₂ chalcogenide glasses were designed and fabricated, and their Faraday effects were investigated at a wavelength of 980 nm. A new parameter, that is, average polarizability, was proposed, and the results show that the Verdet constant has a good linear relationship with average polarizability, meaning that the Verdet constant of a chalcogenide glass can be directly estimated by its chemical constituents. The Verdet constant is as large as 0.200 min G⁻¹ cm⁻¹ at 980 nm for 22.5GeS₂–67.5Sb₂S₃–10PbI₂ composition glass, which is the largest value reported thus far for sulfide glasses; this glass also possesses good thermal and optical properties and therefore might be an attractive candidate for mid-infrared magneto-optical device applications.     

Effect of MgO addition on the properties of PbO –TiO2–B2O3 glass and glass–ceramics

Glass samples with composition of (50?X) PbO–X MgO–25 TiO₂–25B₂O₃ (where X=0, 5, 10 and 15 mol%) were prepared using conventional quenching technique. The amorphous nature of glass samples were confirmed by XRD. The glass transition temperature, T_g and crystallization temperature T_c were determined from the DTA. It has been observed that the addition of MgO enhances the T_g. The rise in T_g with MgO content may be attributed to the greater field strength of Mg²⁺ cation (as compared to Pb²⁺) which leads to the formation of stronger bonds. These glass samples were converted to glass–ceramics by following a two-stage heat treatment schedule. It was observed that there was good correlation between the density and CTE results of the glass–ceramics. The XRD results revealed the formation of tetragonal lead titanate as a major crystalline phase in the glass–ceramics. The addition of MgO to the glass contributes to the formation of MgB₄O₇. The dielectric constant for all the glass–ceramic samples was observed to be higher than that of corresponding glass samples. Further, with addition of MgO the room temperature dielectric constant for glass–ceramic samples increases up to 10 mol% of MgO and then decreases for 15 mol%. It has been further observed that the variation of dielectric constant of glass–ceramic samples with MgO content is exactly opposite to the variation of crystallite size of PbTiO₃ embedded in the glass ceramic-samples.     

Crystallization of LiNbO3 and NaNbO3 in niobiosilicate glass–ceramics

Although glass–ceramics have been widely explored for their thermal stability and mechanical properties, they also offer unique symmetry-dependent properties such as piezoelectricity and pyroelectricity through controlled crystallization of a polar phase. This work examines crystallization of LiNbO₃ in a 35SiO₂–30Nb₂O₅–35Li₂O mol% composition and crystallization of LiNbO₃ and NaNbO₃ in a 35SiO₂–30Nb₂O₅–25Li₂O–10Na₂O mol% composition. Crystallization kinetics are examined using the Johnson–Mehl–Avrami–Kolmogorov (JMAK) theory where the Avrami exponent, n, is calculated to be 1.0–1.5. Microscopical analysis shows dendritic morphology, which when combined with the JMAK analysis, suggests diffusion-controlled one-dimensional growth. Adding Na₂O to the glass composition increases the inter-diffusivity of ions which causes LiNbO₃ to crystallize faster and lowers the activation energy of transformation from 1054 ± 217 kJ/mol in the ternary composition to 882 ± 212 kJ/mol. Time-temperature-transformation diagrams are presented which show that the temperature for maximum rate of transformation for LiNbO₃ is ∼650°C and for NaNbO₃ is ∼715°C.     

Some features of the surface modification of MgO–Al2O3–TiO2–SiO2 glass and glass ceramics by Ag diffusion

Diffusion of Ag species into the surface layers of the MgO–Al₂O₃–TiO₂–SiO₂ glass stimulates the crystallization processes therein during subsequent thermal treatment. It was found that the silver doping significantly increases the microhardness of glass and glass ceramics. The effect of the Ag diffusion and the subsequent high-temperature treatment (T > T_g) on the structure and luminescence properties of the MgO–Al₂O₃–TiO₂–SiO₂ glass was studied. The thermal evolution, structure and properties of the glass and glass ceramics were investigated by the DSC method, XRD analysis and luminescence spectroscopy. It was found that the Ag diffusion into the surface layers leads to the formation of numerous different luminescent molecular Ag_n clusters. The MgO–Al₂O₃–TiO₂–SiO₂ glass and glass ceramics subjected to the Ag diffusion can operate as effective down-converters of the radiation demonstrating the effective transformation of UV and blue light into the radiation of red and NIR spectral range.     

Bioactivity investigation of glass and glass ceramics in Li2O–SiO2–CaO–P2O5–CaF2 system

Abstract

Glass samples in Li₂O–SiO₂–CaO–P₂O₅–CaF₂ system with different contents of P₂O₅, CaO and CaF₂ in relative ratios responded to fluoroapatite (FA) composition (referred to P₂O₅ addition) have been prepared and heat treated at 550 and 750°C to obtain glass ceramics. Bioactivity of all samples has been proved in vitro by the presence of new layer of apatite-like phases formed after soaking in simulated body fluid (SBF). The development and the apatitic character of created layers have been demonstrated by Fourier transform infrared analysis. Scanning electron microscopy and electron probe microanalysis have demonstrated that the density and the thickness of new layer depend on P₂O₅ content, crystallisation temperature and immersion time. The bioactivity has been enhanced by P₂O₅ addition as well in the case of the base glasses as in the case of glass ceramics. The additional heat treatment appeared to inhibit the bioactive behaviour, though the longer SBF acting leads to the additional formation of apatite-like layer. The mechanical properties, expressed as Vicker hardness, have been found higher and increasing with P₂O₅ in glass ceramics treated at 750°C comparatively with base glass samples and the highest value of 7˙37 GPa has been achieved by 14 wt-%P₂O₅ addition. The same content of P₂O₅ in glass ceramics heat treated at 550°C resulted in a decrease in hardness to a minimum value from all samples. The increase and decrease in hardness responded to development and suppression of crystallisation respectively. The inhibition of crystallisation has been affected by the presence of 'amorphous' FA according to X-ray diffraction and differential thermal analysis results.     

GeS2-Sb2S3玻璃的三阶非线性研究

采用熔融-急冷法制备了(100-x)GeS2-xSb2S3(x=10%、15%和20%)系列硫系玻璃,测试了样品的折射率、从可见到近红外的透过特性.采用Z-扫描方法测试了样品的三阶非线性特性,分析了Sb2S3的含量对玻璃的线性折射率,透过率和三阶非线性性能的影响.结果表明样品的线性折射率、非线性折射率n2、非线性吸收系数β以及三阶非线性光学极化率χ(3)随着Sb2S3的含量增加而增大,Sb2S3物质的量含量为20%的样品在800 nm处的三阶非线性折射率n2和非线性吸收系数β分别为:n2=3.27×10-10 esu和β= 31.5 cm/Gw.     

Crystallisation and characterisation of dielectric glass ceramics in Li2O–Al2O3–SiO2 system

Abstract

Glass ceramics in the Li₂O–Al₂O₃–SiO₂ system have been synthesised to produce bulk materials grown in a glass phase via quenching followed by controlled crystallisation. The crystallisation and microstructure of Li₂O–Al₂O₃–SiO₂ (LAS) glass–ceramic with nucleating agents (B₂O₃ and/or P₂O₅) are investigated by differential thermal analysis, X-ray diffraction and scanning electron microscopy and the effects of B₂O₃ and P₂O₅ on the crystallisation of LAS glass are also analysed. The introduction of both B₂O₃ and P₂O₅ promotes the crystallisation of LAS glass by decreasing the crystallisation temperature and adjusting the crystallisation kinetic parameters, allows a direct formation of β spodumene phase and as a result, increases the crystallinity of the LAS glass ceramic. Microstructural observations show that the randomly oriented, nanometre sized crystalline is found with residual glass concentrated at crystallite boundaries. Furthermore, it is interesting that codoping of B₂O₃ and P₂O₅ creates not much effect on the crystallisation temperature. The dielectric properties of the glass–ceramics formed through controlled crystallisation have a strong dependence on the phases that are developed during heat treatment. The dielectric constant is continuously increased and the dielectric loss is decreased with addition of additives where mobile alkali metal ions (e.g. Li⁺) are incorporated in a crystal phase and minimise the residual glass phase.     

Modification of glass network and crystallization of CaO–Al2O3–MgO–SiO2 based glass ceramics with addition of iron oxide

Modification of glass network and crystallization process of a CaO–Al₂O₃–MgO–SiO₂ (CAMS) based glass ceramic to form diopside through addition of iron oxide were investigated using differential thermal analysis (DTA), Raman spectrum, X-ray diffraction, SEM and EBSD techniques. The experimental results showed that addition of Fe₂O₃ led to remarkable reductions in both the glass transition temperature (Tg) and crystallization temperature (Tp) of the CAMS glass ceramic. At addition level below 5 wt%, the Tg and Tp temperatures were 651°C and 903°C, respectively, and the crystallization only occurred on the surface of the glass ceramic samples. Increasing the addition level to 10 wt% and 15 wt%, not only led to reduction in the Tg and Tp temperatures to 643-641°C and 892-876°C, respectively, but also promoted the formation of crystalline diopside throughout the CAMS samples. Based on the results of Raman spectrums, it was confirmed that Fe₂O₃ addition reduced the strength of glass connection as a result of chemical reactions between the isolated Si–O tetrahedron and Fe³⁺ ion, forming Fe³⁺O₄–SiO₄, which can be regarded as Q₂ unit. And this is the first experimental evidence that proving the approach of Fe³⁺ mending glass network. Microstructural examination also identified the formation of large numbers of spherical Fe-enriched regions within the CAMS glass matrix as a result of the amorphous phase separation due to the Fe₂O₃ addition. The interfaces between the Fe-enriched regions and the glass matrix acted as preferred nucleation sites for the diopside, facilitating the crystallization. Crystallographic analysis using EBSD technique determined the <001> as the most favorite growth direction for the diopside crystals in the CAMS based glass ceramic.     

Optimisation of sintered glass–ceramics from an industrial waste glass

Industrial plasma melting of municipal solid waste (MSW) incinerator fly ashes leads to a glass that may be easily crystallised to gehlenite glass–ceramics, by the sintering of fine glass powders. However, since the glass composition is not optimised for glass–ceramic manufacturing, the viscous flow is much hindered by a very significant surface crystallisation and dense glass–ceramics are feasible only by sintering above 1000 °C. This paper reports a new strategy for obtaining dense and strong glass–ceramics at 950 °C, with a holding time of only 30 min, consisting of the mixing of waste glass with a secondary recycled glass, such as soda-lime–silica glass or borosilicate glass. For an optimum balance between the two types of glass also the addition of kaolin clay, in order to favour the shaping, was found to be feasible. The approach had a positive effect, besides on the mechanical properties (e.g. bending strength exceeding 100 MPa), on the chemical stability.     

Intense 2.7 µm emission of Er3+/Pr3+ doped Ga5Ge20Sb10S65 chalcogenide glass

There are numerous vital usages for mid-infrared (MIR) lasers in satellite communication, biomedicine, military, remote sensing, and environmental monitoring. In this work, a progression of Er³⁺ ions doped, Er³⁺/Pr³⁺ ions co-doped Ga₅Ge₂₀Sb₁₀S₆₅ glasses were prepared, and their physical performances and structural characteristics were examined. To understand the non-phonon-assisted energy transfer mechanism, we recorded the up-conversion and infrared fluorescence emission spectra by pumping with a commercial 980 nm LD. Then the 2.7 µm strong fluorescence signal intensity can be obtained when the doped concentration of Pr³⁺ is proper. After the doping of Pr³⁺, fluorescence lifetime results revealed that the lifetimes of the Er³⁺:⁴I_13/2 level fell dramatically from 7.33 to 1.90 ms, which experienced a much more significant decrease in lifetimes than the Er³⁺:⁴I_11/2 level. The MIR fluorescence performances were assessed by the determined J–O parameters and relative emission cross sections. Additionally, the generally huge emission cross sections and the small pump energy show that it is possible to obtain population inversion with relatively small pump energy; thus the Er³⁺/Pr³⁺ glasses have great potential to be 2.7 µm laser materials.     

Electrical properties of Sb and Cr-doped PbZrO3–PbTiO3–PbMg1/3Nb2/3O3 ceramics

The pyroelectric, dielectric and DC resistive properties of Sb and Cr-doped ceramics with a base composition of Pb(Mg_1/3Nb_2/3)_0.025(Zr_0.825Ti_0.175)_0.975O₃ have been studied. Sb doping has been shown to produce a linear reduction in Curie temperature (T_C=−22z+294 °C) with concentration (z) and to give an increase in pyroelectric coefficient from 250 to 310 μCm⁻² K⁻¹ for z increasing from 0 to 3 at.%. It also produces first a reduction and then an increase in both dielectric constant and loss, so that the 33 Hz pyroelectric figures of merit (FOM's) are as follows: F_V peaks at 3.8×10⁻² m² C⁻¹ and F_D peaks at 1.2×10⁻⁵ Pa^−1/2. The resistivity is increased substantially from 1.1×10¹¹ to ca 6×10¹¹ Ωm with 1 at.% Sb, thereafter changing little. The behaviour has been explained in terms of Sb acting as a donor ion, reducing oxygen vacancy concentrations up to 1 at.%, with conductivity dominated by hole hopping between traps (E_a=0.59±0.05 eV) that are not changed by the Sb doping. It is concluded that additions of higher levels of Sb do not produce electron-mediated hopping conduction. The Cr additions have no effect upon T_C, but reduce dielectric constant and loss, pyroelectric coefficient and resistivity at doping levels up to 3 at.%. The FOM F_V peaks at 3.6×10⁻² m² C⁻¹ and F_D at 1.9×10⁻⁵ Pa^−1/2. The behaviour of the electrical resistivity as a function of dopant level is shown to produce a linear ln(σ_o) vs z^−1/3 dependence (σ_o=DC conductivity), as would be expected for hole hopping conduction between Cr³⁺ sites, with an E_a=0.38±0.03 eV.     

Microstructure and properties of CaO–ZrO2–SiO2 glass–ceramics prepared by sintering

For the development of a new wear resistant and chemically stable glass-ceramic glaze, the CaO–ZrO₂–SiO₂ system was studied. Compositions consisting of CaO, ZrO₂, and SiO₂ were used for frit, which formed a glass-ceramic under a single stage heat treatment in electric furnace. In the sintered glass-ceramic, wollastonite (CaSiO₃) and calcium zirconium silicate (Ca₂ZrSi₄O₁₂) were crystalline phases composed of surface and internal crystals in the microstructure. The internal crystal formed with nuclei having a composition of Ca_1.2Si_4.3Zr_0.2O₈. The CaO–ZrO₂–SiO₂ system showed good properties in wear and chemical resistance because the Ca₂ZrSi₄O₁₂ crystals positively affected physical and mechanical properties.