Structured active fiber fabrication and characterization of a chemically high-purified Dy3+-doped chalcogenide glass

By conventional melt-quenching techniques, a series of Dy³⁺-doped (0.1 to 1.0 wt%) Ga₅Ge₂₀Sb₁₅S₆₀ bulk glasses were fabricated and their potential for developing mid-infrared fiber laser beyond 4 μm were evaluated, in which the optimal Dy³⁺ doping concentration was found to be 0.3 wt% and the largest laser quality factor value (σ_e × τ_mea = 2.62 × 10⁻²³ cm² s) among all of the Dy³⁺-doped chalcogenide glass was obtained. On this basis, through using the chemical purification methods with chlorine gas combined with the dynamic distillation process, the high-purity GGSS glasses with low O–H and S–H absorptions were successfully fabricated, which was confirmed by the optimized mid-infrared linear transmittance and improved fluorescent lifetimes of Dy³⁺: ⁶H_13/2, ⁶H_11/2 levels. Furthermore, for the first time to the best of our knowledge, the Dy³⁺-doped, single-mode, and double-cladding chalcogenide fibers with the core/cladding ratios of 125:60:11 and 125:66:11.5 were achieved by a multistage rod-in-tube fiber drawing process and extrusion methods, respectively. The GeS₂-based fiber exhibits excellent transmission performance at 1.0-5.0 μm: 3.0 dB/m at 2.9 μm (O–H), 2.4 dB/m at 4.1 μm (S–H). Combining the advantages of high-purity, high doping concentration and single-mode double-cladding structure, the optimized active fiber should be an ideal efficient and low-threshold medium toward mid-infrared fiber laser beyond 4 μm.     

Enhanced conductivity and fluorescence of polyaniline doped with Eu3+, Tb3+, and Y3+ ions

The doped polyaniline (PANI) with rare earth ions, which exhibits an increasing conductivity and strongly enhanced fluorescence emission, was prepared by dispersing PANI powder suspension in acetonitrile solution containing rare earth ions according to different mass ratios of rare earth ions to PANI at room temperature. The structure of the doped PANI was characterized by the spectra of FTIR, Raman, UV-vis, and XRD. Red-shifted change for the quinoid and benzenoid stretching vibration is observed in IR and Raman spectra after doping rare earth cations, and UV-vis absorption peak also presents a red-shift, indicating that the doped PANI possesses a better delocalization of electrons along the mainchain backbone. The experimental data show that the electrical and optical behaviors of PANI strongly depend on the species of rare earth cations and their concentration. It is found that enhancing fluorescence for the doped PANI is observed by comparing with emeraldine base (EB). Moreover, the conductivity of the protonated PANI samples doped with Eu³⁺, Tb³⁺, and Y³⁺ ions, increases from 2.1 × 10⁻⁴ to 3.33 S cm⁻¹, 1.50 × 10⁻¹ S cm⁻¹ and 2.26 × 10⁻¹ S cm⁻¹. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Energy transfer and luminescence study of Dy3+ doped zinc-aluminoborosilicate glasses for white light emission

A series of Dy³⁺ doped aluminoborosilicate glasses with general formula 20SiO₂-(40-x) B₂O₃–10Al₂O₃–20NaF₂–10ZnO-xDy₂O₃ (x = 0, 0.1, 0.5, 1.0. 1.5, 2.0 and 2.5 mol %) were prepared by melt-quenching method. The FTIR analysis confirms the presence of stretching and bending vibrations of BO₄, BO₃ and SiO₄ units in the prepared glasses. DTA results show that Tg is decreasing with addition of Dy³⁺ ions in the glass system. Theoretically calculated mechanical properties such as elastic modulus, bulk modulus, shear modulus and Poisson's ratio suggest the increase in mechanical stability of glasses with dysprosium addition. Also experimental analysis carried out using Vicker's microhardness suggests glass stability with applied loads. Absorption spectrum shows twelve bands that exist due to transition from ⁶H_15/2 level to different excited levels. Nephelauxetic ratio and bonding parameter calculated shows decreasing ionicity of glasses with increase in Dy³⁺ ions. Judd-Oflet parameter calculated for all the glasses follow the trend Ω₆ > Ω₄ > Ω₄. Luminescence study shows three emission peaks having transitions from ⁴F_9/2 → ⁶H_15/2 (blue), ⁴F_9/2 → ⁶H_13/2 (yellow) and ⁴F_9/2 → ⁶H_11/2 (red). Radiative parameters calculated suggest higher stimulated emission cross-section for present glasses having ⁴F_9/2 → ⁶H_13/2 transition. The decay measurement for all the glass samples were recorded with an excitation at 350 nm and monitoring emission at 575 nm corresponding to the ⁴F_9/2 → ⁶H_13/2 transition and decay curves were fitted to bi-exponential fit. The CIE colour chromaticity coordinates were determined using CIE chromaticity diagram and the values were found to be in close proximity with the standard white light (0.33. 0.33) for all the glasses. Further colour correlated temperature values were found to lie in the near bright white region with CCT around ~4000 K.     

Effect of alkali and alkaline earth metal ion as glass modifiers on the spectroscopic characteristics of Er3+-ion doped lead silicate glasses

The spectroscopic characteristics of Er-doped lead silicate glasses were investigated with respect to the effects of glass modifiers (Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺) with various optical basicities. Using the absorption spectra of the glasses, the Judd–Ofelt parameters of the glasses were calculated and examined, with an emphasis on the glass emission intensity ratio at 1572 nm. The spectra of the samples at low temperatures were examined, and the Stark splitting of Er3+ was investigated. The McCumber method was used to determine the emission cross sections of glasses. The SPM glass exhibited high values of full width at half maximum (51.24 nm) and the emission cross section at 1572 nm (1.908 × 10⁻²¹ cm²), with potential applications for guiding component design of 1.5-μm fiber lasers and amplifiers.     

Near white light emission of Ce3+‐, Ho3+‐, and Sm3+‐doped oxyfluoride silicate glasses

The Ce³⁺‐, Ho³⁺‐, and Sm³⁺‐ single and co‐doped oxyfluoride silicate glasses for light emitting diodes are studied. These glasses were prepared by melt quenching method and their optical and structural properties were investigated by absorption spectra, photoluminescence spectra, Commission International de I'Eclairage chromaticity coordinates, X‐ray diffraction, and Fourier transform infrared spectra. It is found that the introduction of Al₂O₃ in glass composition can improve the emissions of Ho³⁺ and Sm³⁺. While the presence of B₂O₃ has the adverse effect and can suppress the emissions of Ho³⁺ and Sm³⁺. With substituting Na₂O for CaO in the glass compositions, CaF₂ crystals can be formed during the melt quenching process. We find the formation of CaF₂ crystals can change the emission behavior of Ho³⁺ and Sm³⁺ ions. White light emissions can be achieved in the glasses and the luminescence colors can be tuned by varying the concentrations of the doped rare‐earth ions and the composition of glass matrix. The Ce³⁺‐, Ho³⁺‐, and Sm³⁺‐doped oxyfluoride silicate glasses presented here demonstrate promising applications in the fields of light emitting diodes.     

Structural and emission properties of Eu3+‐doped alkaline earth zinc‐phosphate glasses for white LED applications

Quaternary alkaline earth zinc‐phosphate glasses in molar composition (40 ? x)ZnO – 35P₂O₅ – 20RO – 5TiO₂ – xEu₂O₃ (where x=1 and R=Mg, Ca, Sr, and Ba) were prepared by melt quenching technique. These glasses were studied with respect to their thermal, structural, and photoluminescent properties. The maximum value of the glass transition temperature (T_g) was observed for BaO network modifier mixed glass and minimum was observed for MgO network modifier glass. All the glasses were found to be amorphous in nature. The FT‐IR suggested the glasses to be in pyrophosphate structure, which matches with the theoretical estimation of O/P atomic ratio and the maximum depolymerization was observed for glass mixed with BaO network modifier. The intense emission peak was observed at 613 nm (⁵D₀→⁷F₂) under excitation of 392 nm, which matches well with excitation of commercial n‐UV LED chips. The highest emission intensity and quantum efficiency was observed for the glass mixed with BaO network modifier. Based on these results, another set of glass samples was prepared with molar composition (40 ? x)ZnO – 35P₂O₅ – 20BaO – 5TiO₂ – xEu₂O₃ (x=3, 5, 7, and 9) to investigate the optimized emission intensity in these glasses. The glasses exhibited crystalline features along with amorphous nature and a drastic variation in asymmetric ratio at higher concentration (7 and 9 mol%) of Eu₂O₃. The color of emission also shifted from red to reddish orange with increase in the concentration of Eu₂O₃. These glasses are potential candidates to use as a red photoluminsecent component in the field of solid‐state lighting devices.     

Distribution of Tm3+ and Ni2+ in chalcogenide glass ceramics containing Ga2S3 nanocrystals: Influence on photoluminescence properties

The distribution of Tm³⁺ and Ni²⁺ ions is unambiguously exhibited in 80GeS₂-20Ga₂S₃ chalcogenide glass ceramics (GCs) containing Ga₂S₃ nanocrystals (NCs) by using advanced analytical transmission electron microscopy. Distinctively different distribution patterns of Tm³⁺ and Ni²⁺ ions are observed in the GCs obtained by controlled crystallization. The distribution of the dopants imposes strong influence on their optical properties which are revealed by absorption and photoluminescence (PL) spectra. Detailed discussions are given of the mechanisms of the crystallization-induced PL enhancement and quenching of the Tm³⁺ mid-infrared and Ni²⁺ near-infrared emissions, respectively.     

Effect of Gd3+/Ga3+ on Yb3+ emission in mixed YAG at cryogenic temperature

We investigated the effect of Gd³⁺ and Ga³⁺ on Yb:YAG emission at cryogenic temperatures by preparing ceramic pellets by solid state reaction method with different Gd³⁺ and Ga³⁺ content. Incorporation of Gd³⁺ shows only a small effect on spectral broadening whereas incorporation of Ga³⁺ in Yb:YAG results in significant broadening. Such an inhomogeneous broadening is due to the replacement of larger Ga³⁺ ion in two different cationic sites of Al³⁺ which causes a change in local crystal field on the Yb³⁺ site.     

碘化铅对Dy3+掺杂GeS2-Ga2S3玻璃荧光光谱性质的影响

采用熔融淬冷法制备了掺杂浓度为0.3%(质量分数)的Dy3+:(100–x)(0.8GeS2–0.2Ga2S3)–xPbI2(x=5,10,15,摩尔比)系列硫卤玻璃样品,测试了样品热稳定性、折射率、密度、吸收光谱、近红外及中红外荧光光谱。应用Judd–Ofelt理论计算了Dy3+在系列样品中的强度参数(Ωt,t=2,4,6)、自发辐射跃迁几率、荧光分支比以及辐射寿命等光谱参数。讨论了PbI2含量对样品的吸收光谱、光谱参数以及荧光光谱的影响。在Dy3+掺杂样品中,PbI2含量的增加有效地提高了1 330 nm和2 860 nm处的荧光强度。计算了0.3%Dy3+掺杂68GeS2–17Ga2S3–15PbI2玻璃在1 330 nm和2 860 nm处的受激发射截面值分别为3.63×10–20 cm2和1.57×10–20 cm2,2 860 nm处的量子效率为83.8%。     

Experimental and theoretical studies on NIR luminescence of titanate-germanate glasses doped with Pr3+ and Tm3+ ions

Near-infrared (NIR) luminescence of Pr³⁺ and Tm³⁺ ions in titanate-germanate glasses has been studied for laser and fiber amplifier applications. The effect of the molar ratio GeO₂:TiO₂ (from 5:1 to 1:5) on spectroscopic properties of glass systems was studied by absorption, luminescence measurements, and theoretical calculations using the Judd–Ofelt theory. It was found that independent of the TiO₂ concentration, intense NIR emissions at 1.5 and 1.8 μm were observed for glasses doped with Pr³⁺ and Tm³⁺ ions, respectively. Moreover, several spectroscopic and NIR laser parameters for Pr³⁺ and Tm³⁺ ions, such as emission bandwidth, stimulated emission cross-section, quantum efficiency, gain bandwidth, and figure of merit, were determined. The results were discussed in detail and compared to the different laser glasses. Systematic investigations indicate that Pr³⁺-doped system with GeO₂:TiO₂ = 2:1 and Tm³⁺-doped glass with GeO₂:TiO₂ = 1:2 present profit laser parameters and could be successfully applied to NIR lasers and broadband optical amplifiers.     

Effect of glass composition on the hardness of surface layers on aluminosilicate glasses formed through reaction with strong acid

The effect of glass composition on physico‐chemical properties of surface layers formed through reaction between strong acid and several silicate and aluminosilicate glasses was studied through transmission‐IR, ATR‐IR, XPS, SIMS, and nano‐indentation analyses. It was shown that aluminum is depleted from the surface while molecular water is diffused into the surface layer of glasses with high levels of aluminum. Nano‐indentation experiments indicated that the hardness of the surface layers were decreased compared to that of the bulk region and the degree of the softening was more significant in the high aluminum glass.     

Effect of ligand field symmetry on upconversion luminescence in heat‐treated LaBGeO5:Yb3+, Er3+ glass

In this paper, we report upconversion (UC) luminescence enhancement in LaBGeO₅:Yb³⁺, Er³⁺ glass‐ceramics (GCs), surface crystallized glass‐ceramics (SCGCs) and ceramics compared with the as‐melt glass fabricated by the conventional melt‐quenching technique. Based on structural investigations, we find that the nucleation and crystallization of trigonal stillwellite LaBGeO₅:Yb³⁺, Er³⁺ nanocrystals occur first at the glass surface before the following volume crystallization. The local site symmetry around rare earth (RE) ions which was evaluated using the Eu³⁺ ions as a probe together with Judd‐Ofelt theory calculations exhibits a clear increase with the devitrification of the glass. Consequently, complete crystallization of the glass leads to largest enhancement in the UC emissions of the LaBGeO₅:Yb³⁺, Er³⁺ ceramics. We ascribe the enhancement of UC luminescence in the LaBGeO₅:Yb³⁺, Er³⁺ GCs, SCGCs, and ceramics to the structural ordering and the improvement of site symmetry surrounding RE ions that minimizes the rate of nonradiative relaxation process.     

Luminescence performance of yttrium-stabilized zirconia ceramics doped with Eu3+ ions fabricated by Spark Plasma Sintering technique

Yttrium stabilized zirconia (YSZ) ceramics doped with Eu³⁺ ions have been successfully fabricated by Spark Plasma Sintering (SPS) technique. The influence of the europium concentration and post-annealing process on the structural, optical, and luminescent properties of the ceramics has been studied. It is shown that an increase in the europium concentration from 0.1 to 3 wt% does not lead to significant changes in the transmission spectra. However, annealing in air atmosphere at temperature from 700 °C to 1300 °C significantly affects the transmission spectrum, as a possible consequenceofthe formation of oxygen vacancy defects. The analysis of the photoexcitation and photoluminescence spectra showed that the main excitation bands are determined by direct excitation of the ⁷F₀ ground state of Eu³⁺ions to the higher 4f energy levels with further radiation transitionsfrom these states. Moreover, the europium ion in the obtained ceramics occupy low-symmetry sites without inversion center.The luminescence decay kineticsare described by a doubleexponential function with decay time τ₁ ~ 20 ns and τ₂~ 90 ns for intrinsic emission centers and millisecond (τ ~ 1.4 ms) for Eu³⁺emission, for all investigated ceramics. The luminescence spectra in nanosecond time region are characteristic for yttrium-stabilized zirconia and are caused by oxygen vacancies in the presence of heavy cations (Y³⁺ and Eu³⁺).     

Sensitization effect of Nd3+ ions on Yb3+/Nd3+ co-doped oxyfluoride glasses and study of their optical,fluorescence, and upconversion abilities for visible laser and NIR amplifier applications

The development of laser technology has created intense demand for optical confinement materials with high performance. Herein the authors have been investigated Yb³⁺-singly doped and Yb³⁺/Nd³⁺-codoped SiO₂-based oxyfluoride glasses in terms of their optical absorption, and their near-infrared (NIR) and up-conversion (UC) emissions including emission decay profiles. Under 808 nm laser diode (LD) excitation, four NIR emission bands were observed i.e., (Nd³⁺: ⁴F_3/2 → ⁴I_9/2, Yb³⁺: ²F_5/2 → ²F_7/2, Nd³⁺: ⁴F_3/2 → ⁴I_11/2, and Nd³⁺: ⁴F_3/2 → ⁴I_13/2) in co-doped glasses. NIR emission cross-sections [(σ_emi) stimulated, (σ^M_emi) from Mc-cumber theory] were calculated for ²F_5/2 → ²F_7/2 (～1030 nm) transition of Yb³⁺ ion. σ_emi was found to be highest (26.27 × 10^?21 cm²) for the Yb³⁺: ²F_5/2 → ²F_7/2 transition in N2 glass. UC emission spectra recorded at 980 nm LD show bands centered at 500, 536, 595 & 610, and 664 nm, attributed to ⁴G_9/2 → ⁴I_9/2, ⁴G_7/2 → ⁴I_9/2& ⁴G_7/2 → ⁴I_11/2, ⁴G_5/2 → ⁴I_9/2, and ⁴G_9/2 → ⁴I_13/2 transitions, respectively. Decay profiles were analyzed for Yb³⁺: ²F_5/2 → ²F_7/2 (～1030 nm) and Nd³⁺: ⁴F_3/2 → ⁴I_11/2 (～1057 nm) transitions at 808 nm LD. Energy transfer (ET) process from Nd³⁺ to Yb³⁺ in present glasses were detailed.     

Effect of B2O3 addition on structure and properties of Yb3+/Al3+/B3+-co-doped silica glasses

The homogeneous Yb³⁺/Al³⁺/B³⁺-co-doped silica glasses were prepared via a sol-gel method. The impact of B₂O₃ addition on the physical and optical properties and network structure was systematically studied. The network structure was investigated by the Fourier Transform Infrared (FT-IR), Raman spectra, and Solid State Nuclear Magnetic Resonance (SSNMR). Herein, B₂O₃ addition can continuously decrease the refractive index and density. When B₂O₃ is lower than 2 mol%, B₂O₃ addition can obviously decrease the scalar crystal field parameters, Yb³⁺ asymmetry degree, Yb³⁺ cross-sections, due to the generation of Yb–O–B bonds at the cost of partial Yb–O–Al/Si ones. When B₂O₃ is more than 2 mol%, FT-IR, Raman spectra, and SSNMR results indicate that further increased B atoms prefer to connect with Si and Al rather than Yb. Consequently, the above parameters are basically unchanged. Based on the results, an intuitive model of structure and properties evolution during the substitution of SiO₂ by B₂O₃ has been established.     

Eu3+掺杂TiO2荧光探针的制备及对氯氰菊酯的检测应用

以钛酸四丁酯为前体,采用液相法制备了水溶态纳米Eu3+掺杂TiO2荧光探针,并对其发光性质进行了研究。通过紫外吸收和荧光光谱研究了它和氯氰菊酯之间的相互作用,结果发现,氯氰菊酯对Eu3+掺杂TiO2的荧光具有猝灭作用,根据Stern-Volmer猝灭方程,计算出其猝灭常数为1.017×1011 L/(mol.s),并讨论了猝灭机理。依据氯氰菊酯浓度和Eu3+掺杂TiO2的荧光强度成正比,建立了一种快速检测农药的新方法。其检测范围为2.5×10-10～2.5×10-7mol/L,检出限为2.5×10-11mol/L,回收率在89.25%～93.55%之间。     

表面活性剂对掺铁纳米TiO2光催化性能的影响

以钛酸丁酯为原料,采用溶胶-凝胶法制备了纳米TiO2粉末,在其中添加了过渡金属元素铁,并在表面包覆少量的表面活性剂(CTAB)。经紫外光照射后,通过紫外-可见分光光度计测量了光催化降解反应后降解率的变化,探讨了在两者共同作用下的TiO2粉体的光催化活性。实验结果表明:在样品中掺杂一定量的Fe3+并包覆表面活性剂(CTAB),TiO2的结构上并没有发生改变;在Fe3+和CTAB的作用下的纳米TiO2的光催化活性有了显著地提高。     

Nb2O5对Nd3+掺杂锗酸盐玻璃光谱性能的影响

蓝光激光器在彩色激光显示、高密度光储存、海洋资源探测、水下通信以及生物科技等领域具有广泛的应用前景。目前较为成熟的Yb³⁺掺杂光纤激光器倍频后仅能获得~490 nm蓝绿光,因此如何得到接近450 nm的纯蓝光激光器是目前急需解决的问题。Nd³⁺:⁴F_3/2→⁴I_9/2能级跃迁产生的0.9 μm光经倍频后可获得~450 nm光,并可应用于蓝光激光器,但该跃迁产生的光所占荧光分支比较低。本文系统研究了1%(质量分数)Nd₂O₃掺杂50GeO₂-(20-x)PbO-15BaO-15ZnO-xNb₂O₅(x%=0%,2.5%,5%,10%,15%,摩尔分数)玻璃的吸收光谱、荧光光谱和荧光寿命,计算了相应的Judd-Ofelt强度参数以及增益带宽。研究发现,Nb₂O₅的加入会使Nd³⁺在900 nm荧光峰的吸收截面、发射截面、有效线宽和荧光分支比增加。当Nb₂O₅浓度为10%(摩尔分数)时,Judd-Ofelt强度参数Ω₂=5.91×10^-20 cm²,光谱质量参数χ=1.01,荧光分支比为42.9%。综上所述,Nb₂O₅能提高Nd³⁺ 0.9 μm的荧光分支比,从而倍频获得纯蓝光(450 nm),有利于蓝光激光器的发展及应用。     

高价氧化物对掺铒碲酸盐玻璃光谱性质的影响

对比分析了相同铒离子低掺杂浓度下,Y2O3、GeO2、Nb2O5 WO3四种高价氧化物对碲锌玻璃系统光谱性质的影响.测试了四个样品的红外透过光谱,结果表明由于Nb2O5 、WO3二者引入的高价阳离子的极化作用使得二者部分的充当玻璃形成体的角色,使得玻璃的有效红外透过范围降低.同时吸收光谱也表明这两种高价氧化物会使得玻璃紫外吸收边发生明显红移.铒离子的近红外荧光光谱结果表明,引入高价氧化物会由于高价阳离子的极化作用导致铒离子的荧光半高宽增加,特别以含WO3的TZW样品具有最高的荧光半高宽达64nm.     

石墨粉对低锌含量水性环氧富锌漆阴极保护性能的影响

配制了颜料体积浓度(PVC)与临界颜料体积浓度(CPVC)之比为0.9的低锌含量水性环氧富锌漆,加入占锌粉质量1%、2%和3%的石墨粉,研究了石墨粉对水性环氧富锌涂层阴极保护性能的影响。涂层的阴极保护性能评价采用传统的开路电位(OCP)测试法与自行开发设计的恒电流溶解法。OCP测试结果表明,添加石墨后的涂层有更长的阴极保护时间,石墨粉添加量越大,阴极保护时间越长。恒电流溶解法测试结果表明,加入石墨粉之后涂层的活性溶解时间变长,石墨粉添加量越高,活性溶解时间越长。导电胶和涂层电极在3.5%NaCl溶液中的电化学阻抗谱测试结果表明,随着石墨粉含量的增加,涂层阻抗降低,阴极保护作用增强。