Sb3+对Tb3+激活硅酸盐玻璃发光性能的影响

利用高温熔融法分别制备了Sb3 ,Tb3 单掺和共掺的硅酸盐发光玻璃,并分析了它们的光谱性质。根据对Sb3 和Tb3 掺杂硅酸盐玻璃的激发光谱、发射光谱和发光衰减时间等特性的分析,研究了澄清剂Sb2O3的加入对Tb3 激活硅酸盐玻璃发光性能的影响。结果表明,在紫外光激发下,Tb3 激活硅酸盐玻璃中存在Sb3 离子至Tb3 离子的能量传递,但能量传递效率较低,能量传递表现为Sb3 离子的3P1能级与Tb3 离子的5D3能级之间的能量无辐射共振转移。同时Sb3 离子的加入将在Sb3 离子和Tb3 离子的激发重叠区域(200～350nm)对Tb3 离子的激发产生不小的负面影响,尚不足以通过Sb3 离子至Tb3 离子的能量传递得以弥补。因此在使用Sb2O3作为Tb3 激活硅酸盐发光玻璃的澄清剂时,应当注意权衡Sb3 离子对Tb3 离子发光性能的影响。     

Nuclear and electronic contributions to the third-order nonlinearity in different glasses

Using, a time resolved optical heterodyne Kerr effect experiment along with a Raman light diffusion experiment, we have measured the nuclear (non-instantaneous) and electronic (instantaneous) contributions to the nonlinear index of refraction in tellurite niobium-doped and silicate lead-doped glasses. The experimental set-up and the procedure used to measure the nuclear and electronic contribution are detailed. Our experimental results clearly indicate that the ratio between the instantaneous and the non-instantaneous contribution remain constant while the doping concentration or the temperature of the sample vary. These ratios are ∼5 and ∼10 in tellurite niobium-doped and silicate lead glasses, respectively.     

Tb3+掺杂硅酸盐玻璃发光性能的浓度依赖关系

 利用高温熔融法制备了不同浓度的Tb³⁺掺杂硅酸盐玻璃,并分别测量了紫外和X射线激发时的发射光谱。光谱结果表明,不同浓度Tb³⁺掺杂硅酸盐玻璃在紫外和X射线激发时发光行为具有相似的浓度依赖关系：低浓度Tb₄O₇掺杂时主要以蓝光(5D₃→⁷FJ)发射为主,而高浓度掺杂时以绿光(⁵D₄→⁷FJ)发射为主。Tb³⁺发光强度与掺杂浓度的关系分析表明,⁵D₃的浓度猝灭是电偶极-电偶极相互作用引起的, 而⁵D₄的浓度猝灭是交换相互作用引起的。     

Improved control of the phosphorous surface concentration during in‐line diffusion of c‐Si solar cells by APCVD

Emitter formation for industrial crystalline silicon (c‐Si) solar cells is demonstrated by the deposition of phosphorous‐doped silicate glasses (PSG) on p‐type monocrystalline silicon wafers via in‐line atmospheric pressure chemical vapor deposition (APCVD) and subsequent thermal diffusion. Processed wafers with and without the PSG layers have been analysed by SIMS measurements to investigate the depth profiles of the resultant phosphorous emitters. Subsequently, complete solar cells were fabricated using the phosphorous emitters formed by doped silicate glasses to determine the impact of this high‐throughput doping method on cell performance. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Li~+对Tb~(3+)掺杂硅酸盐玻璃闪烁性能的影响

利用高温熔融法制备了Li+掺杂Tb3+激活硅酸盐闪烁玻璃。通过Li+掺杂Tb3+激活硅酸盐玻璃的紫外可见透射光谱、发射光谱和发光衰减时间谱,研究了Li+的加入对Tb3+掺杂硅酸盐玻璃发光性能的影响。结果表明:适量Li+的加入可有效增强Tb3+激活硅酸盐玻璃的发光强度,且相比于不掺杂Li+的Tb3+掺杂硅酸盐玻璃而言,当掺入质量分数为2.0%的Li+时,Tb3+在玻璃中的最佳掺杂质量分数由12.8%提高至15.3%。其原因是Li+掺杂增加了玻璃体系中非桥氧的数量,从而有利于改善Tb3+在玻璃体中的均匀性,降低Tb3+间因非辐射跃迁而引起的能量损失,以及提高Tb3+的最佳掺杂质量分数。但当掺入Li+的质量分数超过2.0%时,会对Tb3+激活硅酸盐玻璃的闪烁光强产生负面影响,这是因为过多的非桥氧阻碍了X射线激发能达到Tb3+离子的能量传递。     

Diffusion behavior of transition metals in field-assisted ion-exchanged glasses

The use of ion-exchange techniques for doping silicate glasses with transition metals has attracted much attention in the last decades for its potential in several applications, namely, light waveguides technology, luminescent materials, and for the possibility to realize systems in which metal nanocluster formation is controlled by suitable post-exchange techniques. In this framework, the control of metal distribution inside the glass is a central issue for both the understanding of the incorporation process and for the definition of effective preparation protocols. In this experiment, metallic films (Ag, Cu, Au, Co) were deposited onto the substrates by the rf-sputtering technique. Metal ions then penetrate to substitute glass alkali by means of field-assisted ion-exchange, realized at different temperature and electric field values. In particular, we present in this paper the Au doping of silicate glasses, successfully realized for the first time with this method. The gold diffusion profiles, as measured by Secondary Ion Mass Spectrometry (SIMS), indicate that the migration depends on the experimental parameters (temperature and electric field), but also on the local structure, as well as on chemical phenomena occurring at the metal/glass interface.     

Fluorine-doped zinc oxide transparent and conducting electrode by chemical spray synthesis

Highly transparent and conducting fluorine-doped zinc oxide thin films, consisting of spherical nanometer-sized grains, were synthesized onto soda-lime glass substrate by using a chemical spray unit. The effect of fluorine doping concentration in starting solution was investigated. Both doped and undoped films were preferentially oriented along [002] direction. Electrical resistivity decreases from 5.7 x 10^-2 to 8.6 x 10^-3 ohm-cm after 1 at.% fluorine doping, and increases for higher doping concentration. However, surface morphology of films obtained at 3 at.% fluorine doping appeared smooth and uniform. A shift of the edge of the optical transmission in the ultraviolet region as a result of fluorine doping was obtained.     

A high-resolution 19F NMR spectroscopic study of barium fluorozirconate glasses and related crystals

Fluorozirconate glasses have attracted considerable attention not only for their transparency in the infrared, but also due to their high fluorine ion conductivities and extreme fragility in the viscosity-temperature relationship. We report on structural studies of binary BaF2-ZrF4 glasses with 58-78 mol% ZrF4 using high-resolution magic-angle-spinning 19F NMR. High-speed 19F MAS NMR allows us to resolve at least three unique fluorine environments in these binary glasses. These fluorine environments are attributed to one type of bridging fluorine, between corner-sharing Zr-F coordination polyhedra, and two types of non-bridging fluorine (NBF), one of which is bonded to one Zr and one Ba atom while the other is bonded to one Zr and two Ba atoms. The concentration of the first type of NBF increases with decreasing ZrF4 concentration, while that of the second type is essentially independent of glass composition. These assignments have been made on the basis of detailed 19F NMR studies of a wide variety of crystalline fluorozirconates with known crystal structures. A comparison between the glass and crystal 19F NMR spectra rules out any significant concentration of edge-shared Zr-F polyhedra in these binary glasses. The Zr atoms in all glasses are found to be coordinated to approximately 7.8+/-0.2F atoms.     

紫外激光照射引起的硅酸铅玻璃结构的变化

采用紫外-可见吸收光谱和电子自旋共振谱(ESR)对硅酸铅玻璃薄膜和体材料受紫外激光照射前后的结构变化进行了研究。研究发现：266 nm的紫外激光照射硅酸铅玻璃体材料时,能使其Urbach能量增大,即玻璃结构的无序性增大。电子自旋共振谱研究表明,266 nm激光照射不会在硅酸铅玻璃中产生顺磁缺陷中心, 也不会对硅酸铅玻璃薄膜在235 nm附近的吸收峰产生影响,但用248 nm紫外激光照射则观察到了235 nm吸收峰的光漂白现象。     

EDWA基质玻璃中Er3+的光谱参数计算

对制备的不同掺杂Er3+浓度的硅酸盐玻璃,测定了吸收光谱和荧光光谱.根据玻璃的光谱特性计算了玻璃吸收面积并确定出体系的最佳掺杂Er2O3浓度为0.2左右.根据Judd-Ofelt理论拟合出光谱强度参数Ωλ(λ=2,4,6);结果分析表明:随着Er3+离子浓度的增加,光谱强度参数Ω2在增大,Ω6在减小,说明玻璃的共价性能增强,Er-O共价性增强.     

不同玻璃组分对β-NaYF4:Yb3+,Er3+/Tm3+粉体的侵蚀性研究及对发光性能的影响

选用硅酸盐、硼酸盐以及磷酸盐3种常用的玻璃体系,与β-NaYF₄:Yb³⁺,Er³⁺/Tm³⁺粉体均匀混合压片后在不同的温度(400～700 ℃)下进行热处理。采用X射线衍射技术和荧光光谱技术等测试手段研究不同玻璃形成体以及碱金属离子对β-NaYF₄:Yb³⁺,Er³⁺/Tm³⁺粉体的侵蚀情况以及对发光性能的影响。研究结果表明,在硼酸盐玻璃体系与β-NaYF₄:Yb³⁺,Er³⁺/Tm³⁺粉体复合热处理过程中,Li⁺和K⁺离子会取代β-NaYF₄晶体中Na原子的位置。 在相同热处理温度下,不同玻璃体系与β-NaYF₄晶体反应剧烈程度:磷酸盐>硼酸盐>硅酸盐。     

Uniform upconversion in high-concentration Er(3+)-doped soda lime silicate and aluminosilicate glasses

Uniform upconversion in erbium-doped silicate glasses is investigated as a function of glass composition, concentration, and fabrication method. Comparisons of upconversion coefficients are made among soda lime silicate and aluminosilicate bulk glasses and soda lime silicate waveguides. Comparisons are also made with studies performed by other researchers. The results indicate that both the composition and the preparation method of the glass affect the value of the upconversion coefficient, with as much as a factor-of-4 variation observed at fixed Er(3+) concentration. Values of the upconversion coefficient are found to be consistent with the F?rster-Dexter microscopic model.     

掺镱硅酸盐玻璃的光谱性质

采用高温熔融工艺制备了掺Yb^3＋硅酸盐玻璃。测试了玻璃的吸收光谱和荧光光谱,计算并分析了Yb^3＋离子在975nm附近的吸收截面和积分吸收截面随掺杂浓度的变化趋势。玻璃光谱曲线表明：吸收主峰位于975nm,在900—960nm范围内有一个弥散的吸收峰,中心波长为930nm;荧光主峰位于975nm,荧光次峰位于1010nm。综合其性能表明实验中硅酸盐玻璃的最佳Yb^3＋掺杂浓度为4mol%。     

Compare of the electronic structures of F- and Ir-doped SmFeAsO

The electronic structures of Fe-based superconductor SmFeAsO_1−xF_x and SmFe_1−yIr_yAsO are compared through X-ray photoemission spectroscopy in this study. With fluorine or iridium doping, the electronic structure and chemical environment of the SmFeAsO system were changed. The fluorine was doped at an oxygen site which introduced electrons to a reservoir Sm–O layer. The iridium was doped at an Fe site which introduced electrons to a conduction Fe–As layer directly. In a parent material SmFeAsO, the magnetic ordering corresponding to Fe3d in the low-spin state is suppressed by both fluorine and iridium doping through suppressing the magnetism of 3d itinerant electrons. Compared to fluorine doping, iridium doping affected superconductivity more significantly due to an iridium-induced disorder in FeAs layers.     

γ辐照对掺Er硅酸盐玻璃吸收和发光特性的影响

用传统的高温熔融法熔制了一系列掺Er硅酸盐玻璃, 并测试了这些样品经5 kGy γ 射线辐照前后紫外至近红外的吸收和荧光光谱. 实验结果表明, 辐致暗化效应使得玻璃材料中形成了大量色心, 导致在400 nm附近出现强吸收带, 其尾端延伸至近红外区. 辐照产生的新能带增加了基质与Er³⁺ 特定能级(如²H_11/2, ⁴S_3/2及⁴F_9/2等) 之间的能量传递, 从而使辐照后的样品荧光寿命减小, 且在相同激发条件下荧光强度下降. 室温下辐照样品在荧光测试过程中出现了漂白现象.     

Approximate chemical analysis of volcanic glasses using Raman spectroscopy

The effect of chemical composition on the Raman spectra of a series of natural calcalkaline silicate glasses has been quantified by performing electron microprobe analyses and obtaining Raman spectra on glassy filaments (~450 µm) derived from a magma mingling experiment. The results provide a robust compositionally‐dependent database for the Raman spectra of natural silicate glasses along the calcalkaline series. An empirical model based on both the acquired Raman spectra and an ideal mixing equation between calcalkaline basaltic and rhyolitic end‐members is constructed enabling the estimation of the chemical composition and degree of polymerization of silicate glasses using Raman spectra. The model is relatively insensitive to acquisition conditions and has been validated using the MPI‐DING geochemical standard glasses 1 as well as further samples. The methods and model developed here offer several advantages compared with other analytical and spectroscopic methods such as infrared spectroscopy, X‐ray fluorescence spectroscopy, electron and ion microprobe analyses, inasmuch as Raman spectroscopy can be performed with a high spatial resolution (1 µm²) without the need for any sample preparation as a nondestructive technique. This study represents an advance in efforts to provide the first database of Raman spectra for natural silicate glasses and yields a new approach for the treatment of Raman spectra, which allows us to extract approximate information about the chemical composition of natural silicate glasses using Raman spectroscopy. We anticipate its application in handheld in situ terrestrial field studies of silicate glasses under extreme conditions (e.g. extraterrestrial and submarine environments). © 2015 The Authors Journal of Raman Spectroscopy Published by John Wiley & Sons Ltd     

A Raman study of lithium fluoride containing fast ionic conducting glasses

The role of fluorine in the structure of fluoro-borate fast ionic conducting glasses has been studied by Raman spectroscopy. It is shown that addition of LiF results in important structural changes, compared to binary glasses with the same O/B ratio. The Raman results are consistent with the participation of fluorine in the network. Careful control of the O/B ratio is required in order to detect the alkali fluoride-induced structural changes by Raman spectroscopy.     

Tunable white luminescence and energy transfer in (Cu+)2, Eu3+ codoped sodium silicate glasses

Luminescent properties of (Cu+)2, Eu3+ single-doped and codoped sodium silicate glasses were systematically investigated by excitation spectra, emission spectra, and decay curves. Due to the efficient energy transfer from (Cu+)2 pairs to Eu3+, varied hues from green to yellowish white and eventually to orange were generated by tuning the content of Eu3+. A perfect white-light emission with CIE coordinates (X=0.336,Y=0.346) was realized in (Cu+)2, Eu3+ and Ce3+ codoped samples. Our research indicates the potential application of (Cu+)2, Eu3+ codoped sodium silicate glasses for converting phosphors for UV LED chips to generate white LEDs.     

氟对连铸保护渣熔体、玻璃和晶体微结构的影响

连铸保护渣的物化性质与其结构密切相关。而氟化物对调节连铸保护渣高温物化性能具有重要作用,因此研究氟对多元硅酸盐结构影响有助于深入了解氟的作用特性,进而为环保型连铸保护渣的开发奠定理论基础。论文通过拉曼光谱研究了氟对保护渣高温熔体、玻璃及晶体中硅酸盐微结构单元的影响。结果表明：随着CaF₂含量的增加,硅酸盐微结构单元种类和相对数量发生变化,硅酸盐网络化程度降低,熔体粘度减小;在性能相近的无氟渣和高氟渣中,高氟渣晶体中硅酸盐微结构单元主要为单体结构硅酸盐,无氟渣主要为链状结构硅酸盐。论文研究结果对无氟保护渣的开发具有一定的指导意义。     

Bismuth silicate glass containing heavy metal oxide as a promising radiation shielding material

Optical and FTIR spectroscopic measurements and electron paramagnetic resonance (EPR) properties have been utilized to investigate and characterize the given compositions of binary bismuth silicate glasses. In this work, it is aimed to study the possibility of using the prepared bismuth silicate glasses as a good shielding material for γ-rays in which adding bismuth oxide to silicate glasses causes distinguish increase in its density by an order of magnitude ranging from one to two more than mono divalent oxides. The good thermal stability and high density of the bismuth-based silicate glass encourage many studies to be undertaken to understand its radiation shielding efficiency. For this purpose a glass containing 20% bismuth oxide and 80% SiO₂ was prepared using the melting–annealing technique. In addition the effects of adding some alkali heavy metal oxides to this glass, such as PbO, BaO or SrO, were also studied. EPR measurements show that the prepared glasses have good stability when exposed to γ-irradiation. The changes in the FTIR spectra due to the presence of metal oxides were referred to the different housing positions and physical properties of the respective divalent Sr²⁺, Ba²⁺ and Pb²⁺ ions. Calculations of optical band gap energies were presented for some selected glasses from the UV data to support the probability of using these glasses as a gamma radiation shielding material. The results showed stability of both optical and magnetic spectra of the studied glasses toward gamma irradiation, which validates their irradiation shielding behavior and suitability as the radiation shielding candidate materials.