若干硫系玻璃黏度变化速率的结构起源探索

用熔融淬冷法制备Ge₃₃As₁₂Se₅₅、Ge₂₂As₂₀Se₅₈、Ge₁₀As₄₀Se₅₀、As₄₀Se₆₀、Se硫系玻璃,采用流变仪测试样品黏弹状态的黏度,计算各样品黏度的Vogel-Fulcher-Tammann 方程和黏度变化速率(即料性)。结合拉曼光谱,根据玻璃微观结构对料性的影响规律进行系统分析。发现随着Ge_xAs_ySe_100-x-y硫系玻璃中Ge、As含量的增加,玻璃黏度随温度的变化速率先降低再升高,料性先变长后变短。在平均配位数=2~2.6时,随着平均配位数的增大,组成玻璃的原子之间的平均键能和网络结构稳定性逐渐变大,黏度变化速率降低,料性变长;在=2.6~2.78时,随着网络结构中As-As/Ge-Ge缺陷键的出现,玻璃网络结构的稳定性降低,玻璃黏度的变化速率加快,料性变短。     

Mo掺杂调控钛酸铋钠铁电陶瓷带隙的实验与第一性原理研究

为改善钛酸铋钠基无铅陶瓷的铁电光伏特性,通过传统固相法制备了B位Mo掺杂的Na_0.5Bi_0.5(Ti_1-xMo_x)O₃(BNT-Mo_x,x=0~0.02)无铅铁电陶瓷。通过XRD、拉曼光谱、吸收光谱等测试方法,结合基于密度泛函理论的第一性原理计算,研究了Mo掺杂对BNT陶瓷体系带隙的影响规律及机理。结果表明:随着Mo掺杂量的增加,光学带隙值先减小后增大,当x=1.0%时带隙达到最小值2.33 eV,并且光吸收强度达到最大值69%;通过对能带和态密度计算结果进行分析,发现Mo掺杂BNT体系能带结构由间接带隙转变为直接带隙,出现由Mo的4d轨道所贡献的杂质能级,导致带隙减小。Mo掺杂导致的杂质能级与莫斯-布尔斯坦效应之间存在带隙调控相互竞争关系,可有效调控BNT体系能带结构。     

B2O3-K2O-Sb2O3系统玻璃的光学折射率及带隙

高折射率和非线性光学玻璃可以用于高速光开关、光学存储器、新型光纤和光学运算元件等，其研究受到各国科技工作者的高度重视，本文采用熔融淬冷法制备了组成为(85-x)B₂O₃-15K₂O-xSb₂O₃(x=70, 75, 80, 85)的4组玻璃，测试了玻璃样品的密度、折射率、热学性能、拉曼光谱和吸收光谱，利用玻璃样品的吸收光谱计算了其直接允许光学带隙、间接允许光学带隙及Urbach能量。结果表明：随着Sb₂O₃含量的增加，玻璃样品的密度从4.445g/cm³逐渐增加到4.767g/cm³，折射率从1.9438增加到2.0058，玻璃转变温度从291℃降低到260℃，玻璃析晶温度从463℃降低到370℃，直接光学带隙从3.2775eV降低到3.1379eV，间接光学带隙从3.1444eV降低到3.0256eV，Urbach能量从0.137eV逐渐减小到0.107eV。说明Sb₂O₃-K₂O-B₂O₃系统玻璃可以作为新型的非线性光学玻璃候选材料之一。     

粉体热压法制备As2Se3硫系玻璃研究

本研究尝试将As₂Se₃红外硫系透镜生产过程中产生的块体玻璃废料进行回收利用,首先将清洗后的块体玻璃废料球磨成粉体,然后采用粉体热压技术实现高光学质量As₂Se₃玻璃片的制备。研究了粉体粒度、热压参数对制备的As₂Se₃玻璃光学性能的影响,对比了粉体热压法和熔融淬冷法制备的As₂Se₃玻璃的性能,评估了通过粉体热压途径制备红外硫系玻璃的可行性。结果表明:随着球磨时间的延长,As₂Se₃玻璃粉体的平均颗粒尺寸逐渐减小,且颗粒尺寸的分布趋于更加均匀;使用平均颗粒尺寸为9.7 μm的粉体(球磨10 min),在压力为40 MPa、热压温度为250 ℃、热压时间为10 min的条件下获得的热压玻璃的致密度达到99.8%,其折射率与熔融淬冷法制备的玻璃的折射率接近(在10 μm波长的折射率差仅为0.003),在10 μm波长的透过率达61%(理论透过率为63.7%)。通过进一步提高玻璃粉体的纯度和尺寸均匀性,有望制备出与熔融淬冷法制备的玻璃性能相当的热压玻璃。     

CsCl对GeS_2-Sb_2S_3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.     

GeS_2–Ga_2S_3–CdS玻璃的折射率与三阶非线性光学性能

采用熔融–急冷法制备了GeS_2–Ga_2S_3–CdS硫系玻璃,用椭圆偏振仪、飞秒光Kerr技术分别测试了在室温玻璃的折射率和三阶非线性光学性能,分析了玻璃的组成、结构对玻璃的折射率与三阶非线性光学性能的影响。结果表明玻璃的折射率主要决定于Ge的含量;玻璃的三阶非线性极化率χ(3)与玻璃中S—Ge,S—Ga键的数量有关,当玻璃中S—Ge,S—Ga键的数量最多时,离子极化程度最大。电子云的变形程度最大时,具有最大的χ(3)。玻璃的超快三阶非线性光学系数与线性折射率n间的关系不遵循Miller规则。     

印刷具有梯度折射率微结构的硫卤玻璃衍射光学元件的研究

通过一种高效而廉价的显微热极化工艺,在硫卤玻璃中刻印出覆盖可见到中红外波长且具有梯度折射率(GRIN)微结构的衍射光学元件(DOE)。研究了显微热极化的主要极化参数(极化电压U)对硫卤玻璃的微观形貌、微结构、衍射效果和梯度折射率的影响规律。在U为0.75~1.00 kV范围内发现了有效印刷GRIN微结构硫卤玻璃的形成区。表面形貌的深度、衍射级数随着U的增加而增加,但显微热极化对光学透过影响较小而不影响实际应用。显微热极化印刷后硫卤玻璃表面可以观察到周期长度为25 μm且最大相位差高达0.60λ(λ=632.8 nm)的GRIN微结构。其衍射性能的主要来源是近阳极一侧亚表面的K⁺迁移和玻璃结构重排形成周期性分布的GRIN微结构。     

GeS2-Ga2S3-CdS玻璃的折射率与三阶非线性光学性能

采用熔融-急冷法制备了GeS2-Ga2S3-CdS硫系玻璃,用椭圆偏振仪、飞秒光Kerr技术分别测试了在室温玻璃的折射率和三阶非线性光学性能,分析了玻璃的组成、结构对玻璃的折射率与三阶非线性光学性能的影响.结果表明:玻璃的折射率主要决定于Ge的含量;玻璃的三阶非线性极化率χ(3)与玻璃中S-Ge,S--Ga键的数量有关,当玻璃中S-Ge,S-Ga键的数量最多时,离子极化程度最大.电子云的变形程度最大时,具有最大的χ(3).玻璃的超快三阶非线性光学系数与线性折射率n间的关系不遵循Miller规则.     

氮掺杂对金红石二氧化钛光电特性影响的理论研究

运用第一性原理LDA+U方法,计算不同浓度氮元素掺杂金红石相二氧化钛的能带结构、态密度和光学性质,研究显示氮元素的掺入使TiO_2-x N _x 体系带隙变窄。而O-2p与N-2p轨道杂化耦合在费米能级附近出现了杂质能级,促使载流子跃迁变容易,从而拓展了TiO_2-x N _x 体系对可见光的响应范围。此外,杂质能级对电子-空穴对的复合有抑制作用,对光催化活性的提升具有积极作用。研究结果表明,当氮元素掺杂量（x）为0.062 5时,TiO_2-x N _x 体系光吸收性能与光电响应较好。     

Bi2O3-B2O3-Ga2O3玻璃的光学折射率和带隙研究

采用传统熔融淬冷法制备了5组高Bi2O3含量的Bi2O3-B2O3-Ga2O3系统玻璃样品.测试了玻璃样品的密度,折射率和吸收光谱.利用经典的Tauc方程计算了样品的间接允许光学带隙Eopgi,直接允许光学带隙Eopgd和Urbach能量ΔE.根据Duffy等人提出的经验推导公式计算了样品的能量带隙Eg.研究了Ga2O3含量对玻璃样品的密度、折射率、摩尔折射度Rm、金属标准值Mm、光学带隙、能量带隙和Urbach能量的影响,并分析了它们之间的关系.结果表明:随着Ga2O3含量的增加,玻璃样品的密度和折射率逐渐增大,但Ga3+对玻璃折射率的影响要小于B3+;玻璃样品的紫外吸收增强,光学带隙和能量带隙逐渐减小,光学带隙和能量带隙的比值约为1:1.1;Urbach能量逐渐减小,即玻璃中带裂变和缺陷形成的趋势越小.     

Correlating Structure with Threshold Behavior of Chalcogenide Glasses Within Ge–Sn–Se Ternary System

A systematic investigation of the optical and structural properties of chalcogenide glasses in Ge–Sn–Se ternary system is presented. We have found a threshold behavior of optical property, namely, existence of transitional composition of the Ge–Sn–Se glasses, with progressive replacement of Se by Sn. Calculation of mean coordination number indicates that the transition‐like feature of optical property is associated with the evolution of chemical ordering of the Ge–Sn–Se network. Analysis of Raman spectra of the glasses explains that the interaction between Se–Se bonds, Sn(Se_1/2)₄ tetrahedra, and Sn–Sn homopolar bonds is the origination of such optical phenomenon.     

Structure and physical properties of Ge15Sb20Se65‐xSx glasses

We explored the structure and physical properties of Ge₁₅Sb₂₀Se_65‐xS_x (with x = 0, 16.25, 32.5, 48.75, and 65) glasses in order to screen the best compositions for the applications in photonics, since the laser damage thresholds in Se‐based glasses are too low although their optical nonlinearities are high. We found that, linear and nonlinear refractive index of the glasses decreased, but glass transition temperature T_g, optical bandgap E_g and the laser damage threshold increased with increasing S content. We further employed Raman scattering and high‐resolution X‐ray photoelectron spectra to probe the structure of the glasses. Through the analysis of the evolution of the different structural units in the glasses, it was concluded that, the heteropolar bonds (Ge–Se/S, Sb–Se/S) were dominated in these glasses. With the increase in chalcogen Se/S ratio, the number of the Se‐related chemical bonds (Ge–Se, Sb–Se and Se–Se) increased and that of S‐related chemical bond (Ge–S, Sb–S and S–S) decreased gradually, and Ge was prior to bond with S rather than Se. The elemental substitution thus had negligible effect on the glass structure. The change of the physical properties was mainly due to the difference of the strength of the chemical bonds between S–Ge(Sb) and Se–Ge(Sb).     

Photosensitivity of barium germano-gallate glasses under femtosecond laser direct writing for Mid-IR applications

Barium germano-gallate glasses are attractive glass hosts for photonic applications in the mid-infrared region up to 6 μm. In this work, we investigate the photosensitivity of such glasses under femtosecond laser, with an emphasize on the formation of refractive index changes. Six glasses with varying compositions (including addition of K, Na, Y, and La) were studied. We observed several transformation regimes in the pulse energy – repetition rate landscape: Type I (isotropic refractive index change) and a spatial broadening regime with a phase shift Δϕ > 2π rad at 550 nm. This translates into refractive index changes Δn > 10⁻² and is comparable to values obtained in most chalcogenide glasses. The effect of glass composition on Δϕ appears correlated to the number of non-bridging oxygen presented in the glass and is brought to evidence by monitoring the Cations/GaO_3/2 ratio. This provides a way to design a range of germano-gallate glasses suitable to imprinting high refractive index contrast.     

MnO x -ZSM-5脱硝催化剂制备的溶剂效应研究

MnO _x -ZSM-5脱硝催化剂具有较好的低温氨选择性催化还原反应（NH₃-SCR）活性,因其原料成本低、脱硝效率高等优点成为研究热点。详细叙述了采用蒸干溶剂法、通过调变制备过程中溶剂组成（乙醇和水或其混合溶液）制备系列MnO _x -ZSM-5催化剂,并首次研究了“溶剂效应”对催化剂脱硝性能产生影响的原因。利用X射线衍射（XRD）、光电子能谱仪（XPS）、程序升温氨吸附法（NH₃-TPD）、N₂物理吸附、氢气程序升温还原（H₂-TPR）以及扫描电子显微镜（SEM）等表征手段分析了催化剂物化性质、锰存在状态与催化性能之间的相互关系。结果发现,随着溶剂中水分占比的提高,MnO _x -ZSM-5脱硝催化剂的比表面积降低,具有高催化活性的Mn⁴⁺物种比例迅速下降,这些原因均导致催化剂的脱硝活性逐步降低。说明溶剂组成会影响催化剂的脱硝性能,因此在制备MnO _x -ZSM-5脱硝催化剂时选取合适的溶剂是至关重要的,这为如何制备高活性的MnO _x -ZSM-5脱硝催化剂提供了重要信息。     

Composition–structure–property relationships of transparent Ca–Al–Si–O–N oxynitride glasses: The roles of nitrogen and aluminum

We explore the formation and composition–structure–property correlations of transparent Ca–Al–Si–O–N glasses, which were prepared by a standard melt-quenching technique using AlN as the nitrogen source and incorporating up to 8 at.% of N. Their measured physical properties of density, molar volume, compactness, refractive index, and hardness—along with the Young, shear, and bulk elastic moduli—depended roughly linearly on the N content. These effects are attributed primarily to the improved glass-network cross-linking from N compared to O, rather than the formation of higher-coordination AlO₅ and AlO₆ groups, where ²⁷Al magic-angle-spinning nuclear magnetic resonance experimentation revealed that aluminum is predominately present in tetrahedral coordination as AlO₄ units. Yet, several physical properties, such as the refractive index along with the bulk, shear, and Young's elastic moduli, increase concomitantly with the Al content of the glass. We discuss the incompletely understood mechanical–property boosting role of Al as observed both herein and in previous reports on oxynitride glasses, moreover suggesting glass-composition domains that are likely to offer optimal mechanical properties.     

Properties and Structure of Lithium Borate and Strontium Borate Glasses

Experimental results for some physical properties of Li₂O-B₂O₃ and SrO-B₂O₃ glasses with high modifier content showed anomalies in the composition dependence of many properties such as thermal expansion coefficient, transformation temperature, softening temperature, density, and refractive index at 30 to 33 mol% modifier oxide in these glasses. These anomalies are attributed to the formation of nonbridging oxygens near this composition.     

Controllable Formation of the Crystalline Phases in Ge–Ga–S Chalcogenide Glass‐Ceramics

We prepared chemically stoichiometric, S‐poor and S‐rich Ge–Ga–S glasses and annealed them at a temperature that was 20°C higher than its respective glass transition temperature. We aimed at tuning the formation of the different crystals in chalcogenide glass‐ceramics. Through systematic characterization of the structure using X‐ray diffraction and Raman scattering spectra, we found that, GeS₂ and GeS crystals only can be created in S‐rich and S‐poor glass‐ceramics, respectively, while all GeS, Ga₂S₃, and GeS₂ crystals exist in chemically stoichiometric glass‐ceramics. Moreover, we demonstrated the homogeneous distribution of the crystals can be formed in the S‐rich glass‐ceramics from the surface to the interior via composition designing. The present approach blazes a new path to control the growth of the different crystals in chalcogenide glass‐ceramics.