GexSb20Se80-x玻璃的拉曼光谱和X射线光电子能谱

用拉曼散射光谱和X射线光电子能谱研究了Ge_xSb₂₀Se_80-x(x=5 mol%, 10 mol%, 15 mol%, 17.5 mol%, 20 mol%和25 mol%)玻璃的结构. 通过对拉曼光谱和X射线光电子能谱(Ge 3d, Sb 4d 和Se 3d谱)进行分解, 发现当硫系玻璃处于富Se状态下时, 玻璃结构中会出现Se–Se–Se结构单元, 其数量随着Ge含量的增加而迅速减少, 并最终在Ge₁₅Sb₂₀Se₆₅玻璃结构中消失; Ge和Sb原子分别以GeSe_4/2 四面体和SbSe_3/2三角锥结构单元在玻璃结构中出现, GeSe_4/2四面体结构单元的数量会随着Ge浓度的增加而增加, 而SbSe_3/2三角锥结构单元的数量基本保持稳定. 另一方面, 在缺Se的硫系玻璃中, 玻璃会有Ge–Ge和Sb–Sb同极键产生, 随着Ge含量的增大, 这种同极键的数量会越来越多; 而GeSe_4/2四面体和SbSe_3/2三角锥结构的数量则相应减少. 在所有玻璃样品的结构中均有同极键Se–Se的存在. 当玻璃组分越接近完全化学计量配比时, 异质键Ge–Se和Sb–Se将占据玻璃结构中的主导地位, 同极键Ge–Ge, Sb–Sb和Se–Se 的比例降为最小.     

低损耗Ge-As-Se-Te硫系玻璃远红外光纤的性能分析

中、远红外光学领域的发展,离不开低损耗光波导材料的发展,因此近年来远红外低损耗光纤一直是光学领域的热点之一.本论文在国内首次报道了一种基于挤压法的低损耗远红外光纤制备技术,获得了具有完整结构的远红外光纤,其损耗为:0.46 d B/m@8.7μm,1.31 d B/m@10.6μm,整体低于1 dB/m@7.2—10.3μm.在实验过程中,首先采用传统的熔融淬冷法和蒸馏纯化工艺制备了Ge-As-Se-Te玻璃样品.利用X射线衍射仪和热膨胀仪等测试了玻璃的结构和物理性质,分析了Ge对玻璃热学性质的影响;利用分光光度计、红外光谱仪等研究了玻璃的光谱性质;综合比较了还原剂铝、镁的除氧效果.最后采用挤压法制备了芯包结构光纤.实验结果表明:镁的除氧效果佳,新型挤压制备工艺和有效提纯技术共同推进了硫系光纤损耗的降低,所获得的Ge-As-Se-Te光纤具有远红外广谱应用的潜能(其透光波长接近12μm).     

Linear optical characterization of chalcogenide glasses

A simple experimental method is used to obtain the evolution of both the refractive index and the linear absorption coefficient as a function of the optical wavelength in the near infrared range (from 900 up to 1700 nm with 10 nm resolution). Several chalcogenide glasses (As₂S₃, As₂Se₃, GeSe₄) are tested and the corresponding Cauchy coefficients are determined. Comparison of our results shows a good agreement with values available in the literature at some wavelength. Application of this method is used to estimate Cauchy coefficients of Ge₁₀As₁₀Se₈₀ for the first time to our best knowledge.     

Ge20Sb15Se65薄膜的热致光学特性变化研究

采用磁控溅射法制备了Ge₂₀Sb₁₅Se₆₅薄膜, 研究热处理温度(150—400 ℃)对薄膜光学特性的影响. 通过分光光度计、X射线衍射仪、显微拉曼光谱仪对热处理前后薄膜样品 的光学特性和微观结构进行了表征, 并根据Swanepoel方法以及Tauc公式分别计算了薄膜折射率色散曲线和光学带隙等参数. 结果表明当退火温度(T_a)小于薄膜的玻璃转化温度(T_g)时,薄膜的光学带隙(E_g^opt)随着退火温度的增加由1.845 eV上升至1.932 eV, 而折射率由2.61降至2.54; 当退火温度大于薄膜的玻璃转化温度时,薄膜的光学带隙随退火温度的增加由1.932 eV降至1.822 eV, 折射率则由2.54增至2.71. 最后利用Mott和Davis提出的非晶材料由非晶到晶态的结构转变模型对结果进行了解释, 并通过薄膜XRD和Raman光谱进一步验证了结构变化是薄膜热致变化的重要原因. 关键词： 20Sb₁₅Se₆₅薄膜')" href="#">Ge₂₀Sb₁₅Se₆₅薄膜 热处理 光学带隙 折射率     

Ionic diffusion and local hopping in copper chalcohalide glasses measured using Cu tracer and I-Mössbauer spectroscopy

For the first time, ⁶⁴Cu tracer measurements of ionic diffusion were performed for several copper-rich glass compositions in the CuI---As₂Se₃, CuI---SbI₃---As₂Se₃, CuI---PbI₂---As₂Se₃, CuI---PbI₂---SbI₃---As₂Se₃ and Cu₂Se---As₂Se₃ systems. In accordance with previous a.c. impedance results and Wagner d.c. polarization measurements, it was found that pure Cu⁺ ion-conducting glasses (50CuI---17PbI₂---33As₂Se₃ and 50CuI---20PbI₂---10SbI₃---20As₂Se₃) exhibit the highest copper tracer diffusion coefficients, D_Cu, and the lowest diffusion activation energies. The values of D_Cu at room temperature are higher by 4.5–5.5 orders of magnitude than those in an As₂Se₃ glass. The Haven ratio, H_R, is found to be 0.52–0.61 (ternary glass) and 0.93–1.00 (quaternary glass). Short-range diffusional displacements of the iodide ions induced by the hopping Cu⁺ ions are also detected in the CuI---PbI₂---SbI₃---As₂Se₃ glassy system using ¹²⁹I-Mössbauer spectroscopy in the temperature range of 4.2 to 305 K. The activation energy of local hopping, E_h ≈ 0.31 eV, is very similar to that of bulk ionic conductivity (0.37 eV) and copper diffusion (≈ 0.33 eV). In contrast to CuI-based vitreous alloys, 50Cu₂Se---50As₂Se₃ glass exhibits D_Cu that are two to five orders of magnitude lower, and the copper ion transport number, t_Cu⁺, is between 10⁻³ and 10⁻⁴ in the temperature range 140–170 °C.     

Structural modulation and physical properties of cobalt-doped layered La_2M_5As_3O_2(M=Cu,Ni) compounds

We investigate the structural variation and physical properties of layered La_2M_5As_3O_2(M=Cu,Ni) compound upon Co doping. It is found that the substitution of Co ion just induces the monotonous change of lattice constants without observing the anomalous kink in superconducting La_2(Cu~(1-x)Nix)_5 As_3O_2 solid-solutions. Meanwhile, this doping barely changes As–As bond length in [M_5As_3]~(2-) subunit(±2%), being significantly smaller than 7% shrinkage of that in La_2(Cu~(1-x)Nix)_5 As_3 O_2. Therefore, the doping dependence of crystal structure exhibits similar trend with Ba~(1-x)K_xFe_2 As_2 without the interference of As1–As 2 bonding, implying that the Co substitution for Cu/Ni is hole-doped. In terms of physical property, La2(Cu1-xCox)~5As_3O_2 turns into itinerant ferromagnetic metal, while La2(Ni1-x Cox)5 As3 O2 shows paramagnetism and suppressed structural phase transition upon Co-doping. The distinct structural variation and absence of superconductivity provide important clues to understand the effect of As–As bond in [M_5 As_3]~(2-) subunit.     

Exploring Majorana zero modes in iron-based superconductors

Majorana zero modes (MZMs) are Majorana-fermion-like quasiparticles existing in crystals or hybrid platforms with topologically non-trivial electronic structures. They obey non-Abelian braiding statistics and are considered promising to realize topological quantum computing. Discovery of MZM in the vortices of the iron-based superconductors (IBSs) has recently fueled the Majorana research in a way which not only removes the material barrier requiring construction of complicated hybrid artificial structures, but also enables observation of pure MZMs under higher temperatures. So far, MZMs have been observed in iron-based superconductors including FeTe_0.55Se_0.45, (Li_0.84Fe_0.16)OHFeSe, CaKFe₄As₄, and LiFeAs. In this topical review, we present an overview of the recent STM studies on the MZMs in IBSs. We start with the observation of MZMs in the vortices in FeTe_0.55Se_0.45 and discuss the pros and cons of FeTe_0.55Se_0.45 compared with other platforms. We then review the following up discovery of MZMs in vortices of CaKFe₄As₄, impurity-assisted vortices of LiFeAs, and quantum anomalous vortices in FeTe_0.55Se_0.45, illustrating the pathway of the developments of MZM research in IBSs. Finally, we give perspective on future experimental works in this field.     

Chalcogenide glass photonic crystals

All-optical switching devices are based on a material possessing a nonlinear optical response, enabling light to control light, and are enjoying renewed interest. Photonic crystals are a promising platform for realizing compact all-optical switches operating at very low power and integrated on an optical integrated circuit. In this review, we show that by making photonic crystals from a highly nonlinear chalcogenide glass, we have the potential to integrate a variety of active devices into a photonic chip. We describe the fabrication and testing of two-dimensional Ge₃₃As₁₂ Se₅₅ chalcogenide glass photonic crystal membrane devices (waveguides and microcavities). We then demonstrate the ability to post-tune the devices using the material photosensitivity. In one proposal we hope to introduce a double-heterostructure microcavity using the photosensitivity alone.     

Composition and thermal-induced effects on the optical constants of Ge20Se80−xBix thin films

 The effects of composition and thermal annealing near crystallization temperature, T_c on the optical and structural properties of Ge₂₀Se_80−xBi_x (x=0, 2.5, 5 and 7.5 at%) was investigated. The influence of incorporation Bi content in Ge₂₀Se_80−xBi_x system results in a gradual decrease in the indirect optical gap from 1.89 to 1.44 eV, this behavior can be explained as increased tailing. On annealing, the optical band gap E_g decreases gradually for the crystallized films while the refractive index increases, this behavior can be attributed to transformation from amorphous to crystalline and was explained in the light of dangling bond model. The refractive index n of as-prepared and annealed films has been analyzed according to the Wwmple–DiDominico single oscillator model and the values of E_o and E_d were determined. The effect of annealing on the nature and degree of crystallization has been investigated by studying the structure using transmission electron microscope, X-ray diffraction and scanning electron microscope.     

Ge-As-S硫系玻璃的结构与性能调控

制备了系列具有不同化学配比特征的Ge-As-S硫系玻璃,并研究了玻璃的结构、折射率和光学带隙(Eg).Ge-As-S玻璃具有以[Ge S_4]四面体和[As S_3]三角锥为骨架结构单元相互交联形成的连续网络结构,当S过量时,结构中出现S链或S_8环;当S不足时,结构中形成As_4S_4/As_4S_3分子,甚至出现大量AsAs/Ge-Ge同极键.玻璃的组成元素在2—10μm波段的摩尔折射度分别为R_(Ge)=9.83—10.42 cm~3/mol,RAs=11.72—11.87 cm~3/mol和R_S=7.78—7.86 cm3/mol.Ge-As-S玻璃的折射率与密度和组成元素的摩尔折射度之间存在较好的定量关系,可根据该定量关系在1%偏差内对玻璃的折射率进行预测或调控.提出了采用玻璃粉末的漫反射光谱确定可靠Eg的方法,通过该方法可获得玻璃的强吸收数据用于确定Eg.Ge-As-S玻璃的Eg与玻璃的平均键能之间存在较好的关联,S含量较高的玻璃更倾向于具有较大的平均键能,因此具有较大的Eg.     

Composition and electric field effects on the transport properties of Bi doped chalcogenide glasses thin films

The temperature dependence of the DC electrical conductivity σ_DC was measured in the temperature range from 300–500 K. It was found that there are double activation energies, E_σ, for Ge₂₀Se_80−xBi_x (x=0, 2.5 and 5 at%) films, while there is single activation energy for Ge₂₀Se_72.5Bi_7.5. when incorporation of Bi=7.5 at%, the pre-exponential value σ₀ decreases by about six order of magnitude, the activation energy in the extended states E_σ decreases from 0.96 to 0.09 eV. Also the effect of applied electric field was studied and observed that, activation energy in high temperature region increases with increasing electric field; this behavior can be understood assuming that the contribution to the conductivity activation process is due to conduction in the extended states and also due to hopping in the localized states. With the increasing electric field, as former process, which is having high activation energy, becomes more predominant due to the dumping of the carriers in the extended states, the effective activation energy of the system increases, in spite of the fact that the activation energy of the extended states conduction may remain constant. Finally, the electrical data suggests that the addition of bismuth produces localized states near the conduction band edge so that the electrical transport is due to hopping of electrons after being excited into localized states at the conduction band edge.     

准一维Cr基超导体RbCr3As3的超导能隙

RbCr₃As₃是具有[（Cr₃As₃）^-]_∞线性链的准一维超导体,超导转变温度约为6.6 K.对RbCr₃As₃单晶进行了电输运和极低温热输运性质的研究.低温下,拟合了RbCr₃As₃正常态电阻率随温度的变化,发现其满足费米液体行为.通过拟合超导转变温度随磁场的关系,得到RbCr₃As₃单晶的上临界场约为25.6 T.对RbCr₃As₃进行了零场下的极低温热导率测量,得到其剩余线性项为7.5 μW·K^-2·cm^-1,占正常态热导率值的24%.测量不同磁场下RbCr₃As₃的热导率,发现与单带s波超导体相比较,RbCr₃As₃剩余线性项随磁场增加相对较快.这些结果表明RbCr₃As₃单晶很可能是有节点的非常规超导体.     

新型单模大模场红外硫系玻璃光子晶体光纤设计研究

大模场光子晶体光纤在高功率激光传输、光纤放大器、光纤激光器中的广泛应用, 使其受到研究者的广泛关注.硫系玻璃在红外波段(1–20μm)具有优良透过性能, 且具有折射率高(2.0–3.5)、声子能量低(小于350 cm^-1)、 组分可调等特性, 成为制备红外光纤的理想材料. 本文设计一种基于Ge₂₀Sb₁₅Se₆₅硫系玻璃基质的新型单模传输、低损耗、超大模场面积光子晶体光纤结构, 经理论验证其在λ =10.6 μm处基模限制损耗远低于0.1 dB/m, 高阶限制模损耗大于2 dB/m, 模场面积约为13333 μm². 关键词： 硫系玻璃 大模场面积 红外光子晶体光纤 结构设计     

ZnSb掺杂的Ge2Sb2Te5薄膜的相变性能研究

本文采用双靶(ZnSb靶和Ge₂Sb₂Te₅靶)共溅射制备了系列ZnSb掺杂的Ge₂Sb₂Te₅(GST)薄膜. 利用X射线衍射、透射电子显微镜、原位等温/变温电阻测量、X射线光电子能谱等测试研究了薄膜样品的非晶形态、电学及原子成键特性. 利用等温原位电阻测试表明ZnSb掺杂的Ge₂Sb₂Te₅薄膜具有更高的结晶温度. 采用Arrhenius 公式计算发现ZnSb掺杂的Ge₂Sb₂Te₅薄膜的十年数据保持温度均高于传统的Ge₂Sb₂Te₅薄膜的88.9℃. 薄膜在200, 250, 300和350℃ 下退火后的X射线衍射图谱表明ZnSb的掺杂抑制了Ge₂Sb₂Te₅薄膜从fcc态到hex态的转变. 通过对薄膜的光电子能谱和透射电镜分析可知Zn, Sb, Te原子之间键进行重组, 形成Zn–Sb 和Zn–Te 键, 且构成非晶物质存在于晶体周围. 采用相变静态检测仪测试样品的相变行为发现ZnSb掺杂的Ge₂Sb₂Te₅薄膜具有更快的结晶速度. 特别是(ZnSb)_24.3(Ge₂Sb₂Te₅)_75.7薄膜, 其结晶温度达到250℃, 十年数据保持温度达到130.1℃, 并且在70 mW激光脉冲功率下晶化时间仅～64 ns, 远快于传统Ge₂Sb₂Te₅薄膜的晶化时间～280 ns. 以上结果表明(ZnSb)_24.3(Ge₂Sb₂Te₅)_75.7薄膜是一种热稳定性好且结晶速度快的相变存储材料.     

Ultra-broadband modulation instability gain characteristics in As_2S_3 and As_2Se_3 chalcogenide glass photonic crystal fiber

Based on the designed As_2Se_3 and As_2S_3 chalcogenide glass photonic crystal fiber(PCF) and the scalar nonlinear Schrdinger equation,the effects of pump power and wavelength on modulation instability(MI) gain are comprehensively studied in the abnormal dispersion regime of chalcogenide glass PCF.Owing to high Raman effect and high nonlinearity,ultra-broadband MI gain is obtained in chalcogenide glass PCF.By choosing the appropriate pump parameter,the MI gain bandwidth reaches 2738 nm for the As_2Se_3 glass PCF in the abnormal-dispersion region,while it is 1961 nm for the As_2S_3 glass PCF.     

GeS2-In2S3硫系玻璃的物化性质与晶化行为研究

认识玻璃组成-性能-结构之间关系是玻璃科学中经久不衰的研究课题之一. 在制得(100-x) GeS₂-xIn₂S₃ (x=10, 15, 20, 25或30 mol%) 系列玻璃和玻璃陶瓷样品的基础上, 利用可见-近红外透过光谱, DSC, XRD和Raman光谱等测试技术表征了随组份变化的光学带隙, 玻璃转变温度以及晶化行为等, 并结合GeS₂-Ga₂S₃玻璃研究结果探讨了Ga, In 元素及其形成的网络结构对玻璃性质的影响.研究发现, 在硫系玻璃中In比Ga对光学带隙和玻璃转变温度等性质的影响要大. 它们所形成玻璃的晶化行为也截然不同, 但与其各自的材料相图有着密切的联系. 利用偏振拉曼光谱获得玻璃网络中的基本结构单元信息.最后, 结合材料相图, 玻璃随组成变化的物化性质和晶化行为以及基本网络结构单元的认识, 探讨了玻璃的化学拓扑与网络拓扑之间的联系, 为今后研究提供一种新的研究思路.     

On the reversibility window in binary As–Se glasses

Physical ageing effects caused by prolonged natural storage are recorded for binary As_xSe_1−x glasses with 0.2x<0.4. Their origin is associated with pure “shrinkage” of under-constrained glass networks. It is shown that only stoichiometric As₂Se₃ composition, which network is formed by a so-called self-organized phase, possesses the ideal non-ageing ability.     

Tm3+/Ho3+掺杂碲酸盐玻璃的上转换发光性能与能量转换机制

采用高温熔融法制备了单掺Tm3+和Tm3+/Ho3+共掺碲酸盐玻璃,测试了808 nm激光泵浦下玻璃的红外和上转换荧光光谱。Tm3+/Ho3+共掺碲酸盐玻璃上转换荧光光谱主要由695 nm红光、544 nm绿光、474 nm蓝光和740 nm红光四个发光带组成。通过分析样品的光谱性能和能量转换机制,发现很少报道的740 nm红光可能是由Tm3+：1D₂ →3F_{2, 3}能级跃迁产生的。在掺杂0.5 mol％ Tm₂O₃的样品中添加0.3 mol％ Ho₂O₃,695 nm红光、740 nm红光和474 nm蓝光等上转换发光强度明显增大,大约分别是单掺0.5 mol％ Tm₂O₃样品中发光强度的3倍,2.5倍和14倍。这些情况说明存在着强烈的Ho3+→Tm3+反向能量传递。单掺Tm3+碲酸盐玻璃中1D₂能级(发射740 nm红光)上的粒子集居主要来源于合作上转换(CU)过程,而3F_{2, 3}能级(发射695 nm红光)上的粒子集居除了来源于CU过程之外,还有740 nm红光的发射和1G₄能级上部分粒子的无辐射跃迁(1G₄→3F_{2, 3})两条途径,因此样品中695 nm红光强度明显要大于740 nm红光强度。通过交叉驰豫作用CR2和CR3以及反向共振能量转移RET2,Tm3+/Ho3+共掺碲酸盐玻璃中Tm3+的1G₄能级(发射474 nm蓝光)上的粒子集居数比单掺Tm3+时出现了净增加。Tm3+的1G₄能级上粒子集居数的增加可能进一步强化了该能级的无辐射跃迁、740 nm红光的发射以及CU过程,并进而促使Tm3+的3F_{2, 3}能级上的粒子集居。所以,当Tm3+/Ho3+共掺碲酸盐玻璃与单掺Tm3+碲酸盐玻璃中掺杂相同浓度的Tm3+时,前者的红光和蓝光等上转换荧光强度均比后者要大。本文还研究了Tm3+之间以及Tm3+与 Ho3+之间的交叉弛豫和能量传递等效应,并进一步探讨了Tm3+与 Ho3+之间的能量转换机制。     

Effects of phosphorus doping on the physical properties of axion insulator candidate EuIn2As2

We report an investigation on the single crystal growth, magnetic and transport properties of EuIn₂(As_1-xP_x)₂ (0≤x≤ 1). The physical properties of axion insulator candidate EuIn₂As₂ can be effectively tuned by P-doping. With increasing x, the c-axis lattice parameter decreases linearly, the magnetic transition temperature gradually increases and ferromagnetic interactions are enhanced. This is similar to the previously reported high pressure effect on EuIn₂As₂. For x=0.40, a spin glass state at T_g=10 K emerges together with the observations of a butter-fly shaped magnetic hysteresis and slow magnetic behavior. Besides, magnetic transition has great influence on the charge carriers in this system and negative colossal magnetoresistance is observed for all P-doped samples. Our findings suggest that EuIn₂(As_1-xP_x)₂ is a promising material playground for exploring novel topological states.     

四方、单斜和正交Ge3N4的结构、电子结构和热力学性质

数值计算了四方、单斜和正交结构Ge₃N₄的点阵常数、晶胞体积、弹性模量、维氏硬度和态密度.计算结果与已有的实验数据和理论值符合得很好.形成焓为负、晶格形变和晶胞体积随压强呈线性变化,表明三种相在0~20 GPa压强范围内可以保持结构稳定.态密度研究表明三种氮化锗内部存在强烈的s-p杂化.三种相都属于脆性半导体材料,具备各向异性且硬度适中.采用包含原子振动和非谐效应的准谐波近似方案,研究材料的热力学性质,发现压强对赫姆霍兹自由能和内能有显著影响.结果为进一步理解氮化锗三种新结构的电子结构和热力学性质提供初步的物理图像.