Neutron scattering studies on heavy-fermion superconductors

We review recent neutron scattering studies on uranium-based heavy-fermion superconductors. The coupling between magnetic and superconducting order parameters was observed in UPt₃, UPd₂Al₃, URu₂Si₂, and UNi₂Al₃. In UPd₂Al₃, the superconducting gap appears in the spin excitation spectra. These results are indicative of the strong interplay between magnetism and superconductivity. We also report the unusual behaviors of the weak antiferromagnetic ordering, the long-range magnetic correlation in UPt₃ at ultra-low temperatures, and the pressure-induced magnetic transition from the weak (0.02μ_B/U) to a high moment state (0.4μ_B/U) at 1.5 GPa in URu₂Si₂.     

Magnetic field dependence of spin-flip cross section for polarized neutron scattering of CeCu2Si2

The magnetic field dependence of the spin-flip cross section for quasielastic polarized neutron scattering is investigated for the Ce Kondo system at zero temperature. An exact calculation is done for the differential cross section with a small energy transfer and also for the total cross section. In particular the latter case is discussed in detail in order to investigate the recent experiment done for the polycrystalline CeCu₂Si₂. With the use of the obtained results, two possibilities are discussed about the wavefunction for the crystal-field ground doublet of the f-electron in CeCu₂Si₂.     

Structural stability of ultra-high temperature refractory material MoSi_2 and Mo_5Si_3 under high pressure

In-situ angle dispersive x-ray diffraction(ADXRD) with synchrotron radiation source is performed on an ultra-high temperature refractory of MoSi_2 and Mo_5Si_3 by using a diamond anvil cell(DAC) at room temperature. While the pressureinduced volume reduction is almost constant, the value of the bulk modulus increases with the decrease of molybdenum content in the system. According to the Brich–Murnaghan equation, the bulk modulus 222.1(2.1) GPa with its pressure derivative 4 of MoSi_2, and the bulk modulus 308.4(7.6) GPa with its pressure derivative 0.7(0.1) of Mo_5Si_3 are obtained.The experimental data show that MoSi_2 has distinct anisotropic behavior, Mo_5Si_3 is less anisotropic than MoSi_2. The result shows that MoSi_2 and Mo_5Si_3 have the structural stabilities under high pressure. When the pressure reaches up to 41.1 GPa, they can still maintain their body-cantered tetragonal structures.     

重费米子超导与竞争序

与其他非常规超导系列相比, 重费米子超导体往往具有丰富多样的竞争序, 超导与各种竞争序相伴而生, 电子配对与反铁磁涨落、铁磁涨落、价态涨落、电四极矩涨落等量子临界涨落密切相关, 扩充了非常规超导的研究内容. 重费米子材料中的f电子往往同时参与超导与各种竞争序的形成, 表现出局域与巡游的二重性. 重费米子二流体理论为理解重费米子超导与竞争序的关系提供了新的思路.     

Non-Fermi-liquid effects in stoichiometric 4f-electron metals at ambient pressure

We discuss strong deviations from the signatures of a heavy Landau–Fermi liquid already at p=0 that are observed for normal (n)-state CeCu₂Si₂, for CeNi₂Ge₂ and YbRh₂Si₂. No quantum critical point could yet be established in the case of CeNi₂Ge₂. For this compound, preliminary investigations of the chemical phase diagram have revealed certain similarities to CeCu₂Si₂. The non-Fermi-liquid (NFL) effects observed for YbRh₂Si₂ suggest a quasi-2D system of magnetic fluctuations. We also discuss briefly disparities between resistivity and specific-heat results in all three compounds as well as the relationship between a NFL n-state and the occurrence of heavy-fermion superconductivity.     

Neutron diffraction study of magnetic ordering in ErMn2Si2, ErMn2Ge2 and ErFe2Si2

Neutron diffraction study of polycrystalline compounds ErMn₂Si₂, ErMn₂Ge₂ and ErFe₂Si₂ was performed in the temperature range between 1.8 and 293 K. All compounds have tetragonal, ThCr₂Si₂-type crystal structure. The antiferromagnetic collinear structure of ErMn₂Si₂ and ErMn₂Ge₂ at both RT and LNT, consists of a sequence + - + - of ferromagnetic layers of Mn atoms. The magnetic moment of an Mn atom (≈2μ_B) is parallel to the c-axist. At low temperatures (LHT and lower), the ferromagnetic ordering within the Er sublattice is observed. The magnetic moment (μ_Er ≈ 9μ_B) is perpendicular to the c-axis. From the temperature dependence of the intensities of the magnetic peaks, the following values for the Curie temperatures were obtained: (10±5) K for ErMn₂Si₂ and (8.5±3) K for ErMn₂Ge₂. For ErFe₂Si₂ a collinear antiferromagnetic structure of the + - - + type was found, the magnetic unit cell consisting of the chemical one, doubled along the c-axis.     

Ru2Si3在应力作用下的第一性原理研究

采用基于第一性原理的密度泛函理论(Density functional theory)赝势平面波方法,对应力下Ru2Si3的电子结构和光学性质进行了理论计算和比较.计算结果表明:随着正应力的逐渐增大,导带向高能方向移动,带隙Eg明显展宽;随着负应力的逐渐增大,带隙缓慢减小并且始终为直接带隙.光学性质曲线随着负应力的不断...     

硼组分在BaAl2Si2O8:Eu2+发光材料中的作用

采用高温固相法在弱还原气氛下制备Ba0.955Al2-xBxSi2O8:Eu2+(x=0～0.5)系列荧光粉,研究B3+置换Al3对晶体结构和光谱特性的影响.B3+以类质同相替代BaAl2Si2O8晶格中的Al3+形成部分连续固溶体,随着B3+置换量的增加,晶胞参数a,b,c和晶胞体积V呈线性递减,晶面夹角β呈线性递增...     

The vacancy defects and oxygen atoms occupation effects on mechanical and electronic properties of Mo_5Si_3 silicides

Improving brittle behavior and mechanical properties is still a big challenge for high-temperature structural materials.By means of first-principles calculations,in this paper,we systematically investigate the effect of vacancy and oxygen occupation on the elastic properties and brittle-orductile behavior on Mo_5Si_3.Four vacancies (Si_(–Va1),Si_(–Va2),Mo_(–Va1),Mo_(–Va2)) and oxygen occupation models (O_(–Mo1),O_(–Mo2),O_(–Si1),O_(–Si2)) are selected for research.It is found that Mo_(–Va2)vacancy has the stronger structural stability in the ground state in comparison with other vacancies.Besides,the deformation resistance and hardness of the parent Mo_5Si_3are weakened due to the introduction of different vacancy defects and oxygen occupation.The ratio of B/G indicates that oxygen atoms occupation and vacancy defects result in brittle-to-ductile transition for Mo_5Si_3.These vacancies and the oxygen atoms occupation change the localized hybridization between Mo–Si and Mo–Mo atoms.The weaker O–Mo bond is a contributing factor for the excellent ductile behavior in the O_(-Si2)model for Mo_5Si_3.     

La3Co29-xFexSi4B10的择优占位、电子结构和晶格振动性质的理论研究

分别用第一性原理及原子间相互作用势对初始模型进行几何优化, 所得稳定结构的晶格参数均与实验值符合较好. 通过第一性原理密度泛函理论, 计算了稳定结构La₃Co_29-xFe_xSi₄B₁₀化合物择优占位情况, 计算结果表明, Fe原子最择优替代Co 原子的2c晶位, 择优占位顺序为2c > 8j1 > 8i2 > 8j2 > 8i3 > 16k > 8i1, 这与实验结果非常符合. Fe原子每次只替代不同晶位的一个Co原子时, La₃Co_29-xFe_xSi₄B₁₀ 体系的晶格常数几乎不变, 磁矩却发生了有趣的变化. 当Fe原子沿着择优顺序依次替代不同晶位的所有Co原子时, 随着La₃Co_29-xFe_xSi₄B₁₀体系中Fe原子含量的增多, 其电子态密度整体向左移动. Fe原子完全替代Co时, 与未掺杂时相比体系的总磁矩增加. 最后, 利用原子间相互作用势进一步预测了La₃Co_29-xFe_xSi₄B₁₀体系的晶格振动及热力学性质. 在低频部分, 振动模式主要由质量较大的Co, Fe和La元素作贡献; 随着掺杂原子Fe的增多, 体系的截止频率先减小后增多, 中频部分由Si元素引起的振动模式减少; B-B强相互作用引起了高频部分的振动模式. 基于声子态密度预测了不同数量Fe掺杂后体系的比热、熵和德拜温度的变化, 当Fe 含量大于Co时, 德拜温度明显升高.     

溶胶-凝胶法合成蓝色荧光粉SrAl2Si2O8：Eu2+

采用溶胶-凝胶(Sol-gel)法以相应的硝酸盐和正硅酸乙酯(TEOS)为反应物在85℃水浴制得胶体,并将干燥后的胶体前驱物在较低温度(921℃)下还原制得蓝色发光材料SrAl₂Si₂O₈:Eu²⁺。分别以热重(TG)-差示扫描量热(DSC)、X射线粉末衍射(XRD)、光致发光(PL)对合成产物进行了表征。并深入研究了溶胶-凝胶法制备过程中的影响因素,如pH值、乙醇含量、柠檬酸含量等,确定了合成SrAl₂Si₂O₈:Eu²⁺的最佳条件。XRD分析表明,当金属离子与柠檬酸的量的比为1:1,无水乙醇的量至少保证TEOS完全溶解于其中,溶液pH值为1.0~2.0时,可得到纯的SrAl₂Si₂O₈六方物相。发光分析表明,产物在监测463nm波长下的激发峰为327nm,在394nm激发下的发射光谱峰为468nm。     

白光LED用Ca3Si3O9：Dy3+荧光粉的制备及其发光性能

采用溶胶-凝胶法制备了可用于白光LED的新型Ca₃Si₃O₉:Dy³⁺荧光粉, 通过对样品的X 射线衍射谱及光致发光光谱的测试和表征, 研究了Ca₃Si₃O₉:Dy³⁺的物相结构和发光性能. 结果显示, Ca₃Si₃O₉:Dy³⁺的发射光谱是由位于483 nm和577 nm处的主峰构成的双峰谱线, 激发光谱为多峰宽谱, 谱峰位于290–480 nm范围内. Dy³⁺掺杂浓度对Ca₃Si₃O₉:Dy³⁺发光性能有明显的影响, 随着Dy³⁺浓度的增大, Ca₃Si₃O₉:Dy³⁺的发光强度和黄、蓝光发射强度比 (Y/B) 均呈现先增大后减小的规律, 最大发光强度值对应的Dy³⁺浓度为1 mol%. 电荷补偿剂Li⁺能提高Ca₃Si₃O₉:Dy³⁺的发光强度, 特别当Li⁺浓度为2–4 mol%时, 荧光粉的蓝光发射强度显著增大. 关键词： 白光LED 溶胶-凝胶法 3Si₃O₉：Dy³⁺')" href="#">Ca₃Si₃O₉：Dy³⁺ 发光特性     

Magnetic structures of R3Cu4Si4 (R=Dy, Ho and Er)

Polycrystalline samples of R₃Cu₄Si₄ (R=Dy, Ho, Er) intermetallics were studied with neutron diffraction methods. All of them crystallize in the orthorhombic structure of Gd₃Cu₄Ge₄-type and order antiferromagnetically at low temperatures. Magnetic moments localized at the rare earth atoms, that occupy two non-equivalent 2d and 4e sublattices, order simultaneously in Dy₃Cu₄Si₄. The order is described by the propagation vector accompanied by , δ=0.025(2). In Ho₃Cu₄Si₄ two propagation vectors are needed to model the magnetic order. These are: for the 4e sublattice, which disorders as the first when the temperature increases, and for the 2d sublattice. A similar situation is observed for Er₃Cu₄Si₄ where the propagation vectors are: k=(0,1−δ,0), δ=0.097(2) for the 4e sublattice, which disorders as the first with increasing temperature, and , δ=0.0015(6) for the 2d sublattice.     

制备红色硅氮化物发光材料的专利综述

随着LED技术的发展,红色硅氮化合物M2Si5N8(M=Ca,Sr,Ba)发光材料逐渐成为了重要的三基色发光材料,有关M2Si5N8发光材料的专利申请逐渐增加,其广阔的应用前景已经引起国内外极大的关注。为了更全面地把握M2Si5N8发光材料的专利申请态势,有利于科学研究和技术进步,本文首次综述了M2Si5N8发光材料的专利申请量和重要申请人,以及该材料的制备工艺方面的基础发明专利的技术演进。从改善红色硅氮化合物M2Si5N8发光性能的角度,对该材料的制备方法进行了分类,并分析了不同方法的优缺点,归纳了有关该材料制备方面的发明点。该综述有助于为本领域技术人员了解发光材料相关行业的技术发展动态、进行专利的有效开发和保护提供一些启示。     

助熔剂对Sr0.97Si2N2O2：0.03Eu2+荧光粉制备及发光性能的影响

在N₂气氛下,以Si₃N₄、SrCO₃和Eu₂O₃为原料,采用自还原高温固相合成法制备了Sr_0.97Si₂N₂O₂：0.03Eu²⁺荧光粉。在近紫外光激发下,该荧光粉发出明亮的黄绿光,发射峰位于533 nm处。采用XRD分析了不同助熔剂（NH₄F,NH₄Cl,Li₂CO₃,H₃BO₃）条件下的荧光粉晶相发育情况。通过SEM和荧光光谱研究了不同助熔剂对Sr_0.97Si₂N₂O₂：0.03Eu²⁺晶粒形貌及发光性能的影响。结果表明,随着助熔剂的添加,荧光粉团聚现象缓解、结晶度增强、分散性提高,且不同程度地提高了荧光粉的发光强度,其中以NH₄Cl的添加效果最佳。     

橙红色荧光粉Ca3Y2Si3O12：Sm3+的制备及发光特性

采用高温固相法在1 400 ℃下经二次煅烧合成了橙红色荧光粉Ca₃Y_2-xSi₃O₁₂：xSm³⁺,研究了Sm³⁺离子掺杂浓度及助熔剂对荧光粉发光性能的影响。XRD结果显示,所合成的荧光粉的主晶相为Ca₃Y₂Si₃O₁₂。荧光光谱分析表明,Ca₃Y₂Si₃O₁₂：Sm³⁺硅酸盐荧光粉可以在320~500 nm范围内得到有效激发,并发射橙红光。在402 nm激发下,样品发射光谱中的主发射峰分别位于562 nm（⁴G_5/2→⁶H_5/2）、598 nm（⁴G_5/2→⁶H_7/2）和646 nm（⁴G_5/2→⁶H_9/2）,其中598 nm处峰值最大。改变Sm³⁺离子掺杂浓度发现：荧光粉发光强度先增大后减小,最佳Sm³⁺掺杂量x（Sm³⁺）为5%,浓度猝灭机理为离子间的相互作用。讨论了几种助熔剂的影响,NH₄F、CaF₂和NaCl均降低荧光粉的发光强度,只有H₃BO₃能够显著增强样品的发光,其最佳掺杂质量分数为1%。     

Tb掺杂的硅铝酸盐的拉曼光谱及其荧光光谱研究

采用高温固相法制备不同浓度Tb元素掺杂的硅铝酸盐荧光材料。当烧结温度为1 350 ℃时其荧光强度达到最大值。通过X射线衍射图谱可知体系中基质材料为CaAl₂Si₂O₈,Tb元素以Ca₂Tb₈(SiO₄)₆O₂相存在。通过拉曼光谱分析可知,870 cm-1处振动峰与Ca₂Tb₈(SiO₄)₆O₂中Tb与硅氧四面体的伸缩振动相关;Tb原子与硅氧四面体之间的弯曲振动产生408 cm-1振动峰。随着Tb掺杂量的增加,拉曼振动峰强度,荧光分光光度计测得的荧光光谱以及拉曼光谱仪测得的光致发光光谱的峰强均呈现先增后减的变化规律。该体系中Tb元素与硅氧四面体匹配数量逐渐增加,当Tb掺杂量超过一定极限值时,体系内发生浓度猝灭,导致荧光性能下降。采用325 nm激光作为激发光源,用拉曼光谱仪的光致发光测量模式产生的峰形与传统荧光分光光度计的光谱曲线一致,但其光谱分辨率明显高于传统荧光分光光度计获得的光谱,有助于对细微能级跃迁现象加以区分。     

Effects of Pr substitution on the hydrogenating process and magnetocaloric properties of La_(1-x)Pr_xFe_(11.4)Si_(1.6)H_y hydrides

In this paper, we study the effects of Pr substitution on the hydrogenating process and magnetocaloric properties of La_(1-x)Pr_xFe_(11.4)Si_(1.6)H_y hydrides. The powder x-ray diffraction patterns of the La_(1-x)Pr_xFe_(11.4)Si_(1.6) and its hydrides show that each of the alloys is crystallized into the single phase of cubic Na Zn_(13)-type structure. There are hydrogen-absorbing plateaus under 0.4938 MPa and 0.4882 MPa in the absorbing curves for the La_(0.8)Pr_(0.2)Fe_(11.4)Si_(1.6) and La_(0.6)Pr_(0.4)Fe_(11.4)Si_(1.6) compounds. The releasing processes lag behind the absorbing process, which is obviously different from the coincidence between absorbing and releasing curves of the La Fe_(11.4)Si_(1.6) compound. The remnant hydrogen content for La_(0.6)Pr_(0.4)Fe_(11.4)Si_(1.6) is significantly more than that for La_(0.8)Pr_(0.2)Fe_(11.4)Si_(1.6) after hydrogen desorption, indicating that more substitutions of Pr for La are beneficial to retaining more hydrogen atoms in the alloys. The values of maximum magnetic entropy change are 14.91 J/kg·K and 17.995 J/kg·K for La_(0.8)Pr_(0.2)Fe_(11.4)Si_(1.6)H_(0.13) and La_(0.6)Pr_(0.4)Fe_(11.4)Si_(1.6)H_(0.87),respectively.     

Shape memory and associated properties in Fe–Mn–Si-based ribbons produced by melt-spinning

Four Fe–Mn–Si alloys, Fe₆₂Mn₃₂Si₆, Fe₆₂Mn₂₀Si₅Cr₈Ni₅, Fe₆₂Mn₁₆Si₅Cr₁₂Ni₅ and Fe₆₅Mn₉Si₇Cr₁₀Ni₉, were obtained by the melt-spinning method. The samples were structurally, magnetic and shape memory effect (SME) investigated, both “as quenched” and thermally treated. The Mn-rich compositions show different phase, magnetic behavior and SME in comparison with Mn-poor compositions. The thermal treatments generate transformation between the two existing majority phases ( and γ), related magnetization and SME behavior. The features are derived from the corroboration of structural, magnetic interaction and magnitude of SME data.     

Magnetic and transport properties of the extended s—f model

On the basis of the extended s-f model including 5d-4f electron-hole attraction and the hybridization between the 4f and 5d electrons the coexistence between ferromagnetism and fluctuating valence has been considered. The Curie temperature, effective magnetic moment, the phase diagram of the system and dc conductivity (resistivity) has been found by using in all numerical calculations the triple integration over the Brillouin zone (s.c.lattice). The calculations of the dc conductivity (resistivity) as a function of temperature has been performed for the semiconducting and metallic state of the system by using different parameter constellations of the model. The calculated conductivities and resistivities show great similarities in shape to the experimentally observed in the real mixed-valent or heavy fermion systems as e.g. EuO, US, UN, NpAl₂, NpOs₂, CePd₃, CeAl₃, PuAl₂, EuNi₂P₂, Ce_xLa_1-xSi₂,…