(Sr,Ca)4Si3O8Cl4基质中Eu2+的发光特性研究

采用高温固相法合成Sr4-xCaxSi3O8Cl4：Eu^2＋荧光材料,利用Van Uitert公式讨论Sr4-xCaxSi3O8Cl4：Eu^2＋中yEu^2＋的晶格环境和发光特性,确定晶体中有蓝色和黄绿色两种发光中心,并讨论了它们与光谱结构的对应关系。当0〈x〈0．5,Ca^2＋固溶入Sr4Si3O8Cl4基质晶格,Eu^2＋占据八配位Si^2＋格位,晶体主要产生蓝色中心的蓝绿色发射;当0．5〈x〈2,较大的Ca^2＋掺杂使晶胞参数变小,品格中的杂质束缚激子态的束缚增强,Eu^2＋处于杂质束缚激子中心所形成的激发态能量进一步降低,发射位于长波段方向并具有较大的Stokes位移,Sr4-xCaxSi3O8Cl4：yEu^2＋主要产生黄绿色中心的黄绿色发射光。     

Ca~(2+)离子替代对Sr_4Al_(14)O_(25):Eu~(2+),Dy~(3+)结构和发光性能的影响

采用高温固相反应按化学式Sr4-xCaxAl14O25:Eu2+,Dy3+(x=0,0.8,1.6,2.4,3.2,4)配比原料,合成长余辉发光材料.X射线衍射分析表明当x2.4时,产物物相均为Sr4Al14O25正交结构;当x2.4时,产物物相转变为CaAl4O7单斜结构.对掺Ca量不同,但结构仍保持Sr4Al14O25的样品采用360nm激光照射,发射光谱表明样品发光均由以Eu2+为发光中心的电子4f65d→4f7跃迁所致,并且随着Ca掺入量的增加,样品发射光谱峰位逐渐蓝移.这是由于Ca2+取代Sr2+位置后,导致晶格收缩,影响Eu2+的5d能级劈裂情况,从而影响电子4f65d→4f7跃迁.余辉衰减检测和热释光谱分析发现,不同Ca掺入量的样品余辉衰减快慢不同,是由于其中存在的陷阱能级深度不同,且陷阱能级越深,其余辉时间越长.     

Eu2+激活的硅酸锶材料的发光特性

采用高温固相法制备了Sr₃SiO₅ : Eu²⁺黄色发光材料,研究了Eu²⁺浓度及共激活剂等对材料发光性能的影响。结果显示,随Eu²⁺浓度的增大,Sr₃SiO₅ : Eu²⁺材料发射强度先增强后减弱,即存在浓度猝灭效应,根据Dexter理论,其浓度猝灭机理为电偶极-偶极相互作用。掺入共激活剂Yb、Tm均能提高材料的发射强度。利用InGaN管芯分别激发Sr_2.98Eu_0.01Tm_0.01SiO₅和Sr_2.98Eu_0.01Yb_0.01SiO₅材料,获得了很好的白光发射。     

基质组成对Eu,Dy共掺杂铝酸锶发光性能的影响

研究了基质组成对xSrO·yAl₂O₃:Eu²⁺,Dy³⁺体系长余辉发光性能的影响,并对其影响机理进行了探讨.XRD分析结果和长余辉发光性能表明,改变Al₂O₃/SrO比率可以获得长余辉发光性能较好的三种基质相:SrAl₂O₄:Eu²⁺,Dy³⁺、Sr₄Al₁₄O₂₅:Eu²⁺,Dy³⁺和SrAl₄O₇:Eu²⁺,Dy³⁺.激发与发射光谱性能分析和余辉衰减特性分析结果表明,随着基质中Sr/Al比例的减小,激发光谱向短波方向延伸,发射峰蓝移,初始余辉亮度越高,余辉持续时间越长.热释光谱分析表明,贫锶相晶格中的陷阱深度与密度较大,因而显示出较好的长余辉发光性能.     

纳米棒状长余辉材料BaAl_2O_4:Eu~(2+),Dy~(3+)的制备与发光性能

利用硝酸铝、硝酸钡、尿素为原料,以一定比例H_2O/正丁醇及H_2O/正丁醇/SBS的混合液作传递压力的介质,进行反应,然后将得到的前驱体在还原气氛下高温煅烧,得到亮度高,余辉时间长的BaAl_2O_4:Eu~(2+),Dy~(3+)纳米棒状长余辉发光材料。TEM和SEM测试表明高温煅烧后得到的BaAl_2O_4:Eu~(2+),Dy~(3+)为棒状结构,其激发光谱和发射光谱均为宽带,主发射峰分别为498 nm,是典型的Eu~(2+)5d→4f跃迁。该方法的特点在于:采用水热法合成的BaAl_2O_4:Eu~(2+),Dy~(3+)长余辉发光材料一般需经过高温煅烧,容易结块,而在合成制得的产品经1 300℃高温煅烧后仍呈现分散性良好的棒状结构,不需球磨,且发光性能良好,可直接应用。同时将2种不同的实验条件进行比较,发现在不使用表面活性剂的条件下依然可得到分散性良好的棒状BaAl_2O_4:Eu~(2+),Dy~(3+)长余辉发光材料。该制备方法有望在其他铝酸盐和硅酸盐系长余辉发光材料的制备中得到应用。     

Ca9R(VO4)7 : Eu3+ 发光粉的发光特性

采用高温固相法制备了Eu³⁺离子激活的Ca₉R(VO₄)₇(R = Y, La, Gd)红色发光粉,并利用荧光光谱对发光粉的特性进行研究。激发光谱中,Ca₉Y(VO₄)₇ : Eu³⁺ , Ca₉La(VO₄)₇ : Eu³⁺和Ca₉Gd(VO₄)₇ : Eu³⁺都有两个宽的VO^3-₄激发带和Eu³⁺的特征激发峰。发射光谱中,在Ca₉Y(VO₄)₇ : Eu³⁺ 和Ca₉La(VO₄)₇ : Eu³⁺中的350~550 nm范围内出现VO^3-₄的发射带,而在Ca₉Gd(VO₄)₇ : Eu³⁺中却没有观察到VO^3-₄的发射。在这三种发光粉中,Ca₉Gd(VO₄)₇ : Eu³⁺的发光强度远远高于其它两种,这是由于Gd³⁺的存在有效地使能量通过Gd³⁺ →VO^3-₄ → Eu³⁺及Gd³⁺ → Eu³⁺的两种方式进行能量传递,从而提高了Eu³⁺发光效率。     

Photoluminescence properties of Ca_4La_6(SiO_4)_4(PO_4)_2O_2-based phosphors for wLEDs

The apatite compound Ca_4La_6(SiO_4)_4(PO_4)_2O_2(CLSPO) was explored as the host material for phosphors used in white light-emitting diodes(w LEDs). The crystal structure of the CLSPO host prepared by the solid-state reaction method was investigated with Rietveld refinement. The rare earth ions(Eu~(3+)/Tb~(3+)/Ce~(3+), Tb~(3+)/Tb~(3+), Mn~(2+))activated CLSPO phosphors were synthesized, and their photoluminescence properties, quantum yields, as well as thermal stabilities, were studied. Under near-ultraviolet excitations, the Eu~(3+) and Tb~(3+) -doped CLSPO compounds exhibited red and green emissions with high luminescence efficiencies. Besides, tunable emissions from green to orange were obtained by introducing Mn~(2+) ions into the Tb~(3+) -doped CLSPO samples. The results showed that the phosphors studied may have potential applications for w LEDs.     

Co掺杂对铁磁金属La0.8Sr0.2MnO3磁电阻影响机理

通过对La_0.8Sr_0.2Mn_1-yCo_yO₃(y≤02)饱和磁矩和输运的测量,研究了Co对La_0.8Sr_0.2MnO₃的磁电阻影响机制.结果表明,在La_0.8Sr_0.2Mn_1-yCo_yO₃（y≤02）中Co³⁺离子是低自旋态.由于Mn³⁺—O—Co³⁺—O—Mn³⁺类型的磁交换与Mn³⁺-Mn⁴⁺离子间双交换作用相比较弱,Curie温度T_C附近的磁电阻随着Co掺杂量的增加而降低.与此相反,由于Co²⁺离子与e_g巡游电子的反铁磁交换耦合作用,低温区间的磁电阻随着Co掺杂量的增加而升高. 关键词： 低自旋 磁电阻 磁交换作用     

Imaging the diffusion pathway of Al~(3+) ion in NASICON-type(Al_(0.2)Zr_(0.8))_(20/19)Nb(PO_4)_3 as electrolyte for rechargeable solid-state Al batteries

Among all-solid-state batteries, rechargeable Al-ion batteries have attracted most attention because they involve threeelectron-redox reactions with high theoretic specific capacity. However, the solid Al-ion conductor electrolytes are less studied. Here, the microscopic path of Al~(3+)-ion conduction of NASICON-type(Al_(0.2)Zr_(0.8))_(20/19)Nb(PO_4)_3 oxide is identified by temperature-dependent neutron powder diffraction and aberration-corrected scanning transmission electron microscopy experiments.(Al_(0.2) Zr_(0.8))_(20/19) Nb(PO_4)_3 shows a rhombohedral structure consisting of a framework of(Zr,Nb)O_6 octahedra sharing corners with(PO_4) tetrahedra; the Al occupy trigonal antiprisms exhibiting extremely large displacement factors. This suggests a strong displacement of Al ions along the c axis of the unit cell as they diffuse across the structure by a vacancy mechanism. Negative thermal expansion behavior is also identified along a and b axes, due to folding of the framework as temperature increases.     

荧光粉(Ca2.94-xLuxCe0.06)(ScMg)Si3O12的晶体结构和荧光性质

利用高温固相反应制备了一种由Lu改进的黄色荧光粉(Ca2.94-x LuxCe0.06)(ScMg)Si3O12(缩写为CKSMS:Ce3+),其中,0≤x≤0.94.同时研究了Lu含量对荧光粉的晶相、发光性质以及温度特性的影响.结果表明,Lu的引入导致荧光增强,其原因是由于Ce3+吸收增强而不是荧光粉内量子效率增加....     

Extraction of tight binding parameters from in-situ ARPES on the continuously doped surface of cuprates

Recently we developed a technique of ozone/vacuum annealing to continuously change the doping level of the surface of Bi_2Sr_2CaCu_2O_(8+x)and measured a nearly whole superconducting dome on one surface by in-situ angle-resolved photoemission spectroscopy [arXiv: 1805.06450]. Here we study the evolution of the electronic structures of Bi_2Sr_2CaCu_2O_(8+)xusing this technique together with tight binding fits. The tight binding parameters are extracted to study their evolution with doping.     

聚(2-甲氧基-5-辛氧基)对苯乙炔/Y_2O_3:Eu~(3+)纳米复合材料的光致电子转移效应

采用原位脱氯化氢缩合聚合法制备了聚(2-甲氧基-5-辛氧基)对苯乙炔/Y_2O_3:E~(3+)(PMOCOPV/Y_2 O_3:Eu~(3+))纳米复合材料。红外光谱证实了在Y_2O_3:Eu~(3+)表面的包覆层为PMOCOPV。紫外-可见吸收光谱表明与PMOCOPV相比,PMOCOPV/Y_2O_3:Eu~(3+)的最大吸收峰发生红移且强度提高。荧光光谱研究表明PMOCOPV/Y_2O_3:Eu~(3+)的最大发射波长发生红移且强度提高,荧光寿命得到增强,Y_2O_3:Eu~(3+)与PMOCOPV之间形成了光致电子转移体系,使得π电子离域程度增加,并且导致荧光量子效率提高。根据E_g与入射光子能量hv的关系,拟合了PMOCOPV/Y_2O_3:Eu~(3+)薄膜的光学禁带宽度,发现E_g减小。采用简并四波混频方法测试它们的三阶非线性极化率x~((3)),结果发现与PMOCOPV相比,PMOCOPV/Y_2O_3:Eu~(3+)纳米复合体的非线性光学响应逐渐增强,进一步说明PMOCOPV与Y_2O_3:Eu~(3+)之间形成了分子间光致电子转移体系,产生了复杂的分子间离域π电子非线性运动。     

磁性和非磁性元素掺杂的自旋梯状化合物Sr_(14)(Cu_(0.97)M_(0.03))_(24)O_(41)(M=Zn,Ni,Co)的结构和电输运性质

利用固相反应法制备了Sr14Cu24O41及其系列B位掺杂Sr14(Cu0.97M0.03)24O41(M=Zn,Ni,Co)的样品.X射线衍射分析显示,所有样品均为纯相,晶格常数a与c没有明显的变化;Zn掺杂样品晶格常数b没有明显变化,而Ni,Co掺杂样品晶格常数b分别稍有增加.选区电子衍射研究揭示:磁性元素Ni,Co及非磁性元素Zn掺杂,可能主要替代了Sr14Cu24O41结构中自旋链上的Cu原子,从而影响了自旋链上的dimer排列,破坏电荷有序超结构.电输运测量显示:Zn2+,Ni2+,Co3+离子掺杂样品的电阻率降低,但仍体现半导体行为,所有的掺杂样品都存在一个渡越温度Tρ,当TTρ时,其导电机理是以单空穴热激发导电占主要地位,在TTρ时,配对的局域化空穴的一维变程跳跃导电占主要优势;在相同的掺杂量下,非磁性元素Zn掺杂对电阻率值的影响大于磁性元素Ni,Co掺杂的影响,而磁性元素Ni,Co掺杂对渡越温度Tρ的影响大于非磁性元素Zn掺杂的影响.     

掺杂Sr8 CaRe3 Cu4 O24:一种可能具有半金属性和大的氧磁矩的材料

用密度泛函理论方法仔细研究了新型钙钛矿铜氧材料Sr8CaRe3Cu4O24的电子结构和磁性性质，发现掺杂将使得这种材料表现出非常奇特的性质：（1）用W或Mo替代Re，将使得材料变成半金属，同时它的磁转变温度仍然很高；（2）对Sr8CaRe3Cu4O24进行空穴掺杂，也将使它变为具有高磁转变温度的半金属材料。更为奇特的是，空穴掺杂将导致O原子上有很大的磁矩。因此，Sr8CaRe3Cu4O24很有可能是一种有广阔应用前景的磁性材料。     

Magnetoelectric effects in multiferroic Y-type hexaferrites Ba(0.3)Sr(1.7)CoxMg(2-x)Fe(12)O(22)

Y-type hexaferrites with tunable conical magnetic structures are promising single-phase multiferroics that exhibit large magnetoelectric effects. We have investigated the influence of Co substitution on the magnetoelectric properties in the Y-type hexaferrites Ba(0.3)Sr(1.7)CoxMg(2-x)Fe(12)O(22)(x = 0.0, 0.4, 1.0, 1.6). The spin-induced electric polarization can be reversed by applying a low magnetic field for all the samples. The magnetoelectric phase diagrams of BaBa(0.3)Sr(1.7)CoxMg(2-x)Fe(12)O(22) are obtained based on the measurements of magnetic field dependence of dielectric constant at selected temperatures. It is found that the substitution of Co ions can preserve the ferroelectric phase up to a higher temperature, and thus is beneficial for achieving single-phase multiferroics at room temperature.     

Eu2+激活的Ba5-xSrx(PO4)3Cl的发光性质

采用高温固相法合成了Eu2+激活的Ba5-zSrx(PO4)3cl(x=0,1,2,3,4,5)蓝色发光粉.样品的XRD衍射光谱表明,随着Ba2+浓度的增加,衍射峰向小角度方向移动.所有样品的激发光谱都存在两个激发峰,随着Ba2+浓度的增加,两个尖峰逐渐靠近,同时激发峰强度降低,这种现象可以通过位形坐标解释.激发和发射...     

纳米级发光材料A2SnO4(A=Ca,Sr,Ba):Eu发光性质的研究

采用络合溶胶-凝胶法制备出系列纳米级发光材料A2SnO4(A=Ca,Sr,Ba):Eu.并采用相关光谱、X射线衍射(XRD)、荧光光谱(PL)对所制备的纳米发光粉体进行表征.结果表明:制备的纳米发光粉体的粒径均匀,集中在100 nm左右;XRD结果证明碱土金属锡酸盐结构均为具有确定结构的单一物相;并且这些发光粉体的性质与碱土金属离子的半径密切相关.     

热致变色材料辐射和光学特性研究

采用固相反应法制备了相变温度接近室温的热致变色材料,研究了不同掺杂元素和掺杂浓度对热致变色材料辐射和光学特性的影响,并利用K-K分析模型导出了热致变色材料的光学常数。结果表明:热致变色材料LCSMO和LSMO(x=0.175)的发射率在相变温度附近出现剧烈变化,并且光常数在很大的频域范围内可自主调制。     

Superconductivity in Sm-doped CaFe_2As_2 single crystals

In this article,the Sm-doping single crystals Ca_(1-x)Sm_xFe_2As_2(x = 0 ~0.2) were prepared by the Ca As flux method,and followed by a rapid quenching treatment after the high temperature growth.The samples were characterized by structural,resistive,and magnetic measurements.The successful Sm-substitution was revealed by the reduction of the lattice parameter c,due to the smaller ionic radius of Sm~(3+)than Ca~(2+).Superconductivity was observed in all samples with onset T_c varying from 27 K to 44 K upon Sm-doping.The coexistence of a collapsed phase transition and the superconducting transition was found for the lower Sm-doping samples.Zero resistivity and substantial superconducting volume fraction only happen in higher Sm-doping crystals with the nominal x 0.10.The doping dependences of the c-axis length and onset T_c were summarized.The high-T_c observed in these quenched crystals may be attributed to simultaneous tuning of electron carriers doping and strain effect caused by lattice reduction of Sm-substitution.     

纳米Gd2O3中两种格位Eu3+的电荷迁移态激发跃迁

观测了粒径分别为15,23,135m的立方相Gd2O3：Eu^3 的选择激发光谱、发射光谱和激发光谱。受强量子限域效应的影响,纳米Gd2O3：Eu^3 的激发光谱的强度表现出对颗粒尺寸的明显依赖性。用Jorgensen公式计算电荷迁移带的位置,与实验测得激发光谱中位置相一致。通过电荷迁移带不同位置的选择激发光谱可以分辨出立方相Gd2O3：Eu^3 中C2和S6格位Eu^3 的发光,从选择激发的发射光谱和激发光谱结果计算出C2和S6格位电荷迁移带的激发光谱,与实验结果相符合。