白光LED用蓝色荧光粉Sr10（PO4）6Cl2:Eu2+合成及其光谱特性

本文采用传统的高温固相法合成白光LED用Sr10(PO4)6Cl2:Eu2+蓝色荧光粉,利用X-射线粉末衍射和荧光光谱进行表征。实验结果表明,在紫外近紫外区(200～400 nm)激发下荧光粉发射光谱主峰位于447 nm。当灼烧温度为1000℃,Eu2+掺杂浓度为0.12,SrCl2.6H2O添加量过量20%,发光强度最高。与商业近紫外LED芯片发射相匹配,是一种优秀的近紫外白光LED用的蓝色荧光粉。     

红色荧光粉LiGd(MoO4)2:Sm3+的制备与性能

利用Sm3+作为激活剂采用高温固相法制备了LiGd1-x(MoO4)2:xSm3+(x=0,0.005,0.010,0.015,0.020,0.030,0.040,0.050,0.060,0.080,0.100)系列红色荧光材料.测量了荧光粉的X射线衍射谱、激发光谱和发射光谱.在紫外光的激发下,该荧光粉的发射光谱为峰值位于564、608、648nm的三峰谱线,其中位于648nm处的红光发射最强.监测648nm发射峰得到的材料的激发光谱为一峰值位于275nm的宽谱和主峰位于363、376、404nm的线状谱线,说明该荧光粉可被紫外光和近紫外光有效地激发.研究了Sm3+掺杂浓度对LiGd(MoO4)2:Sm3+荧光粉的各发射峰发光强度的影响,得出Sm3+的最佳掺杂量(摩尔分数)为3.0％.对浓度猝灭的原因进行了探讨,结果表明该荧光粉是一种较好的用于白光LED的红色发光材料.     

LED用的Gd2(MoO4)3:Eu3+红色荧光粉的制备和性能研究

本文利用液相沉积法合成白光LED用的Gd2(MoO4)3:Eu3+红色荧光粉,利用X射线衍射、荧光光谱以及扫描电镜进行系列表征,系统研究掺杂离子浓度、退火温度等条件对Gd2(MoO4)3:Eu3+荧光粉的发光性能影响。结果表明:当pH=7,退火温度为1100℃,Gd:Eu摩尔比例为1.8:0.2时,所合成的荧光粉为正交晶系的类白钨矿结构Gd2(MoO4)3化合物(20-0408),荧光粉在395 nm左右有高的激发效率,发射主峰位置位于615 nm是近紫外LED中一种比较有应用价值的红色荧光粉。     

Dy3+掺杂的LiY（MoO4）2发光材料的制备与光谱特性

采用高温固相法在800℃制备了LiY(MoO4)2:Dy3+荧光粉。研究了Dy3+掺杂量、合成温度以及Li+的过量加入对LiY(MoO4)2:Dy3+荧光粉发光强度的影响。结果表明:在紫外光(386nm)激发下,该荧光粉的发射光谱为1个峰值位于488nm和575nm的双峰谱线,其中位于575nm处的黄光发射最强;监测575 nm发射峰得到的激发光谱为主峰位于351、366、386 nm和426 nm的线状谱线。煅烧温度为800℃时合成的荧光粉样品的发光强度达到最大,加入过量的Li+会降低发光强度。随Dy3+掺杂量的增大,荧光粉的发光强度逐渐增强,当Dy3+掺杂量为6%时发射的谱线强度最大。荧光粉的色参数表明,该荧光粉是一种较好的用于白光LED的黄色发光材料。     

Gd~(3+)/Si~(4+)掺杂对LiZnPO_4:Eu~(3+)荧光粉发光性能的影响

采用高温固相法制备了LiZnPO4:Eu3+红色荧光粉,分别研究了Eu3+掺量、Eu3+和Gd3+共掺杂以及SiO2掺杂对材料发光性能的影响。结果表明:在395nm近紫外光激发下,发射光谱峰值位于593nm,属于Eu3+的5D0→7F1辐射跃迁;激发光谱由200~280nm的宽带和310~500nm的一系列尖峰组成,分别对应于O2–→Eu3+电荷迁移带和Eu3+的f→f能级跃迁吸收,主激发峰位于395nm左右,与近紫外发光二极管(NUV-LED)的发射光谱(360~410nm)匹配。Eu3+最佳掺杂摩尔分数为12%,超过12%后发生浓度猝灭现象,浓度猝灭机理为电多极–电多极相互作用。掺杂Gd3+、SiO2使Eu3+在593nm处的发射分别增强了107%、105%。LiZnPO4:Eu3+是适合NUV-LED管芯激发的白光发光二极管用高亮度橙红色荧光粉。     

Ce~(3+)在Na_2Ca_(1-x)SiO_4:xCe~(3+)中的发光特性及晶体学格位

采用高温固相法合成了Na2Ca1-xSiO4:xCe3+蓝色发光材料,并对其发光特性进行了研究。测得激发光谱为双峰宽谱,峰值分别位于279nm和360 nm,属于Ce3+的4f-5d跃迁,可被紫外-近紫外LED芯片有效激发。样品的发射光谱为不对称单峰宽谱,主峰位于439nm。利用van Uitert公式证明了Ca在Na2CaSiO4中只存在一种晶体学格位,判定经Gauss分峰拟合后的425 nm与460 nm子发射峰均来自于八配位Ce3+的发射,非对称发射的原因是局部晶体场的不对称和Ce3+能级劈裂。研究了Ce3+掺杂量对Na2Ca1-xSiO4:xCe3+材料发光特性的影响。结果显示,随Ce3+掺杂量的增大,发光强度先增大后减小,且发射光谱红移。Ce3+掺杂量为4%(摩尔分数)时,出现浓度猝灭,根据Dexter理论分析猝灭机理为电偶极-电四极相互作用。     

燃烧法制备白光LED用红色荧光粉SrBPO_5∶Sm~(3+)及发光性能

用H3BO3作为助熔剂、尿素为燃料,采用燃烧法在较低的起始温度(650℃)下制备了的纳米级SrBPO5∶Sm3+红色荧光粉。研究了该荧光粉样品的相结构、形貌和发光特性。结果表明:SrBPO5∶Sm3+样品属于三方晶系,空间群为P3121;该荧光粉平均粒径为200nm、分散性较好。样品在近紫外光404nm的激发下发射红光,发射主峰位于558、596和645nm处,分别对应于Sm3+的4 G5/2→6 H5/2、4 G5/2→6 H7/2和4 G5/2→6 H9/2的跃迁;当Sm3+的最佳摩尔掺杂量为10%,对于既可作为助熔剂又是原料的H3BO3过量0.8%时,样品的发射峰强度最强。SrBPO5∶Sm3+有望成为近紫外激发的白光LED用新型红色荧光粉。     

白光LED用K_2ZnSiO_4:Sm~(3+)橙红色荧光粉的制备及发光性能

用溶胶-凝胶法合成白光LED用K2Zn Si O4:Sm3+橙红色荧光粉,研究了样品结构及发光性能。X射线衍射分析表明,微量Sm3+掺杂的样品主晶相为正交晶系结构的K2Zn Si O4。该荧光粉能被近紫外光有效激发,在403 nm激发下,发射光谱由4个发射峰组成,最强峰位于605 nm处,是由Sm3+的4G5/2→6H7/2跃迁引起的。增大Sm3+掺杂量,发光强度先增大后减小,Sm3+最佳掺杂摩尔分数为7%。随着Sm3+掺杂量的增加,样品的色坐标基本不变,位于橙红光区。     

白光LED照明用新型荧光粉的制备和性能研究

首次报道利用高温固相法结合超声波分散技术合成了Sr3-xMgSi2O8:xEu2 高亮度白色荧光粉,并对其发光性能进行了研究。该荧光粉在近紫外光激发下发出较强的白光,发射光谱由两个主峰组成,分别位于468.4nm和546.0nm处,并具有不同的荧光寿命,归结为处于不同格位上的Eu2 离子的5d-4f电子的跃迁发射,从而在单一基质中混合得到了白光,这两个发射峰所对应的激发光谱均分布在250nm-450nm的紫外区,该荧光粉可以被具有400nm的近紫外光发射的InGaN管芯产生的紫外辐射有效激发而产生白光,是一种性能良好的很有前途的单一基质白光LED照明用稀土荧光粉。     

白光LED照明用新型荧光粉的制备和性能研究

首次报道利用高温固相法结合超声波分散技术合成了Sr3-xMgSi2O8：xEu2＋高亮度白色荧光粉,并对其发光性能进行了研究。该荧光粉在近紫外光激发下发出较强的白光,发射光谱由两个主峰组成,分别位于468.4nm和546.0nm处,并具有不同的荧光寿命,归结为处于不同格位上的Eu2＋离子的5d-4f电子的跃迁发射,从而在单一基质中混合得到了白光,这两个发射峰所对应的激发光谱均分布在250nm-450nm的紫外区,该荧光粉可以被具有400nm的近紫外光发射的InGaN管芯产生的紫外辐射有效激发而产生白光,是一种性能良好的很有前途的单一基质白光LED照明用稀土荧光粉。     

Comparison of microwave dielectric behavior between Bi1.5Zn0.92Nb1.5O6.92 and Bi1.5ZnNb1.5O7

The microwave dielectric, Bi_1.5ZnNb_1.5O₇ exhibits low-temperature dielectric relaxation. To find the origin of the dielectric relaxation of Bi_1.5ZnNb_1.5O₇, we studied the structure and dielectric behavior of Bi_1.5ZnNb_1.5O₇ in detail. The Bi_1.5ZnNb_1.5O₇ is not composed of a single phase pyrochlore structure. Instead, it consists of unusual structure of Bi_1.5Zn_0.92Nb_1.5O_6.92 and ZnO. The ZnO is distributed evenly in the grain and at the boundary of the Bi_1.5Zn_0.92Nb_1.5O_6.92 structure. Many small voids (<1 μm) were observed in the samples due to the loss of volatile Bi during sintering. The Bi_1.5Zn_0.92Nb_1.5O_6.92 exhibited a broad dielectric relaxation between 100 and 400 K at 1.8 GHz, peaking around 230 K. The Fourier transformation IR spectra predict that dielectric relaxation may occur near room temperature during extremely high frequencies (THz). The substitutional point defects in Bi_1.5Zn_0.92Nb_1.5O_6.92 provide room for dielectric relaxation at microwave frequencies. The low quality factor Q × f (∼520 GHz) of Bi_1.5Zn_0.92Nb_1.5O_6.92 results from both the dielectric relaxation of the material and the voids within its microstructure. The presence of ZnO phase in the Bi_1.5ZnNb_1.5O₇ produces interstitial defects that further enhance the dielectric relaxation with reduced quality factor Q × f (∼426 GHz).     

Bi1.5ZnNb1.5O7纳米粉体的水热合成与表征

以分析纯的Bi(NO_3)_3·5H_2O,ZnO和Nb_2O_5为初始原料,KOH为矿化剂,采用水热法合成立方焦绿石结构的Bi_(1.5)ZnNb_(1.5)O_7纳米粉体。通过XRD分析其物相组成,TEM分析其形貌和尺寸,Scherrer公式计算其晶粒的大小。结果表明,在KOH浓度为1.8mol/L,温度为180～220℃反应6～48h,可以合成立方焦绿石结构的Bi_(1.5)ZnNb_(1.5)O_7纳米粉体,粉体颗粒尺寸约30～50nm,形貌呈较为规则的颗粒状。合成温度和反应时间对合成粉体的物相和粒径都有一定的影响,并讨论了水热法合成Bi_(1.5)ZnNb_(1.5)O_7纳米粉体的机理。     

熔盐法制备Bi1.5ZnNb1.5O7陶瓷粉体

以Bi2O3,ZnO和Nb2O5为原料,KCl为熔盐,用熔盐法合成了单相Bi1.5ZnNb1.5O7陶瓷粉体.XRD和SEM分析表明,在950～1000 ℃,合成了单相Bi1.5ZnNb1.5O7粉体,粉体呈颗粒状,尺寸约2～5 μm.研究了合成温度、熔盐含量和保温时间对粉体颗粒形貌和尺寸的影响.结果表明,合成温度对Bi1.5ZnNb1.5O7粉体形貌和尺寸影响较大,熔盐含量和保温时间对其形貌和尺寸的影响相对较小.     

水热法合成Bi1.5ZnNb1.5O7纳米粉体

以Bi(NO3)3·5H2O,ZnO和Nb2O5为原料,KOH作为矿化剂,用水热法合成了单相Bi1 5ZnNb1.5O7粉体.用N2吸附法测定单相Bi1.5ZnNb1.5O7粉体的比表面积并计算相应的粒径.研究了KOH浓度、合成温度和反应时间对粒径的影响.用X射线衍射分析合成粉体的物相组成,并通过Scherrer公式计算粉体晶粒的尺寸.用透射电子显微镜分析合成粉体的形貌.结果表明:采用水热法可以合成单相立方焦绿石结构的Bi1.5ZnNb1.5O7纳米粉体.改变水热反应条件,可以控制合成粉体的粒径和比表面积大小.当KOH浓度为1.8 mol/L,温度为180～220 ℃,反应时间为24h时,合成的Bi1.5ZnNb1.5O7纳米粉体的最小粒径为51 nm,最大比表面积为28.8 m2/g.     

CeO2–YO1.5–NdO1.5 system: An extensive phase relation study

The sub-solidus phase relations in the CeO₂–YO_1.5–NdO_1.5 system have been studied. About 45 compositions in the series Ce_1?x(Y_0.70Nd_0.30)_xO_2?0.5x, Y_1?x(Ce_0.50Nd_0.50)_xO_1.5+0.25x and Nd_1?x(Ce_0.55Y_0.45)_xO_1.5+0.275x were prepared and characterized by powder XRD. In the Ce_1?x(Y_0.70Nd_0.30)_xO_2?0.5x series, there was a gradual transformation from the defective F-type cubic lattice to an ordered C-type phase with increasing x, whereas in the Y_1?x(Ce_0.50Nd_0.50)_xO_1.5+0.25x series, the C-type cubic lattice of yttria was retained over the entire range. In the Nd_1?x(Ce_0.55Y_0.45)_xO_1.5+0.275x system, the compositions with NdO_1.5 content greater than 95 mol% showed coexistence of hexagonal, monoclinic and cubic phases. A biphasic region of monoclinic and C-type cubic phases was observed as NdO_1.5 decreases from 90 to 70 mol%. All the compositions below 70 mol% NdO_1.5, were found to be C-type cubic solid solutions. The phase relations are distinctly characterized by an extensive range of cubic solid solutions, stable under the slow-cooled conditions. To the best of our knowledge, this is the first detailed sub-solidus study reported in CeO₂–YO_1.5–NdO_1.5 system.     

Dielectric properties and electrical behaviors of tunable Bi1.5MgNb1.5O7 thin films

The Bi_1.5MgNb_1.5O₇ (BMN) thin films were prepared on Au-coated Si substrates by rf magnetron sputtering. We systematically investigated the structure, dielectric properties and voltage tunable property of the films with different annealing temperatures. The relationships of leakage current and breakdown bias field with annealing temperature were firstly studied and a possible explanation was proposed. The deposited BMN thin films had a cubic pyrochlore phase when annealed at 550 °C or higher. With the increasing of annealing temperature, the dielectric constant and tunability also went up. BMN thin films annealed at 750 °C exhibited moderate dielectric constant of 106 and low dielectric loss of 0.003–0.007 between 10 kHz and 10 MHz. The maximum tunability of 50% was achieved at a bias field of 2 MV/cm. However, thin films annealed at 750 °C had lower breakdown bias field and higher leakage current density than films annealed below 750 °C. The excellent physical and electrical properties make BMN thin films promising for potential tunable capacitor applications.     

Ni替代Nb对Bi1.5ZnNb1.5O7陶瓷介电性能的影响

以分析纯级原料,按照一定比例混合,利用固相反应制备Bi1.5ZnNb1.5O7陶瓷.研究结果表明:Ni掺杂样品能够有效地降低烧结温度至960℃;样品相结构保持立方焦绿石相;随着Ni3+替代量的增加,介质材料的介电常数及介电损耗逐渐增大;在-195～150℃的温度范围内,介电常数存在明显的弛豫现象,随Ni3+的掺杂量增加,逐渐向高温方向移动,在1 MHz下其峰值温度为:-98.1℃,-97.7℃,-97.1℃,-94.2℃.     

Green emitting Ba1.5Lu1.5Al3.5Si1.5O12: Ce3+ phosphor with high thermal emission stability for warm WLEDs and FEDs

By hetero-valence substituting Ba²⁺-Si⁴⁺ for Lu³⁺-Al³⁺ pair in Lu₃Al₅O₁₂: Ce³⁺, a new green phosphor Ba_1.5Lu_1.5Al_3.5Si_1.5O₁₂: Ce³⁺ (BLAS: Ce³⁺) has been obtained. It crystallizes in garnet structure with space group Ia-3d (230). In the structure, Ba²⁺ ions are incorporated into both dodecahedral Lu³⁺ and octahedral Al³⁺ sites while Si⁴⁺ ions only occupy tetrahedral Al³⁺ sites. Under the blue light irradiation of 450 nm, an intense green light peaking at 520 nm was observed and the PL spectrum can be fitted in two Gaussian components, due to the crystal field splitting of Ce³⁺ 5d states under D₂ symmetry constrains. The optical doping concentration of BLAS: Ce³⁺ is 6% mol, of which the IQE and EQE are 89.1% and 51.8%, respectively. Furthermore, this sample exhibits an extremely good thermal stability, i.e. the integrated emission intensity is still more than 90% of the initial intensity at 480 K. Then, a w-LED device was fabricated from this new green phosphor BLAS: Ce³⁺ and commercial red phosphor (Ca,Sr)AlSiN₃: Eu²⁺, which shows a quite high color rendering (Ra = 88.2) and a relatively low color temperature 4772 K. Besides, the phosphor exhibits a stable chromaticity under different acceleration voltages. The phosphor may be promising material for the development of solid-state lighting and display systems.     

Production and properties of In and Ir doped Bi1.5Zn0.92Nb1.5O6.92 pyrochlores

In and Ir were doped into Bi_1.5Zn_0.92Nb_1.5O_6.92 (BZN) pyrochlore using the chemical formulas of Bi_1.5Zn_0.92?3x/2In_xNb_1.5O_6.92 and Bi_1.5Zn_0.92Nb_1.5?4x/5Ir_xO_6.92. While In was doped into Zn site of BZN, Ir was added into the Nb site. The solubility limits of In and Ir cations in BZN were x = 0.1 and x = 0.12–0.15, respectively. Above the solubility limits second phases of BiNbO₄ and InNbO₄ formed for In doping but Bi₂Ir₂O₇ and ZnO phases appeared in Ir doping. SEM investigation confirmed the XRD results. Lattice parameters of BZN pyrochlores slightly increased with In doping but decreased with Ir due to their ionic radii. The dielectric constant of Ir doped BZN slightly decreased with Ir content. However, In doping into the BZN generally decreased the dielectric constant at low doping ratios but increased it at high dopings. Temperature coefficients of Ir and In doped BZN ceramics were significantly affected by doping amount.     

Cold sintering process of Li1.5Al0.5Ge1.5(PO4)3 solid electrolyte

The recently developed technique of cold sintering process (CSP) enables densification of ceramics at low temperatures, i.e., <300°C. CSP employs a transient aqueous solvent to enable liquid phase‐assisted densification through mediating the dissolution‐precipitation process under a uniaxial applied pressure. Using CSP in this study, 80% dense Li_1.5Al_0.5Ge_1.5(PO₄)₃ (LAGP) electrolytes were obtained at 120°C in 20 minutes. After a 5 minute belt furnace treatment at 650°C, 50°C above the crystallization onset, Li‐ion conductivity was 5.4 × 10^?5 S/cm at 25°C. Another route to high ionic conductivities ~10^?4 S/cm at 25°C is through a composite LAGP ‐ (PVDF‐HFP) co‐sintered system that was soaked in a liquid electrolyte. After soaking 95, 90, 80, 70, and 60 vol% LAGP in 1 M LiPF₆ EC‐DMC (50:50 vol%) at 25°C, Li‐ion conductivities were 1.0 × 10^?4 S/cm at 25°C with 5 to 10 wt% liquid electrolyte. This paper focuses on the microstructural development and impedance contributions within solid electrolytes processed by (i) Crystallization of bulk glasses, (ii) CSP of ceramics, and (iii) CSP of ceramic‐polymer composites. CSP may offer a new route to enable multilayer battery technology by avoiding the detrimental effects of high temperature heat treatments.