(La,Ce,Tb)(PO_4,BO_3)绿粉的合成及发光研究

首次用磷酸硼和稀土氧化物为主要原料制备铈、铽共激活的硼磷酸盐绿色荧光粉 ,并对Ce3+-Tb3+的能量传递进行了研究 ,发现在该基质中Ce3+、Tb3+间的能量传递为电多极子相互作用的共振传递 ,能量传递效率可高达 90 %。还研究了助熔剂对荧光粉粒度和发光特性的影响 ,实验结果表明 ,加了助熔剂后所得样品的颗粒明显变大 ,在 2 54nm紫外激发下Tb3+发射大大增强 ,光的纯度也得到改善。对不同基质荧光粉的研究发现 ,用硼磷酸盐绿粉比用硼酸盐和磷酸盐绿粉更适合做三基色粉配料。     

（La,Ce,Tb）（PO4,BO3）绿粉的合成及发光研究

首次用磷酸硼和稀土氧化物为主要原料制备铈、铽共激活的硼磷酸盐绿色荧光粉,并对Ｃ３＾３＋－Ｔｂ＾３＋的能量传递进行了研究,发现在该基质中Ｃｅ＾３＋、Ｔｂ＾３＋间的能量传递为电多极子相互作用的共振传递,能量传递效率可高达９０％。还研究了助熔剂对荧光粉粒度和发光特性的影响,实验结果表明,加了助熔剂后增强,光的纯度也得的改善。对不同基质荧光粉的研究发现,用硼磷酸盐绿粉比用硼酸盐和磷酸盐绿粉更适合做三基色粉     

La(BO_3,PO_4):Ce,Tb,Gd的发光研究

以 BPO4和稀土氧化物为原料制备了铈、铽、钆共掺杂的硼磷酸镧绿色荧光粉,研究了基质中 Gd3＋、 Ce3＋、 Tb3＋的发光特性及它们之间的相互作用。在该基质中存在 Ce3＋→ Gd3＋、Gd3＋→ Tb3＋、 Ce3＋→ Tb3＋的能量传递;当钆加入到铈、铽共掺杂的硼磷酸镧基质中会导致铈离子的发射减弱,铽离子 5D4→ 7FJ的发射显著增强,而 5D3→ 7FJ的发射没有明显变化,故有利于提高荧光粉的发光强度和绿色发射纯度。用硼磷酸钆作基质比用硼磷酸镧更能提高荧光粉的发光强度、发光纯度以及发光色坐标 x的值,所以 La(BO3,PO4):Ce,Tb,Gd和 Gd(BO3,PO4):Ce,Tb均是理想的绿色发射材料。     

红色荧光粉Ca3Y2Si3O12∶Pr3+的制备及发光特性

通过高温固相方法合成了红色荧光粉Ca3Y2Si3O12∶Pr3+,研究了Pr3+掺杂浓度及助熔剂对荧光粉发光性能的影响。结果显示,所合成的荧光粉的主晶相为Ca3Y2Si3O12。通过分析荧光光谱,发现Ca3Y2Si3O12∶Pr3+硅酸盐荧光粉的有效激发范围可以在430~490nm范围内,并发射红光。在445nm激发下,样品发射光谱中的主发射峰分别位于610nm(3P0→3 H6)和644nm(3P0→3F2),其中610nm处峰值最大。通过改变Pr3+掺杂浓度,发现荧光粉发光强度先增大后减小,最佳Pr3+掺杂量x(Pr3+)为2.0%,超过最佳掺杂浓度表现为由离子间的相互作用导致的浓度淬灭。该荧光粉色温为2261℃。通过观察助熔剂的助熔效果,发现最佳的助熔剂H3BO3添加量为2.0%。     

PDP用高亮度(Y,Gd)BO_3:Tb~(3+)绿色荧光粉的合成

采用共沉淀法制备了稀土氧化物前体,再将其和H3BO3及BaB4O7混合后,用高温固相合成法制备出了2.0-3.0μm粒径的(Y,Gd)BO3:Tb3+绿色荧光粉。研究发现,荧光粉的粒度随前驱体粒度与助熔剂引入量的增加而增大,助熔剂的引入量超过0.18%会使荧光粉的亮度猝灭;随着灼烧温度的增高,荧光粉的亮度会变大。综合PDP用荧光粉的使用特性,BaB4O7的引入量在0.10%,灼烧温度为1100℃时,采用共沉淀法前驱体可得到亮度104,粒度2.5um,晶型完美的(Y,Gd)BO3:Tb3+绿色荧光粉。     

La(BO3,PO4):Ce,Tb,Gd的发光研究

以BPO4和稀土氧化物为原料制备了铈、铽、钇共掺杂的硼磷酸镧绿色荧光粉,研究了基质中Gd^3 、Ce^3 、Tb^3 的发光特性及它们之间的相互作用。在该基质中存在Ce^3 →Gd^3 、Gd^3 →Tb^3 、Ce^3 →Tb^3 的能量传递;当钆加入到铈、铽共掺杂的硼磷酸镧基质中会导致铈离子的发射减弱,铽离子^5D4→^7F1的发射显著增强,而^5D3→^7F1的发射没有明显变化,故有利于提高荧光粉的发光强度和绿色发射纯度。用硼磷酸钆作基质比用硼磷酸镧更能提高荧光粉的发光强度、发光纯度以及发光色坐标x的值,所以La(BO3,PO4):Ce,Tb,Gd和Gd(BO3,PO4):Ce,Tb均是理想的绿色发射材料。     

白光LED用Ca2SiO3Cl2:Tb3+单一基质荧光粉的制备及性能研究

采用溶胶-凝胶法在较低温度下合成了不同浓度Tb3+掺杂的Ca2SiO3Cl2∶mTb3+单一基质白光荧光粉,并对其发光性质进行了研究。近紫外光激发下,发射光谱出现了明显的多色谱(415、440、460、486、544、595、619和700 nm)混合后发射白光。随着Tb3+浓度的增加,蓝光强度先增强后减弱,绿光不断增强,红光不断减弱,当m=0.003时荧光粉的色坐标为x=0.3174,y=0.3485,非常接近标准白光(x=0.33,y=0.33),样品呈现色温TC=6161K的正白色发光。Ca2SiO3Cl2∶Tb3+是一种具有良好白光发射的LED用单一基质荧光粉。     

新型白光LED用SrMg_2(PO_4)_2单-基质荧光粉

本文通过高温固相法合成了紫外光LED用SrMg2(PO4)2为基质Eu2+,Tb3+和Mn2+为激活剂的白色荧光粉。采用XRD对荧光粉的结构和相纯度进行分析,Eu2+、Tb3+及Mn2+的加入对其结构没有明显的影响,且无杂相生成;当用Ca部分取代Sr时Eu2+和Mn2+的发射带分别发生红移和蓝移且二者之间存在着明显的能量传递;当引入共激活剂Tb3+时对其荧光光谱进行了详细研究,发现Eu2+和Tb3+,Eu2+和Mn2+之间存在部分的能量传递,通过调整它们的相对掺杂浓度可以得到发白光的荧光粉。     

新型白光LED用SrMg_2(PO_4)_2单一基质荧光粉

本文通过高温固相法合成了紫外光LED用SrMg2(PO4)2为基质Eu2+,Tb3+和Mn2+为激活剂的白色荧光粉。采用XRD对荧光粉的结构和相纯度进行分析,Eu2+、Tb3+及Mn2+的加入对其结构没有明显的影响,且无杂相生成;当用Ca部分取代Sr时Eu2+和Mn2+的发射带分别发生红移和蓝移且二者之间存在着明显的能量传递;当引入共激活剂Tb3+时对其荧光光谱进行了详细研究,发现Eu2+和Tb3+,Eu2+和Mn2+之间存在部分的能量传递,通过调整它们的相对掺杂浓度可以得到发白光的荧光粉。     

Ba2Gd2Si4O13∶Dy3+的能量传递和热稳定性研究

利用高温固相反应合成了Ba2Gd2Si4O13∶Dy3+荧光粉,从激发光谱、发射光谱、衰减寿命3个方面详细研究了不同激发波长下Gd3+→Dy3+的能量传递和热稳定性能。研究表明,由于Ba2Gd2Si4O13基质中Gd3+→Dy3+的能量传递,Dy3+在274nm激发的发光强度是在349nm激发的5倍;Ba2Gd2Si4O13∶Dy3+荧光粉表现出较好的热稳定性,在250℃的发光强度为常温的85%;随着加热温度的升高,兰光比黄光强度下降更多,而Gd3+发光有所增加。Ba2Gd2Si4O13∶Dy3+荧光粉可作为潜在的单一基质单一掺杂发光材料。     

K2(Rb2,Cs2,Tl2)TeBr6(I6) and Rb3(Cs3)Sb2(Bi2)Br9(I9) perovskite compounds

We systematize available experimental data on the crystal structure of the ternary halides K₂(Rb₂,Cs₂,Tl₂)TeBr₆(I₆) and Rb₃(Cs₃)Sb₂(Bi₂)Br₉(I₉), analyze the general trends in the properties of their single crystals, and examine the key features of the physicochemical interaction in related systems.     

(K0.44,Na0.52,Li0.04) (Nb0.84,Ta0.10,Sb0.06)O3 Ferroelectric Ceramics

Recent progress in (K_0.44,Na_0.52,Li_0.043-based ceramics (KNN) with special emphasis on (K_0.44,Na_0.52,Li_0.040.84,Ta_0.10,Sb_0.06))O₃ (KNN-LT-LS) is reviewed concisely. The base KNN and its compositional derivatives are analyzed in terms of dopant-property relationships, which are then extended to the ternary derivatives. The effects of processing conditions such as humidity, precursor purity, and oxygen partial pressure during sintering are elaborated on from a phenomenological perspective. It is also shown that the spontaneous polarization is sensitive to the processing route chosen for synthesis (mixed oxide versus perovskite routes). Special attention is devoted to the discussion of the morphotropic phase boundary (MPB) dilemma in the KNN-LT-LS system, where it is shown that the origin of high piezoelectric activity is actually due to a polymorphic transition at room temperature. It is shown that prototype transducers based on pure and 1 mol% Ba²⁺ doped KNN-LT-LS exhibit performance metrics comparable to those fabricated using PZT-5H. Overall, KNNLT- LS ceramics show great promise for lead-free applications, although issues such as temperature dependence of properties and strong sensitivity to processing conditions remain as the 2 major challenges.     

Hydrothermal Crystallization in the Systems La2(CO3)3 ? 6H2O-CaCO3(BaCO3)-R-H2O (R = Na2CO3, K2CO3, NaHCO3, KHCO3, NaCl, NH4Cl, CO(NH2)2)

Crystallization in the systems La₂(CO₃)₃ ⋅ 6H₂O-CaCO₃(BaCO₃)-R-H₂O (R = Na₂CO₃, K₂CO₃, NaHCO₃, KHCO₃, NaCl, NH₄Cl, CO(NH₂)₂) was studied under hydrothermal conditions (400–450°C). The solid reaction products were found to contain LaOHCO₃ and NaLa(CO₃)₂. Detailed thermal decomposition schemes were proposed for these phases, and their lattice parameters were refined. __________ Translated from Neorganicheskie Materialy, Vol. 41, No. 11, 2005, pp. 1366–1372. Original Russian Text Copyright ? 2005 by Nikol'skaya, Dem'yanets.     

Preparation of (NH4)Zr2(PO4)3 and HZr2(PO4)3

(NH₄)Zr₂(PO₄)₃ has been prepared, hydrothermally, from α-zirconium phosphate in three different ways; (1) from amine intercalates at 300°C, (2) from mixtures of ZrOCl₂·8H₂O in excess (NH₄)H₂PO₄ and (3) reaction of NH₄Cl with Zr(NaPO₄)₂. Ammonium dizirconium triphosphate is rhombohedral with a = 8.676(1) and $\text{c}\text{= 24.288(5)}\text{A}\text{?}$. It decomposed on heating to HZr₂(PO₄)₃. Below 600°C a complex, as yet unindexed, X-ray pattern was obtained. A very similar X-ray pattern was obtained by washing LiTi_0.1Zr_1.9(PO₄)₃ with 0.3N HCl. Heating this phase or NH₄Zr₂(PO₄)₃, above 600°C resulted in the appearance of a rhombohedral phase of HZr₂(PO₄)₃ with cell dimensions a = 8.803(5) and $\text{c}\text{= 23.23(1)}\text{A}\text{?}$. The protons were not completely removed until about 1150°C. Decomposition of (NH₄)Zr₂(PO₄)₃ at 450°C yielded an acidic gas whereas at 700°C NH₃ was evolved. A possible explanation for this behavior is presented.     

Crystal Structure of Tl2[(UO2)2(MoO4)3] and Crystal Chemistry of the Compounds M2[(UO2)2(MoO4)3] (M = Tl, Rb, Cs)

A new compound, Tl₂[(UO₂)₂(MoO₄)₃], was prepared by a solid-phase reaction. The compound crystallizes in a rhombic system, space group Pna2₁, a = 20.1296(9), b = 8.2811(4), c = 9.7045(4), V = 1617.69(13) ų, Z = 4. The crystal structrue was solved by the direct method and refined to R ₁ = 0. 04 for 4884 unique reflections. The structural motif is a framework consisting of UO₇ pentagonal bipyramids and MoO₄ tetrahedra. The Tl coordination polyhedra are irregular, with seven and eight vertices. Large channels of the size 6 × 10.8 Å, occupied by Tl⁺ cations, are arranged parallel to the [001] direction. The compound is isostructural to the previously described α-Cs₂(UO₂)₂(MoO₄)₃ and Rb₂(UO₂)₂ (MoO₄)₃. __________ Translated from Radiokhimiya, Vol. 47, No. 5, 2005, pp. 408–411. Original Russian Text Copyright ? 2005 by Nazarchuk, Krivovichev, Burns.     

Microstructure, domain structures and ferroelectric properties in (Pb0.8,La0.1,Ca0.1)TiO3/Pb(Zr0.2,Ti0.8)O3 bilayered thin film

Ferroelectric (Pb_0.8,La_0.1,Ca_0.1)TiO₃/Pb(Zr_0.2,Ti_0.8)O₃ (PLCT/PZT) bilayered thin film was prepared on Pt(111)/Ti/SiO₂/Si(100) substrate by RF magnetron sputtering technique. Pure perovskite crystalline phase, determined by X-ray diffraction, was formed in the PLCT/PZT bilayer. The bilayered film exhibited a very dense and smooth surface morphology with a uniform grain size distribution. The ferroelectric domain structures were investigated by a combination of vertical and lateral piezoresponse force microscopy (VPFM and LPFM, respectively). It is demonstrated by both VPFM and LPFM observations that out-of-plane and in-plane lamellar ferroelectric domains coexist in the bilayered thin film. The PLCT/PZT bilayered film possesses good ferroelectric properties with relatively high spontaneous polarization (2P_s = 82 µC/cm²) and remnant polarization (2P_r = 26.2 µC/cm²).     

Crystal structure of complexes of Np(VI) and Pu(VI) perchlorates with triphenylphosphine oxide, [NpO2(OP(C6H5)3)4](ClO4)2 and [PuO2(OP(C6H5)3)4](ClO4)2

Single crystals of [NpO₂(TPPO)₄](ClO₄)₂ and [PuO₂(TPPO)₄](ClO₄)₂ isostructural to the complex [UO₂(TPPO)₄](ClO₄)₂ [TPPO = OP(C₆H₅)₃] studied previously were prepared, and the structures of these compounds were determined. The coordination polyhedron of these compounds is a tetragonal bipyramid. The geometric characteristics of the tetragonal bipyramids in the compounds are practically the same despite the actinide contraction of the central atoms, whereas the unit cell volume decreases in the series U-Np-Pu. The equality of the volumes of the coordination polyhedra of the U, Np, and Pu atoms is attributed to the influence of TPPO containing phenyl radicals with negative effective charge. Original Russian Text ? I.A. Charushnikova, N.N. Krot, Z.A. Starikova, I.N. Polyakova, 2007, published in Radiokhimiya, 2007, Vol. 49, No. 5, pp. 407–411.     

Crystal Structure of (H3O)2[(UO2)2(SeO4)3(H2O)2](H2O)3.5

Crystals of (H₃O)₂[(UO₂)₂(SeO₄)₃(H₂O)₂](H₂O)_3.5 were prepared from aqueous solutions by evaporation. The crystal structure [monoclinic system, space group P2₁/m, a = 11.9402(11), b = 13.6452(14), c = 13.7271(12) Å, β = 109.436(7)°, V = 2109.1(3) ų] was solved by the direct method and refined to R ₁ = 0. 048 (wR ₂ = 0. 082) for 3677 reflections with |F _hkl |F _hkl |. The structure consists of [(UO₂)₂(SeO₄)₃(H₂O)₂]₂₋ layers arranged parallel to the (010) plane. The layers are formed by uranium and selenium coordination polyhedra sharing common vertices and are linked with each other by hydrogen bonds through the H₂O and H₃O⁺ groups arranged between the layers. __________ Translated from Radiokhimiya, Vol. 47, No. 5, 2005, pp. 412–414. Original Russian Text Copyright ? 2005 by Krivovichev, Kahlenberg.     

Crystal Structure of (H3O)6[(UO2)5(SeO4)8(H2O)5](H2O)5

Crystals of (H₃O)₆[(UO₂)₅(SeO₄)₈(H₂O)₅](H₂O)₅ were prepared from aqueous solutions by evaporation. The crystal structure [monoclinic system, space group P2₁/m, a = 13.835(2), b = 13.4374(16), c = 14.310(3) Å, β = 108.004(14)°, V = 2530.1(7) Å ³] was solved by the direct method and refined to R ₁ = 0.090 for 4409 reflections with |F _hkl ≥ 4σ|F _hkl |. The structure is based on [(UO₂)₅(SeO₄)₈(H₂O)₅]⁶⁻ layers arranged parallel to the (101) plane; these layers have a unique topological structure. The U(1)O₆(H₂O) and U(3)O₆(H₂O) linked through selenate groups form chains running along [ [`1]\bar 1 01] direction. The chains are combined in layers by U(2)O₆(H₂O) bipyramids. The layers are linked with each other by hydrogen bonds through the H₂O and H₃O⁺ groups located between the layers.     

Syntheses and structures of Ta2(WO2)0.87H0.26(PO4)4 and Ta2(MoO2)(PO4)4

Tantalum hydrogen phosphate, β-TaH(PO₄)₂, has a three-dimensional structure that is stable to remarkably high temperature (∼600 °C) presumably due to the presence of strong hydrogen bonds. Impedance measurements indicate a low conductivity, 2.0 × 10⁻⁶ S/cm at 200 °C in 5% H₂. In further studies aimed at enhancing the conductivity by aliovalent doping, we have investigated systematically the synthesis of compounds in the TaH(PO₄)₂-W₂P₂O₁₁ system at 380 °C. As a result, a new phase, Ta₂(WO₂)_0.87H_0.26(PO₄)₄, was identified and subsequently the molybdenum analog Ta₂(MoO₂)(PO₄)₄ was also prepared. The structures were determined by single crystal X-ray diffraction techniques. The structures of Ta₂(WO₂)_0.87H_0.26(PO₄)₄ and Ta₂(MoO₂)(PO₄)₄ can be formally derived from the structure of β-TaH(PO₄)₂ by the replacement of two P-OH protons with an MO₂²⁺ (M = Mo and W) group together with a change in the orientation of some phosphate tetrahedra.