新型红色荧光粉Na2Ca4(PO4)2SiO4:Eu3+,Bi3+的制备及发光特性

用高温固相法合成了用于白光LED的Na2Ca4(1-x-y)(PO4)2SiO4:xEu3+,yBi3+红色荧光粉.研究了助熔剂H3BO3、二次煅烧时间和稀土掺杂量等制备条件对样品发光性质的影响.结果表明,在1 200℃、助熔剂H3BO3加入量为样品质量的3.8%时可得到更有利于发光的α-NCPS基质,而且掺入Eu3+...     

白光LED用荧光材料Sr3B2O6:Eu3+,Na+的制备及发光性能

采用高温固相法合成了可用于白光LED的Sr3 B2 O6:Eu3+,Na+荧光粉.研究了煅烧时间、稀土Eu3+掺杂量等条件对材料发光性能的影响.结果表明:适量掺人Eu3+、Na+之后,基质的晶格结构未发生变化;稀土Eu3+掺杂摩尔分数为6％,煅烧时间为3h时最佳;作为电荷补偿剂的Na+的引入,较大地提高了荧光粉发光强度...     

Ca_xSi合金前驱物常压氮化制备Ca_(1-x)AlSiN_3∶xEu~(2+)红色荧光粉及发光性能研究

采用CaxSi合金前驱物和Eu B6常压氮化制备了Ca Al Si N3∶Eu2+氮化物红色荧光粉。研究了不同烧结温度、添加助熔剂及二次烧结对发光性能的影响。通过扫描电子显微镜(SEM)、X射线衍射(XRD)、荧光分光光度计对发光材料的形貌、晶体结构、发光性能与热稳定性进行了研究。分析结果表明:通过合金前驱物常压氮化法得到的氮化物荧光粉具有Ca Al Si N3结构,空间群为Cmc21。Ca Al Si N3∶Eu2+红色荧光粉的最佳烧结温度为1 550℃。添加质量分数为6%的Sr F2助熔剂后,荧光粉发光强度的提升效果最好。添加6%Sr F2助熔剂及二次烧结后得到的荧光粉的晶粒生长更加完整,颗粒度明显改善,发射光谱的相对强度也明显提高,比未加助熔剂单次烧结的荧光粉相对强度提高了近一倍。将发射峰位在640 nm的Ca0.98Al Si N3∶0.02Eu2+红色荧光粉应用在白光LED的封装中,获得了色温为3 109 K、显色指数为92.5以及色温为4 989K、显色指数为95.8的高显色白光LED,说明本文合成的氮化物红色荧光粉可以实现暖白光和正白光高显色的白LED发光器件。     

Eu3+掺杂的α-Gd2(MoO4)3荧光粉合成与表征

采用固相反应法合成了Eu³⁺掺杂的α-Gd₂(MoO₄)₃荧光粉。通过XRD、SEM以及激发和发射光谱对样品进行了研究,结果发现助熔剂为3%时样品的结晶较好,样品的发光强度最强,并且样品粉末不团聚。光谱测量的结果表明该荧光粉与其他商品荧光粉不同,其最有效的激发波长不在电荷迁移带范围,其f-f跃迁的465,395nm吸收更强,这就意味着该类荧光粉可作为目前已商品化的白光LED的红色补偿荧光粉,也可作为近紫外LED和三基色荧光粉组合型白光器件的红色荧光粉的候选材料。     

Zn_(1-x)Mo_(1-y)Si_yO_4∶Eu_x~(3+)红色荧光粉的合成及发光性能研究

通过固相法合成LED用Zn-Mo1-ySiyO4:Eu3+x红色荧光粉(0.05≤x≤0.30,0≤y≤0.09),讨论了助熔剂、温度等合成条件对Zn1-xMo1-ySiyO4:Eux3+荧光粉发光性质的影响.当烧结温度为800℃时,可以生成ZnMoO4纯相目标产物.由于荧光粉的结晶度和粒径随烧结温度的升高而增大,所以随着烧结温度的升高,样品的发光强度有所提高;当助熔剂Na2CO3的用量约为4%时的样品发射光的强度比未使用助熔剂时明显增强,说明在此体系中,当Eu3+取代Zn2+时,Na2CO3充当助熔剂的同时,Na+起到了电荷补偿作用.荧光光谱实验显示Zn1-xMo1-ySOyO4:Eux3+能够被393和464 nm的紫外光激发,在616 nm处发出强烈的红色荧光.当Eu3+掺杂量约为20%mol时,Zn1-xMo0.97Si0.03O4:Eux3+荧光粉在616 nm处的发光强度达到最大.在引入Si4+离子后能显著增强Zn1-xMoO4:Eux3+的发光强度,组成为Zn0.80 Mo0.97Si0.03O4:Eu0.203+.样品(激发峰值为393 nm)的荧光强度要比Y2O2S:Eu0.053+荧光粉的发光强度强2倍.所以这种荧光物质能够更好地适用于白光LED.     

Ce3+/Eu2+共掺Ca3Si2O4N2荧光粉的光学特性

采用高温固相法制备了一种新型的白光LED用Ca3Si2O4N2∶Eu2+,Ce3+,K+荧光粉。利用X射线衍射仪对样品的物相结构进行了分析,结果表明:Ce3+和K+离子的掺杂没有改变Ca3Si2O4N2∶Eu2+荧光粉的主晶相。利用荧光光谱仪对样品的发光性能进行了测试,发现样品在355 nm激发下得到的发射光谱为峰值位于505 nm的单峰,是Eu2+离子5d-4f电子跃迁引起的。Ca3Si2O4N2∶Eu2+荧光粉通过Ce3+和K+离子的掺杂,发光明显增强。当Ce3+的摩尔分数为1%时,荧光粉的发光强度达到最大值,是单掺Eu2+离子荧光粉发光强度的168%。通过光谱重叠的方法计算Ce3+→Eu2+能量传递临界的距离为2.535 nm。     

近紫外光激发单一基质白光荧光粉Ca_3Y_2Si_3O_(12)∶Dy~(3+)的制备及发光特性

采用高温固相法在1 400℃下合成了近紫外光激发的单一基质白光荧光粉Ca3Y2-xSi3O12∶xDy3+。XRD检测结果显示,合成的荧光粉主晶相为Ca3Y2Si3O12。荧光光谱分析结果表明:Ca3Y2-xSi3O12∶xDy3+硅酸盐荧光粉可以被348 nm的近紫外光激发,产生白光发射,两个主发射峰位于481 nm(4F9/2→6H15/2)和572 nm(4F9/2→6H13/2)。用481 nm最强峰监测,得到主激发峰位于348 nm的激发光谱,该光谱覆盖了300~450 nm的波长范围。研究了Dy3+离子掺杂浓度及助熔剂H3BO3对荧光粉发光特性的影响,Dy3+离子的最佳掺杂量x(Dy3+)为5%,助熔剂的最佳质量分数为2%。色坐标分析显示:荧光粉的色坐标随着掺杂离子浓度及助熔剂加入量改变而发生变化。x(Dy3+)为5%且H3BO3的质量分数为2%的样品的色坐标为(0.29,0.33),位于标准白光点的色坐标范围内。     

发光二极管用红色荧光粉SrMoO4:Eu3+的制备和发射性质

采用化学共沉淀法制备了适合于紫外、近紫外、蓝光发光二极管(LED)激发的红色荧光粉SrMoO4:Eu3+.研究了样品的晶体结构和发光性质.结果表明:化学共沉淀法合成的SrMoO4:Eu3+荧光粉为四方纯相,其激发光谱包括一个宽带峰和一系列尖峰,峰值位于280nm(宽带峰中心),395nm,465nm,可以被紫外LED和蓝光LED有效激发.在395nm的激发下,测得发射光谱的强发射峰位于613nm,对应Eu3+离子的5D0→7F2跃迁.Eu3+离子掺杂浓度的改变对基质的晶格常数、Eu3+离子在晶体中对称性及发光性能有较大影响.通过对比不同掺杂浓度Eu3+离子的发射谱,发现在SrMoO4基质中Eu3+离子掺杂存在浓度猝灭现象,其最佳掺杂浓度为15%.     

Al~(3+)掺杂ScVO_4∶Eu~(3+),Bi~(3+)荧光粉的制备及发光性质

采用高温固相法在1 000℃下煅烧6 h合成了Sc VO4∶Eu3+,Bi3+,Al3+荧光粉。使用X射线粉末衍射仪和扫描电镜对样品的结构和形貌进行了表征,采用荧光分光光度计研究了样品的发光性质。用315 nm波长激发Sc VO4∶Eu3+,Bi3+,Al3+样品时,样品在590~620 nm范围内发射强烈的橙红光,最大发射峰位于615nm。少量Al3+的掺入可以增强Sc VO4∶Eu3+,Bi3+荧光粉的发光,而掺入过量Al3+时会使Sc VO4∶Eu3+,Bi3+荧光粉的发光变弱。当Al3+在Sc VO4∶Eu3+,Bi3+中的摩尔分数达到4%时,样品的发光最强且其发光强度较未掺杂Al3+的样品提高了约30%。     

白光LED用红色荧光粉Gd_2Mo_3O_9∶Eu~(3+)的制备及表征

利用Na2CO3作为助熔剂,采用高温固相反应方法制备了三价铕离子激活的Gd2Mo3O9红色荧光粉。利用XRD和荧光光谱,研究了助熔剂的量、制备时的温度以及激活剂Eu3 的浓度对荧光粉的晶体结构和发光性能的影响。测试结果表明,这种新型的荧光粉可以被紫外光280nm,近紫外光395nm和蓝光465nm有效激发,发射主峰位于613nm,并且证明Eu3 离子在晶体结构中占据了非反演对称中心的位置。395,465nm的吸收与目前广泛应用的紫外和蓝光LED芯片的输出波长相匹配。因此,这种荧光粉是一种可能应用在白光LED上的红色荧光粉材料。     

Anomalous diamagnetic transitions in Ba2Cu3O4Cl2 and Sr2Cu3O4Cl2 antiferromagnets

The magnetic properties of Ba₂Cu₃O₄Cl₂ and Sr₂Cu₃O₄Cl₂ oxychlorides have been studied. A spontaneous manifestation of diamagnetism has been found at quasi-zero and low fields. The temperature of these transitions coincides with the temperature of the antiferromagnetic ordering in Ba₂Cu₃O₄Cl₂ (T _NI ≈ 337 K) and Sr₂Cu₃O₄Cl₂ (T _NI ≈ 386 K). The recorded diamagnetic signal is ?10^?4 emu. It is comparable with the percentage of the superconducting phase in the sample. It is supposed that the arising superconductivity is due to the formation of the superconducting clusters with the direct overlap of the copper d orbitals owing to the frustration processes.     

Luminescence of orthovanadates M 3 + M3+(VO4)2 and M 2 + M4+ (VO4)2

The absorption, excitation, and luminescence spectra of vanadates of type M ₃ ⁺ M³⁺(VO₄)₂ and M ₂ ⁺ M⁴⁺(VO₄)₂ are studied, where M⁺ is Na, K, Rb, Cs; M³⁺ is Al, Sc; M⁴⁺ is Zr, Sn, Ti. The luminescence spectra maxima are located at 490–510 nm, while those of the excitation spectra are at 360–375 nm. Temperature characteristics of luminescence and thermostimulated luminescence are studied. The question of activation of complex vanadates by rare-earth ions is considered.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 24–28, March, 1976.     

Chlorine-35 nuclear quadrupole resonance and phase transitions in (4ClC6H4NH3)2MnCl4, (4-Cl6H4NH3)2CUCl4, and (4-ClC6H4NH3)2CUBr4

The temperature dependence of the ³⁵Cl NQR frequencies of 4-chloroanilinium cations in (4-ClC₆H₄NH₃)₂MnCl₄, (4-ClC₆H₄NH₃)₂CuCl₄, and (4-ClC₆H₄NH₃)₂CuBr₄ was studied over a wide range of temperature. For the two copper(II) complexes, magnetic susceptibilities were measured below approximately 20 K. The lattice constants of these isomorphous orthorhombic crystals were determined. Magnetic phase transitions to three-dimensionally long-range-ordered states were found at 40, 8, and 13 K for the respective complexes. Additional structural phase transitions were also found at higher temperatures for all of the complexes studied. Magnetic properties in the ordered state and the nature of both types of phase transitions are discussed.     

固体超强酸催化剂C3 N4-SO2-4的制备与表征

通过双氰胺的热解法制备了C3 N4,将C3 N4通过硫酸铵溶液浸渍制备了固体超强酸.通过红外光谱法、紫外吸收法、X射线衍射法、扫描透射电镜法对固体超强酸催化剂C3 N4-SO2-4进行了表征.固体超强酸C3 N4-SO2-4应用乙酸乙酯的酯化反应,结果表明固体超强酸催化活性强,酯化率较高.     

钪原子的自电离里德伯能级3d4s(~1D_2)nf~2D_(3/2),3d4s(~1D_2)nf~2F_(5/2)和3d4s(~1D_2)np~2D_(3/2)的理论研究

在多通道量子亏损理论框架下,利用相对论多通道理论,分别在冻结实近似和考虑偶极极化下计算钪原子的Jπ=(3/2)-,(5/2)-的三个收敛于[Ar]3d4s(1D2)的自电离里德伯系列的能级.对3d4s(1D2)np2D3/2和3d4s(1D2)nf2F5/2这两个系列,计算结果表明,考虑偶极极化效应后,理论计算和实验测量的量子数亏损之差普遍小于0.01.而对3d4s(1D2)nf2D3/2系列,考虑偶极极化效应后的结果和仅考虑冻结实的结果比较接近,理论计算和实验测量的量子数亏损之差普遍在0.04左右.     

The thermoelastic properties of [N(CH3)4]2ZnBr4 and [N(CH3)4]2MnBr4

The ferrodistortive phase transition in the bis-tetramethylammonium tetrabromide crystals below room temperature is studied within the framework of the Landau theory. The specific heats of [N(CH₃)₄]₂MnBr₄ and [N(CH₃)₄]₂ZnBr₄ are correctly described down to 40°C below the transition temperature. The phenomenological parameters are determined from calorimetric results, elastic constants and thermal expansion data. Using these coefficients, the monoclinic angle in the ferrodistortive phases is obtained. The anharmonic quantities, such as the isothermal compressibility, calculated from the specific heat data, are in good agreement with the values derived from the elastic measurements.     

Ionic conductivity of isostructural crystals of the superionic conductors Li3Fe2(PO4)4 and Li3Sc2(PO4)3

The results of measurements of the ionic conductivity σ in Li₃M₂(PO₄)₃ (M=Fe, Sc) single crystals along various crystallographic directions are analyzed. Possible causes of the different behavior of σ in the isostructural crystals are discussed: a jump of the conductivity in the transition to the superionic phase in Li₃Sc₂(PO₄)₃ and its absence in Li₃Fe₂(PO₄)₃; the existence of a conductivity maximum in different crystallographic directions (along the c axis in Li₃Sc₂(PO₄)₃ and along the a axis in Li₃Fe₂(PO₄)₃). Fiz. Tverd. Tela (St. Petersburg) 39, 83–86 (January 1997)     

Optical studies of the ferroelastic phase transitions in Rb3H(SeO4)2, (NH4)3H(SO4)2 and (NH4)3H(SeO4)2

Optical observations of growth twins and ferroelastic domains and measurements of the rotation of the optical indicatrix were carried out for Rb₃H(SeO₄)₂ and (NH₄)₃H(SO₄)₂ using an optical microscope. Taking into account the symmetry reduction from the rhombohedral (Rm) to the monoclinic phase (B2/a) the occurrence of domains and growth twins can be well described. The orientations of oblique ferroelastic walls are well determined by the spontaneous strains ^s e ₁₁ and ^s e ₂₃ at room temperature.