Eu~(2+),Mn~(2+)在CaZn_2(PO_4)_2中的发光及Eu~(2+)→Mn~(2+)能量传递

Mn2+作为激活剂加入一些基质中,发光比较弱。因此常常选择使用合适的敏化剂来提高Mn2+的发光效率,本文的研究目就是验证Eu2+是Mn2+的良好的敏化剂。采用高温固相法合成了Eu2+,Mn2+掺杂激活的CaZn2(PO4)2荧光粉,并对其发光性质进行了研究。单掺杂Eu2+时呈现发射峰位于504nm的带谱,属于Eu2+离子的5d-4f能级跃迁辐射,激发峰位于380nm,属于Eu2+的f-d跃迁特征激发谱带。单掺Mn2+时CaZn2(PO4)2不发光。当Eu2+和Mn2+共掺时,出现Mn2+的673nm发射峰,样品发红光,表明Eu2+对Mn2+的发光有很强的敏化作用。研究了Eu2+和Mn2+掺杂浓度对激发光谱和发射光谱的影响,证明在CaZn2(PO4)2:Eu2+,Mn2+中Eu2+对Mn2+的能量传递属于共振能量传递。     

Ca_3B_2O_6:Eu~(3+),A(A=Li~+,Na~+,K~+)红色荧光粉的合成条件的优化

采用高温固相法合成Ca3B2O6:Eu3+,A(A=Li+,Na+,K+)系列红色荧光粉。以395nm的近紫外光激发样品,Ca3B2O6:Eu3+,A(A=Li+,Na+,K+)荧光粉发红光,以614nm附近的5 D0→7F2电偶极跃迁发光最强。材料能非常好地吸收395nm波长的光,与近紫外光LED芯片匹配良好。Ca3B2O6:Eu3+红色荧光粉合成最佳条件为Eu3+掺杂浓度为4%,Li+的掺杂浓度为8%,在900℃灼烧2h。从而简化了合成工艺,优化了合成条件。     

Eu2+、Dy3+、Li+共掺杂CaSi2O2N2荧光粉的发光性能

采用高温固相反应法制备了一系列白光LED用CaSi2O2N2:0.05Eu2+,xDy3+,xLi+(0≤x≤0.03)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:Dy3+和Li+离子的掺入没有改变CaSi2O2N2: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,发现所有样品的激发光谱均覆盖了从近紫外到蓝光的较宽范围,400 nm激发下得到的发射光谱为宽波段的单峰,峰值位于545 nm左右,是Eu2+离子5d-4f电子跃迁引起的.Dy3+离子掺杂可以提高CaSi2O2N2:Eu2+荧光粉的发光强度,Dy3+与Li+共掺杂可进一步提高荧光粉的发光强度,当Dy3+和Li+的掺杂量为1mol%时,荧光粉的发光强度达到最大值,是单掺杂Eu2+的荧光粉发光强度的157%.     

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。     

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。     

白光LED用白光荧光粉Gd_2MoB_2O_9:Eu~(3+),Tb~(3+)的制备及其发光性能研究

采用高温固相法首次合成了由Eu3+和Tb3+共激活的Gd2MoB2O9白色荧光粉,并对其发光性质进行研究。该荧光粉在近紫外光(375nm)激发下发出较强的白色荧光(常温),光谱测试显示Gd2MoB2O9∶Eu3+,Tb3+的发射光谱中存在3个发射峰,分别位于486,543和613nm处,能够合成较理想的白光;激发光谱在250~400nm处均有较强的吸收,能与紫外LED很好地匹配,适用于白光LED。     

Zn_4B_6O_(13)∶Eu~(3+)的合成与光致发光

用高温固相扩散方法首次合成了由Eu3 + 离子激活的Zn4B6O13 红色光致发光材料。用XRD分析了样品结构 ,结果表明 :Zn3 .94B6O13 ∶Eu3 + 为立方晶系 ,晶胞参数a =0 .7471nm ,V =0 .4170nm3 。研究了Eu3 + 在Zn4B6O13 中的强激发带位于 3 94nm ,主要发射峰位于610nm归属Eu3 + 离子的5D0 →7F2 电偶极跃迁发射 ,根据发射光谱计算色坐标为x =0 .2 81,y =0 .619。SEM摄取了样品的清晰晶体外貌 ,平均颗粒度为 15 μm左右。加入一定量助熔剂使发射光谱的相对发射强度增加了 2 .3 2～ 3 .86倍。     

CaO:Eu~(3+),A(A=Li~+,Na~+,K~+)荧光粉的合成与发光性能

采用固相反应法合成了CaO:Eu3+,A(A=Li+,Na+,K+)荧光粉,研究了CaO:Eu3+,A(A=Li+,Na+,K+)荧光粉的发光性能。结果表明:CaO:Eu3+,A(A=Li+,Na+,K+)荧光粉具有面心立方结构,Eu3+、Li+、Na+、K+的加入没有改变CaO基质的结构。主激发峰均位于200~310nm之间,对应于Eu3+-O2-的电荷迁移跃迁(CTB),属于宽带激发。在紫外光激发下,CaO:Eu3+,Li+和CaO:Eu3+,Na+荧光粉均发出橙色光,CaO:Eu3+,K+荧光粉发射出红色光。CaO:Eu3+,K+荧光粉是一种极具潜力的近紫外光激发的红色荧光粉。     

红色荧光粉Ca_9Al(Po_4)_7:Eu~(3+)的制备与发光特性

本文采用高温固相法合成了Ca9Al(Po4)7:Eu3+红色荧光粉,并对其发光特性进行了研究。该荧光粉在350nm-410nm有一个宽带激发峰,适用于UVLED管芯的激发;在紫外激发下的发射峰由位于589nm和593nm,612nm、616nm和619nm,654nm及688nm四组线状峰构成,分别对应于Eu3+的(5D0～7F1)、(5D0～7F2)、(5D0～7F3)及(5D0～7F4)特征跃迁,呈现红色发光。探讨了掺杂的Eu3+浓度对样品发光强度的影响,其最佳掺杂浓度为5%。研究了其自身浓度猝灭机理,为电偶极-电四极相互作用。发现不同电荷补偿剂Li+,Na+,K+的引入均能使发光强度得到提高,尤其以Li+最佳,发光强度提高了大约35%。结果表明,Ca9Al(Po4)7:Eu3+是一种适用于UVLED管芯激发的用于白光LED的红色荧光粉。     

绿色荧光粉Zn_2Ca(PO_4)_2:Tb~(3+)的制备及发光性能研究

采用高温固相法合成了绿色荧光粉Zn2Ca(PO4)2:Tb3+,测定了该荧光粉的XRD图谱、激发光谱及发射光谱。XRD图谱表明在高温还原气氛下合成了纯相的荧光粉Zn2Ca(PO4)2:Tb3+。该荧光粉的激发谱位于340～400nm。在紫外激发下主要发射峰位于490、544、584、622nm,对应于Tb3+的5D4→7F6、5D4→7F5、5D4→7F4、5D4→7F3的特征发射。考察了Tb3+的掺杂浓度对样品发光效率的影响,分析了Tb3+的544nm发射的自身浓度猝灭机理并探讨了敏化剂Ce3+离子的加入对荧光粉发光的影响。此绿色荧光粉Zn2Ca(PO4)2:Tb3+是一种很有潜力的适于UVLED管芯激发的发光粉。     

Luminescence properties of nano-sized Sr2MgSiO5: Eu2+, Mn2+ phosphors prepared by the sol-gel method

Nano-sized Sr2MgSiO5:Eu2+, Mn2+ phosphor was synthesized by the sol-gel method. The preparation conditions of the precursor were determined. The effect of Eu2+ and Mn2+ content on the luminescence intensity was studied. X-ray diffraction (XRD), photoluminescence spectra (PL), and photoluminescence excitation spectra (PLE) were used to characterize the samples. The results showed that the excitation bands ranged from 250 to 450 nm, and their peaks positioned around 365 nm. The emission spectrum consists of three bands: blue, green, and red, respectively. The blue and green emission bands originate from the center of the Eu2+, while the red emission band is attributed to the energy transfer from Eu2+ to Mn2+. White light can be obtained by mixing the three emission colors. The experiment results show that the Sr2MgSiO5:Eu2+, Mn2+ is a single host phosphor with superior properties for use in white light emitting diodes (white LED).     

Luminescence properties of nano-crystalline Ba3MgSi2O8:Eu2+, Mn2+ phosphors

Ba3MgSi2O8:Eu2+, Mn2+ phosphors were synthesized by the sol-gel method and high temperature solid-state reaction method, respectively. XRD (X-ray diffraction), FT-IR (Fourier transform infrared spectroscopy), PL (photoluminescence spectra), and PLE (photoluminescence excitation spectra) were measured to characterize the samples. Emission and excitation spectra of our Ba3MgSi2O8:Eu2+, Mn2+ phosphors monitored at 441, 515, and 614 nm are depicted in the paper. The emission intensities of 441 and 515 nm emission bands increase with increasing Eu2+ concentration, while the peak intensity of the 614 nm band increases with increasing Mn2+ concentration. We conclude that the 515 nm emission band is attributed to the 4f(6)5d transition of Eu2+ ions substituted by Ba2+ sites in Ba2SiO4. The 441 nm emission band originates from Eu2+ ions, while the 614 nm emission band originates from Mn2+ ions of Ba3MgSi2O8:Eu2+, Mn2+. Nano-crystalline Ba3MgSi2O8:Eu2+, Mn2+ phosphors prepared by the sol-gel method show higher color rendering and better color temperature in comparison with the samples prepared by high temperature solid-state reaction method.     

Eu2+掺杂硅基氮氧化物荧光粉的制备与发光特性

为获得接近太阳光的自然发光效果,制备了Eu2+掺杂的硅基氮化物系列荧光粉,并对其发光特性及原理进行研究.采用碳热还原氮化法制备了Eu2+掺杂Sr Si O3-Sr2Si5N8-Sr Si2O2N2红色荧光粉.利用X射线衍射仪(XRD)、荧光分光光度计、MS-CASTEP对产物物相、发光光谱、电子结构进行了测试分析.结果发现:通过调节煅烧工艺参数,可同时获得2种主要物相或者单一物相的荧光粉;所制备的荧光粉,能够在350~400 nm范围内被UVLED很好地激发,根据主晶相的不同,产物的发射光谱可以在400~700 nm波段内调控.采用第一性原理分析了发射峰位于650 nm附近橙红色主晶相Sr2Si5N8∶Eu2+的电子结构和光物理性能,发现该物相为直接带隙半导体材料,Eu2+的4f轨道对费米面电子峰起主要作用.Eu2+掺杂Sr Si O3-Sr2Si5N8-Sr Si2O2N2是优良的、颜色可调控的红色荧光粉材料.     

The sol-gel process synthesis of GdAl3(BO3)4:Eu3+ nanophosphors

GdAl3(BO3)4:Eu3+ red phosphors were prepared using citric acid as complex agent by sol-gel technique. The preparation conditions of the precursor synthesis, including crystallization temperature and crystallization time were investigated. Their structure and luminescence properties were characterized by X-ray diffraction (XRD) analysis and fluorescence spectrometry. The results showed that GdAl3(BO3)4:Eu3+ phosphor crystallized at 960 degrees C for 2 h have been synthesized by sol-gel method. The phosphor is distributed into hexagonal system and the lattice parameters are a = 9.2992 nm c = 7.2577 nm. The excitation spectrum of Gd(0.95)Al3(BO3)4:Eu(0.05)3+ samples is complex and the frequency scale is wide. It consists of a number of main excitation transitions namely 8S(7/2) --> 6IJ (270 nm) of Gd3+, and the others 7F0 --> 5L6 (400 nm), 7F0 --> 5D2 (472 nm) and 7F0 --> 5D1 (542 nm) of Eu3+. The main emission peaks are 614 nm and 619 nm, which are the characteristic emission peaks of Eu3+. These emission peaks correspond to the transition from 5D0 to 7F2 of Eu3+. The shape and the wavelength range of the emission spectrum are similar when the sample was excited by different excitation spectrum. Only the relative intensity of the emission peaks is different from each other.     

Y2O2S:0.03Eu,0.03Ti的长余辉特性及Ti向Eu3+的余辉传能机制

采用高温还原法合成了Eu，Ti共激活橙红色Y2O2S长余辉发光材料，并测量了Y2O2S：0．03Eu,0．03Ti磷光体的荧光光谱，余辉分辨和余辉衰减曲线谱．实验结果表明，Y2O2S：0．03Eu,0．03Ti磷光体的发射谱由一系列Eu^3＋离子内部能级跃迁的尖峰组成；余辉分辨谱则不同，由一个主峰位于565nm的宽发射带和一系列波长范围位于500nm以上的窄发射带两种峰形组成，可分别归为Ti离子的宽带余辉发射和三价Eu^3＋的线状余辉发射,分析认为，样品中存在Ti余辉发射向Eu^3＋内部能级间产生选择性的余辉传能机制，从而导致Y2O2S：0．03Ti，0．03Eu磷光体中同时出现两种发光中心离子的余辉分辨谱现象．     

Characterization and luminescence of Eu3+ ions doped 12CaO 7Al2O3 nanopowders

Eu3+ ions doped 12CaO 7Al2O3 (C12A7) powders with different Eu3+ concentrations were prepared by sol-gel combined with solid state reaction method. The results of XRD and Raman spectra showed that single cubic phase polycrystalline C12A7:Eu3+ powders were prepared. The absorption peaks attributed to f-f transition of Eu3+ ion can be observed, indicating that Eu3+ had been incorporated into C12A7 lattice site. Visible PL peaks around 578, 588, 614 nm were ascribed to 5D0 --> 7FJ (J = 0, 1, 2) transitions of Eu3+ under the excitation of 488 nm line. The PL of C12A7:Eu3+ showed the strongest emission intensity at Eu3+ concentration of 0.5 at%. Two different types of Eu3+ centers were identified by the two lines from 5D0 --> 7F0 transition emission. The doping mechanism of C12A7:Eu3+ might be attributed to Eu3+ ions substitution for two types of Ca2+ lattice sites in C12A7. The temperature dependent PL spectra of Eu-doped C12A7 were measured in the range from 100 to 300 K under the excitation of 488 nm laser line. The PL intensities as a function of temperature were well fitted by using a unified theoretical model, considering thermal activation and nonradiative energy transfer processes.     

Synthesis and luminescence properties of Sr2SiO4: Eu3+, Dy3+ phosphors by the sol-gel method

The Sr2SiO4:Eu3+, Dy3+ phosphors for white light emitting diodes (LEDs) were synthesized by the sol-gel method. The microstructure and luminescent properties of the obtained Sr2SiO4:Eu3+, Dy3+ particles were well characterized. The results demonstrate that the Sr2SiO4:Eu3+, Dy3+ particles, which have spherical morphology, emitted an intensive white light emission under excitation at 386 nm. The phosphors show three emission peaks: the blue emission at 486 nm corresponding to the 4F(9/2)-6H(15/2) transition of Dy3+, the yellow emission at 575 nm corresponding to the 4F(9/2)-6H(13/2) transition of Dy3+, and the red emission at 615 nm corresponding to the 5D0-7F2 transition of Eu3+. At the same time, the effect of Eu3+ concentration on the emission intensities of Sr2SiO4:Eu3+, Dy3+ was investigated in detail. The phosphors used for white LEDs were obtained by combining near ultraviolet (NUV) light (386 nm) with Sr2SiO4:0.04Dy3+, 0.01Eu3+ phosphors with the characteristic of Commission Internationale de l'Eclairage (CIE) chromaticity coordinate (x, y) of (0.33, 0.34), and color temperature Tc of 5,603 K. In addition, the effect of the charge compensators (Li+, Na+, and K+ ions) on the photoluminescence (PL) emission intensities were studied.     

Eu2+离子在Sr2Al6O11基磷光体中发光行为的研究

研究了不同Eu掺杂浓度对Sr2Al6O11基磷光体发光性能的影响。结果发现，当Eu掺杂浓度低于0.01mol时，在其发射光谱中存在403和493nm的主发射峰，对应着Sr2Al6O11基质中Sr的两种不同位置Sr1和Sr2位。随着Eu掺杂浓度增加，由于能量传递作用，导致403nm的发射峰消失，493nm的发射峰增强。余辉衰减曲线表明，未掺杂Dy的磷光体没有余辉性能，当Eu掺杂量在0.01mol时，余辉性能最好，进一步提高Eu的掺杂量，由于浓度猝灭作用，导致发光性能下降。     

The effects of Mn2+ doping on the luminescence properties of 12CaO 7Al2O:Eu2+ nanocrystal phosphor

The long lasting blue phosphorescence (LLP) and photostimulated luminescence (PSL) after ultraviolet light irradiation at room temperature in 12CaO 7Al2O3:xEu2+, yMn2+ (x = 0, 0.001; y = 0, 0.01) prepared by the chemical co-precipitation method were observed. It was shown that novel oxide 12CaO 7Al2O3:Eu2+, Mn2+ (C12A7:Eu2+, Mn2+) with unique nanocage structure can store energy when irradiated with 365 nm photons. And photon energy can be subsequently released by exposed to 980 nm light. The codopant Mn2+ enhances the intensity of the persistent phosphorescence and PSL due to the existence of more shallow and new deeper electron traps in C12A7: Eu2+, Mn2+. A model for energy storing and recovering and the detailed mechanism of PSL are presented through comparing with the luminescence properties of the co-doped C12A7:Eu2+, Mn2+ and C12A7:Eu2+.     

Eu3+掺杂的硼酸锶系列荧光体的合成及其发光性能

采用溶胶-凝胶法和高温固相反应法合成了Eu^3 掺杂的SrB4O7、SrB2O4、Sr2B2O5、Sr3B2O6荧光体．荧光光谱测试结果表明在不同基质中Eu^3 的荧光发射是有区别的，Sr2B2O5：Eu^3 、Sr3B2O7：Eu^3 发射峰在610nm左右的红光区，SrB2O4：Eu^3 的发射峰在593nm的橙色区，而SrB4O7：Eu^3 则表现出了Eu^2 离子的特征峰，产生这种区别主要是由Eu^3 所处的配位环境不同造成的．荧光体SrB4O7：Eu^3 、SrB2O4：Eu^3 、Sr2B2O5：Eu^3 、Sr3B2O6：Eu^3 的最佳掺杂浓度为2％左右．