Sr0.95Zn0.05Se:Eu2+ and CdSe/ZnS nanocrystals hybrid phosphors for enhancing color rendering index of white light emitting diode

In this study, the yellow emitting cubic structure of Sr0.95Zn0.05Se:Eu2+ phosphors were prepared by high temperature solid state reaction. The Sr0.95Zn0.05Se:Eu2+ phosphors exhibited strong excitation intensity under 400-460 nm region, and broad band emission appeared at around 545-600 nm due to the d-f transition of Eu2+. To enhance the red emission, HDA/TOP/TOPO capped CdSe/ZnS NCs were synthesized via fast nucleation and slow growth method. The narrow emission peak was located at 615 nm with 69% of high quantum yield. Bright white emission was generated by combining a 460 nm InGaN LED chip with CdSe/ZnS NCs and Sr0.95Zn0.05Se:Eu2+ hybrid phosphors. The fabricated white LEDs showed warm white light with acceptable CIE chromaticity coordinate variation from (0.343, 0.255) at 20 mA to (0.335, 0.250) at 50 mA. The addition of CdSe/ZnS NCs contributed to the extension of white light spectrum by supplement of the red region. The color rendering index was largely enhanced from 41.7 to 79.7 compared to the Sr0.95Zn0.05Se:Eu2+ based phosphors white LED.     

Ca10K（PO4）7:Eu3+红色荧光粉的制备及其发光性质

高温固相法合成了Ca10-xK(PO4)7:xEu3+(x=0.02,0.04,0.06,0.08,0.10,0.12,0.14和0.16)的红色荧光粉。X射线衍射表明,样品具有标准的Ca10K(PO4)7六角晶体结构,且无第二相存在。在393nm的波长激发下,样品获得由Eu3+的4f-4f跃迁产生红光发射,其中以613nm附近的5 D0→7F2电偶极跃迁发射为最强。通过调节Eu3+的掺杂浓度,获得了色坐标与商业化Y2O2S:Eu3+荧光粉十分接近的接近纯色的红色荧光粉。Ca10K(PO4)7:Eu3+是一种可望应用于紫外激发的白光LED的红色荧光粉。     

助熔剂和还原气氛对掺铕硅酸锶荧光粉发光性能的影响

采用传统高温固相反应法制备了掺铕硅酸锶荧光粉。在近紫外光激发下,Sr2SiO4:Eu2+发出明亮的黄绿光。其发射光谱由峰值分别位于490nm和550nm的两个属于Eu2+的5d→4f发射带叠加组成。当Eu2+浓度为0.005mol时,发光最强。研究了不同助熔剂(NH4F、NH4Cl、NaF、Li2CO3、H3BO3)及不同还原气氛(5%H2-95%N2混合气体和C粒)对Eu2+掺杂的Sr2SiO4发光性能的影响。结果表明添加助熔剂后大大降低了烧结温度,并不同程度地提高了2个发射峰的强度。结果还表明5%H2-95%N2混合气体还原效果比C粒好。     

Ca2SiO3Cl2∶Dy3+单一基质白光荧光粉的制备及发光特性

采用溶胶-凝胶法合成了发射白光的Ca2SiO3Cl2∶Dy3+荧光粉。利用XRD分析了荧光粉的晶体结构,其为四方晶系。在350nm近紫外光激发下,荧光粉呈白光发射,有两个主发射峰位分别于482和573nm,分别对应于Dy3+的4F9/2→6H15/2和4F9/2→6H13/2跃迁;监测573nm最强发射峰,激发光谱覆盖200～450nm,主激发峰位于350nm。研究结果表明保温时间的延长有利于发射强度的提高,伴随着Dy3+浓度的增大,发射光谱图中的两个主发射峰先增强后减弱,Dy3+的最佳浓度为2%(摩尔分数)。     

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.     

煅烧温度对红色长余辉发光材料Sr_3Al_2O_6:Eu~(2+),Dy~(3+)性能的影响

采用溶胶凝胶法合成了Sr3Al2O6:Eu2+,Dy3+长余辉发光材料,利用X射线衍射仪(XRD)对材料的物相进行了分析,采用荧光分光光度计、照度计测定了样品的发光特性。XRD结果表明:随着煅烧温度的升高,SrCO3杂相的衍射峰越来越弱,Sr3Al2O6相的衍射峰越来越强,1200℃时发光基质为纯的Sr3Al2O6相,1250℃时出现新的SrAl2O4杂相。激发光谱和发射光谱结果表明:长余辉发光材料的激发峰位于473nm,发射峰位于612nm,归属于Eu2+的4f65d1→4f7特征发光。温度升至1250℃时,Eu2+的发射峰为612nm和520nm,后者归属于Eu2+在发光基质SrAl2O4中的发光。综合分析得制备Sr3Al2O6:Eu2+,Dy3+发光材料合适的煅烧温度为1200℃,在此温度下,材料具有较好的初始亮度和余辉时间。     

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．     

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%.     

Ln(Ln=Gd3+,Cu+,Sm3+,Dy3+)助激活的Ca8Mg（SiO4）4Cl2∶Eu2+荧光粉的光谱特性和Eu2+的格位计算

采用高温固相法合成了掺杂Ln(Ln=Gd3+,Cu+,Sm3+,Dy3+)作助激活离子的氯硅酸镁钙荧光粉。通过X射线衍射(XRD)对Ca8Mg(SiO4)4Cl2∶Eu2+,Ln进行了表征,结果表明Ln的共掺杂并没有影响基质晶体的面心立方结构。所合成的荧光粉发射峰值位于507nm的绿光区,激发光谱在330~430nm之间均有较强吸收,与紫光InGaN芯片(395nm)相匹配。掺杂Ln作助激活剂增强了荧光粉的发光强度。借助Uitert经验公式计算出Eu2+在Ca8Mg(SiO4)4Cl2基质中占据八配位Ca(Ⅱ)格位。     

荧光粉Sr3-x-yAl2O6∶xCe3+,yEu2+的制备及其发光特性

采用高温固相反应法制备了Sr3-x-yAl2O6:xCe3+,yEu2+(x=0,y=0;x=0.04,y=0;x=0.04,y=0.02;x=0.04,y=0.04;x=0.04,y=0.06;x=0.04,y=0.08;x=0,y=0.04)荧光粉,研究其相组成与荧光特性,结果表明,样品具有单相Sr3Al2O6晶体结构。在360nm波长的紫外光激发下,Ce3+离子辐射出峰值在434nm附近的宽谱蓝光。通过能量传递作用,Eu2+离子辐射峰值为517nm左右的宽谱绿光。Ce3+和Eu2+的荧光组合获得了色坐标为(0.2611,0.3313)的近白光发射。样品的激发光谱分布在250～400nm的波长范围,这种荧光粉有望在紫外或近紫外激发的白光LED中获得应用。     

Spherical SiO2 @ GdPO4: Eu3+ core-shell phosphors: sol-gel synthesis and characterization

Nanocrystalline GdPO4 : Eu3+ phosphor layers were coated on non-aggregated, monodisperse and spherical SiO2 particles by Pechini sol-gel method, resulting in the formation of core-shell structured SiO2 @ GdPO4 : Eu3+ particles. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), photoluminescence (PL), low-voltage cathodoluminescence (CL), time-resolved PL spectra and lifetimes were used to characterize the core-shell structured materials. Both XRD and FT-IR results indicate that GdPO4 layers have been successfully coated on the SiO2 particles, which can be further verified by the images of FESEM and TEM. Under UV light excitation, the SiO2 @ GdPO4 : Eu3+ phosphors show orange-red luminescence with Eu3+ 5D0-7F1 (593 nm) as the most prominent group. The PL excitation and emission spectra suggest that an energy transfer occurs from Gd3+ to Eu3+ in SiO2 @ GdPO4 : Eu3+ phosphors. The obtained core-shell phosphors have potential applications in FED and PDP devices.     

稀土掺杂双钙钛矿结构红色荧光粉的制备及其发光性能

采用高温固相反应法制备了Sr_(2-x)BaxMgMoO_6∶Eu~(3+)(x=0~1)双钙钛矿结构红色荧光粉。探讨了预处理及煅烧制度、Ba取代量对Sr_(2-x)BaxMgMoO_6∶Eu~(3+)荧光粉的相结构和发光性能的影响。Sr_2Mg_(0.94)Eu_(0.06)MoO_6荧光粉最佳制备工艺为:在700℃下预处理1h再升温至1050℃预处理1h并随炉降温后研细,再在1300℃煅烧4h,所得样品主相为双钙钛矿结构的Sr2MgMoO6四方相。其最强发光峰位于617nm附近,对应于Eu3+的5D0→7F2电偶极跃迁。随着Ba2+对Sr2+的取代量的增加晶体对称性提高,晶体结构由四方相变为立方相,样品的激发峰强度显著提高。由于晶体对称性的提高,抑制了荧光粉在617nm处5D0→7F2红光发射,其发光由电偶极跃迁占主导转变为磁偶极跃迁占主导。     

Tunable luminescence and energy transfer properties of Sr₃AlO₄F:RE³+ (RE = Tm/Tb, Eu, Ce) phosphors

Sr(3)AlO(4)F:RE(3+) (RE = Tm/Tb, Eu, Ce) phosphors were prepared by the conventional solid-state reaction. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), photoluminescence (PL) spectra, as well as lifetimes were utilized to characterize samples. Under the excitation of UV light, Sr(3)AlO(4)F:Tm(3+), Sr(3)AlO(4)F:Tb(3+), and Sr(3)AlO(4)F:Eu(3+) exhibit the characteristic emissions of Tm(3+) ((1)D(2)→(3)F(4), blue), Tb(3+) ((5)D(4)→(7)F(5), green), and Eu(3+) ((5)D(0)→(7)F(2), red), respectively. By adjusting the doping concentration of Eu(3+) ions in Sr(3)AlO(4)F:0.10Tm(3+), 0.10Tb(3+), zEu(3+), a white emission in a single composition was obtained under the excitation of 360 nm, in which an energy transfer from Tb(3+) to Eu(3+) was observed. For Sr(3)AlO(4)F:Ce(3+),Tb(3+) samples, the energy transfer from Ce(3+) to Tb(3+) is efficient and demonstrated to be a resonant type via a dipole-quadrupole interaction by comparing the experimental data and theoretical calculation. Furthermore, the critical distance of the Ce(3+) and Tb(3+) ions has also been calculated to be 9.05 ?. The corresponding luminescence and energy transfer mechanisms have been proposed in detail. These phosphors might be promising for use in near-UV LEDs.     

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.     

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.     

Sol-gel fabrication and photoluminescence properties of SiO2 @ Gd2O3:Eu3+ core-shell particles

A uniform nanolayer of europium-doped Gd2O3 was coated on the surface of preformed submicron silica spheres by a Pechini sol-gel process. The resulted SiO2 @ Gd2O3:Eu3+ core-shell structured phosphors were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), photoluminescence (PL) spectra as well as kinetic decays. The XRD results show that the Gd2O3:Eu3+ layers start to crystallize on the SiO2 spheres after annealing at 400 degrees C and the crystallinity increases with raising the annealing temperature. The core-shell phosphors possess perfect spherical shape with narrow size distribution (average size: 640 nm) and non-agglomeration. The thickness of the Gd2O3:Eu3+ shells on the SiO2 cores can be adjusted by changing the deposition cycles (70 nm for three deposition cycles). Under short UV excitation, the obtained SiO2@Gd2O3:Eu3+ particles show a strong red emission with 5D0-7F2 (610 nm) of Eu3+ as the most prominent group. The PL intensity of Eu3+ increases with increasing the annealing temperature and the number of coating cycles.     

Optical properties of eu doped M-Ga2S4 (M: Zn, Ca, Sr) phosphors for white light emitting diodes

Eu2+ doped M-thiogallate (MGa2S4, M: Zn, Ca, Sr) phosphors were prepared by solid-state reaction. The dependence of luminescent properties, photoluminescence and cathodoluminescence, on M2+ ions was investigated. ZnGa2S4: Eu2+, CaGa2S4: Eu2+, and SrGa2S4: Eu2+ exhibited a green emission band at 540 nm, 560 nm, and 535 nm, respectively. The red-shift between CaGa2S4: Eu2+ and SrGa2S4: Eu2+ was originated from the radius difference of Ca2+ and Sr2+ ions. However, it did not apply to ZnGa2S4 : Eu2+ despite of smaller radius of Zn2+ ion. The particle size of ZnGa2S4 : Eu2+ was much smaller than those of the other thiogallates, leading to extremely low CL emission.     

Temperature-Dependent Luminescence Characteristic of SrSi2O2N2：Eu2＋ Phosphor and Its Thermal Quenching Behavior

The yellow SrSi2O2N2：Eu2＋ phosphor has been synthesized by using a simple solid-state reaction method with Sr2SiO4：Eu2＋ as the precursor. It shows a broad excitation band extending from 250 to 520 nm and an asymmetric emission band with a main peak at about 550 nm. The emission intensity of the SrSi202N2：Eu2＋ is about 1.2 times higher than the commercial yellow phosphor YAG：Ce3＋ （P46-Y3）. The temperature- dependent luminescence characteristic of SrSi202N2：Eu2＋ has been investigated in this paper. With increasing temperature, the emission band of SrSi202N2：Eu2＋ shows anomalous blue-shift along with decreasing emission intensity and the broadening full width at half maximum （FWHM）. Particularly, compared with YAG：Ce3＋ （P46-Y3）, the yellow SrSi202N2：Eu2＋ phosphors exhibit higher thermal stability due to their weaker electron-phonon coupling strength （1.1）, lower stokes shift （0.0576 eV） and larger activation energy （0.288 eV）. All these results indicate that SrSi202N2：Eu2＋ yellow phosphors have potential application for white light-emitting diodes （LEDs）, What＇s more, an energy level scheme is constructed to explain the anomalous blue-shift phenomenon.     

Study on luminescent properties of Eu3+ doped new type yttrium tungsten oxide nanophosphors

In this paper, a novel nanophosphor, Y10W2O21:Eu, was synthesized through co-precipitation which is a simple and low-costing method. The structure and morphology of the nanocrystal samples were characterized by using XRD and FE-SEM. The emission spectra, excitation spectra and fluorescence decay curves were measured. J-O parameters, quantum efficiencies of Eu3+ 5D0 energy level, color coordinates and Huang-Rhys factor of Y10W2O21:Eu nanophosphors were calculated. The results indicate that EU3+ 5D0-7F2 red luminescence at 610 nm can be effectively excited by 394 nm near-UV light and 464 nm blue light in Y10W2O21 host, which is similar to the familiar Eu3+ doped tungstate phosphors (e.g., Gd2(WO4)3:Eu, CaWO4:Eu). Besides, compared with the other types of tungstate phosphors, a less expensive tungsten was used, which can effectively reduce cost. Therefore, the Y10W2O21:Eu red nanophosphors may have a potential application for white LED.     

Eu3+对Na3Gd2(BO3)3∶Tb3+发光性能的影响及其能量传递

采用高温固相法制备了Na_3Gd_2(BO_3)_3∶Tb~(3+),Eu~(3+)荧光粉,并对样品的物相组成、微观形貌、发光性能和能量传递进行了分析。结果表明,Na_3Gd_(2-x)(BO_3)_3∶xTb~(3+)荧光粉在紫外和近紫外区域有较强的激发峰,在368nm波长激发下,发射光呈绿色,Tb~(3+)最佳掺杂量为x=0.04。随着在Na_3Gd_(1.96)(BO_3)_3∶0.04Tb~(3+)中掺入Eu~(3+),Tb~(3+)对Eu~(3+)产生了以电偶极-电偶极相互作用为主的能量传递,且传递效率随Eu~(3+)掺杂量的增加而逐渐增大。发射光谱中Tb~(3+)的发射峰强度逐渐减弱,而Eu~(3+)的发射峰强度逐渐增强,导致Na_3Gd_(1.96-y)(BO_3)_3∶0.04Tb~(3+),yEu~(3+)荧光粉发光颜色由绿色向橙色变化。