复合钙钛矿型NaLaMgWO_6:Eu~(3+)红色荧光材料的制备及发光性能研究

采用固相法合成了新型白光LED用红色NaLa_(1-x)Eu_xMgWO_6(0≤x≤1)系列荧光粉。分别采用X射线衍射、扫描电子显微镜、发光光谱等测试手段分析了粉体样品的物相、形貌与发光性质。XRD分析结果表明:NaLaMgWO_6具有单斜晶系的复合钙钛矿结构,空间群为C2/m。光谱测试结果表明:NaLa_(1-x)Eu_xMgWO_6系列荧光粉均可被近紫外光(397 nm)和蓝光(465 nm)有效激发,其最强发射峰位于617 nm处,属于Eu~(3+)的~5D_0→~7F_2电偶极跃迁。Eu~(3+)的最佳掺杂浓度为x=0.5。对荧光粉的发光浓度猝灭曲线分析表明,在NaLaMgWO_6基质中,Eu~(3+)是通过电偶极-电偶极的多极矩相互作用的方式来实现能量传递的。采用Judd-Ofelt理论计算了基质的折射率、Eu~(3+)离子的辐射跃迁强度参数(?λ)和荧光分支(β)等辐射跃迁参数。     

Eu~(3+)掺杂Sr_3La_2(BO_3)_4荧光粉的制备及发光性能研究

以高温固相法制备铕离子(Eu~(3+))掺杂硼酸盐红色荧光粉Sr_3La_2(BO_3)_4∶Eu~(3+),用X衍射(XRD)、扫描电镜(SEM)研究了荧光粉的结构和表面形貌,测定了其在近紫外光激发下的发光特征。研究结果表明,焙烧温度为1000℃,保温时间为5h,Eu3+摩尔掺杂分数为7.5%时,荧光粉具有较强的发光强度;以394nm的紫外光激发,荧光粉最强发射为波长618nm的红光,为Eu~(3+)的5 D0→7F2的电偶极跃迁,计算其色坐标为x=0.65,y=0.35。     

白光LED用红色荧光粉MMoO4:Eu3+（M=Ca,Sr,Ba）的制备与表征

采用高温固相法制备了红色荧光粉MMoO4:Eu3+(M=Ca,Sr,Ba),用XRD和荧光分光光度计对其物相及发光性能进行表征和研究。结果表明,在800℃时可得到MMoO4(M=Ca,Sr,Ba)物相结构。分别以395nm的近紫外光和465nm的可见光激发样品,MMoO4:Eu3+(M=Ca,Sr,Ba)荧光粉发红光,对应于Eu3+的4f-4f跃迁,其中以616nm发光最强。荧光粉在395nm和465nm的吸收分别与紫外光和蓝光LED芯片相匹配。     

共沉淀法合成CaO:Eu~(3+)红色荧光粉的研究

采用共沉淀法合成CaO:Eu3+红色荧光粉,探讨了Eu3+离子的掺杂量、煅烧温度和煅烧时间对样品发光性能的影响,并利用X-射线衍射仪(XRD)、扫描电镜(SEM)和荧光光度仪(PL-PLE)等仪器对样品的性能进行表征.结果表明:掺杂Eu3+作为发光中心进入到CaO基质的晶格中,其最佳掺杂量为1.5%(摩尔含量);最佳煅烧温度和煅烧时间分别为1100℃和4h,样品的激发峰位于200~290nm之间,对应于Eu3+-O2-的电荷迁移跃迁(CTB),属于宽带激发;Eu3+离子主要占据严格对称的格位,其最大发射峰位于592nm,对应于5D0→7F1磁偶极跃迁,属于红色发光.     

掺Sr的BaTiO_3∶Eu~(3+)红色荧光粉的发光性能研究

以BaCO_3、SrCO_3、TiO_2和Eu_2O_3为原料,采用高温固相法制备了不同浓度的Eu~(3+)掺杂的Ba(0.8-x)Sr_(0.2)TiO_3∶xEu~(3+)(x=0.02~0.1)系列红色荧光粉。采用荧光分光光度计对其发光强度和吸收强度进行研究得出,最佳的Eu~(3+)摩尔分数x=0.08。考察了不同电荷补偿剂对Ba_(0.72)Sr_(0.2)TiO_3∶0.08Eu~(3+)荧光粉激发光谱和发射光谱的影响,结果表明,Li+是制备Ba_(0.72)Sr_(0.2)TiO_3∶0.08Eu~(3+)荧光粉的最佳电荷补偿剂。     

Eu3+掺杂的钼酸盐微纳米材料制备和光致发光性能研究

分别采用沉淀法和水热法成功制备了Y_2(MoO_4)_3∶Eu~(3+)红色荧光粉,使用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)和荧光光谱对其物相结构、形貌和发光性能进行表征。结果表明:Eu~(3+)含量低于20%(摩尔分数,下同)不会改变Y_2(MoO_4)_3的晶体结构;沉淀法得到荧光粉呈花状,而水热法主要得到层层堆积结构的荧光粉;所制荧光粉的主激发峰和发射峰分别位于394和614nm,这是来自掺杂Eu~(3+)的f-f电子跃迁。Y_2(MoO_4)_3荧光粉中Eu~(3+)最佳摩尔分数为20%,当Eu~(3+)含量大于20%时,出现浓度猝灭现象,其5D_0→7F_2发光浓度猝灭机理是电偶极-电偶极相互作用。     

红色荧光粉Zr(MoO4)2· MoO3∶Eu3+的发光性能和能量转移

采用共沉淀法制备了一系列Zr(MoO_4)_2·MoO_3∶Eu~(3+),并对荧光粉进行了X射线衍射仪和荧光光谱仪分析。结果表明:荧光粉为一混晶,由Zr(MoO4)2和MoO3组成。荧光粉在465nm的激发下,在617nm处产生强的红光发射,发射光谱在617nm处的强度是激发光谱在465nm处强度的2.26倍。这是因为在465nm的激发下,Eu3+的能量从磁偶极中心转移到电偶极中心,使617nm处发光增强。对蓝光激发白光LED而言,Zr(MoO4)2·MoO3∶Eu3+是具有一定应用前景的红色荧光粉。     

白光LED用双层钙钛矿Sr_3Ti_2O_7:Eu~(3+)荧光粉的制备及其发光性能

采用高温固相法制备双层钙钛矿Sr3Ti2O7:Eu3+系荧光粉。利用X射线衍射(XRD)、扫描电子显微镜(SEM)和荧光光谱,研究了不同煅烧温度对双层钙钛矿Sr3Ti2O7:Eu3+荧光粉的晶体结构、形貌和发光性能的影响。结果表明:荧光粉在煅烧温度为1300℃时为纯双层钙钛矿Sr3Ti2O7相,且其有效激发波长为在395nm和465nm,这与当前近紫外和蓝光LED芯片的输出波长相匹配,激发产生的相应发射波长分别为618nm和626nm。该荧光粉是一种理想的白光LED用红色荧光粉。     

近紫外白光LED用Ca2-xSiO3Cl2∶xEu3+高效红色荧光粉的发光性能研究

采用传统的高温固相反应法在较低温度下制备红色荧光体Eu~(3+)掺杂的Ca_2SiO3_Cl_2,研究了Ca_(2-x)SiO_3Cl_2∶xEu~(3+)(x=3%～18%)的晶体结构和发光性质。激发和发射光谱表明,样品可以被近紫外350～420nm波段激发,最强激发峰位置位于394nm,发射光谱呈现出Eu~(3+)的特征红色发光,谱带峰值位置在592nm和620nm,分别对应于~(5 )D_0→~7F_1和~(5 )D_0→~7F_2特征跃迁。结果表明:最强发射对应的掺杂浓度是15%(摩尔分数),样品Ca_(1.85)SiO_3Cl_2∶0.15Eu~(3+)荧光粉是一种具有应用潜力的近紫外激发三基色白光LED用红色荧光粉。     

白光LED用GdVO_4:Eu~(3+)红色荧光粉的制备及性能

采用高温固相法制备了GdVO_4:Eu~(3+)红色荧光粉。通过X射线粉末衍射(XRD)、扫描电子显微镜(SEM)和光致发光光谱(PL)对样品的物相、形貌及发光性能进行了表征。结果表明:所合成的GdVO_4:Eu~(3+)红色荧光粉为四方晶系,表面为类球形。激发光谱中,位于382 nm、395 nm、418 nm和466 nm的激发峰分别归属于~7F_0→~5L_7、~7F_0→~5L_6、~7F_0→~5D_3及~7F_0→~5D_2跃迁。发射光谱中,位于593 nm、625 nm、654 nm和701 nm的发射峰对应Eu~(3+)的~5D_0→~7F_1、~5D_0→~7F_2、~5D_0→~7F_3及~5D_0→~7F_4跃迁。当Eu~(3+)掺杂量为7%,800℃煅烧8 h时,GdVO_4:Eu~(3+)红色荧光粉CIE色坐标为(0.6426,0.3530),荧光寿命为0.52 ms,是一种有望用于白光LED的高效红色荧光粉。     

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．     

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.     

白光LED用BaMgAl_(10)O_(17):Eu~(2+)Mn~(2+)蓝绿荧光粉

采用高温固相法制备出一种Eu2+,Mn2+共掺的蓝绿色荧光粉BaMgAl10O17:Eu2+,Mn2+(BAM:Eu2+,Mn2+),对其进行了X射线衍射分析和光谱特性的测试.研究表明,它的发射光谱为双峰结构,峰值分别位于455 nm和525 nm处.455 nm发射峰归结为BAM中部分取代Ba2+离子的Eu2+离子的5d→4f的跃迁辐射;525 nm的发射峰源于部分Eu2+能量传递给Mn2+离子,Mn2+的4T1→6A1的跃迁辐射.采用近紫外LED芯片与该荧光粉以及一种红色荧光粉Ca(La0.5Eu0.5)4Si3O13封装,在20 mA前向电流驱动下,获得了显色指数为88的白光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。     

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。     

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.     

甘氨酸燃烧法合成Sr2CeO4及其发光性质研究

为制备具有优良性能的蓝色荧光粉,首次采用甘氨酸-硝酸盐燃烧法合成了Sr2CeO4,利用热重-差热分析仪、X射线粉末衍射仪、扫描电镜等技术对其形成过程、物相结构、形貌粒度、发光性质进行了研究.结果表明:燃烧后的前驱物经800℃焙烧已有目标产物Sr2CeO4生成,1100℃时可得到较纯正交晶系的Sr2CeO4相.颗粒的形貌为不规则球形,平均粒径在80 nm左右.发光性质研究表明:Sr2CeO4荧光粉的激发光谱是宽带双峰结构,此宽带属于Ce4+的电荷迁移带,两个峰分别位于305 nm和348 nm,后者为主峰.用348 nm紫外光激发样品,发出明亮的蓝光,其发射光谱也是一个宽带,最大峰位于470 nm,此峰属于Ce4+的f→t1g跃迁.发光强度在800~1100℃随温度升高而增强.     

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.