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。     

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.     

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。     

溶胶凝胶-燃烧法制备SrMgAl_(10)O_(17)∶Eu~(2+)、Mn~(2+)高效蓝绿荧光粉及其发光特性研究

采用溶胶凝胶-燃烧法制备了SrMgAl10O17∶Eu2+,Mn2+(SAM∶Eu2+、Mn2+)高效蓝绿双峰荧光粉,并利用X射线衍射仪(XRD)、荧光光谱仪(PL)、场发射扫描电子显微镜(FE-SEM)和EDX能谱分析仪(EDS)等测试手段对所得样品进行表征。结果表明,Eu2+、Mn2+共掺杂的SAM荧光粉颗粒长度约为1μm,产物结晶度高,形貌规则,且均匀性好。随着Mn2+的掺入,发射光谱出现了双峰,分别为465nm的蓝光和515nm的绿光。当Mn2+掺杂浓度达到11%时,对应515nm的绿光发射光谱峰值达到最大值,Eu2+→Mn2+间的能量传递也达到饱和。与传统燃烧法相比,溶胶凝胶-燃烧法提高了荧光粉的猝灭浓度,且增强了荧光强度。还以Dexter能量传递理论为依据,通过能量转移效率和临界距离的计算,对体系中存在的能量传递机制进行了讨论。此外,与单独掺杂Eu2+的SAM相比,Eu2+、Mn2+共掺的SAM荧光粉具有较好的热稳定性。     

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。     

La~(3+)掺杂对BaSi_2O_2N_2∶Eu~(2+)荧光粉发光性能的影响

研究了La3+掺杂对BaSi2O2N2∶Eu2+发光性能的影响。通过高温固相反应制备了纯相的Ba0.94-Si2O2N2∶0.06Eu2+荧光粉。在此基础上进行La3+的掺杂,并对少量La3+掺杂的LaxBa0.94-1.5xSi2O2N2∶0.06Eu2+荧光粉的结构和光学性能进行了研究。XRD图谱表明粉体在低掺杂时保持了基质BaSi2O2N2的晶格结构。通过共掺x=0.035的La3+可使荧光粉的发光效率提高到157%,原因是La3+部分取代Ba2+产生了阳离子缺陷,其可以吸收光源能量并将能量传递给Eu2+。最终这些能量通过Eu2+的4f65d→4f7跃迁以光辐射的形式释放出来。     

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%.     

微波场作用下球形亚超细 CaS:Mn2+，Eu2+的快速合成

在微波场作用下,首次快速合成了球形亚超细尺寸的CaS: Mn2+,Eu2+ 深红色荧光体,SEM 照片显示其粒径为250 400nm,并可观察到纳米粒子的团聚现象,呈现零维纳米材料的特性. 实验结果证实,Mn2+与Eu2+离子间存在着能量传递过程,因而Mn2+对Eu2+的发光具有明显的敏化和增强作用.     

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。     

Effect of La3+ Doping on the Luminescence of BaSi2O2N2 : Eu2+ Phosphors

研究了L3+掺杂对BaSi2O2N2∶Eu2+发光性能的影响.通过高温固相反应制备了纯相的Ba0.94-Si2O2N2∶0.06Eu2+荧光粉.在此基础上进行La3+的掺杂,并对少量La3+掺杂的LaxBa0.94-1.5xSi2O2N2∶0.06Eu2+荧光粉的结构和光学性能进行了研究.XRD图谱表明粉体在低掺杂时保持了基质BaSi2O2N2的晶格结构.通过共掺x=0.035的La3+可使荧光粉的发光效率提高到157％,原因是La3+部分取代Ba12+产生了阳离子缺陷,其可以吸收光源能量并将能量传递给Eu2+.最终这些能量通过Eu2+的4f65d→4f7跃迁以光辐射的形式释放出来.     

长余辉材料Sr_4Al_(14)O_(25)∶Eu~(2+),Nd~(3+)的溶胶凝胶法制备及性能研究

首次研究了以Nd~(3+)离子为辅助激活剂,对Eu~(2+)掺杂的发光材料Sr_4Al_(14)O_(25):Eu~(2+)余辉性能的影响.用溶胶凝胶法合成了Eu~(2+), Nd~(3+)共掺杂的Sr_4Al_(14)O_(25):Eu~(2+),Nd~(3+)发光粉末,并用扫描电镜、X射线衍射计、荧光分光光度计、余辉亮度测试仪、热释光剂量计等手段对粉末样品进行了表征.结果表明,在1350℃得到了单一的Sr_4Al_(14)O_(25)相,粉末颗粒平均粒度在1μm左右.Eu~(2+), Nd~(3+)共掺杂的Sr_4Al_(14)O_(25):Eu~(2+),Nd~(3+)发光粉末有402和485nm两个发射峰,与Eu~(2+)单掺杂的Sr_4Al_(14)O_(25):Eu~(2+)相比,发射峰位置没有变化,但适量的掺杂可以大大提高余辉时间和余辉亮度,余辉时间可达18h以上.最后通过对热释光谱的分析解释了双掺杂发光粉余辉性能增强的原因,适宜深度的陷阱可以有效存储光能,增强余辉的时间和强度.     

水热-均匀沉淀法制备亚微米长余辉发光材料SrAl_2O_4∶Eu,Dy

采用水热-均匀沉淀法,以尿素为沉淀剂,在聚四氟乙烯低温反应釜中160℃水热,在较低的煅烧温度下制备了亚微米级长余辉发光材料Sr0.97Al2O4∶Eu0.01,Dy0.02。XRD结果表明,在1000℃煅烧4h能得到单相的SrAl2O4∶Eu,Dy,SEM测试显示SrAl2O4∶Eu2+,Dy3+发光材料为球状形貌,粒径大小约为200～500nm,激发和发射光谱结果表明,随着煅烧温度升高,SrAl2O4∶Eu2+,Dy3+的发光强度也随之增强,其激发光谱峰值位于360nm,发射光谱峰值位于513nm,SrAl2O4∶Eu2+,Dy3+在1100℃煅烧后的余辉衰减时间比1000℃煅烧后显著提高,其热释光谱峰值在80～90℃。     

柠檬酸溶胶燃烧工艺参数对Ca_3(VO_4)_2:Eu~(3+)发光性能的影响

采用柠檬酸溶胶燃烧法合成了Ca3(VO4)2:Eu3+红色发光材料。利用XRD、SEM、荧光分光光度计等测试分析方法研究了合成温度、柠檬酸用量以及Eu3+含量等对合成样品组成、结构、显微特征和发光性能的影响。结果表明,采用柠檬酸溶胶燃烧法可以在700～1000℃范围内合成纯度高、结晶度好、粒度均匀的Ca3(VO4)2:Eu3+红色发光粉。优化条件为温度900℃、n(柠檬酸):n(Ca2++V5+)=0.8、Eu3+摩尔分数6%,合成产物的红光发光效果最好。     

燃烧法合成SrZnO_2:Eu~(3+),Li~+及荧光性能

采用燃烧法合成了SrZnO2:Eu3+,Li+发光材料,用X射线衍射谱、荧光光谱对样品进行了表征。结果表明,Eu3+和Li+成功掺入SrZnO2基质中,Eu3+离子在基质中主要占据Sr2+离子不对称性格位,发射来源于5D0→7F2615nm为主的红光。加入电荷补偿剂Li+离子的掺入能显著提高发光强度,其影响程度与Eu3+、离子和Li+离子的掺杂比例密切相关。     

Single-composition trichromatic white-emitting Ca4Y6(SiO4)6O: Ce3+/Mn2+/Tb3+ phosphor: luminescence and energy transfer

A series of Ca(4)Y(6)(SiO(4))(6)O (CYS): Ce(3+)/Mn(2+)/Tb(3+) oxyapatite phosphors were prepared via high-temperature solid-state reaction. Under UV excitation, there exist dual energy transfers (ET), i.e., Ce(3+)→Mn(2+) and Ce(3+)→Tb(3+) in the CYS: Ce(3+), Mn(2+), Tb(3+) system and their emitting colors can be adjusted from blue to orange-red via ET of Ce(3+)→Mn(2+) and from blue to green via ET of Ce(3+)→Tb(3+), respectively. Moreover, a wide-range-tunable white light emission with high quantum yields (13%-30%) were obtained by precisely controlling the contents of Ce(3+), Mn(2+) and Tb(3+) ions. On the other hand, the CL properties of CYS: Ce(3+), Mn(2+), Tb(3+) phosphors have been investigated in detail. The studied results indicate that the as-prepared CYS: Ce(3+), Mn(2+), Tb(3+) phosphors have good CL intensity and CIE color coordinate stability with a color-tunable emission crossing the whole white light region under low-voltage electron beam excitation. In general, the white light with varied hues has been obtained in Ce(3+), Mn(2+), and Tb(3+)-triactivated CYS phosphors by utilizing the principle of energy transfer and properly designed activator contents under UV (284, 358 nm) and low-voltage (1-5 kV) electron beam excitation, which make them as a potential single-composition trichromatic white-emitting phosphor.     

Ce~(3+)和Y~(3+)掺杂对Ca_2MgSi_2O_7:Eu~(2+)荧光粉发光性能的影响

在还原气氛下,采用高温固相法合成了Ca_2MgSi_2O_7:Eu~(2+),Rs~(3+) (R~(3+)=Ce~(3+),Y~(3+))系列荧光粉.结果表明,少量稀土离子的掺入没有改变晶体的物相结构.在Ca_2MgSi_2o_7:Euz~(2+)荧光粉中,Ce~(3+)和y~(3+)的掺入对荧光强度的影响较大,且与掺杂元素、掺杂量相关.当掺杂Ce~(3+)和Y~(3+)的量分别为0.007mol和0.05mol时,所得荧光粉在532nm处的发光强度分别是未掺杂时的127%和117%.结果表明,在Ca_2MgSi_2O_7中Ce~(3+)与Eu~(2+)存在能量传递,Ce~(3+)的加入显著敏化了Eu~(2+)的发光,导致荧光强度的进一步提高;Y~(3+)的掺杂可以使荧光粉的粒径减小,并导致基质中的电荷缺陷而敏化Eu~(2+)发光,从而使荧光强度进一步提高.     

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。     

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.     

燃烧法合成长余辉发光材料SrAl2O4:Eu2+,Dy3+

以尿素和硝酸盐溶液为反应介质,在600℃下用燃烧法一次合成出了Eu2+,Dy3+掺杂的铝酸锶(SrAl2O4)磷光体。用SEM、XRD研究了产物的形态、粒度和物相组成,用荧光分光光度计测定了产物的发光性能。结果表明,合成产物的晶体结构属于单斜晶系结构,在520nm处有很强的发射峰,它的激发光谱是激发峰峰值290nm的宽带激发。产物的形貌呈疏松多孔状,晶粒形状为针状,长度有200nm左右,直径在80nm以下。文中还探讨了该材料发光性能的影响因素。     

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.