Mn^(2+)掺杂对YAG∶Ce^(3+)荧光陶瓷发光性能的影响

过渡族金属Mn^(2+)掺杂的石榴石荧光陶瓷被认为是实现高显色激光照明的候选材料。然而,由于Mn^(2+)在不同配位环境下离子半径的多样性,Mn^(2+)掺杂石榴石陶瓷体系设计方案尚不明确。本文采用真空烧结技术制备得到不同浓度Mn^(2+)掺杂的YAG∶Ce^(3+)荧光陶瓷,并将Mn^(2+)分别设计进入八面体(OC)和十二面体(DO)格位。通过表征样品物相和显微结构、光致发光、荧光寿命、量子效率等,并通过LD激光器激发对荧光陶瓷的发光性能进行研究。实验结果表明,在添加电荷与体积补偿剂SiO_(2)的前提下,相比Mn^(2+)进入十二面体格位,Mn^(2+)进入八面体后石榴石的晶体结构更加稳定。因此,当Mn^(2+)的浓度控制在0.5%^(6)%(at)范围内,OC系列样品的量子效率高于DO系列样品。此外,OC系列样品的PL谱中位于588 nm和725 nm处的发射峰分别对应于Mn^(2+)占据八面体和十二面体格位的^(4)T_(1)→^(6)A_(1)电子跃迁,而DO系列样品中位于572 nm处的发射峰则源于Mn^(2+)占据扭曲的十二面体格位产生的电子跃迁。得益于Ce^(3+)→Mn^(2+)间高效的能量传递,将浓度为6%(at)的Mn^(2+)设计进入YAG∶Ce^(3+)中八面体格位制得荧光陶瓷,封装得到的激光白光光源的显色指数为70.8,相对色温为5117 K。本文对于Mn^(2+)掺杂的石榴石发光材料的开发研究是有力补充,也为提升YAG∶Ce^(3+)荧光陶瓷光谱中的红光成分,进而提高医疗、显示等领域的激光光源的显色性能提供借鉴。

Mn^(2+)、Ce^(3+)共掺杂Zn_2SiO_4材料的溶胶-凝胶法制备及光学性能研究

采用溶胶-凝胶、化学掺杂方法制备了Mn2+、Ce3+离子掺杂Zn2SiO4材料;用X射线衍射仪、透射电子显微镜、吸收光谱仪以及荧光光谱仪对其结构、形貌和光致发光性能进行测试分析;结果表明,900℃热处理基本形成Zn2SiO4晶体,一次颗粒尺寸大约为200 nm左右;在空气中1 100℃和H2气氛中900℃热处理后,样品中存在2个发光峰:Mn2+产生的522 nm强绿光发射,Ce3+离子产生的398 nm弱紫光发射。

Ce^(3+),Mn^(2+)共掺Sr_2 SiO_4的合成和发光性能的研究

采用溶胶-凝胶法合成了Sr_2SiO_4:Ce^(3+),Mn^(2+)荧光粉,合成温度为900℃,这远低于固相法制备同类硅酸盐材料所需的温度。X射线衍射图表明,所得样品主要为纯相Sr_2SiO_4晶体。样品发射光谱为峰值位于472 nm的不对称单峰宽带谱,是典型的蓝白光发射。通过改变Ce^(3+)、Mn^(2+)的浓度,进一步研究了掺杂浓度对发光强度的影响。

Tunable emission properties of tri-doped Ca_(9)LiY_(2/3)(PO_(4))_(7):Ce^(3+),Tb^(3+),Mn^(2+) phosphors with warm white emitting based on energy transfer

Tri-doped Ca_(9)LiY_(2/3)(PO_(4))_(7):Ce^(3+),Tb^(3+),Mn^(2+)phosphors were prepared by a high-temperature solid state method.Under UV light excitation,Ca_(9)LiY_(2/3)(PO_(4))_(7):Ce^(3+)samples exhibit a broad band ranging from 320 to 500 nm.At 77 K,the emission spectra of Ca_(9)LiY_(2/3)(PO_(4))7:Ce^(3+)samples present two obvious emission peaks,indicating that Ce^(3+)ions occupy two different kinds of lattice sites(Ca(1/2)and Ca(3)),As a good sensitizer for Tb^(3+),Ce^(3+)ions in Ca_(9)LiY_(2/3)(PO_(4))_(7)lattice can effectively transfer part of energy to Tb^(3+),and the energy trans fer mechanism is determined to be dipole-dipole interaction.Consequently,the emitting color for Ce^(3+)and Tb^(3+)co-doped Ca_(9)LiY_(2/3)(PO_(4))_(7)samples can be tuned from bluish violet to green.In order to further enlarge the emission gamut,Mn^(2+)ions as red emission components were added,forming tri-doped single-phase Ca_(9)LiY_(2/3)(PO_(4))_(7):Ce^(3+),Tb^(3+),Mn^(2+)phosphors.The Ca_(9)LiY_(2/3)(PO_(4))_(7):Ce^(3+),Tb^(3+),Mn^(2+)phosphors exhibit tunable emission properties through controlling the relative doping concentration of Ce^(3+),Tb^(3+)and Mn^(2+).Especially,Ca_(9)LiY_(2/3)(PO_(4))_(7):0.09 Ce^(3+),0.12 Tb^(3+),0.30 Mn^(2+)can emit warm white light.The sample shows good thermal stability.At 150℃,the emission intensity for Ce^(3+)(360 nm),Tb^(3+)(545 nm)and Mn^(2+)(655 nm)decreases to 63%,69%,and 72%of its initial intensity,respectively.Moreover,the sample obtains good stability after 10 cycles between room temperature and150℃.

Ce^(3+),Mn^(2+)共掺NaYF_4微米六棱柱的发光性能和能量传递研究

通过水热法合成了单分散的六方相NaYF_4:5%Ce^(3+),x%Mn^(2+)(摩尔分数,x=0,5,10,15)微米六棱柱。扫描电镜(SEM)分析表明,样品尺寸均匀,平均长度和平均高度约为2.02μm和700 nm。NaYF_4:5%Ce^(3+),x%Mn^(2+)发光性质的研究结果表明,在激发谱中,245 nm的激发峰来自于Ce^(3+)的4f→5d跃迁;332 nm的激发峰对应于Mn^(2+)的6A1(6S)→4E(4D)跃迁和自陷激子(STE)的激发。在发射谱中,302和422 nm的宽带发射峰分别对应Ce^(3+)的5d→4f跃迁和基质中自陷激子的发光;538和587 nm的宽带发射峰分别对应Mn^(2+)的~4A_1(~4G)→6A1(6S)跃迁和4T1(4G)→6A1(6S)跃迁。随着Mn^(2+)含量的增加,Ce^(3+)的发射强度逐渐减弱,而Mn^(2+)的538 nm(~4A_1(~4G)→6A1(6S))发射峰强度逐渐增强,这表明在NaYF_4基质中,存在Ce^(3+)和Mn^(2+)之间的能量传递。

Color-tunable Ca10Na(PO4)7：Ce^3＋/Tb^3＋/Mn^2＋ phosphor via energy transfer

A series of Ca10Na(PO4)7:Ce3+/Tb3+/Mn2+(CNPO:Ce3+/Tb3+/Mn2+) phosphors with high brightness were synthesized by high-temperature solid-state method. X-ray diffraction(XRD), scanning electron microscopy(SEM), diffuse reflectance spectra(DRS), photo luminescence(PL) spectra, luminescence decay curves and thermally stability were performed to characterize the as-prepared samples. For Ce3+-doped samples, an intense and broad band emission is present under 265 nm excitation. When Ce3+and Tb3+are codoped, energy transfer(ET) process from Ce3+ to Tb3+ is demonstrated with electric dipole-dipole interaction. The internal and external quantum efficiencies(QEs) of CNPO:0.15 Ce3+, 0.04 Tb3+, 0.005 Mn2+are measured to 76.79% and 54.11% under 265 nm excitation and temperature-dependent PL intensity can remain 51.78% at 150 ℃ of its initial intensity at 25 ℃. It is indicated that single-phased white lightemitting CNPO:Ce3+/Tb3+/Mn2+phosphor can serve as a promising phosphor for illumination devices.

偏硼酸钆镁∶铈(Ⅲ)、铽(Ⅲ)、锰(Ⅱ)高显色性荧光粉的研制

用高温固相反应法合成了高显色性橙红粉(Gd,Ce,Tb)(Mg,Mn)B5O10,研究了硼酸用量、Tb Ce比例、氢气浓度和灼烧温度等对合成产物发光性能的影响。实验表明,当硼酸过量8%、Tb Ce≥2.5、氢气浓度≤10%、灼烧温度≥1000℃时,可制得发光亮度较高的高显色性橙红色荧光粉。为进一步探讨Tb,Mn的激活机制,制备了高显色性绿粉(Gd,Ce,Tb)MgB5O10和高显色性红粉(Gd,Ce)(Mg,Mn)B5O10作对比。研究表明,通过无辐射能量机制,Ce3+能够有效地将吸收的紫外能量传递给Tb3+,Gd3+作为能量传递过程中的中间体,其作用是增强Tb3+的发光,即发生了"激发→Ce3+→(Gd3+)n→Tb3+→发射"过程。此外,Mn2+发光不能被Ce3+直接敏化,也是通过Gd3+作为中间体,发生Gd3+→Mn2+的能量传递。

连续可调宽光谱荧光玻璃的制备及性能

宽带荧光转换发光二极管(LED)用荧光玻璃具有良好的热稳定性和光学性质,可以避免传统的有机树脂封装荧光粉方案中存在的热稳定性差和重吸收问题,提高LED的使用寿命和发光效率。本文采用熔融淬冷法制备了一种连续可调宽光谱的Ce^(3+)/Mn^(2+)共掺氟硅酸盐玻璃,并对其发光性能进行了研究。为了探究Ce^(3+)/Mn^(2+)之间的能量传递,分别制备了掺Ce^(3+)、掺Mn^(2+)氟硅酸盐玻璃作为比对。结果表明,在紫外光激发下,可以观察到Ce^(3+)对Mn^(2+)发光的敏化现象,分别由掺Ce^(3+)荧光玻璃的蓝光发射和掺Mn^(2+)荧光玻璃的黄色发射,拓展为Ce^(3+)/Mn^(2+)共掺荧光玻璃的白光宽光谱发射,范围为380~780 nm;对比掺Mn^(2+)的荧光玻璃,Ce^(3+)/Mn^(2+)共掺荧光玻璃中Mn^(2+)的发光强度提升了3倍;随着Mn^(2+)浓度从0.8%增加到2.0%,Ce^(3+)向Mn^(2+)的能量传递效率从12.5%提升至24.2%。此外,通过调节紫外激发波长(353~369 nm),实现了从蓝光到红光区域的连续可调宽带发射。这种新型Ce^(3+)/Mn^(2+)共掺玻璃有望替代目前常规的多组分荧光粉LED光源应用于分光光度计、荧光光谱仪等光学领域。