Luminescence Characteristics of Polyaluminate Broadband Cyan Phosphor Enhanced Publication

多铝酸盐宽带青色荧光粉发光特性 Luminescence Characteristics of Polyaluminate Broadband Cyan Phosphor 1 first-author 李婉璐(1996-)，女，新疆库尔勒人，硕士研究生，2018年于新疆师范大学获得学士学位，主要从事固体发光的研究。 E-mail: lwl13579961995@sina.com http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210734&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210739&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210744&type= 李婉璐 (1996-)，女，新疆库尔勒人，硕士研究生，2018年于新疆师范大学获得学士学位，主要从事固体发光的研究。 E-mail: lwl13579961995@sina.com lwl13579961995@sina.com 1 corresp E-mail: daipp614@nenu.edu.cn E-mail: daipp614@nenu.edu.cn 戴鹏鹏(1982-)，男，重庆人，博士，教授，博士研究生导师，2012年于东北师范大学获得博士学位，主要从事无机光功能材料的结构设计及其在照明、显示、传感器中应用的基础研究。 E-mail:daipp614@nenu.edu.cn http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210747&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210752&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210757&type= 戴鹏鹏 (1982-)，男，重庆人，博士，教授，博士研究生导师，2012年于东北师范大学获得博士学位，主要从事无机光功能材料的结构设计及其在照明、显示、传感器中应用的基础研究。 E-mail: daipp614@nenu.edu.cn daipp614@nenu.edu.cn 新疆师范大学物理与电子工程学院　新疆矿物发光及其微结构重点实验室，新疆 　 乌鲁木齐 　 830054 新疆师范大学物理与电子工程学院　新疆矿物发光及其微结构重点实验室，新疆 　 乌鲁木齐 　 830054 Xinjiang Key Laboratory of Mineral Luminescence and Microstructure, School of Physics and Electronic Engineering, Xinjiang Normal University, Urumqi 830054, China Xinjiang Key Laboratory of Mineral Luminescence and Microstructure, School of Physics and Electronic Engineering, Xinjiang Normal University, Urumqi 830054, China 通过高温固相法成功合成了系列宽带发射且发光颜色可调的Ba 1- x Al 12 O 19 ∶ x Ce 3+ (0.01≤ x ≤0.09)荧光粉。X射线衍射、扫描电子显微镜和能量色散X射线能谱元素映射图像结果证明合成了纯相且元素分布均匀的铝酸盐荧光粉。在361 nm近紫外光激发下，随着Ce 3+ 掺杂浓度逐渐增加，Ba 1- x Al 12 O 19 ∶ x Ce 3+ 样品的发光强度逐渐增强且发光颜色由蓝光逐渐调节到青光。在 x =0.05 mol时，Ba 0.95 Al 12 O 19 ∶0.05Ce 3+ 样品发光强度达到最大值，荧光内量子产率为30.8%。稳态光谱和荧光寿命结果证实， 当Ce 3+ 掺杂浓度大于0.05 mol时，Ba 1- x Al 12 O 19 ∶ x Ce 3+ 样品发生浓度猝灭，该浓度猝灭主要归因于邻近的Ce 3+ -Ce 3+ 之间的能量传递。Ba 0.95 Al 12 O 19 ∶0.05Ce 3+ 样品表现出光谱覆盖范围为365~650 nm、主峰位于450 nm的青光发射，其半高宽为120 nm。该不对称的宽发射带主要源于占据基质晶格中Ba1和Ba2格位的两个Ce 3+ 发光中心。将Ba 0.95 Al 12 O 19 ∶0.05Ce 3+ 和商用红色荧光粉混合制备出简单的可被紫外光( λ ex =365 nm)激发的二色pc-WLEDs，并实现了显色指数和相关色温可调的全可见光谱白光。 该宽带青色发光的Ba 0.95 Al 12 O 19 ∶0.05Ce 3+ 荧光粉在全光谱照明领域具有潜在应用。 In this paper, a series of broadband-emitting and tunable Ba 1- x Al 12 O 19 ∶ x Ce 3+ (0.01≤ x ≤0.09) phosphors were successfully synthesized by the high-temperature solid-phase method. The results of X-ray diffraction, scanning tunnel electron microscopy and EDS mapping proved that we synthesized aluminate phosphor with pure phase and uniform element distribution. Under the excitation of near-ultraviolet light wavelength of 361 nm, we found that the luminous intensity of Ba 1- x Al 12 O 19 ∶ x Ce 3+ samples gradually increased and the luminous color of Ba 1- x Al 12 O 19 ∶ x Ce 3+ samples gradually change from blue to cyan as the Ce 3+ concentration increased. When x =0.05 mol, the luminescence intensity of the Ba 0.95 Al 12 O 19 ∶0.05Ce 3+ sample reaches the maximum, and the fluorescence internal quantum yield is 30.8%. Steady-state spectroscopy and fluorescence lifetime results confirm that when the doped Ce 3+ concentration is greater than 0.05 mol, the Ba 1- x Al 12 O 19 ∶ x Ce 3+ sample undergoes concentration quenching, and the concentration quenching is mainly due to the energy transfer between adjacent Ce 3+ -Ce 3+ . The Ba 0.95 Al 12 O 19 ∶0.05Ce 3+ sample exhibits a cyan emission with a spectral coverage of 365-650 nm, a main peak at 450 nm, and its full width at half maximum is 120 nm. The asymmetric broad emission band mainly originates from the two Ce 3+ emission centers occupying the Ba1 and Ba2 sites in the host lattice. Simple dichromatic pc-WLEDs with UV excitation( λ ex =365 nm), full-visible-spectrum white light with adjustable color index and associated color temperature were prepared by mixing Ba 0.95 Al 12 O 19 ∶0.05Ce 3+ with a commercial red phosphor. The Ba 0.95 Al 12 O 19 ∶0.05Ce 3+ phosphor with broadband cyan luminescence developed in this work has potential applications in the field of full-spectrum lighting. 宽带发射 青色光谱间隙 Ce 3+ 掺杂 铝酸盐 全光谱 broadband emission cyan spectral gap Ce 3+ doped aluminate full spectrum 1　引言 1 荧光粉转换型白光发光二极管(pc-WLEDs)由于其发光效率高、寿命长、环境友好、稳定性好等优点而倍受学术界和照明产业界的广泛关注 [ 1 1 ] 。目前，商用的pc-WLEDs制备方法是将蓝色LED芯片与黄色荧光粉(Y 3 Al 5 O 12 ∶Ce 3+ )相结合，通过蓝光+黄光复合得到白光。然而，由于商用pc-WLEDs光谱中红光成分不足，致使该类型的pc-WLEDs器件的显色指数偏低(CRI < 75)，不能满足室内低色温、暖白光的照明需求 [ 2 2 ] 。产生白光的另一种方法是将近紫外LED芯片与三基色(红/绿/蓝)荧光粉相结合，这种方法几乎克服了上面提到的所有缺点。目前在这种方法中使用的蓝色和绿色荧光粉缺少可覆盖480~520 nm区域的青色发光成分，从而产生“青色间隙”，仍对全光谱发射有一定抑制作用。因此，开发在近紫外LED芯片驱动下能够弥补这一间隙的青色荧光粉尤为重要 [ 3 3 - 5 5 3-5 ] 。据报道，宽带的青色发光材料在一定程度上可以替代传统三基色荧光粉中蓝色和绿色荧光粉，并能覆盖它们之间的光谱间隙，将这种青色发光材料与宽带的红色荧光粉相结合，可以产生高质量的白光 [ 6 6 - 7 7 6-7 ] 。例如，中科院宁波物构所刘永福课题组提出将研发的半高宽为118 nm的Ba 9 Lu 2 Si 6 O 24 ∶Ce 3+ 青色荧光粉与商用宽带红色荧光粉CaAlSiN 3 ∶Eu 2+ 结合，获得了显色性为90.6和色温为4 193 K的高质量白光 [ 8 8 ] 。因此，开发一种宽带的青色发光材料替代传统三基色荧光粉中的蓝色和绿色荧光粉，不仅可以弥补三基色转换白光方法中青色发光不足的缺陷，同时还可以简化pc-WLEDs的制备工艺，降低其生产成本。 在荧光粉体系中，稀土Ce 3+ 离子由于具有自旋允许的4f-5d特征跃迁，因而成为众多发光中心离子中最为常用的一种离子 [ 9 9 ] 。值得注意的是，稀土Ce 3+ 的4f 1 基态可以分裂为两个能级( 2 F 7/2 和 2 F 5/2 能级)，因此，大多数Ce 3+ 激活的发光材料都会很自然地表现出一个不对称的宽带发射。这个不对称的宽发射带主要归因于5d能级上的电子跃迁至 2 F 7/2 和 2 F 5/2 能级所产生的两个发射带叠加所致 [ 10 10 - 11 11 10-11 ] 。因此，Ce 3+ 离子被认为是一种获取宽带发射荧光材料的最理想的激活剂离子。此外，众所周知，Ce 3+ 发射强烈地依赖于其所占据晶体学格位的局部配位场环境 [ 12 12 ] 。如果发光中心Ce 3+ 在基质晶格中能够占据多个具有不同配位环境的阳离子格位，那么这些具有不同配位环境的Ce 3+ 离子的发射谱带很有可能同时叠加形成一种超宽的发射带 [ 13 13 ] 。例如，Y 3 Si 5 N 9 O∶Ce 3+ 橙色荧光粉中Ce 3+ 通过取代两个晶体场环境不同的Y 3+ 离子实现了半高宽为178 nm的宽带发射 [ 14 14 ] 。最近还报道了一种半高宽为165 nm的新型Li 2 CaSi 2 N 4 ∶Ce 3+ 黄色荧光粉，这种宽带发射来自于基质中两个不同的Ce 3+ 发光中心 [ 15 15 ] 。这些研究表明，在不同的荧光粉体系中，形成多个发光中心可以有效地产生宽带发射。据报道，六铝酸盐结构的BaAl 12 O 19 化合物由于晶体结构刚性强、多阳离子格位、化学性质稳定等特性，已在等离子体显示器(PDPs)、场发射显示器(FEDs)和太阳能电池等技术领域被广泛应用 [ 16 16 - 17 17 16-17 ] 。目前，许多研究小组已经对稀土(Eu 2+ 和Tb 3+ )、过渡金属(Mn 2+ 和Cr 3+ )和主族元素Bi 3+ 掺杂的BaAl 12 O 19 发光材料的发光进行了大量报道 http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210762&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210773&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210767&type= 。然而，稀土Ce 3+ 掺杂的BaAl 12 O 19 的报道很有限。BaAl 12 O 19 化合物的晶体结构中包含了五种Al晶体学格位和两种Ba晶体学格位( 图1(a) 图1(a) )。这种多阳离子格位的晶体结构所产生的丰富的晶体场环境为我们设计Ce 3+ 激活宽带的发光材料提供大量的机会。因此，在上述研究的启发下，我们期望合成Ce 3+ 激活的BaAl 12 O 19 宽带发射荧光材料。 本文通过高温固相法合成了系列发光颜色可调的、宽谱带的Ba 1- x Al 12 O 19 ∶ x Ce 3+ (0.01≤ x ≤0.09)(BAO∶ x Ce 3+ )荧光粉。X射线衍射(XRD)、扫描电子显微镜(SEM)和能量色散X射线能谱元素映射图像(EDS mapping)结果证实我们合成了纯相且元素分布均匀的六铝酸盐荧光粉。稳态光谱和荧光寿命结果表明，当Ce 3+ 掺杂的浓度为0.05 mol时，样品呈现为半高宽为120 nm的青光发射，发光强度达到最大值，荧光内量子产率(Photoluminescence quantum yield,PLQY)为30.8%。当进一步增加Ce 3+ 浓度，发光强度逐渐减弱，这主要归因于邻近的Ce 3+ -Ce 3+ 之间的能量传递引起的浓度猝灭，临界距离约为1.581 nm。此外，BAO∶ x Ce 3+ 样品的光谱连续红移，从峰位为433 nm的蓝光到峰位为450 nm的青光连续可调，这与CIE色度坐标结果一致。文中发射光谱的红移归因于斯托克斯位移增大以及晶体场劈裂增强。我们将BAO∶0.05Ce 3+ 青色荧光粉与商用红色发光(Sr,Ca)AlSiN 3 ∶Eu 2+ 荧光粉混合，并结合近紫外光LED芯片，获得了系列发光颜色和色温可控的白光LED器件。本工作表明，我们所合成的这种宽谱带BAO∶0.05Ce 3+ 青色荧光粉在pc-WLEDs领域具有广阔的应用前景。 2　实验 1 2.1　合成方法 2 采用高温固相法合成一系列Ba 1- x Al 12 O 19 ∶ x Ce 3+ (0.01≤ x ≤0.09)粉末样品。按化学计量比准确称量，原料为BaCO 3 (99.99%)、Al 2 O 3 (99.99%)和CeO 2 (99.99%)，并加入质量百分比为5%的H 3 BO 3 (99.99%)作为助熔剂。在玛瑙研钵中研磨40 min后，将形成的混合物转移至氧化铝坩埚中，然后放置在高温管式炉中，在H 2 (5%)和N 2 (95%)的还原气氛下高温1 500 ℃煅烧6 h。待管式炉自然冷却至室温后取出氧化铝坩埚，将退火后的样品进行二次研磨，得到最终的粉末样品。 2.2　样品表征 2 使用日本岛津XRD-700型粉末衍射仪进行物相鉴定和结构分析。X射线光源为单色器过滤的Cu-Kα1射线(波长 λ =0.154 06 nm)，工作电压为40 kV，工作电流为30 mA，扫描范围15°~70°，扫描速度为5(°)/min。通过场发射扫描隧道电子显微镜(FE-SEM,S-4800,Hitachi)采集SEM图像和能量色散X射线能谱(EDS)元素映射图像。使用紫外-可见漫反射光谱仪(UV-2550 PC，日本岛津公司)测定漫反射(DR)光谱。采用英国爱丁堡稳态/瞬态荧光光谱仪(FLS920)测量样品的激发(PLE)、发射光谱(PL)和荧光寿命衰减曲线，在测量过程中，采用450 W氙灯(Ushio UXL-500D)作为激发光源。PL量子产率(PLQY)由PLQY测量系统(C11347-11,Hamamatsu Photonics,Japan)采集。所有测试结果均在室温下测量得到。 3　结果与讨论 1 3.1　晶体结构与物相表征 2 BaAl 12 O 19 基质属于空间群为 P 63 /mmc (No.194)的六方晶系，呈高度凝聚的层状反中心对称结构，它包含了五种Al晶体学格位和两种Ba晶体学格位( 图1(a) 图1(a) )。Al4格位与6个氧原子配位形成AlO 6 八面体，而Al1、Al2、Al3、Al5格位与4个氧原子配位形成AlO 4 四面体( 图1(b) 图1(b) )，这些AlO 4 四面体和AlO 6 八面体通过共享BAO晶格中的顶点、边和面来构成一个刚性的三维网络结构。Ba1和Ba2分别与9个O和10个O原子配位，形成9配位的Ba1O 9 和10配位的Ba2O 10 多面体( 图1(c) 图1(c) )，Ba1(Wyck.2d)位于AlO 4 周围，Ba2(Wyck.4f)位于AlO 6 的间隔层。如上所述，BaAl 12 O 19 基质具有相对稳定的刚性晶体结构，包含多个配位环境不同的阳离子格位，为发光中心Ce 3+ 掺杂提供了丰富的晶体场环境，从而为实现宽带发射提供了可能性。 图2(a) 图2(a) 为BAO∶ x Ce 3+ (0.01≤ x ≤0.09)荧光粉的XRD图谱。所有样品的X射线衍射图谱都与BaAl 12 O 19 的标准卡片(PDF#26-0135)相对应，证明我们成功合成了不同浓度的BAO∶ x Ce 3+ (0.01≤ x ≤0.09)化合物。在放大的32°~40°衍射峰图谱中( 图2(b) 图2(b) )，随着 x 不断增加，样品的X射线衍射峰逐渐向大角度方向偏移，这归因于Ce 3+ 的离子半径( r =0.119 6 nm,CN=9; r =0.125 nm,CN=10)小于Ba 2+ 的离子半径( r =0.147 nm,CN=9; r =0.152 nm,CN=10),Ce 3+ 倾向于占据Ba 2+ 的位置，导致晶胞收缩和晶面间距减小，衍射峰向大角度移动，说明Ce 3+ 成功进入到BaAl 12 O 19 基质晶格中。 我们又进一步调查了BAO∶0.05Ce 3+ 荧光粉颗粒形貌和粒径尺寸，发现BAO∶0.05Ce 3+ 样品颗粒呈现不规则图案，平均颗粒尺寸为2~15 μm(如 图3(a) 图3(a) 所示)。 图3(b) 图3(b) 显示的是从 图3(a) 图3(a) 中选出形貌特征相对规则的荧光粉颗粒的SEM照片，可以看到样品颗粒表面粗糙，几何形状不规则。为了进一步调查元素在颗粒中的分布情况，我们对该荧光粉颗粒进行原位的EDS mapping图像分析。从 图3(c)~(f) 图3(c)~(f) 可以清楚地看到样品颗粒中含有Ba、Al、O和Ce元素，且各元素在该颗粒中分布均匀。上述结果表明，我们成功地合成了纯相且元素分布均匀的BAO∶ x Ce 3+ (0.01≤ x ≤0.09)荧光粉。 3.2　BaAl 12 O 19 ∶Ce 3+ 荧光粉的光致发光特性 2 图4 图4 为BAO∶ x Ce 3+ ( x =0.01,0.05,0.09)样品的漫反射光谱。所有样品在200~400 nm区域有一个宽的吸收带，这主要归因于基质的电荷迁移带和Ce 3+ 的4f-5d电子跃迁吸收。随着Ce 3+ 浓度的逐渐增加，吸收强度逐渐增大，表明我们合成的BAO∶ x Ce 3+ (0.01≤ x ≤0.09)荧光粉的吸收范围与近紫外光LED芯片的发射波长(360~400 nm)可以较好地匹配。 图5(a) 图5(a) 是BAO∶ x Ce 3+ (0.01≤ x ≤0.09)样品的光致发光光谱。在波长为361 nm的近紫外光激发下，样品发射光谱表现为覆盖蓝、青、绿区域的宽带发射(365~650 nm)，发射主峰值位于450 nm左右，这个宽的发射带主要归于发光中心Ce 3+ 的5d到4f的能级跃迁。如 图5(b) 图5(b) 所示，随着Ce 3+ 浓度增加，样品的发光强度逐渐增强。在 x =0.05时，发光强度达到最大值，PLQY达到30.8%，当掺杂浓度超过0.05 mol时，发射强度逐渐降低，我们推测这可能归因于Ce 3+ 的浓度猝灭效应。荧光寿命衰减结果进一步证实了我们的上述猜测。在近紫外光361 nm激发下，监测450 nm处的发射峰我们得到了BAO∶ x Ce 3+ (0.01≤ x ≤0.09)的荧光寿命衰减曲线(如 图5(c) 图5(c) 所示)。随着Ce 3+ 掺杂量的增加，荧光寿命衰减曲线呈非线性变化，且非线性衰减行为越来越明显，结果表明随着Ce 3+ 浓度增加，Ce 3+ 去激发过程路径增加，致使这种Ce 3+ 荧光寿命衰减非线性变化凸显。所有样品的平均寿命 τ 可通过下列公式计算 [ 24 24 ] : http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210853&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210858&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210863&type= 得到的BAO∶ x Ce 3+ (0.01≤ x ≤0.09)的平均寿命分别为49.762,45.206,44.195,42.563,42.432 μs。随着Ce 3+ 掺杂浓度的增加，荧光寿命逐渐减小。这是因为当Ce 3+ 掺杂浓度增加时，Ce 3+ 离子之间的平均距离减小，当小到临界距离时，Ce 3+ 发光中心间的相互作用增强，相邻Ce 3+ 之间的能量转移变得更频繁，从而为猝灭点提供了额外的衰减通道 [ 25 25 ] 。为了进一步分析Ce 3+ 离子之间的能量传递机理，我们粗略估计发光中心的临界距离( R c )为 [ 26 26 ] : http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210868&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210873&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210878&type= 其中， V 为单位晶胞的体积， http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210883&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210890&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210887&type= 为Ce 3+ 的临界掺杂浓度， N 表示单位晶胞内可以被Ce 3+ 占据的格位数。在该工作中， χ c =0.05, V =0.620 13 nm 3 , N =6，计算得到 R c 约为1.581 nm。据报道，当 R c < 0.5 nm时，能量转移主要由交换相互作用导致 [ 27 27 ] 。显然，在这里交换相互作用机制对能量转移并不起主导作用。因此，我们认为在BAO∶ x Ce 3+ (0.01≤ x ≤0.09)体系中，能量传递机制可能通过多极-多极相互作用发生。这种相互作用可以用Dexter提出的方程来确定 [ 28 28 ] : http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210896&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210900&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210901&type= 其中， I 为发射强度， x 表示掺杂Ce 3+ 浓度， K 和 β 是相同激发条件下的常数。 θ =3,6,8,10分别表示邻近的Ce 3+ -Ce 3+ 之间的能量传递、偶极-偶极、偶极-四极和四极-四极相互作用 [ 29 29 ] 。 图5(c) 图5(c) 显示了lg( I/x )和lg x 之间的线性关系，斜率为1.183 66。计算得到的 θ 值为3.551，接近于3，由此说明在BAO∶ x Ce 3+ (0.01≤ x ≤0.09)体系中，Ce 3+ 浓度猝灭机制源于邻近的Ce 3+ -Ce 3+ 之间的能量传递。 图6(a) 图6(a) 显示了BAO∶ x Ce 3+ (0.01≤ x ≤0.09)荧光粉的光致激发光谱( λ em =450 nm)，在200~400 nm近紫外光范围内有较强的吸收，这与漫反射光谱相对应。其激发光谱存在两个激发峰，归因于Ce 3+ 从4f基态到不同5d轨道的电子跃迁。激发强度随 x 值的增加而逐渐增强，在 x =0.05时达到最大值，然后随着Ce 3+ 浓度的进一步增加而减小，与其对应的PL光谱强度变化趋势相同。此外，随着Ce 3+ 浓度增加，发射光谱的中心波长从433 nm红移到450 nm( 图6(b) 图6(b) )。通常光谱红移主要归结于:(1)斯托克斯位移，(2)光谱重叠，(3)晶体场劈裂。为了明确产生光谱红移的原因，我们计算了掺杂不同Ce 3+ 浓度样品的斯托克斯位移，分别为4 944.45,5 178.31,5 527.88,5 604.85,5 788.98 cm -1 ，发现随着掺杂浓度逐渐增加样品的斯托克斯位移逐渐增加，表明斯托克斯位移是引起光谱红移原因之一。此外，我们从 图6(b) 图6(b) 中可以观察到光谱重叠部分(光致激发光谱与光致发光光谱之间)逐渐减小。因此，我们考虑光谱重叠对光谱红移的贡献不大。最后由下式确定了晶体场劈裂( Dq ) [ 30 30 ] : http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210918&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210923&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210927&type= 其中 Z 和 e 分别为阴离子和电子的电荷， r 是d波函数的半径， R 是键长。当半径较大的Ba 2+ 被半径较小的Ce 3+ 占据时，Ce 3+ 与O 2- 之间的距离变得更短。由于晶体场劈裂 Dq 与1/ R 5 成正比，Ce 3+ 与O 2- 之间的距离变短会导致Ce 3+ 周围的晶体场强度增大，从而导致Ce 3+ 离子5d能级的晶体场劈裂程度增加，发射光谱向长波方向移动，这与发射光谱产生红移的现象相符。因此，光谱红移现象是斯托克斯位移增大和晶体场劈裂增强共同引起的。 根据PL光谱可知，BAO∶ x Ce 3+ (0.01≤ x ≤0.09)荧光粉呈现出一个宽的不对称发射带，半高宽均约为120 nm，我们推测该宽带发射可能是由于不同Ce 3+ 发光中心的光谱叠加所致。为了进一步验证上述猜测，我们对 x =0.05样品的发射光谱进行高斯拟合( 图6(c) 图6(c) )。光谱拟合结果显示，这个宽带发射峰可以拟合为4个高斯谱，其发射峰的峰位分别位于561 nm(17 825 cm -1 , Peak 1)、507 nm(19 724 cm -1 ,Peak 2)、469 nm(21 322 cm -1 , Peak 3)和430 nm(23 256 cm -1 ,Peak 4)。通过计算得到Peak 1与Peak 2之间以及Peak 3与Peak 4之间的能量差，发现其能量差分别为1 899 cm -1 和1 934 cm -1 ，该结果与理论上Ce的 2 F 5/2 和 2 F 7/2 能级的能量差(2 000 cm -1 )基本一致 [ 31 31 - 35 35 31-35 ] ，说明这个宽谱带发射主要归因于两个不同的Ce 3+ 中心，分别标记为Ce1和Ce2。为了证实这一结果，我们进一步调查依赖于波长的寿命衰减曲线( 图6(d) 图6(d) )，监测4个不同的发射峰561,507,469,430 nm，这4个不同发射波长的平均寿命分别为51.230,50.993,44.683,41.303 μs，发现其荧光寿命衰减行为不同，该结果与高斯分峰拟合结果一致，进一步证实了我们制备的样品发出的宽带发射来源于两个不同的Ce 3+ 中心。我们根据Van Uitert公式分析4个发射峰的起源 [ 36 36 ] : http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210930&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210935&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210939&type= 其中 E 代表Ce 3+ 的发射峰所对应的能量(cm -1 ), Q 表示激活剂离子d激发态低能带的位置， Q 对于Ce 3+ 有固定值， http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210943&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210950&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210947&type= =50 000 cm -1 , V 代表离子的价态( http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210955&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210963&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210959&type= =3), n 是Ce 3+ 离子周围壳层中阴离子的数量， E a 表示形成阴离子的原子的活化能(对于同一基质，它是一个常数), r 是被Ce 3+ 取代的主阳离子半径( http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210966&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210974&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210970&type= =0.147 nm, CN=9; http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210977&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210984&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210982&type= =0.152 nm,CN=10)。由公式(5)可知， E 与 n 和 r 成正比，在这里 http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210986&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210990&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210988&type= < http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210991&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210998&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21210993&type= , http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21211001&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21211006&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21211004&type= < http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21211008&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21211012&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21211010&type= ，得出 http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21211013&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21211018&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21211016&type= < http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21211020&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21211027&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21211024&type= , E 的值越大发射波长越短。因此，我们认为Peak 1和Peak 2来源于Ce 3+ 占据Ba1格位，Peak 3和Peak 4来源于Ce 3+ 占据Ba2格位 [ 37 37 ] 。上述结果证明，由于Ce 3+ 分别占据Ba1和Ba2格位导致了BAO∶ x Ce 3+ (0.01≤ x ≤0.09)荧光粉不对称的宽谱带发射。 图7 图7 展示的是BAO∶ x Ce 3+ (0.01≤ x ≤0.09)荧光粉在室温下的CIE色度坐标图。我们可以清楚地观察到，随着 x 的增加，BAO∶ x Ce 3+ 荧光粉的发光颜色从蓝色( x =0.01)逐步转变为青色( x =0.09)，相应的色坐标从(0.182 0,0.169 8)连续移动到(0.205 6,0.229 3)。插图显示了在365 nm紫外灯照射下BAO∶0.05Ce 3+ 荧光粉发出明亮的青光的照片。 BAO∶0.05Ce 3+ 荧光粉实现了覆盖可见光谱蓝、青、绿区域的宽带青光发射，有望替代传统三基色荧光粉中的蓝色和绿色荧光粉。因此，通过将制备的BAO∶0.05Ce 3+ 宽带青色荧光粉和商用(Sr,Ca)AlSiN 3 ∶Eu 2+ 红色荧光粉按不同比例混合与近紫外光LED芯片( λ ex =365 nm)结合，制备出三种简单的二色白光LED器件(WLED 1~WLED 3)。器件由60 mA电流驱动产生相应的发光光谱( 图8(a) 图8(a) )。由于BAO∶0.05Ce 3+ 的宽带青色发射和(Sr,Ca)AlSiN 3 ∶Eu 2+ 的宽带红色发射，即使没有混合另一种通常用于其他全可见光谱pc-WLEDs的绿色发光荧光粉，也能获得覆盖整个可见区域的连续光谱。如 图8(b) 图8(b) 所示，其CIE色度坐标分别为(0.307 5,0.304 6)、(0.322 8,0.309 2)、(0.342 2, 0.304 1)。随着商用红色荧光粉比例逐渐增加，器件的发光性能有了明显的变化。这些结果验证了新开发的BAO∶0.05Ce 3+ 宽带青色荧光粉在未来近紫外光驱动pc-WLEDs中具有一定的应用潜力。 4　结论 1 本文采用高温固相法成功合成了系列宽带发射且发光颜色可调的Ba 1- x Al 12 O 19 ∶ x Ce 3+ (0.01≤ x ≤0.09)荧光粉。X射线衍射、扫描电子显微镜和能量色散X射线能谱元素映射图像结果证实我们合成了纯相且元素分布均匀的铝酸盐荧光粉。在361 nm近紫外光激发下，随着掺杂Ce 3+ 浓度逐渐增加，Ba 1- x Al 12 O 19 ∶ x Ce 3+ 样品的发光强度逐渐增大且发光颜色由蓝光逐渐调节到青光。在 x =0.05 mol时，Ba 0.95 Al 12 O 19 ∶0.05Ce 3+ 样品的发光强度达到最大值，荧光内量子产率为30.8%。该样品表现出覆盖可见光谱蓝、青、绿区域(365~650 nm)的主峰位于450 nm的青光发射，其半高宽为120 nm。不对称的宽发射带源于占据基质晶格中Ba1和Ba2格位的两个Ce 3+ 发光中心。稳态光谱和荧光寿命测试结果证实，当掺杂Ce 3+ 浓度大于0.05 mol时Ba 1- x Al 12 O 19 ∶ x Ce 3+ 样品发生浓度猝灭，计算结果表明该浓度猝灭主要归因于邻近的Ce 3+ -Ce 3+ 之间的能量传递。此外，Ba 1- x Al 12 O 19 ∶ x Ce 3+ 样品的光谱发生连续红移，这归因于斯托克斯位移增大以及晶体场劈裂增强。最后，我们在近紫外光LED芯片驱动下，将Ba 0.95 -Al 12 O 19 ∶0.05Ce 3+ 样品与商用红色荧光粉混合形成二色白光，并通过改变混合比例获得了系列发光颜色和色温可控的白光LED器件。研究结果表明，本文合成的宽带青色荧光粉在高质量的pc-WLEDs中具有潜在的应用前景。 本文专家审稿意见及作者回复内容的下载地址:http://cjl.lightpublishing.cn/thesisDetails#10.37188/CJL.20210178. 参考文献: DAI P P , CAO J , ZHANG X T , et al . 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Preparation and optical properties of CeF3-containing oxide fluoride glasses 10.37188/CJL.20210178 O482.31 A 1000-7032(2021)09-1376-10 国家自然科学基金（517040）；自治区科技部高层次人才引进计划项目；天山人才三期；新疆师范大学教育厅重点实验室招标课题（KWFG2002）资助项目 Supported by National Natural Science Foundation of China (517040); High-level Talents Introduction Program of the Ministry of Science and Technology of the Autonomous Region; Tianshan Talent Phase Ⅲ; Key Laboratory of Education Department of Xinjiang Normal University (KWFG2002) 2021-05-07 2021-06-06 2021-09-01 2021-10-19 2021 发光学报 09 42