Advances in Theoretical Research on Eu<sup>2+</sup> Doped Narrow-band Emitting Fluorescent Materials

ZHU Kun-ling; YOU Huan-huan; GAO Fa-ming; JIA Yong-chao

doi:10.37188/CJL.20220189

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Advances in Theoretical Research on Eu²⁺ Doped Narrow-band Emitting Fluorescent Materials

Invited Paper | Updated：2023-02-13

- Advances in Theoretical Research on Eu²⁺ Doped Narrow-band Emitting Fluorescent Materials Enhanced Publication
- Chinese Journal of Luminescence Vol.43, Issue 9, (2022)
- Affiliations：
  
  School of Environmental and Chemical Engineering， Yanshan University,Qinhuangdao,China,066000
- Author bio：
- Funds：
  
  Natural Science Foundation of Hebei Province(E2021203126);Cultivation Project for Basic Research and Innovation of Yanshan University(2021LGQN033)
- DOI：10.37188/CJL.20220189 CLC： O482.31
- Published：05 September 2022，
  
  Received：08 May 2022，
  
  Revised：23 May 2022，
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朱坤领,游欢欢,高发明等.窄带型Eu²⁺掺杂荧光粉理论研究进展[J].发光学报,2022,43(09):1405-1412.

ZHU Kun-ling,YOU Huan-huan,GAO Fa-ming,et al.Advances in Theoretical Research on Eu²⁺ Doped Narrow-band Emitting Fluorescent Materials[J].Chinese Journal of Luminescence,2022,43(09):1405-1412.
朱坤领,游欢欢,高发明等.窄带型Eu²⁺掺杂荧光粉理论研究进展[J].发光学报,2022,43(09):1405-1412. DOI： 10.37188/CJL.20220189.

ZHU Kun-ling,YOU Huan-huan,GAO Fa-ming,et al.Advances in Theoretical Research on Eu²⁺ Doped Narrow-band Emitting Fluorescent Materials[J].Chinese Journal of Luminescence,2022,43(09):1405-1412. DOI： 10.37188/CJL.20220189.

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"2+" } ] }, { "name": "text", "data": "离子独特的4f⁃5d跃迁以及与局部环境的依赖性，为制备窄带发射荧光粉提供了可能。但是，目前窄带发射的理论尚不完备，大多Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂窄带发射荧光粉的研发均基于大量的重复性试验。本文以位形坐标模型为基础，从理论计算方面对窄带型Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂荧光粉的研究进行综述，重点讨论局部配位环境、晶体结构、斯托克斯位移以及耦合声子频率等因素对Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子发射半峰宽（FWHM）的影响，期望为新型Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂窄带发射荧光粉提供理论依据。" } ] } ] }, { "lang": "en", "data": [ { "name": "p", "data": [ { "name": "text", "data": "In recent years， narrow-band emitting phosphors used to fabricate white LEDs play an important role in reducing energy consumption， improving light quality， and maintaining chromaticity stability， and have been widely paid attention to by researchers. The unique character of the 4f-5d transition of Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " ions with host dependence provides the possibility of the design of Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "-activated narrow-band emitting phosphors. However， most of the works relies on trial and error， and theoretical understanding is lacking of the emission width of Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " ions in solids. With this background， here we review the theoretical efforts on this topic in the past ten years. Based on configuration coordinate diagram， the effect of structure rigidity， local environment and phonon frequency on full-width at half-maximum（FWHM） of Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " ions have been analyzed. The obtained conclusions are expected to give the design clue for the related experimentalist." } ] } ] } ], "keyword": [ { "lang": "zh", "data": [ [ { "name": "text", "data": "Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂荧光粉" } ], [ { "name": "text", "data": "窄带发射" } ], [ { "name": "text", "data": "配位环境" } ], [ { "name": "text", "data": "斯托克斯位移" } ], [ { "name": "text", "data": "声子频率" } ] ] }, { "lang": "en", "data": [ [ { "name": "text", "data": "Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "- doped phosphors" } ], [ { "name": "text", "data": "narrow emission" } ], [ { "name": "text", "data": "coordination environment" } ], [ { "name": "text", "data": "Stokes shift" } ], [ { "name": "text", "data": "phonon frequency" } ] ] } ], "highlights": [], "body": [ { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "1　引　　言" } ], "level": "1", "id": "s1" } }, { "name": "p", "data": [ { "name": "text", "data": "发光二极管（LED）照明具有寿命超长、高效节能、全固态照明、抗恶劣环境、响应快、工作电压低、抗震性及安全性好等诸多优点，被公认为21 世纪最有潜力替代传统照明器具的新光源。近几年来，LED 作为下一代新型照明光源逐渐进入如汽车、LCD 背光源、室内、室外照明等广泛的行业中，LED 应用正在变得更加普遍。目前，白光LED 的实现主要基于InGaN蓝光LED芯片和具有石榴石结构的Y" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "Al" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "12" } ] }, { "name": "text", "data": "∶Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "（YAG∶Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "）黄色荧光粉组合方法得到，即荧光粉吸收一部分来自于LED芯片的蓝光转化为黄光，进而通过颜色互补原理实现白光器件" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "1", "type": "bibr", "rid": "R1", "data": [ { "name": "text", "data": "1" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。该白光实现方法简单有效，在工业界被广泛使用。但其亦存在YAG∶Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "发射光谱中红色成分不足的问题，导致难以获得高显色指数的暖白光器件" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "2", "type": "bibr", "rid": "R2", "data": [ { "name": "text", "data": "2" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。因此，为提升白光LED在显色指数方面的性能，亟需研发得到可蓝光激发的高效红光材料。Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子凭借独特的4f-5d光谱跃迁特性，其相应的发光材料引起了广泛关注。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "在以上背景下，世界照明协会与美国能源部对白光LED灯用Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "基红色荧光材料做出以下性能参数要求" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "3", "type": "bibr", "rid": "R3", "data": [ { "name": "text", "data": "3" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "：（1）红色荧光粉的发射位置要位于610 nm左右；（2）在LED工作温度450 K条件下，红色荧光粉的热猝灭应低于5%；（3）红色荧光粉的发射峰宽要小于30 nm。对于上述性能参数（1）和（2）的要求，已有相对应的理论模型进行指导分析。例如，代尔夫特理工大学Dorenbos教授在近20年的工作基础上" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "4", "type": "bibr", "rid": "R4", "data": [ { "name": "text", "data": "4" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "6", "type": "bibr", "rid": "R6", "data": [ { "name": "text", "data": "6" } ] } } ], "rid": [ "R4", "R5", "R6" ], "text": "4-6", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，获得了一系列定量拟合公式来进行荧光粉发射位置和热猝灭性质的计算，获得了与实验值非常匹配的结果。总而言之，对Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子在晶体中的发射位置和热猝灭两个方面的发光行为，人们已经有了从原子尺度上的认识，这些认识可以精确地指导实验。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "然而，在性能参数（3）方面的研究现状却表现得非常不理想。事实上，我们缺乏对Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子激活发光材料发射峰宽从微观尺度的理解。为得到窄带型Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子激活发光材料，目前的研究工作主要基于实验经验。例如，近期德国慕尼黑大学Schnick教授、华南理工大学夏志国教授、因斯布鲁克大学Huppertz教授成功合成了一系列窄峰宽的Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "激活发光材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "7", "type": "bibr", "rid": "R7", "data": [ { "name": "text", "data": "7" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } } ], "rid": [ "R7", "R8", "R9", "R10", "R11", "R12", "R13" ], "text": "7-13", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，在很大程度上弥补了稀土发光领域在峰宽研究方面的不足，进而获得了广色域的显示器件。尽管如此，已有的实验工作仍然缺乏对晶体中Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子的发光材料发射峰宽从原子尺度的理解。因此，为实现参数（3）的性能要求，亟需进行更深入的理论研究工作，进而为窄带型Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子激活发光材料的设计提供指导。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "针对以上问题，本文拟从位形坐标模型出发，讨论结构弛豫、斯托克斯位移、声子频率等因素对固体中Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子发射半峰宽（FWHM）的影响，并结合局部配位环境、激发态电子云分布等信息，综述Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂窄带发射荧光粉的形成原因，尝试为发展新型Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "窄带发射荧光粉提出理论依据。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2　发射峰宽计算的理论基础" } ], "level": "1", "id": "s2" } }, { "name": "p", "data": [ { "name": "text", "data": "与原子跃迁的线状光谱不同，Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子的4f-5d光谱跃迁在晶体中表现出带状发射。该发射带由零声子线（Zero-phonon line）和声子伴带（Phonon sidebands）构成。零声子线和声子伴带则可以依据位形坐标模型进行计算分析。因此，为理解发射光谱峰宽的影响因素，应该清楚位形坐标模型（Configuration coordinate diagram，CCD）的具体含义。位形坐标模型的发展源自于康登对双原子分子的研究" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "14", "type": "bibr", "rid": "R14", "data": [ { "name": "text", "data": "14" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "15", "type": "bibr", "rid": "R15", "data": [ { "name": "text", "data": "15" } ] } } ], "rid": [ "R14", "R15" ], "text": "14-15", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，该模型依赖于基态和激发态的平衡核构型的线性组合，后被广泛地应用于分析分子和掺杂固体中的光致发光，开拓了发光定性分析的领域。" } ] }, { "name": "p", "data": [ { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "为Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂荧光粉的4f-5d跃迁的一维位形坐标模型示意图" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "16", "type": "bibr", "rid": "R16", "data": [ { "name": "text", "data": "16" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "17", "type": "bibr", "rid": "R17", "data": [ { "name": "text", "data": "17" } ] } } ], "rid": [ "R16", "R17" ], "text": "16-17", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。图中下方的4f曲线表示Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "最外层电子构型为4f" }, { "name": "sup", "data": [ { "name": "text", "data": "7" } ] }, { "name": "text", "data": "的势能线，而5d曲线表示Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "最外层电子构型为4f" }, { "name": "sup", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "5d激发态的势能线。激发和发射过程为：在外来光子的激发下，处于4f的电子吸收光子带来的能量（" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

E_{a b s}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822242&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822238&type=", "width": "5.07999992", "height": "3.72533321", "fontsize": "" } } } ] }, { "name": "text", "data": "）发生跃迁，至5d能级（" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

A_{0}

A_{0}^{*}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822261&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822256&type=", "width": "3.47133350", "height": "4.06400013", "fontsize": "" } } } ] }, { "name": "text", "data": "），从而得到激发态Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "。此时稳定的基态结构平衡（" }, { "name": "italic", "data": [ { "name": "text", "data": "Q" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "g" } ] }, { "name": "text", "data": "）被打破，原子位置将发生弛豫过程（" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

A_{0}^{*}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822273&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822268&type=", "width": "3.47133350", "height": "4.06400013", "fontsize": "" } } } ] }, { "name": "text", "data": "→" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

A^{*}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822293&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822291&type=", "width": "3.21733332", "height": "2.96333337", "fontsize": "" } } } ] }, { "name": "text", "data": "）。结构弛豫后，整个系统将达到一个新的平衡态（" }, { "name": "italic", "data": [ { "name": "text", "data": "Q" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "e" } ] }, { "name": "text", "data": "），然后电子从5d能级跃迁回4f能级并放出光子（" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

A^{*}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822293&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822291&type=", "width": "3.21733332", "height": "2.96333337", "fontsize": "" } } } ] }, { "name": "text", "data": "→" }, { "name": "italic", "data": [ { "name": "text", "data": "A" } ] }, { "name": "text", "data": "）。最后体系再次通过多声子弛豫过程使结构回到基态（" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

A

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822301&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822297&type=", "width": "2.28600001", "height": "2.62466669", "fontsize": "" } } } ] }, { "name": "text", "data": "→" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

A_{0}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822306&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822304&type=", "width": "3.47133350", "height": "3.72533321", "fontsize": "" } } } ] }, { "name": "text", "data": "）。基于这一模型便可以对Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子激活荧光粉发射半峰宽进行预测。" } ] }, { "name": "fig", "data": { "id": "F1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图1" } ], "title": [ { "name": "text", "data": "Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子掺杂荧光粉的一维位形坐标模型" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.1" } ], "title": [ { "name": "text", "data": "Configuration coordinate diagram of Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "-doped phosphors" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822309&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822318&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822315&type=", "width": "69.40756226", "height": "51.89437866", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "势能曲线表示能量与位形坐标" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

Q

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822327&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822321&type=", "width": "2.53999996", "height": "3.38666677", "fontsize": "" } } } ] }, { "name": "text", "data": "之间的依赖关系。在单一声子频率以及简谐近似条件下，基态和激发态的势能曲线分别可以表示为：" } ] }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（1）" } ], "data": [ { "name": "math", "data": { "math": "

E_{g} = \frac{1}{2} {(ћ Ω_{g})}^{2} Q^{2}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822339&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822334&type=", "width": "24.72266769", "height": "7.28133297", "fontsize": "" } } }, { "name": "text", "data": " " } ], "id": "DF1" } }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（2）" } ], "data": [ { "name": "math", "data": { "math": "

E_{e} = \frac{1}{2} {(ћ Ω_{e})}^{2} {(Q - Δ Q)}^{2} + E_{z_{P l}}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822350&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822343&type=", "width": "46.39733505", "height": "7.28133297", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF2" } }, { "name": "p", "data": [ { "name": "text", "data": "其中，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

E_{z_{P l}}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822365&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822359&type=", "width": "4.31799984", "height": "3.80999994", "fontsize": "" } } } ] }, { "name": "text", "data": "为零声子线的能量，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

Δ Q

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822376&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822369&type=", "width": "4.99533367", "height": "3.55599999", "fontsize": "" } } } ] }, { "name": "text", "data": "代表从基态到激发态下的晶体结构弛豫值，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

Ω_{g}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822388&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822382&type=", "width": "3.72533321", "height": "3.89466691", "fontsize": "" } } } ] }, { "name": "text", "data": "和" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

Ω_{e}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822398&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822393&type=", "width": "3.72533321", "height": "3.89466691", "fontsize": "" } } } ] }, { "name": "text", "data": "分别是基态和激发态曲线中与4f-5d跃迁耦合的的声子频率，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

ћ

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822408&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822403&type=", "width": "1.94733346", "height": "2.70933342", "fontsize": "" } } } ] }, { "name": "text", "data": "为狄拉克常数。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子4f-5d光谱跃迁过程所吸收和发射的能量分布为" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

E_{a b s}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822419&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822413&type=", "width": "5.07999992", "height": "3.72533321", "fontsize": "" } } } ] }, { "name": "text", "data": "和" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

E_{e m}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822429&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822425&type=", "width": "4.74133301", "height": "3.72533321", "fontsize": "" } } } ] }, { "name": "text", "data": "。另外，在光吸收过程中电子-声子耦合导致了能量损失，定义为Franck-Condon位移，用" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

E_{F c, e}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822439&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822433&type=", "width": "5.84200001", "height": "3.72533321", "fontsize": "" } } } ] }, { "name": "text", "data": "来表示，类似地，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

E_{F c, g}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822453&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822445&type=", "width": "5.84200001", "height": "3.72533321", "fontsize": "" } } } ] }, { "name": "text", "data": "表示在光发射过程中晶格损失的能量" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "18", "type": "bibr", "rid": "R18", "data": [ { "name": "text", "data": "18" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。依据" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

E_{F c, g}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822463&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822457&type=", "width": "5.84200001", "height": "3.72533321", "fontsize": "" } } } ] }, { "name": "text", "data": "和" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

E_{F c, e}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822471&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822467&type=", "width": "5.84200001", "height": "3.72533321", "fontsize": "" } } } ] }, { "name": "text", "data": "可以对" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

Ω_{g}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822659&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822657&type=", "width": "3.72533321", "height": "3.89466691", "fontsize": "" } } } ] }, { "name": "text", "data": "和" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

Ω_{e}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822489&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822484&type=", "width": "3.72533321", "height": "3.89466691", "fontsize": "" } } } ] }, { "name": "text", "data": "值进行如下计算" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "16", "type": "bibr", "rid": "R16", "data": [ { "name": "text", "data": "16" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "：" } ] }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（3）" } ], "data": [ { "name": "text", "data": "Δ" }, { "name": "math", "data": { "math": "

ћ Ω_{g} = \sqrt[]{\frac{2 E_{F C, g}}{Δ Q^{2}}}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822496&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822492&type=", "width": "22.52133369", "height": "10.41399956", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF3" } }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（4）" } ], "data": [ { "name": "math", "data": { "math": "

ћ Ω_{e} = \sqrt[]{\frac{2 E_{F C, e}}{Δ Q^{2}}}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822509&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822502&type=", "width": "22.52133369", "height": "10.15999985", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF4" } }, { "name": "p", "data": [ { "name": "text", "data": "为描述电子-声子耦合的强度，可以引入黄-里斯因子" }, { "name": "italic", "data": [ { "name": "text", "data": "S" } ] }, { "name": "text", "data": "，即结构弛豫过程中释放声子的数目。激发和发射过程的" }, { "name": "italic", "data": [ { "name": "text", "data": "S" } ] }, { "name": "text", "data": "因子分别用" }, { "name": "italic", "data": [ { "name": "text", "data": "S" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "abs" } ] }, { "name": "text", "data": "和" }, { "name": "italic", "data": [ { "name": "text", "data": "S" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "em" } ] }, { "name": "text", "data": "来表示，可以依据公式（" }, { "name": "xref", "data": { "text": "5", "type": "disp-formula", "rid": "DF5", "data": [ { "name": "text", "data": "5" } ] } }, { "name": "text", "data": "）~（" }, { "name": "xref", "data": { "text": "6", "type": "disp-formula", "rid": "DF6", "data": [ { "name": "text", "data": "6" } ] } }, { "name": "text", "data": "）进行计算：" } ] }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（5）" } ], "data": [ { "name": "math", "data": { "math": "

S_{a b s} = \frac{E_{F C, e}}{ћ Ω_{e}}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822521&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822516&type=", "width": "16.51000023", "height": "8.21266651", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF5" } }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（6）" } ], "data": [ { "name": "math", "data": { "math": "

S_{e m} = \frac{E_{F C, g}}{ћ Ω_{g}}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822529&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822524&type=", "width": "16.17133331", "height": "8.89000034", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF6" } }, { "name": "p", "data": [ { "name": "text", "data": "依据以上计算得到的信息，表征发射峰宽的物理量半峰宽（Full-width at half-maximum, " }, { "name": "italic", "data": [ { "name": "text", "data": "W" } ] }, { "name": "text", "data": "）在0 K条件下可以表示为" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "16", "type": "bibr", "rid": "R16", "data": [ { "name": "text", "data": "16" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "：" } ] }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（7）" } ], "data": [ { "name": "math", "data": { "math": "

W (0) = S_{e m} ћ Ω_{g} \sqrt[]{8 l n 2} / \sqrt[]{S_{a b s}}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822539&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822533&type=", "width": "45.55066681", "height": "5.50333309", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF7" } }, { "name": "p", "data": [ { "name": "text", "data": "进而，在任意温度" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "text", "data": "（K）条件下，发射半峰宽的值为：" } ] }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（8）" } ], "data": [ { "name": "math", "data": { "math": "

W (T) = W (0) \sqrt[]{c o t h (\frac{ћ Ω_{e}}{2 k_{B} T})}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822548&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822543&type=", "width": "44.53466415", "height": "9.73666668", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF8" } }, { "name": "p", "data": [ { "name": "text", "data": "通过上述计算公式，可以看到影响半峰宽的本质参数为晶体结构弛豫和有效声子频率以及所对应的斯托克斯位移和黄-里斯因子的大小。以下将分别对这些参数进行讨论。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3　Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子光谱跃迁中的结构弛豫" } ], "level": "1", "id": "s3" } }, { "name": "p", "data": [ { "name": "text", "data": "固体荧光粉在吸收一定能量的光子后，受激辐射出能量小于原吸收的光子，从而导致发射光谱相较于激发光谱向能量较低的方向偏移。这一过程是由于晶体结构弛豫所造成的，进而使两个光子的能量存在差值，即为斯托克斯位移。对于Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "激活发光材料的斯托克斯位移，刘泉林教授课题组等对其影响因素进行了总结分析，并提出斯托克斯位移与Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子局部配位环境平均键长表现出正相关性" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "19", "type": "bibr", "rid": "R19", "data": [ { "name": "text", "data": "19" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。本小节着重讨论斯托克斯位移对发射半峰宽的影响。该影响可以通过固定声子频率的位形模型进行直观的表现，如" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "所示。由此可以看出，Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子4f-5d光谱跃迁中结构弛豫越小，所得到发光材料会具有越窄的发射峰宽。因此，如何获得具有较小结构弛豫的Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂荧光材料成为关键。下文分别从配位环境和结构刚性角度对以往研究进行说明。" } ] }, { "name": "fig", "data": { "id": "F2", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图2" } ], "title": [ { "name": "text", "data": "结构弛豫对Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂荧光粉发射峰宽的影响" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.2" } ], "title": [ { "name": "text", "data": "Schematic representation of the effect of geometry relaxation on FWHM of Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "-doped phosphors" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822552&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822562&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822557&type=", "width": "63.27148438", "height": "50.35330200", "fontsize": "" } ] } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.1　配位环境" } ], "level": "2", "id": "s3a" } }, { "name": "p", "data": [ { "name": "text", "data": "通过以往的研究可知，Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "激活发光材料实现窄带发射通常需要化合物具有单一的掺杂位点以减少多发射中心造成光谱重叠，进而造成发射光谱出现展宽。与此同时，在窄峰宽发光材料的设计中，高对称性的配位环境被认为是制备窄带发射荧光粉的关键因素之一。常见的高对称性配位Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子掺杂窄带发射LED灯用荧光粉有以下三种典型种类，" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "列举了其代表性化合物的晶体结构以及Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子掺杂的局部配位环境。" } ] }, { "name": "fig", "data": { "id": "F3", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图3" } ], "title": [ { "name": "text", "data": "三类Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂窄带发射荧光粉晶体结构及其对应的局部配位环境" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.3" } ], "title": [ { "name": "text", "data": "Three representative crystal structures and local coordination environments of Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "-doped narrow-band emitting phosphors" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822563&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822568&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822566&type=", "width": "73.70195007", "height": "93.72935486", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "第Ⅰ类是BaSi" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "N" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "型结构。这类荧光粉晶体结构属于正交" }, { "name": "italic", "data": [ { "name": "text", "data": "Pbcn" } ] }, { "name": "text", "data": "空间群，阴离子形成高度凝聚的SiON" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "四面体， Ba" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子作为电荷补偿剂填充到孔道之中，以类立方配位的环境存在。Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子占据到Ba" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的晶体格位。在405 nm的近紫外激发条件下，Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子的发射光谱的峰值和FWHM分别为494 nm和968 cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1[" }, { "name": "xref", "data": { "text": "20", "type": "bibr", "rid": "R20", "data": [ { "name": "text", "data": "20" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，表现出青光窄带发射特点。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "第Ⅱ类为β-SiAlON型结构。该类窄带发射荧光粉晶体结构属于六方" }, { "name": "italic", "data": [ { "name": "text", "data": "P" } ] }, { "name": "text", "data": "6" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "空间群，其化学式为β-Si" }, { "name": "sub", "data": [ { "name": "text", "data": "6-" } ] }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "z" } ] } ] }, { "name": "text", "data": "Al" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "z" } ] } ] }, { "name": "text", "data": "O" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "z" } ] } ] }, { "name": "text", "data": "N" }, { "name": "sub", "data": [ { "name": "text", "data": "8-" } ] }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "z" } ] } ] }, { "name": "text", "data": "（0 " }, { "name": "text", "data": "<" }, { "name": "text", "data": " " }, { "name": "italic", "data": [ { "name": "text", "data": "z " } ] }, { "name": "text", "data": "≤4.2）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "21", "type": "bibr", "rid": "R21", "data": [ { "name": "text", "data": "21" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。β-SiAlON型结构由共享的（Si，Al）-（O，N）" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": " 四面体和沿[001]方向六边形通道所组成。与第一类荧光粉明显不同的是，Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "活化剂并不是取代已有原子的格位，而是占据其六边形孔道的空位中，Kimoto 等已直接通过扫描透射电子显微镜观察到" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "22", "type": "bibr", "rid": "R22", "data": [ { "name": "text", "data": "22" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，随后Wang等也通过理论计算进一步证明" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "23", "type": "bibr", "rid": "R23", "data": [ { "name": "text", "data": "23" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。六边形空位的占据使得其结构不会因Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的引入而发生剧烈畸变，同时在激发和发射的弛豫过程中结构也会保持较高的稳定性，最终表现为较大刚性的窄带发射。同时，在β-SiAlON型结构中，" }, { "name": "italic", "data": [ { "name": "text", "data": "z" } ] }, { "name": "text", "data": "值的大小会导致发光特性不同，如在相同激发光源下（325 nm），高" }, { "name": "italic", "data": [ { "name": "text", "data": "z" } ] }, { "name": "text", "data": "（0.18）-β-SiAlON发射峰位置和FWHM分别为540 nm和1 870 cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "，而低 " }, { "name": "italic", "data": [ { "name": "text", "data": "z" } ] }, { "name": "text", "data": "（0.03）-β-SiAlON发射峰位置和FWHM分别为528 nm和1 772 cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1[" }, { "name": "xref", "data": { "text": "21", "type": "bibr", "rid": "R21", "data": [ { "name": "text", "data": "21" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。尽管" }, { "name": "italic", "data": [ { "name": "text", "data": "z" } ] }, { "name": "text", "data": "值不同会导致其发光性质改变，但仍可以看出不同" }, { "name": "italic", "data": [ { "name": "text", "data": "z" } ] }, { "name": "text", "data": "值下发射光谱均表现出窄带发射特性。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "第Ⅲ类为UCr" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "C" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "型结构。近期报道的UCr" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "C" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "化物包括Schnick教授课题组开发的Eu掺杂SrLiAl" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "N" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "（SLA）、SrMg" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "N" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "（SMA）、SrMg" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "SiN" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "（SMS）等一系列荧光粉。其中，SLA属于三斜晶系" }, { "name": "italic", "data": [ { "name": "text", "data": "P" } ] }, { "name": "text", "data": "1空间群，Li" }, { "name": "sup", "data": [ { "name": "text", "data": "+" } ] }, { "name": "text", "data": "和Al" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "与阴离子组成[LiN" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "]、[AlN" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "]四面体构成刚性通道。SLA∶Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "为红色窄带发射光谱，在440 nm的激发波长下，峰值和FWHM分别为650 nm和1 180 cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1[" }, { "name": "xref", "data": { "text": "7", "type": "bibr", "rid": "R7", "data": [ { "name": "text", "data": "7" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。SLA∶Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "还表现出较为优秀的热稳定性质，与室温相比，其在500 K时的发光强度仅降低了约5%，由此它被认定为下一代红色荧光粉的候选者。SMA属于四方晶系" }, { "name": "italic", "data": [ { "name": "text", "data": "I" } ] }, { "name": "text", "data": "4" }, { "name": "italic", "data": [ { "name": "text", "data": "/m" } ] }, { "name": "text", "data": "空间群，Mg" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "和Al" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "与阴离子组成[MgN" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "]、[AlN" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "]四面体构成刚性通道。与SLA相比其构成通道四面体表现出更大的无序性，这也使得结构的刚性有所减弱，从而进一步导致其发射光谱出现一定程度的展宽。SMA∶Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "同样为红色窄带发射光谱，在440 nm的激发波长下，峰值和FWHM分别为610 nm和1 838 cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1[" }, { "name": "xref", "data": { "text": "24", "type": "bibr", "rid": "R24", "data": [ { "name": "text", "data": "24" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，略宽于SLA∶Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "。SMS属于四方晶系" }, { "name": "italic", "data": [ { "name": "text", "data": "I" } ] }, { "name": "text", "data": "4" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "/" }, { "name": "italic", "data": [ { "name": "text", "data": "a" } ] }, { "name": "text", "data": "空间群，与前两者相似，Mg" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "和Si" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "与阴离子组成[MgN" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "]、[SiN" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "]四面体构成刚性通道。相较于前者，两种配位四面体有序排列，使得其结构表现出较大的刚性。在450 nm的激发波长下，峰值和FWHM分别为615 nm和1 170 cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "，发射半峰宽为三者之中最窄" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "25", "type": "bibr", "rid": "R25", "data": [ { "name": "text", "data": "25" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。近期夏志国教授课题组报道了一些新型UCr" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "C" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "氧化物类型荧光粉，如RbLi（Li" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "（RLSO）和Na" }, { "name": "sub", "data": [ { "name": "text", "data": "0.5" } ] }, { "name": "text", "data": "K" }, { "name": "sub", "data": [ { "name": "text", "data": "0.5" } ] }, { "name": "text", "data": "Li" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "（NKLSO）等。其中RLSO晶体属于" }, { "name": "italic", "data": [ { "name": "text", "data": "C2/m" } ] }, { "name": "text", "data": "（单斜晶系）空间群，在460 nm的激发光源下表现为绿色窄带发射，其峰值和发射峰宽分别为530 nm和1 497 cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1[" }, { "name": "xref", "data": { "text": "26", "type": "bibr", "rid": "R26", "data": [ { "name": "text", "data": "26" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。而NKLSO晶体则属于" }, { "name": "italic", "data": [ { "name": "text", "data": "I" } ] }, { "name": "text", "data": "4" }, { "name": "italic", "data": [ { "name": "text", "data": "/m" } ] }, { "name": "text", "data": "（四方晶系），在400 nm的激发光源下，光谱由 486 nm（FWHM约为847 cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "）处的主要不对称窄带峰和530 nm 处的从属肩峰组成" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "27", "type": "bibr", "rid": "R27", "data": [ { "name": "text", "data": "27" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，表现出青色发射。" } ] }, { "name": "p", "data": [ { "name": "xref", "data": { "text": "表1", "type": "table", "rid": "T1", "data": [ { "name": "text", "data": "表1" } ] } }, { "name": "text", "data": "中列举了以上三类窄峰型Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂荧光粉的光谱信息和配位环境。" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "展示了上述三种典型的Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂窄带发射荧光粉的激发和发射光谱。由上述分析可知，为实现Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂更窄的发射特性，通常对局部配位环境的对称性有较高的要求。衡量局部配位环境的畸变程度可以通过以下公式来描述" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "28", "type": "bibr", "rid": "R28", "data": [ { "name": "text", "data": "28" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "：" } ] }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "(9)" } ], "data": [ { "name": "math", "data": { "math": "

D = \frac{1}{n} \sum_{i = 1}^{n} \frac{\"|\"l_{i} - l_{a v}\"|\"}{l_{a v}},

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822571&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822570&type=", "width": "28.19400024", "height": "9.05933285", "fontsize": "" } } }, { "name": "text", "data": " " } ], "id": "DF9" } }, { "name": "p", "data": [ { "name": "text", "data": "其中" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

D

l_{i}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822580&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822578&type=", "width": "1.77800000", "height": "3.72533321", "fontsize": "" } } } ] }, { "name": "text", "data": "是中心原子到第" }, { "name": "italic", "data": [ { "name": "text", "data": "i" } ] }, { "name": "text", "data": "个配位原子的键长，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

l_{a v}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822588&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822585&type=", "width": "2.96333337", "height": "3.72533321", "fontsize": "" } } } ] }, { "name": "text", "data": "则为配位多面体的平均键长。由以往的研究可知，较大的配位环境畸变往往导致4f-5d光谱跃迁中较大的晶体结构弛豫，进而展宽其发射光谱带。而在UCr" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "C" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "11", "type": "bibr", "rid": "R11", "data": [ { "name": "text", "data": "11" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "类型Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "激活荧光粉中，Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子占据U离子的晶体格位，局部配位环境由六面体构成。以SLA∶Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "为例，该荧光粉中Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子局部配位环境的畸变指数" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

D

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822591&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822589&type=", "width": "2.53999996", "height": "2.62466669", "fontsize": "" } } } ] }, { "name": "text", "data": "近乎为0，保证了窄带发射。" } ] }, { "name": "table", "data": { "id": "T1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "表1" } ], "title": [ { "name": "text", "data": "三类Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂窄带发射荧光粉的发光特性" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Tab.1" } ], "title": [ { "name": "text", "data": "The luminescent properties of Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "-doped narrow-band emitting phosphors with three representative crystal structures" } ] } ], "note": [], "table": [ { "head": [ [ { "align": "center", "style": "border-top:solid;border-bottom:solid;", "data": [] }, { "align": "center", "style": "border-top:solid;border-bottom:solid;", "data": [ { "name": "text", "data": "荧光粉" } ] }, { "align": "center", "style": "border-top:solid;border-bottom:solid;", "data": [ { "name": "text", "data": "激发光源/nm" } ] }, { "align": "center", "style": "border-top:solid;border-bottom:solid;", "data": [ { "name": "text", "data": "发射峰位置/nm" } ] }, { "align": "center", "style": "border-top:solid;border-bottom:solid;", "data": [ { "name": "text", "data": "半峰宽/cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] } ] }, { "align": "center", "style": "border-top:solid;border-bottom:solid;", "data": [ { "name": "text", "data": "参考文献" } ] } ] ], "body": [ [ { "align": "center", "data": [ { "name": "text", "data": "Ⅰ" } ] }, { "align": "center", "data": [ { "name": "text", "data": "BaSi" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "N" }, { "name": 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"name": "text", "data": "450" } ] }, { "align": "center", "data": [ { "name": "text", "data": "615" } ] }, { "align": "center", "data": [ { "name": "text", "data": "1 170" } ] }, { "align": "center", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "25", "type": "bibr", "rid": "R25", "data": [ { "name": "text", "data": "25" } ] } }, { "name": "text", "data": "］" } ] } ], [ { "align": "center", "data": [ { "name": "text", "data": "RbLi（Li" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] } ] }, { "align": "center", "data": [ { "name": "text", "data": "460" } ] }, { "align": "center", "data": [ { "name": "text", "data": "530" } ] }, { "align": "center", "data": [ { "name": "text", "data": "1 497" } ] }, { "align": "center", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "26", "type": "bibr", "rid": "R26", "data": [ { "name": "text", "data": "26" } ] } }, { "name": "text", "data": "］" } ] } ], [ { "align": "center", "style": "border-bottom:solid;", "data": [ { "name": "text", "data": "Na" }, { "name": "sub", "data": [ { "name": "text", "data": "0.5" } ] }, { "name": "text", "data": "K" }, { "name": "sub", "data": [ { "name": "text", "data": "0.5" } ] }, { "name": "text", "data": "Li" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] } ] }, { "align": "center", "style": "border-bottom:solid;", "data": [ { "name": "text", "data": "400" } ] }, { "align": "center", "style": "border-bottom:solid;", "data": [ { "name": "text", "data": "486" } ] }, { "align": "center", "style": "border-bottom:solid;", "data": [ { "name": "text", "data": "847" } ] }, { "align": "center", "style": "border-bottom:solid;", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "27", "type": "bibr", "rid": "R27", "data": [ { "name": "text", "data": "27" } ] } }, { "name": "text", "data": "］" } ] } ] ], "foot": [] } ], "graphics": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822601&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822596&type=", "width": "162.79998779", "height": "61.64444733", "fontsize": "" } } }, { "name": "fig", "data": { "id": "F4", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图4" } ], "title": [ { "name": "text", "data": "三类Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂窄带发射荧光粉的激发和发射光谱" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.4" } ], "title": [ { "name": "text", "data": "The excitation and emission spectra of Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "-doped narrow-band emitting phosphors" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822604&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822608&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822606&type=", "width": "75.85479736", "height": "63.51367188", "fontsize": "" } ] } } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.2　结构刚性" } ], "level": "2", "id": "s3b" } }, { "name": "p", "data": [ { "name": "text", "data": "通过上述近期研究较多的三类Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "激活窄带发射荧光粉，不难看出高对称性的晶体格位往往可以导致Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子的窄带发射。但实际研究表明，在一些低对称性的配位环境中，Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子也可以表现出窄带型发射。该类材料以硼酸盐居多，例如SrB" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "7" } ] }, { "name": "text", "data": "∶Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+[16]" } ] }, { "name": "text", "data": "。对于该类型发光材料，其窄带发射的解释往往归结到材料刚性，即材料晶体结构的高稳定性使得其在光谱跃迁中具有较小的弛豫，这就使得电子跃迁过程与周围环境存在较少的能量传递，从而使其发射半峰宽具有较小值。化合物结构刚性可以通过计算材料的德拜温度来判定：高德拜温度对应高的结构刚性。因而德拜温度为实现Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂窄带荧光粉的筛选提供了依据" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "29", "type": "bibr", "rid": "R29", "data": [ { "name": "text", "data": "29" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。德拜温度（" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

θ_{D}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822611&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822610&type=", "width": "3.21733332", "height": "3.80999994", "fontsize": "" } } } ] }, { "name": "text", "data": "）的大小可采用如下公式进行计算：" } ] }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（10）" } ], "data": [ { "name": "math", "data": { "math": "

C_{p} \approx \frac{12 N k_{B} π^{4}}{5} {(\frac{T}{θ_{D}})}^{3}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822616&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822614&type=", "width": "30.90333366", "height": "9.65200043", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF10" } }, { "name": "p", "data": [ { "name": "text", "data": "其中" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

C_{p}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822621&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822618&type=", "width": "3.47133350", "height": "3.72533321", "fontsize": "" } } } ] }, { "name": "text", "data": "代表化合物的比热容，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

N

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822626&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822623&type=", "width": "2.62466669", "height": "2.62466669", "fontsize": "" } } } ] }, { "name": "text", "data": "是每个分子式单元的原子数乘以阿伏伽德罗常数，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

k_{B}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822635&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822631&type=", "width": "3.04800010", "height": "3.72533321", "fontsize": "" } } } ] }, { "name": "text", "data": "是玻尔兹曼常数，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

T

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822790&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822788&type=", "width": "2.28600001", "height": "2.62466669", "fontsize": "" } } } ] }, { "name": "text", "data": "是温度，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

θ_{D}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822643&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822641&type=", "width": "3.21733332", "height": "3.80999994", "fontsize": "" } } } ] }, { "name": "text", "data": "则为该化合物的德拜温度。以β-Sialon荧光粉体系为例，低" }, { "name": "italic", "data": [ { "name": "text", "data": "z" } ] }, { "name": "text", "data": "（0.03）-β-SiAlON和高" }, { "name": "italic", "data": [ { "name": "text", "data": "z" } ] }, { "name": "text", "data": "（0.18）-β-SiAlON材料所计算得到的" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

θ_{D}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822647&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822645&type=", "width": "3.21733332", "height": "3.80999994", "fontsize": "" } } } ] }, { "name": "text", "data": "分别为901 K和747 K，这表明低" }, { "name": "italic", "data": [ { "name": "text", "data": "z" } ] }, { "name": "text", "data": "（0.03）-β-SiAlON比高" }, { "name": "italic", "data": [ { "name": "text", "data": "z" } ] }, { "name": "text", "data": "（0.18）-β-SiAlON具有更高的热稳定性，前者的结构刚性同样高于后者，从而前者表现出更窄的发射半峰宽" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "21", "type": "bibr", "rid": "R21", "data": [ { "name": "text", "data": "21" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "4　声子频率的影响" } ], "level": "1", "id": "s4" } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "4.1　基态与激发态声子频率做相等近似情况" } ], "level": "2", "id": "s4a" } }, { "name": "p", "data": [ { "name": "text", "data": "在一般体系中，基态和激发态中有效声子频率 " }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

Ω_{g}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822724&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822720&type=", "width": "3.72533321", "height": "3.89466691", "fontsize": "" } } } ] }, { "name": "text", "data": "和" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

Ω_{e}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822655&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822654&type=", "width": "3.72533321", "height": "3.89466691", "fontsize": "" } } } ] }, { "name": "text", "data": "的值非常相近，通常仅存在~0.005 eV的能量差距，所以可以近似认为" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

Ω_{g}

Ω_{e}

E_{F c, e}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822676&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822672&type=", "width": "5.84200001", "height": "3.72533321", "fontsize": "" } } } ] }, { "name": "text", "data": "=" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

E_{F c, g}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822682&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822679&type=", "width": "5.84200001", "height": "3.72533321", "fontsize": "" } } } ] }, { "name": "text", "data": "。这样我们就可以把斯托克斯位移引入到计算公式之中。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "根据斯托克斯位移（" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

Δ

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822691&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822689&type=", "width": "2.53999996", "height": "2.70933342", "fontsize": "" } } } ] }, { "name": "italic", "data": [ { "name": "text", "data": "S" } ] }, { "name": "text", "data": "）的定义，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

Δ

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822691&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822689&type=", "width": "2.53999996", "height": "2.70933342", "fontsize": "" } } } ] }, { "name": "italic", "data": [ { "name": "text", "data": "S" } ] }, { "name": "text", "data": "和Franck-Condon位移的关系如下：" } ] }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（11）" } ], "data": [ { "name": "math", "data": { "math": "

Δ S = E_{F c, g} + E_{F c, e}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822698&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822695&type=", "width": "25.82333374", "height": "3.89466691", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF11" } }, { "name": "p", "data": [ { "name": "text", "data": "从而对" }, { "name": "xref", "data": { "text": "公式（7）", "type": "disp-formula", "rid": "DF7", "data": [ { "name": "text", "data": "公式（7）" } ] } }, { "name": "text", "data": "进行整理，得到新的半峰宽计算公式" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "30", "type": "bibr", "rid": "R30", "data": [ { "name": "text", "data": "30" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": ":" } ] }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（12）" } ], "data": [ { "name": "math", "data": { "math": "

W (0) = 2 \sqrt[]{Δ S ћ Ω l n 2}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822703&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822701&type=", "width": "33.86666870", "height": "4.82600021", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF12" } }, { "name": "p", "data": [ { "name": "text", "data": "由上述公式可以清晰地看出，当斯托克斯位移相同时，高频声子模式会导致样品的发射半峰宽值增大。这一分析可通过位形坐标进行表达，如" }, { "name": "xref", "data": { "text": "图5", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5" } ] } }, { "name": "text", "data": "所示。具体而言，声子频率的大小将会对基态/激发态的势能曲线形状产生影响。由公式（" }, { "name": "xref", "data": { "text": "1", "type": "disp-formula", "rid": "DF1", "data": [ { "name": "text", "data": "1" } ] } }, { "name": "text", "data": "）~（" }, { "name": "xref", "data": { "text": "2", "type": "disp-formula", "rid": "DF2", "data": [ { "name": "text", "data": "2" } ] } }, { "name": "text", "data": "）可知，当声子频率增大，平衡位形抛物线开口将会变得更窄。因此我们便可通过不同声子频率下的一维构型坐标模型对发射半峰宽进行一定的分析。通过" }, { "name": "xref", "data": { "text": "图5", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5" } ] } }, { "name": "text", "data": "可见，为获得窄峰宽的Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂荧光材料，应尽量减小有效声子频率的值。在具体开发中，可以利用低频局域声子模式的概念进行材料的设计。" } ] }, { "name": "fig", "data": { "id": "F5", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图5" } ], "title": [ { "name": "text", "data": "相同斯托克斯位移下，不同声子频率对半峰宽的影响。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.5" } ], "title": [ { "name": "text", "data": "Schematic representation of the effect of effective phonon frequency on FWHM of Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "-doped phosphors" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822707&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822716&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822711&type=", "width": "63.06257629", "height": "50.52713013", "fontsize": "" } ] } } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "4.2　基态与激发态声子频率不相同情况" } ], "level": "2", "id": "s4b" } }, { "name": "p", "data": [ { "name": "text", "data": "上述有效声子频率对FWHM影响的讨论是以基态声子频率（" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

Ω_{g}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822724&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822720&type=", "width": "3.72533321", "height": "3.89466691", "fontsize": "" } } } ] }, { "name": "text", "data": "）与激发态声子频率（" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

Ω_{e}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822728&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822726&type=", "width": "3.72533321", "height": "3.89466691", "fontsize": "" } } } ] }, { "name": "text", "data": "）相等为基础。在实际的设计中，可以进一步利用两者的差异，进行窄峰型Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "激活荧光粉的开发。根据公式（" }, { "name": "xref", "data": { "text": "3", "type": "disp-formula", "rid": "DF3", "data": [ { "name": "text", "data": "3" } ] } }, { "name": "text", "data": "）~（" }, { "name": "xref", "data": { "text": "4", "type": "disp-formula", "rid": "DF4", "data": [ { "name": "text", "data": "4" } ] } }, { "name": "text", "data": "）可知，声子频率的大小将会直接影响Franck-Condon 位移的大小。因此，可以引入一个新的参数来定义二者的差别，此处称为Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "C" } ] }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "16", "type": "bibr", "rid": "R16", "data": [ { "name": "text", "data": "16" } ] } }, { "name": "text", "data": "," }, { "name": "xref", "data": { "text": "30", "type": "bibr", "rid": "R30", "data": [ { "name": "text", "data": "30" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "：" } ] }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（13）" } ], "data": [ { "name": "math", "data": { "math": "

Δ C = E_{F c, e} - E_{F c, g}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822735&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822731&type=", "width": "26.24666595", "height": "3.89466691", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF13" } }, { "name": "p", "data": [ { "name": "text", "data": "上述公式和" }, { "name": "xref", "data": { "text": "公式（11）", "type": "disp-formula", "rid": "DF11", "data": [ { "name": "text", "data": "公式（11）" } ] } }, { "name": "text", "data": "联立可得出新的Franck-Condon 位移表述形式" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "28", "type": "bibr", "rid": "R28", "data": [ { "name": "text", "data": "28" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "：" } ] }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（14）" } ], "data": [ { "name": "math", "data": { "math": "

E_{F c, e} = \frac{1}{2} (Δ S + Δ C)

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822742&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822738&type=", "width": "30.56466866", "height": "7.28133297", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF14" } }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（15）" } ], "data": [ { "name": "math", "data": { "math": "

E_{F c, g} = \frac{1}{2} (Δ S - Δ C)

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822748&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822745&type=", "width": "30.56466866", "height": "7.28133297", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF15" } }, { "name": "p", "data": [ { "name": "text", "data": "在LED工作温度条件450 K下，玻色-爱因斯坦分布可以用玻尔兹曼分布代替。该条件下，FWHM与" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

Δ C

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822753&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822750&type=", "width": "4.74133301", "height": "2.79399991", "fontsize": "" } } } ] }, { "name": "text", "data": "、" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

Δ S

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822786&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822784&type=", "width": "4.31799984", "height": "2.79399991", "fontsize": "" } } } ] }, { "name": "text", "data": "以及温度（" }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "text", "data": "）的关系可以表示为" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "30", "type": "bibr", "rid": "R30", "data": [ { "name": "text", "data": "30" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "：" } ] }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（16）" } ], "data": [ { "name": "math", "data": { "math": "

W (T) = 2 \sqrt[]{l n 2 Δ S} \frac{(1 - Δ C / Δ S)}{(1 + Δ C / Δ S)} \sqrt[]{2 K_{B} T}

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822768&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822763&type=", "width": "61.80666733", "height": "9.14400005", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF16" } }, { "name": "p", "data": [ { "name": "text", "data": "其中" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

W (T)

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822794&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822792&type=", "width": "8.97466660", "height": "3.72533321", "fontsize": "" } } } ] }, { "name": "text", "data": "是LED工作温度下的半峰宽值。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "由" }, { "name": "xref", "data": { "text": "公式（16）", "type": "disp-formula", "rid": "DF16", "data": [ { "name": "text", "data": "公式（16）" } ] } }, { "name": "text", "data": "可知，在固定发射能量和斯托克斯位移下，激发和发射过程中Franck-Condon 位移的差异是决定半高宽的关键因素。由于基态和激发态下的Franck-Condon 位移均为正值，因此" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

Δ C / Δ S

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822782&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822778&type=", "width": "10.58333302", "height": "3.21733332", "fontsize": "" } } } ] }, { "name": "text", "data": "的范围处于-1~1之间" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "30", "type": "bibr", "rid": "R30", "data": [ { "name": "text", "data": "30" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。在固定荧光粉" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

Δ S

T

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822790&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822788&type=", "width": "2.28600001", "height": "2.62466669", "fontsize": "" } } } ] }, { "name": "text", "data": "时，发射峰宽" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

W (T)

Δ C / Δ S

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822804&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822801&type=", "width": "10.58333302", "height": "3.21733332", "fontsize": "" } } } ] }, { "name": "text", "data": "表现出负相关性，这一比值越大，半高宽越小。这就使得激发态和基态之间的正Franck-Condon 位移差距有利于实现窄带发射，如" }, { "name": "xref", "data": { "text": "图6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6" } ] } }, { "name": "text", "data": "所示。虽然该结论仅仅是基于简单的单声子位形模型来讨论，其在考虑详细振动模式频率的情况下可能会有部分变化，但是在新型Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂荧光粉的高通量计算筛选时，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

Δ C / Δ S

Δ S

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822811&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822807&type=", "width": "3.72533321", "height": "2.37066650", "fontsize": "" } } } ] }, { "name": "text", "data": "和发射频率固定的条件下，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "

Δ C

Δ C

Δ C

", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822825&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822823&type=", "width": "4.06400013", "height": "2.37066650", "fontsize": "" } } } ] }, { "name": "text", "data": "为正值。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.6" } ], "title": [ { "name": "text", "data": "Schematic representation of excited state phonon frequency on FWHM of Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "-doped phosphors， with fixed Stokes shift and ground state phonon mode. The blue curve stands for a smaller excited state phonon frequency than ground state value， and the red lines stand for the opposite situation." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822828&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822835&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39822832&type=", "width": "65.63090515", "height": "50.52713013", "fontsize": "" } ] } } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "5　结　　论" } ], "level": "1", "id": "s5" } }, { "name": "p", "data": [ { "name": "text", "data": "本文以位形坐标模型为理论依据，分析了Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "激活荧光粉的局部配位环境、结构刚性、声子频率等多个方面对其发射峰宽的影响，进而对实现窄带发射的要点进行了归纳与总结，最终得到如下结论：（1）从结构方面，高刚性的晶体结构会使晶体弛豫程度减小，这就要求所选荧光粉基质材料晶体结构具有较高的结构刚性。（2）从配位环境方面，较大空间、较小畸变程度以及较大相邻发射位点距离的高对称性局部配位环境不仅能减小晶体的弛豫程度，还会使发射过程中能量重叠减小，进而减小光谱展宽效应。（3）从声子频率方面，在激发和发射过程中，耦合声子频率的大小对峰宽的影响也尤其重要，可以分为两种情况：在基态与激发态声子频率近似相等时，较小的声子频率会引起更小的发射半峰宽；在二者不等时，激发态的高频声子耦合能够导致窄峰宽。上述关于窄带发射的各种因素可以为Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂窄带发射荧光粉基质材料的筛选提供思路，有望作为描述因子来进行高通量计算筛选。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "本文专家审稿意见及作者回复内容的下载地址：" } ] }, { "name": "p", "data": [ { "name": "extlink", "data": { "text": [ { "name": "text", "data": "http://cjl.lightpublishing.cn/thesisDetails#10.37188/" } ], "href": "http://cjl.lightpublishing.cn/thesisDetails#10.37188/" } } ] }, { "name": "p", "data": [ { "name": "text", "data": "CJL.20220189." } ] } ] } ], "footnote": [], "reflist": { "title": [ { "name": "text", "data": "参考文献" } ], "data": [ { "id": "R1", "label": "1", "citation": [ { "lang": "en", "text": [ { "name": "text", "data": "NAKAMURA S" }, { "name": "text", "data": "， " }, { "name": "text", "data": "FASOL G" }, { "name": "text", "data": ". 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