Analysis of Site-occupation of Activator in Phosphors Enhanced Publication

{ "defaultlang": "zh", "titlegroup": { "articletitle": [ { "lang": "zh", "data": [ { "name": "text", "data": "荧光粉中激活剂离子掺杂格位分析" } ] }, { "lang": "en", "data": [ { "name": "text", "data": "Analysis of Site-occupation of Activator in Phosphors" } ] } ] }, "contribgroup": { "author": [ { "name": [ { "lang": "zh", "surname": "姬", "givenname": "海鹏", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "JI", "givenname": "Hai-peng", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "1" } ], "role": [ "corresp", "first-author" ], "corresp": [ { "rid": "cor1", "lang": "zh", "text": "*E-mail: jihp@zzu.edu.cn", "data": [ { "name": "text", "data": "*E-mail: jihp@zzu.edu.cn" } ] } ], "bio": [ { "lang": "zh", "text": [ "姬海鹏(1989-)，男，河南南阳人，博士，讲师/校聘副教授，2017年于中国地质大学(北京)获得博士学位，主要从事固体发光材料的研究。E-mail: jihp@zzu.edu.cn" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777014&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777015&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777020&type=" } ], "data": [ [ { "name": "text", "data": "姬海鹏" }, { "name": "text", "data": "(1989-)，男，河南南阳人，博士，讲师/校聘副教授，2017年于中国地质大学(北京)获得博士学位，主要从事固体发光材料的研究。E-mail: " }, { "name": "text", "data": "jihp@zzu.edu.cn" } ] ] } ], "email": "jihp@zzu.edu.cn", "deceased": false } ], "aff": [ { "id": "aff1", "intro": [ { "lang": "zh", "label": "1", "text": "郑州大学　材料科学与工程学院，河南　郑州　450001", "data": [ { "name": "text", "data": "郑州大学　材料科学与工程学院，河南　郑州　450001" } ] }, { "lang": "en", "label": "1", "text": "School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, China", "data": [ { "name": "text", "data": "School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, China" } ] } ] } ] }, "abstracts": [ { "lang": "zh", "data": [ { "name": "p", "data": [ { "name": "text", "data": "荧光粉的发光特性由激活剂离子的电子构型决定，同时也受激活剂离子在基质中的配位环境的影响。配位环境对激活剂离子发光性能的影响主要体现在电子云膨胀效应和晶体场劈裂效应这两个方面。电子云膨胀效应的强弱取决于激活剂离子与配体离子的成键特性(离子键与共价键成分的比例)以及阴离子极化率的大小；而晶体场劈裂效应的大小取决于激活剂离子与配体离子所形成最近邻配位多面体的配位数、平均键长、畸变程度和点群对称性等。了解激活剂离子所占据格位以分析其所形成最近邻配位多面体构型，对理解荧光粉的发光特性和开发新型荧光粉具有重要意义。本综述总结了文献中所用研究激活剂离子格位占据的8种方法，并通过荧光粉研究实例(主要是以Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "、Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "或Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "为激活剂离子的白光LED用荧光粉)展示了每种方法的特点，通过对比分析指出了各种方法的优势和劣势。这8种方法可归为三类:光谱学方法、结构分析法和计算光谱学方法，其中光谱学方法包括以下五类谱图的测试和分析:激发波长依赖的发光光谱与监测波长依赖的激发光谱、波长依赖的荧光衰减曲线、时间分辨发射光谱、变温发射光谱与变温荧光衰减曲线，以及掺杂浓度依赖的发射光谱。" } ] } ] }, { "lang": "en", "data": [ { "name": "p", "data": [ { "name": "text", "data": "Besides the electron configuration of the activator, the luminescent properties of a phosphor are also influenced by the nephelauxetic effect and crystal field splitting effect that the activator experiences in a matrix. The degree of the nephelauxetic effect depends on the bonding features between the activator and the ligands(the ratio between the ionic bonding content and the covalent bonding content) as well as the polarizability of the anions, while the degree of the crystal field splitting effect depends on the coordination number, the average bond length, the distortion, and the point group symmetry of the coordination polyhedron composed by the nearest coordinating anions around the activator. Identification of the doping site, which helps analyze the coordination polyhedron, is of great significance in understanding the luminescence properties of the phosphor and developing new phosphors. This mini-review summarizes the eight methods used to identify the site-occupancy of an activator in a phosphor matrix, which can be classified into three categories, " }, { "name": "italic", "data": [ { "name": "text", "data": "i.e." } ] }, { "name": "text", "data": ", the spectroscopy methods, the structural analysis method, and the theoretical calculation method. Among them, the spectroscopy methods include five different measurements:(1)excitation wavelength dependent emission spectra and emission wavelength dependent excitation spectra, (2)emission wavelength dependent luminescence decay curves, (3)time-resolved emission spectra, (4)temperature-dependent emission spectra and/or luminescence decay curves, (5)activator-concentration-dependent emission spectra. For clarifying the features of the above methods, some related researches were introduced as examples, which refer to some Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": ", Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": ", or Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": " activated phosphors for application in white light emitting diodes. The pros and cons of each method were also analyzed." } ] } ] } ], "keyword": [ { "lang": "zh", "data": [ [ { "name": "text", "data": "荧光材料" } ], [ { "name": "text", "data": "激活剂" } ], [ { "name": "text", "data": "掺杂格位" } ] ] }, { "lang": "en", "data": [ [ { "name": "text", "data": "luminescent materials" } ], [ { "name": "text", "data": "activator" } ], [ { "name": "text", "data": "site occupancy" } ] ] } ], "highlights": [], "body": [ { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "1" } ], "title": [ { "name": "text", "data": "引言" } ], "level": "1", "id": "s1" } }, { "name": "p", "data": [ { "name": "text", "data": "当前主流白光半导体发光二极管(LED)器件采用蓝光LED芯片复合多色荧光粉方案。大多数荧光粉是某种离子取代型固溶体，固溶体的母体被称为基质，进行掺杂取代的离子常被称作激活剂离子。某一荧光粉是否可用于白光LED，以及所封装光谱转换型白光LED器件的流明效率、相关色温、显色指数等，很大程度上取决于荧光粉的发光特性，因此荧光粉的发光特性研究至关重要。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "商业化的白光LED荧光粉中所用激活剂离子主要为稀土离子Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "、Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "与过渡金属离子Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "。其中，稀土离子Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "和Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的荧光来自于宇称允许的d→f跃迁。该电子构型下，最外层为裸露的5d轨道电子，易受晶体场效应和电子云膨胀效应影响。研究表明，d→f跃迁所受晶体场强度(以" }, { "name": "italic", "data": [ { "name": "text", "data": "ε" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "cfs" } ] }, { "name": "text", "data": "表示)取决于稀土离子在基质中形成的最近邻配位多面体的配位数、平均键长、点群对称性和畸变程度，而其所受电子云膨胀效应的强弱(以" }, { "name": "italic", "data": [ { "name": "text", "data": "ε" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "c" } ] }, { "name": "text", "data": "表示)取决于成键的离子键/共价键性和成键阴离子的极化率" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "1", "type": "bibr", "rid": "R1", "data": [ { "name": "text", "data": "1" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "2", "type": "bibr", "rid": "R2", "data": [ { "name": "text", "data": "2" } ] } } ], "rid": [ "R1", "R2" ], "text": "1-2", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "(有兴趣的读者可参考代尔夫特理工大学Dorenbos教授对" }, { "name": "italic", "data": [ { "name": "text", "data": "ε" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "cfs" } ] }, { "name": "text", "data": "和" }, { "name": "italic", "data": [ { "name": "text", "data": "ε" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "c" } ] }, { "name": "text", "data": "的定量计算" }, { "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": ")；因此，Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "/Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "在不同基质中掺杂时可表现出在发光波长、发光光谱半高宽、量子效率、热猝灭稳定性等方面迥异的荧光性质。比如，在Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "/Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "掺杂的硫化物或氮化物类基质中更容易得到长波长发光荧光粉，因为此时Eu/Ce原子(电负性分别为1.01/1.06)与S原子或N原子(电负性S" }, { "name": "text", "data": "<" }, { "name": "text", "data": "N" }, { "name": "text", "data": "<" }, { "name": "text", "data": "O" }, { "name": "text", "data": "<" }, { "name": "text", "data": "F)成键时，两种元素原子间电负性差值最小，所成键的共价性更强而使其受到更强的电子云膨胀效应" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "4", "type": "bibr", "rid": "R4", "data": [ { "name": "text", "data": "4" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。而关于晶体场强度，夏志国等指出，将Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂在具有较小配位数、较短成键键长和较大多面体畸变的晶体学格位有利于得到相对更强的晶体场劈裂效应" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "5", "type": "bibr", "rid": "R5", "data": [ { "name": "text", "data": "5" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。例如，在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": "黄光荧光粉中进行单一阳离子或离子对取代(Tb" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "/Gd" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "取代Y" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "、Mg" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "-Si" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "取代Al" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "-Al" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "等)，增强Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "离子所受晶体场效应后可得到橙红光发光" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "6", "type": "bibr", "rid": "R6", "data": [ { "name": "text", "data": "6" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "9", "type": "bibr", "rid": "R9", "data": [ { "name": "text", "data": "9" } ] } } ], "rid": [ "R6", "R7", "R8", "R9" ], "text": "6-9", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。再如，在Rb" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "YSi" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "7" } ] }, { "name": "text", "data": "∶Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "中设计Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "占据具有较小配位数的[YO" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "]八面体和[Rb2O" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "](Rb2是相对于形成九配位的Rb1而言)多面体中的Y" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "和Rb" }, { "name": "sup", "data": [ { "name": "text", "data": "+" } ] }, { "name": "text", "data": "离子格位，可实现蓝光激发下的红光发光(622 nm)" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "10", "type": "bibr", "rid": "R10", "data": [ { "name": "text", "data": "10" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "过渡金属离子Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "具有3d" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "电子构型，其荧光来自于宇称禁戒的d→d跃迁。Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "离子d轨道在八面体配位晶体场中发生能级劈裂，形成e" }, { "name": "sub", "data": [ { "name": "text", "data": "g" } ] }, { "name": "text", "data": "轨道和" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777025&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777035&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777030&type=" } } } ] }, { "name": "text", "data": "轨道，后者可供Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "离子的3个d轨道电子占据。由于正电荷数多，Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "常受强晶体场作用，最低激发态为" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "E" }, { "name": "sub", "data": [ { "name": "text", "data": "g" } ] }, { "name": "text", "data": "(" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "G)能级，其在Tanabe-Sugano图中几乎是一条直线，因此" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "E" }, { "name": "sub", "data": [ { "name": "text", "data": "g" } ] }, { "name": "text", "data": "→" }, { "name": "sup", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "A" }, { "name": "sub", "data": [ { "name": "text", "data": "2g" } ] }, { "name": "text", "data": "跃迁受晶体场的影响较小。但Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "离子的发射跃迁(" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "E" }, { "name": "sub", "data": [ { "name": "text", "data": "g" } ] }, { "name": "text", "data": "→" }, { "name": "sup", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "A" }, { "name": "sub", "data": [ { "name": "text", "data": "2g" } ] }, { "name": "text", "data": "跃迁)受电子云膨胀效应影响很大，发光能量与Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "和配体离子(如F" }, { "name": "sup", "data": [ { "name": "text", "data": "-" } ] }, { "name": "text", "data": "或O" }, { "name": "sup", "data": [ { "name": "text", "data": "2-" } ] }, { "name": "text", "data": ")所成键的离子键/共价键性密切相关" }, { "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": "。" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "E" }, { "name": "sub", "data": [ { "name": "text", "data": "g" } ] }, { "name": "text", "data": "→" }, { "name": "sup", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "A" }, { "name": "sub", "data": [ { "name": "text", "data": "2g" } ] }, { "name": "text", "data": "跃迁为自旋禁戒跃迁，当Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "所处八面体格位存在畸变(如MnO" }, { "name": "sub", "data": [ { "name": "italic", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "F" }, { "name": "sub", "data": [ { "name": "text", "data": "6-" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "构型)而导致点群对称性低于O" }, { "name": "sub", "data": [ { "name": "text", "data": "h" } ] }, { "name": "text", "data": "时，电偶极跃迁选律可得到放宽而使Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "离子的荧光寿命缩短" }, { "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": "及得到强零声子线发光和发光峰的劈裂" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "12", "type": "bibr", "rid": "R12", "data": [ { "name": "text", "data": "12" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "综上，Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "/Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "/Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "离子的荧光性质很大程度上取决于其在基质晶格中所形成最近邻配位多面体的特征。了解其所占据格位是了解其所形成最近邻配位多面体特征的第一步，对于理解其构效关系、开发新型荧光粉具有重要意义。目前文献报道采用不同方法来研究激活剂离子的格位占据情况，本文总结了这些方法，将其归为三大类(即光谱学方法、结构分析法和计算光谱学方法)，并通过相关研究实例进行对比分析。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2" } ], "title": [ { "name": "text", "data": "激活剂离子格位占据研究方法" } ], "level": "1", "id": "s2" } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2.1" } ], "title": [ { "name": "text", "data": "光谱学方法" } ], "level": "2", "id": "s2a" } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2.1.1" } ], "title": [ { "name": "text", "data": "激发波长依赖的发光光谱和监测波长依赖的激发光谱" } ], "level": "3", "id": "s2a1" } }, { "name": "p", "data": [ { "name": "text", "data": "激活剂离子的荧光特性受配位环境影响，因此其在基质中占据具有不同晶体学特征的格位时将分别表现出相应的荧光特性；因此，对该荧光粉而言，改变激发波长将得到激发波长依赖的发射光谱，而改变监测波长将得到监测波长依赖的激发光谱。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "梁宏斌等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "研究了Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "5.982" } ] }, { "name": "text", "data": "Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "0.988" } ] }, { "name": "text", "data": "Eu" }, { "name": "sub", "data": [ { "name": "text", "data": "0.03" } ] }, { "name": "text", "data": "P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "17" } ] }, { "name": "text", "data": "荧光粉激发波长依赖的发射光谱。如" }, { "name": "xref", "data": { "text": "图1(a)", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1(a)" } ] } }, { "name": "text", "data": "所示，当用400 nm激发时，发射光谱中只含有一个半高宽较宽、非对称、主峰位于588 nm的发射带；而改用300 nm激发时，发射光谱中除上述宽发射带外，新出现了一个半高宽较窄、主峰位于389 nm的发射带(" }, { "name": "xref", "data": { "text": "图1(b)", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1(b)" } ] } }, { "name": "text", "data": ")。在晶体场理论指导下，作者将这两个发射带分别归属于Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "占据基质中Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "和Ba" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "格位时的发光。Shi等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "14", "type": "bibr", "rid": "R14", "data": [ { "name": "text", "data": "14" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "通过激发波长依赖的发射光谱和监测波长依赖的激发光谱方法证明Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "在SrAl" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "基质中占据两个晶体学格位。如" }, { "name": "xref", "data": { "text": "图1(c)", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1(c)" } ] } }, { "name": "text", "data": "所示，改变激发波长后得到了不同的发射光谱:在328 nm激发下，发射光谱中包含两个峰值波长分别为361 nm和384 nm的发光带，来自于Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "最低5d" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "能级到4f能级(" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "F" }, { "name": "sub", "data": [ { "name": "text", "data": "5/2" } ] }, { "name": "text", "data": "和" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777040&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777050&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777045&type=" } } } ] }, { "name": "text", "data": "光谱项)的跃迁(标记为Ce1)；而在312 nm激发下，发射光谱中包含一个涵盖320~440 nm、峰值波长分别为336~361 nm发光带，这与Ce1的发光带明显不同，因此推断其来自于占据另一Sr" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "格位的Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "(标记为Ce2)。如" }, { "name": "xref", "data": { "text": "图1(d)", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1(d)" } ] } }, { "name": "text", "data": "所示，当监测不同波长时得到了不同的激发光谱，进一步证明Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "同时占据SrAl" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "基质中两个Sr" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "格位，其所受晶体场效应明显不同且主要占据Ce1格位(因其发光强度更高)。" } ] }, { "name": "fig", "data": { "id": "F1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图1" } ], "title": [ { "name": "text", "data": "(a)~(b)Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "5.982" } ] }, { "name": "text", "data": "Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "0.988" } ] }, { "name": "text", "data": "Eu" }, { "name": "sub", "data": [ { "name": "text", "data": "0.03" } ] }, { "name": "text", "data": "P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "17" } ] }, { "name": "text", "data": "荧光粉在液氮温度(77 K)及不同激发波长下的发射光谱" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": ";Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "0.998" } ] }, { "name": "text", "data": "Ce" }, { "name": "sub", "data": [ { "name": "text", "data": "0.001" } ] }, { "name": "text", "data": "Na" }, { "name": "sub", "data": [ { "name": "text", "data": "0.001" } ] }, { "name": "text", "data": "-Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "荧光粉在液氦温度(15 K)及不同激发波长下的发射光谱(c)和紫外-可见光区不同监测波长下的激发光谱(d)" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "14", "type": "bibr", "rid": "R14", "data": [ { "name": "text", "data": "14" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "; 液氦温度(8 K)下Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "2.98" } ] }, { "name": "text", "data": "Ce" }, { "name": "sub", "data": [ { "name": "text", "data": "0.02" } ] }, { "name": "text", "data": "AlO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "F荧光粉的发射光谱(e)和多种监测波长下的激发光谱(g)以及Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "1.98" } ] }, { "name": "text", "data": "-Ce" }, { "name": "sub", "data": [ { "name": "text", "data": "0.02" } ] }, { "name": "text", "data": "GdAlO" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "的发射光谱(f)和多种监测波长下的激发光谱(h)(为方便对比，将监测其他发光波长处的激发光谱强度设置为监测最强发光峰所得激发光谱强度的一半)" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "15", "type": "bibr", "rid": "R15", "data": [ { "name": "text", "data": "15" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 1" } ], "title": [ { "name": "text", "data": "(a)-(b)Photoluminescence emission spectra of Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "5.982" } ] }, { "name": "text", "data": "Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "0.988" } ] }, { "name": "text", "data": "Eu" }, { "name": "sub", "data": [ { "name": "text", "data": "0.03" } ] }, { "name": "text", "data": "P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "17" } ] }, { "name": "text", "data": " phosphor with various excitation wavelengths at liquid nitrogen temperature(77 K)" }, { "name": "sup", "data": [ { "name": "text", "data": " [" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": ". Photoluminescence emission(c) and excitation(d) spectra of Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "0.998" } ] }, { "name": "text", "data": "Ce" }, { "name": "sub", "data": [ { "name": "text", "data": "0.001" } ] }, { "name": "text", "data": "-Na" }, { "name": "sub", "data": [ { "name": "text", "data": "0.001" } ] }, { "name": "text", "data": "Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": " in the UV-Vis region measured with various excitation wavelengths or various monitoring wavelengths at liquid-helium temperature(15 K)" }, { "name": "sup", "data": [ { "name": "text", "data": " [" }, { "name": "xref", "data": { "text": "14", "type": "bibr", "rid": "R14", "data": [ { "name": "text", "data": "14" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": ". Photoluminescence emission(e) and excitation(g) spectra of Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "2.98" } ] }, { "name": "text", "data": "Ce" }, { "name": "sub", "data": [ { "name": "text", "data": "0.02" } ] }, { "name": "text", "data": "AlO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "F with various monitoring wavelengths, and photoluminescence emission(f) and excitation(h) spectra of Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "1.98" } ] }, { "name": "text", "data": "Ce" }, { "name": "sub", "data": [ { "name": "text", "data": "0.02" } ] }, { "name": "text", "data": "GdAlO" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": " with various monitoring wavelengths phosphor at liquid nitrogen temperature(8 K)(For clarity, the peak intensity of the PLEs monitored at the other emission wavelengths were set to be half of the PLE monitored at the peaking emission)" }, { "name": "sup", "data": [ { "name": "text", "data": " [" }, { "name": "xref", "data": { "text": "15", "type": "bibr", "rid": "R15", "data": [ { "name": "text", "data": "15" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777055&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777065&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777060&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "值得注意的是，当激活剂离子只占据基质晶格中的一种晶体学格位时，也可能因为存在不同的电荷补偿机制而出现多种微观配位体，而表现出与上述占据多种格位时相似的荧光特征。笔者曾报道Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "1.98" } ] }, { "name": "text", "data": "Ce" }, { "name": "sub", "data": [ { "name": "text", "data": "0.02" } ] }, { "name": "text", "data": "GdAlO" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "和Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "2.98" } ] }, { "name": "text", "data": "Ce" }, { "name": "sub", "data": [ { "name": "text", "data": "0.02" } ] }, { "name": "text", "data": "AlO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "F两种同构荧光粉的荧光光谱，如" }, { "name": "xref", "data": { "text": "图1(e)~(h)", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1(e)~(h)" } ] } }, { "name": "text", "data": "所示" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "15", "type": "bibr", "rid": "R15", "data": [ { "name": "text", "data": "15" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。经验推算及理论计算都表明Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "离子在Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "GdAlO" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "和Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "AlO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "F中都只占据8" }, { "name": "italic", "data": [ { "name": "text", "data": "h" } ] }, { "name": "text", "data": "格位(即Gd" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "或Sr" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "所处格位)。在基质本身可产生激子的高能激发下(216 nm或192 nm)，所得发射光谱主峰分别位于580 nm(" }, { "name": "xref", "data": { "text": "图1(f)", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1(f)" } ] } }, { "name": "text", "data": ")和465 nm(" }, { "name": "xref", "data": { "text": "图1(e)", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1(e)" } ] } }, { "name": "text", "data": ")。从监测主发射峰及其他发射波长的系列激发光谱可见，激发光谱随监测波长的改变而改变，且监测主发射波长所得激发光谱是监测其他发射波长所得激发光谱的叠加(" }, { "name": "xref", "data": { "text": "图1(g)、(h)", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1(g)、(h)" } ] } }, { "name": "text", "data": ")。结合宁利新等" }, { "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": " 的密度泛函理论超晶格总形成能计算结果，将" }, { "name": "xref", "data": { "text": "图1(g)", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1(g)" } ] } }, { "name": "text", "data": "中Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "AlO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "F∶Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "荧光粉激发光谱中峰值" }, { "name": "italic", "data": [ { "name": "text", "data": "a" } ] }, { "name": "text", "data": "(2.830 eV)和" }, { "name": "italic", "data": [ { "name": "text", "data": "c" } ] }, { "name": "text", "data": "(4.049 eV)归属于C" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777070&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777082&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777076&type=" } } } ] }, { "name": "text", "data": "-2O'" }, { "name": "sub", "data": [ { "name": "text", "data": "F" } ] }, { "name": "text", "data": "微观配位体(电荷完全平衡)的4f→5d" }, { "name": "sub", "data": [ { "name": "text", "data": "1,2" } ] }, { "name": "text", "data": "跃迁，而" }, { "name": "italic", "data": [ { "name": "text", "data": "b" } ] }, { "name": "text", "data": "(3.017 eV)和" }, { "name": "italic", "data": [ { "name": "text", "data": "d" } ] }, { "name": "text", "data": "(4.290 eV)归属于C" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777087&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777099&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777093&type=" } } } ] }, { "name": "text", "data": "-O'" }, { "name": "sub", "data": [ { "name": "text", "data": "F" } ] }, { "name": "text", "data": "微观配位体(电荷不完全平衡)的4f→5d" }, { "name": "sub", "data": [ { "name": "text", "data": "1,2" } ] }, { "name": "text", "data": "跃迁；将" }, { "name": "xref", "data": { "text": "图1(h)", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1(h)" } ] } }, { "name": "text", "data": "中Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "GdAlO" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "∶Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "荧光粉激发光谱中峰值" }, { "name": "italic", "data": [ { "name": "text", "data": "a" } ] }, { "name": "text", "data": "(2.642 eV)和" }, { "name": "italic", "data": [ { "name": "text", "data": "c" } ] }, { "name": "text", "data": "(3.718 eV)归属于C" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777104&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777114&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777109&type=" } } } ] }, { "name": "text", "data": "-O-Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "rich" } ] }, { "name": "text", "data": "，而峰值" }, { "name": "italic", "data": [ { "name": "text", "data": "b" } ] }, { "name": "text", "data": "(2.865 eV)和" }, { "name": "italic", "data": [ { "name": "text", "data": "d" } ] }, { "name": "text", "data": "(3.879 eV)归属于C" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777119&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777129&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777124&type=" } } } ] }, { "name": "text", "data": "-O-Gd" }, { "name": "sub", "data": [ { "name": "text", "data": "rich" } ] }, { "name": "text", "data": "的4f→5d" }, { "name": "sub", "data": [ { "name": "text", "data": "1,2" } ] }, { "name": "text", "data": "跃迁。因此，当激活剂离子只占据一种晶体学格位但形成不同微观配位体时，也将出现上述类似于占据多个晶体学格位的荧光光谱特征。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "当基质晶格中含有多种晶体学格位时，激活剂离子是否都占据这些晶体学格位，也可通过激发波长依赖的发光光谱和监测波长依赖的激发光谱方法进行研究。Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "中含有两个不同的Ba" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "格位，分别与10个或9个O" }, { "name": "sup", "data": [ { "name": "text", "data": "2-" } ] }, { "name": "text", "data": "配位。为研究Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "在Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "中的格位占据情况，Lin等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "17", "type": "bibr", "rid": "R17", "data": [ { "name": "text", "data": "17" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "测试了Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "1.999" } ] }, { "name": "text", "data": "Ce" }, { "name": "sub", "data": [ { "name": "text", "data": "0.0005" } ] }, { "name": "text", "data": "Na" }, { "name": "sub", "data": [ { "name": "text", "data": "0.0005" } ] }, { "name": "text", "data": "SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "在不同激发波长下的发光光谱，监测不同发光的激发光谱，示于" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "。当掺杂Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "后，荧光粉在不同波长紫外光激发下都发出两个峰值分别为375 nm和405 nm的宽带光谱且两个峰值之间的能量差为1 940 cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "，这与Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "离子5d" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "能级到4f(" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "F" }, { "name": "sub", "data": [ { "name": "text", "data": "5/2" } ] }, { "name": "text", "data": "和" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "F" }, { "name": "sub", "data": [ { "name": "text", "data": "7/2" } ] }, { "name": "text", "data": "光谱项)跃迁发光特征一致，故推断Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "在Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "中只占据其中一个Ba" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "格位；监测发射光谱中360,376,405,430 nm发光所得系列真空紫外激发光谱可见，所得激发光谱的相对强度与所监测发光波长的强度具有一致性，且各个峰值波长位置一致，佐证了Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "离子在该基质中只占据了一种晶体学格位。" } ] }, { "name": "fig", "data": { "id": "F2", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图2" } ], "title": [ { "name": "text", "data": "Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "1.999" } ] }, { "name": "text", "data": "Ce" }, { "name": "sub", "data": [ { "name": "text", "data": "0.0005" } ] }, { "name": "text", "data": "Na" }, { "name": "sub", "data": [ { "name": "text", "data": "0.0005" } ] }, { "name": "text", "data": "SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "荧光粉的发射光谱(EM," }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "text", "data": "=4 K)与真空紫外激发光谱(EX," }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "text", "data": "=26.5 K)" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "17", "type": "bibr", "rid": "R17", "data": [ { "name": "text", "data": "17" } ] } }, { "name": "text", "data": "]" } ] } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 2" } ], "title": [ { "name": "text", "data": "Photoluminescence emission spectra(EM, " }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "text", "data": "=4 K) and the synchrotron radiation VUV-UV excitation spectra(EX, " }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "text", "data": "=26.5 K) of Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "1.999" } ] }, { "name": "text", "data": "Ce" }, { "name": "sub", "data": [ { "name": "text", "data": "0.0005" } ] }, { "name": "text", "data": "Na" }, { "name": "sub", "data": [ { "name": "text", "data": "0.0005" } ] }, { "name": "text", "data": "SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": " " }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "17", "type": "bibr", "rid": "R17", "data": [ { "name": "text", "data": "17" } ] } }, { "name": "text", "data": "]" } ] } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777133&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777142&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777138&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "此外，值得一提的是，还有一些激活剂离子，随基质格位点群对称性或晶体场强度效应不同而表现出相应具有独特特征的荧光光谱，因此根据该荧光光谱特征可推断其所占据格位的点群对称性(包括是否存在反演对称性)或配位体形状。如Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "离子的发射光谱来自于" }, { "name": "sup", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "D" }, { "name": "sub", "data": [ { "name": "text", "data": "0" } ] }, { "name": "text", "data": "能级到" }, { "name": "sup", "data": [ { "name": "text", "data": "7" } ] }, { "name": "text", "data": "F" }, { "name": "sub", "data": [ { "name": "italic", "data": [ { "name": "text", "data": "J" } ] } ] }, { "name": "text", "data": "(" }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "=0,1,2,3,4,5,6)能级的f→f跃迁，在其发射光谱中强度最高的谱线分别来自于" }, { "name": "sup", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "D" }, { "name": "sub", "data": [ { "name": "text", "data": "0" } ] }, { "name": "text", "data": "→" }, { "name": "sup", "data": [ { "name": "text", "data": "7" } ] }, { "name": "text", "data": "F" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "电偶极跃迁(613 nm处)和" }, { "name": "sup", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "D" }, { "name": "sub", "data": [ { "name": "text", "data": "0" } ] }, { "name": "text", "data": "→" }, { "name": "sup", "data": [ { "name": "text", "data": "7" } ] }, { "name": "text", "data": "F" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "磁偶极跃迁(596 nm处)，两者的相对强度与Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "离子所处格位是否具有反演对称性密切相关" }, { "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": "；此外，" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777147&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777152&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777149&type=" } } } ] }, { "name": "text", "data": "F" }, { "name": "sub", "data": [ { "name": "text", "data": "0" } ] }, { "name": "text", "data": "跃迁发射峰的数量与Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "离子在晶体中所占据的格位数一致，且" }, { "name": "sup", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "D" }, { "name": "sub", "data": [ { "name": "text", "data": "0" } ] }, { "name": "text", "data": "→" }, { "name": "sup", "data": [ { "name": "text", "data": "7" } ] }, { "name": "text", "data": "F" }, { "name": "sub", "data": [ { "name": "text", "data": "0" } ] }, { "name": "text", "data": "发射峰强度较高时说明Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "占据的格位非中心对称，而" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777156&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777166&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777162&type=" } } } ] }, { "name": "text", "data": "F" }, { "name": "sub", "data": [ { "name": "text", "data": "0" } ] }, { "name": "text", "data": "发射峰观测不到强度时说明Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "占据中心对称的晶体学格位。还有，Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子的发射光谱来自于从" }, { "name": "sup", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "到" }, { "name": "sup", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "A" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "能级的d→d跃迁，该跃迁受制于基质格位的晶体场强度" }, { "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": ":在四面体配位(弱晶体场)时，Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "通常为绿光发光；而在八面体配位(强晶体场)时，Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "通常为橙光与红光之间发光。因此，根据Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子的发光颜色可推断其占据四面体还是八面体格位。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "综上所述，通过激发波长依赖的发光光谱和监测波长依赖的激发光谱方法，可以方便地研究激活剂离子在基质中形成的发光中心的种类；此外，对于Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "和Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "等，还可判定其所占据格位的点群对称性或配位体形状。但当基质中存在多个晶体学格位时，不能明确确定具体占据哪些格位；且在一些情况下，激活剂离子虽只占据一种晶体学格位，但因多种电荷平衡机制而形成多种发光中心。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2.1.2" } ], "title": [ { "name": "text", "data": "波长依赖的荧光衰减曲线" } ], "level": "3", "id": "s2a2" } }, { "name": "p", "data": [ { "name": "text", "data": "激活剂离子受激后从基态跃迁到激发态，停止激发后又从激发态跃迁回基态；荧光粉表现出的荧光强度(统计信息)达到激发时最大强度的1/e时所需时间被称为荧光寿命，而荧光寿命由自发辐射跃迁几率和无辐射跃迁几率共同决定。占据不同格位时激活剂离子荧光特性不同，不仅体现在荧光光谱上，也表现在其荧光衰减曲线和荧光寿命上。因此，可通过测试波长依赖的荧光衰减曲线来分析激活剂离子的格位占据。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "如" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "所示，笔者曾报道Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "2.98" } ] }, { "name": "text", "data": "Ce" }, { "name": "sub", "data": [ { "name": "text", "data": "0.02" } ] }, { "name": "text", "data": "AlO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "F和Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "1.98" } ] }, { "name": "text", "data": "Ce" }, { "name": "sub", "data": [ { "name": "text", "data": "0.02" } ] }, { "name": "text", "data": "GdAlO" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "两种同构荧光粉监测不同发光波长的荧光衰减曲线" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "15", "type": "bibr", "rid": "R15", "data": [ { "name": "text", "data": "15" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。首先，这些荧光衰减曲线表现出依赖于监测波长的特点；其次，各荧光衰减曲线无法用单指数函数拟合而需要用双指数拟合。如" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "所示，采用公式(1)所示的双指数函数进行拟合:" }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "(1)" } ], "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777170&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777174&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777178&type=" } } } ], "id": "DF1" } }, { "name": "text", "data": "其中，" }, { "name": "italic", "data": [ { "name": "text", "data": "I" } ] }, { "name": "text", "data": "(" }, { "name": "italic", "data": [ { "name": "text", "data": "t" } ] }, { "name": "text", "data": ")是时间" }, { "name": "italic", "data": [ { "name": "text", "data": "t" } ] }, { "name": "text", "data": "时的荧光强度，" }, { "name": "italic", "data": [ { "name": "text", "data": "A" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "和" }, { "name": "italic", "data": [ { "name": "text", "data": "A" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "是常数，" }, { "name": "italic", "data": [ { "name": "text", "data": "τ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "和" }, { "name": "italic", "data": [ { "name": "text", "data": "τ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "是荧光衰减时间。" } ] }, { "name": "fig", "data": { "id": "F3", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图3" } ], "title": [ { "name": "text", "data": "Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "2.98" } ] }, { "name": "text", "data": "Ce" }, { "name": "sub", "data": [ { "name": "text", "data": "0.02" } ] }, { "name": "text", "data": "AlO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "F(a)和Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "1.98" } ] }, { "name": "text", "data": "Ce" }, { "name": "sub", "data": [ { "name": "text", "data": "0.02" } ] }, { "name": "text", "data": "GdAlO" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "(b)荧光粉在" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "=405 nm激发下监测不同发光波长所得室温荧光衰减曲线" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "15", "type": "bibr", "rid": "R15", "data": [ { "name": "text", "data": "15" } ] } }, { "name": "text", "data": "]" } ] } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 3" } ], "title": [ { "name": "text", "data": "Decay profiles(under " }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "=405 nm excitation) of Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "2.98" } ] }, { "name": "text", "data": "Ce" }, { "name": "sub", "data": [ { "name": "text", "data": "0.02" } ] }, { "name": "text", "data": "AlO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "F(a) and Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "1.98" } ] }, { "name": "text", "data": "Ce" }, { "name": "sub", "data": [ { "name": "text", "data": "0.02" } ] }, { "name": "text", "data": "GdAlO" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "(b) at room temperature monitored at selected emission wavelengths" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "15", "type": "bibr", "rid": "R15", "data": [ { "name": "text", "data": "15" } ] } }, { "name": "text", "data": "]" } ] } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777182&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777190&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777186&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "各曲线可用双指数函数很好地拟合，拟合所得" }, { "name": "italic", "data": [ { "name": "text", "data": "τ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "和" }, { "name": "italic", "data": [ { "name": "text", "data": "τ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "差别较大，分别对应于Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "在Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "AlO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "F和Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "GdAlO" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "基质中占据8" }, { "name": "italic", "data": [ { "name": "text", "data": "h" } ] }, { "name": "text", "data": "格位时由于电荷平衡机制不同而形成的两种微观配位多面体。再通过公式(2)计算监测各发光波长时的平均荧光寿命" }, { "name": "italic", "data": [ { "name": "text", "data": "τ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ave" } ] }, { "name": "text", "data": ":" }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "(2)" } ], "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777194&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777198&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777201&type=" } } } ], "id": "DF2" } }, { "name": "text", "data": "得到Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "2.98" } ] }, { "name": "text", "data": "Ce" }, { "name": "sub", "data": [ { "name": "text", "data": "0.02" } ] }, { "name": "text", "data": "AlO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "F荧光粉发射光谱中505,460,550 nm发光的" }, { "name": "italic", "data": [ { "name": "text", "data": "τ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ave" } ] }, { "name": "text", "data": "分别为38.1,32.5,47.0 ns，而Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "1.98" } ] }, { "name": "text", "data": "Ce" }, { "name": "sub", "data": [ { "name": "text", "data": "0.02" } ] }, { "name": "text", "data": "GdAlO" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "荧光粉发光光谱中570,525,640 nm发光的" }, { "name": "italic", "data": [ { "name": "text", "data": "τ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ave" } ] }, { "name": "text", "data": "分别为36.1,26.8,42.3 ns。可见，发射较高能量的Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "离子微观配位多面体的荧光寿命明显短于发射较低能量的Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "离子微观配位多面体的荧光寿命。可能原因是两者之间存在能量转移，或者发射高能量的微观配位多面体的室温热猝灭效应更显著。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2.1.3" } ], "title": [ { "name": "text", "data": "时间分辨荧光光谱" } ], "level": "3", "id": "s2a3" } }, { "name": "p", "data": [ { "name": "text", "data": "荧光粉的荧光强度与其中处于激发态的激活剂离子的数目成正比，荧光强度随时间的衰减速率可反映相应离子在激发态的停留时间。当处于激发态的离子发生无辐射跃迁回基态或发生离子间能量转移时，所测荧光强度的衰减速率将变化，这为研究荧光粉中激活剂离子的格位占据提供了一种手段。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "梁宏斌等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "报道采用时间分辨荧光光谱手段研究Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "BaP" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "17" } ] }, { "name": "text", "data": "∶Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "荧光粉中Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子所占据格位。如" }, { "name": "xref", "data": { "text": "图4(a)", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4(a)" } ] } }, { "name": "text", "data": "所示，406 nm激发下，在延迟时间" }, { "name": "italic", "data": [ { "name": "text", "data": "t" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "d" } ] }, { "name": "text", "data": "=100 ns时，荧光发射光谱呈不对称特征且半高宽相对窄。随着延迟时间" }, { "name": "italic", "data": [ { "name": "text", "data": "t" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "d" } ] }, { "name": "text", "data": "增加为500,1 500,4 020 ns，荧光光谱逐渐宽化(在长波长一侧更加显著)。时间分辨发射光谱的变化说明该发射光谱来自于占据不同阳离子格位而具有不同荧光寿命的Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子的荧光，即Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "同时占据Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "BaP" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "17" } ] }, { "name": "text", "data": "结构中的两种Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子格位。在其晶体结构中，Ca(2)—O的平均键长(0.242 0 nm)略短于Ca(1)—O的平均键长(0.251 0 nm)，且[Ca(2)O" }, { "name": "sub", "data": [ { "name": "text", "data": "7" } ] }, { "name": "text", "data": "]多面体的点群对称性(" }, { "name": "italic", "data": [ { "name": "text", "data": "C" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": ")低于[Ca(1)O" }, { "name": "sub", "data": [ { "name": "text", "data": "8" } ] }, { "name": "text", "data": "]多面体的点群对称性(" }, { "name": "italic", "data": [ { "name": "text", "data": "C" } ] }, { "name": "sub", "data": [ { "name": "italic", "data": [ { "name": "text", "data": "s" } ] } ] }, { "name": "text", "data": ")，因此将荧光光谱中高能侧发光归因于占据Ca(1)格位的Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "，而低能侧发光归因于占据Ca(2)格位的Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "。" } ] }, { "name": "fig", "data": { "id": "F4", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图4" } ], "title": [ { "name": "text", "data": "(a)77 K下Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "5.994" } ] }, { "name": "text", "data": "Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "0.996" } ] }, { "name": "text", "data": "Eu" }, { "name": "sub", "data": [ { "name": "text", "data": "0.01" } ] }, { "name": "text", "data": "P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "17" } ] }, { "name": "text", "data": "荧光粉在406 nm激发下的归一化时间分辨发射光谱；所选定延迟时间下发射光谱的高斯拟合:(b)" }, { "name": "italic", "data": [ { "name": "text", "data": "t" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "d" } ] }, { "name": "text", "data": "=100 ns,(c)" }, { "name": "italic", "data": [ { "name": "text", "data": "t" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "d" } ] }, { "name": "text", "data": "=4 020 ns" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 4" } ], "title": [ { "name": "text", "data": "(a)Normalized time-resolved emission spectra of Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "5.994" } ] }, { "name": "text", "data": "Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "0.996" } ] }, { "name": "text", "data": "Eu" }, { "name": "sub", "data": [ { "name": "text", "data": "0.01" } ] }, { "name": "text", "data": "P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "17" } ] }, { "name": "text", "data": " under 406 nm excitation at 77 K. Gaussian fitting results of selected curves: (b)" }, { "name": "italic", "data": [ { "name": "text", "data": "t" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "d" } ] }, { "name": "text", "data": "=100 ns, (c)" }, { "name": "italic", "data": [ { "name": "text", "data": "t" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "d" } ] }, { "name": "text", "data": "=4 020 ns" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777206&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777218&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777211&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "为进一步明确Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "占据Ca(1)和Ca(2)格位的发射峰位置(发射能量)，选取" }, { "name": "italic", "data": [ { "name": "text", "data": "t" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "d" } ] }, { "name": "text", "data": "=100 ns和" }, { "name": "italic", "data": [ { "name": "text", "data": "t" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "d" } ] }, { "name": "text", "data": "=4 020 ns两个时间分辨发射光谱进行高斯拟合分峰。如" }, { "name": "xref", "data": { "text": "图4(b)", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4(b)" } ] } }, { "name": "text", "data": "所示，两个光谱可分别经高斯拟合分为两个发光峰，峰值分别在2.37 eV和2.18 eV，彼此一致，分别归属于E" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777226&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777235&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777230&type=" } } } ] }, { "name": "text", "data": "和E" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777237&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777242&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777241&type=" } } } ] }, { "name": "text", "data": "。对于给定的跃迁，荧光衰减时间可认为与其发光波长的三次方成正比" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "20", "type": "bibr", "rid": "R20", "data": [ { "name": "text", "data": "20" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，因此随着延迟时间" }, { "name": "italic", "data": [ { "name": "text", "data": "t" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "d" } ] }, { "name": "text", "data": "从100 ns增加到4 020 ns,E" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777247&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777254&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777251&type=" } } } ] }, { "name": "text", "data": "发光的衰减更快而对整个发光光谱的贡献逐渐减小，解释了" }, { "name": "xref", "data": { "text": "图4(a)", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4(a)" } ] } }, { "name": "text", "data": "所示发光光谱逐渐向长波长低能侧宽化的现象。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "时间分辨荧光光谱也被用于证明多格位占据的激活剂离子间存在能量传递。Sohn等" }, { "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": "报道了Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Si" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "N" }, { "name": "sub", "data": [ { "name": "text", "data": "8" } ] }, { "name": "text", "data": "∶0.0005Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "和Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Si" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "N" }, { "name": "sub", "data": [ { "name": "text", "data": "8" } ] }, { "name": "text", "data": "∶0.02Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "荧光粉的时间分辨荧光光谱及其高斯分峰结果(原文在波长坐标下分峰，笔者建议在波数坐标下进行)，如" }, { "name": "xref", "data": { "text": "图5", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5" } ] } }, { "name": "text", "data": "所示。当掺杂浓度为0.05%时，两个高斯拟合所得发射峰之间的强度比不随延迟时间的变化而变化；而当掺杂浓度增大到2%时，这两个高斯拟合所得发射峰之间的强度比随延迟时间变化而显著不同，证明Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "在Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Si" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "N" }, { "name": "sub", "data": [ { "name": "text", "data": "8" } ] }, { "name": "text", "data": "中占据两个Sr" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子格位；此外，短波长发射峰的荧光衰减更快而长波长发射峰衰减较慢，可能原因是在高Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂浓度时，占据两个Sr" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "格位的Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子间存在明显的能量传递。" } ] }, { "name": "fig", "data": { "id": "F5", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图5" } ], "title": [ { "name": "text", "data": "Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Si" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "N" }, { "name": "sub", "data": [ { "name": "text", "data": "8" } ] }, { "name": "text", "data": "∶0.0005Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "(a)和Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Si" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "N" }, { "name": "sub", "data": [ { "name": "text", "data": "8" } ] }, { "name": "text", "data": "∶0.02Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "(b)荧光粉的时间分辨荧光光谱及其高斯分峰结果" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "21", "type": "bibr", "rid": "R21", "data": [ { "name": "text", "data": "21" } ] } }, { "name": "text", "data": "]" } ] } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 5" } ], "title": [ { "name": "text", "data": "Time-resolved emission spectra of Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Si" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "N" }, { "name": "sub", "data": [ { "name": "text", "data": "8" } ] }, { "name": "text", "data": "∶0.0005Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " (a) and Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Si" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "N" }, { "name": "sub", "data": [ { "name": "text", "data": "8" } ] }, { "name": "text", "data": "∶0.02Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " (b). Gaussian fittings are also shown" }, { "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": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777258&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777265&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777261&type=" } ] } } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2.1.4" } ], "title": [ { "name": "text", "data": "变温发射光谱与变温荧光衰减曲线" } ], "level": "3", "id": "s2a4" } }, { "name": "p", "data": [ { "name": "text", "data": "当激活剂离子占据不同格位且在不同格位表现出不同的热猝灭特征时，根据其荧光随温度升高发生热猝灭行为的不同，可判断激活剂离子所占据格位数。荧光热猝灭本质是无辐射跃迁几率的提高，可表现为荧光强度的减弱或荧光寿命的缩短，因此可分别测试变温发射光谱或变温荧光衰减曲线，以期表征激活剂离子在不同格位的热猝灭行为。" } ] }, { "name": "p", "data": [ { "name": "xref", "data": { "text": "图6(a)", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6(a)" } ] } }, { "name": "text", "data": "所示为Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "5.982" } ] }, { "name": "text", "data": "Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "0.988" } ] }, { "name": "text", "data": "Eu" }, { "name": "sub", "data": [ { "name": "text", "data": "0.03" } ] }, { "name": "text", "data": "P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "17" } ] }, { "name": "text", "data": "荧光粉归一化的变温发射光谱。在77~500 K温度范围内，随温度升高，长波长发光强度较快发生猝灭而短波长发光强度较慢发生猝灭，使得归一化发光光谱表现出主峰蓝移53 nm的特征。这是因为Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子占据其晶体结构中的Ca(1)和Ca(2)格位且表现出不同的热猝灭行为。进一步采用变温荧光衰减光谱表征Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "在上述两格位的不同热猝灭行为。" }, { "name": "xref", "data": { "text": "图6(b)、(c)", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6(b)、(c)" } ] } }, { "name": "text", "data": "为在406 nm激发下分别检测500 nm(对应于E" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777267&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777270&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777268&type=" } } } ] }, { "name": "text", "data": ")和640 nm(对应于E" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777272&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777276&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777274&type=" } } } ] }, { "name": "text", "data": ")发光在50~430 K温度范围内的变温荧光衰减曲线。随温度升高，热猝灭效应产生，荧光衰减曲线逐渐偏离指数衰减特征" }, { "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": "。将不同温度下的荧光寿命按照Mott公式进行拟合(分别示于" }, { "name": "xref", "data": { "text": "图6(b)、(c)", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6(b)、(c)" } ] } }, { "name": "text", "data": "插图中):" }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "(3)" } ], "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777278&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777281&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777283&type=" } } } ], "id": "DF3" } }, { "name": "text", "data": "其中，" }, { "name": "italic", "data": [ { "name": "text", "data": "τ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "0" } ] }, { "name": "text", "data": "为Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "在50 K时的荧光寿命，" }, { "name": "italic", "data": [ { "name": "text", "data": "A" } ] }, { "name": "text", "data": "为常数，" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "a" } ] }, { "name": "text", "data": "为热活化能，" }, { "name": "italic", "data": [ { "name": "text", "data": "k" } ] }, { "name": "text", "data": "为玻尔兹曼常数(8.6172×10" }, { "name": "sup", "data": [ { "name": "text", "data": "-5" } ] }, { "name": "text", "data": " eV·K" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": ")," }, { "name": "italic", "data": [ { "name": "text", "data": "T" } ] }, { "name": "text", "data": "为温度。可得相应热活化能分别为0.16 eV和0.11 eV，即Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "在两个Ca格位中表现出不同的热猝灭行为。因此，根据" }, { "name": "xref", "data": { "text": "图6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6" } ] } }, { "name": "text", "data": "所示变温发光光谱和变温荧光衰减曲线可断定Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "占据两个具有不同热猝灭特性的格位中。" } ] }, { "name": "fig", "data": { "id": "F6", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图6" } ], "title": [ { "name": "text", "data": "Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "5.982" } ] }, { "name": "text", "data": "Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "0.988" } ] }, { "name": "text", "data": "Eu" }, { "name": "sub", "data": [ { "name": "text", "data": "0.03" } ] }, { "name": "text", "data": "P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "17" } ] }, { "name": "text", "data": "在77~500 K温度范围内归一化的发射光谱(a)、该样品中Eu" }, { "name": "sub", "data": [ { "name": "text", "data": "Ca(1)" } ] }, { "name": "text", "data": "(b)和Eu" }, { "name": "sub", "data": [ { "name": "text", "data": "Ca(2)" } ] }, { "name": "text", "data": "(c)在50~430 K温度范围内的荧光衰减曲线(插图所示为Eu" }, { "name": "sub", "data": [ { "name": "text", "data": "Ca(1)" } ] }, { "name": "text", "data": "和Eu" }, { "name": "sub", "data": [ { "name": "text", "data": "Ca(2)" } ] }, { "name": "text", "data": "在不同温度下的荧光寿命及其拟合结果)" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 6" } ], "title": [ { "name": "text", "data": "Normalized photoluminescence emission spectra of Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "5.982" } ] }, { "name": "text", "data": "Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "0.988" } ] }, { "name": "text", "data": "Eu" }, { "name": "sub", "data": [ { "name": "text", "data": "0.03" } ] }, { "name": "text", "data": "P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "17" } ] }, { "name": "text", "data": " at 77-500 K(a),decay curves of Eu" }, { "name": "sub", "data": [ { "name": "text", "data": "Ca(1)" } ] }, { "name": "text", "data": "(b) and Eu" }, { "name": "sub", "data": [ { "name": "text", "data": "Ca(2)" } ] }, { "name": "text", "data": "(c) in this sample at 50-430 K. The insets of (b) and (c) show the lifetime of Eu" }, { "name": "sub", "data": [ { "name": "text", "data": "Ca(1)" } ] }, { "name": "text", "data": " and Eu" }, { "name": "sub", "data": [ { "name": "text", "data": "Ca(2)" } ] }, { "name": "text", "data": " as a function of temperature as well as their corresponding fitting results, respectively" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777284&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777289&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777287&type=" } ] } } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2.1.5" } ], "title": [ { "name": "text", "data": "掺杂浓度依赖的发射光谱" } ], "level": "3", "id": "s2a5" } }, { "name": "p", "data": [ { "name": "text", "data": "当激活剂离子在基质中占据多个格位且其在多格位中的占据倾向性不同或因在某一格位的发射光谱与其在另一格位的激发光谱重叠而可发生能量转移时，随掺杂浓度的逐渐提高，将观察到其在不同格位因浓度猝灭行为不同而表现出的光谱演变；此外，根据低掺杂浓度和高掺杂浓度时荧光光谱的不同，可确定激活剂离子的优先占据格位。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "Piao等" }, { "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": "报道了变Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "浓度系列Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "2-" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Eu" }, { "name": "sub", "data": [ { "name": "italic", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "-Si" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "N" }, { "name": "sub", "data": [ { "name": "text", "data": "8" } ] }, { "name": "text", "data": "氮化物荧光粉的荧光光谱。如" }, { "name": "xref", "data": { "text": "图7", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7" } ] } }, { "name": "text", "data": "所示，当" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=0.04时，为发射峰值在580 nm的橙光宽带光谱；继续增加Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂浓度，在640 nm处新出现了一个红光发射峰；当" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=0.15时，该红光发射峰强度与橙光发光峰强度接近；而当" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=0.20时，荧光光谱中只可观察到该红光发射峰。这两个发光峰分别来自于占据Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Si" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "N" }, { "name": "sub", "data": [ { "name": "text", "data": "8" } ] }, { "name": "text", "data": "结构中两个Ba" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "格位的Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子，且Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "优先占据产生较小晶体场劈裂效应的、具有更长成键键长的Ba" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "格位。随着掺杂浓度的增加，该Ba" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "格位上的Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子首先发生浓度猝灭，同时把能量传递给产生较大晶体场劈裂效应而发射红光的Ba" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "格位上的Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子。因此，通过该变掺杂浓度发射光谱可知，Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "占据基质晶格中两个不同的Ba" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子格位，且表现出明显的占据倾向性，即优先占据形成较大体积最近邻多面体的Ba" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子格位。" } ] }, { "name": "fig", "data": { "id": "F7", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图7" } ], "title": [ { "name": "text", "data": "不同Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "浓度掺杂Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "2-" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Eu" }, { "name": "sub", "data": [ { "name": "italic", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Si" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "N" }, { "name": "sub", "data": [ { "name": "text", "data": "8" } ] }, { "name": "text", "data": "的发射光谱" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "23", "type": "bibr", "rid": "R23", "data": [ { "name": "text", "data": "23" } ] } }, { "name": "text", "data": "]" } ] } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 7" } ], "title": [ { "name": "text", "data": "Photoluminescence emission spectra of Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "2-" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Eu" }, { "name": "sub", "data": [ { "name": "italic", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "-Si" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "N" }, { "name": "sub", "data": [ { "name": "text", "data": "8" } ] }, { "name": "text", "data": " with different Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " concentrations" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "23", "type": "bibr", "rid": "R23", "data": [ { "name": "text", "data": "23" } ] } }, { "name": "text", "data": "]" } ] } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777291&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777294&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777293&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "在Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "BaP" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "17" } ] }, { "name": "text", "data": "∶Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "荧光粉中也报道了随Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂浓度增加而变化的荧光光谱。在该基质中Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子可同时占据Ba" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "、Ca(1)" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "和Ca(2)" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "格位" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，且在这三种格位中占据的倾向性不同，经晶体结构精修，确定其不同Eu掺杂浓度样品的化学组分可写作C" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777296&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777300&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777299&type=" } } } ] }, { "name": "text", "data": "Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "1-2" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "E" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777304&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777309&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777305&type=" } } } ] }, { "name": "text", "data": "P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "17" } ] }, { "name": "text", "data": "。在" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": " = 0.001~0.022范围内制备一系列不同Eu掺杂浓度样品，其荧光光谱示于" }, { "name": "xref", "data": { "text": "图8", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8" } ] } }, { "name": "text", "data": "。可以看出，该系列荧光粉的荧光光谱中包含一个位于短波长区的较窄的发射带和一个位于长波长区的较宽的发射带；随着Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂浓度的增加，两个发射带的演变行为有显著差异。在" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=0.001时，高能发射带强度很高而低能发射带强度很低；随着Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂浓度逐渐增加，两个发射带强度都有所提高；之后，高能发射带强度降低，低能发射带强度增加并超越高能发射带强度(得益于占据低能发射带晶体学格位的Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "数量的增加和来自于高能发射带的能量转移)；最后，由于浓度猝灭效应，继续提高Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "浓度使得两个发射带的强度都有所降低。因此，当激活剂离子在不同掺杂格位表现不同的掺杂倾向性时，可从其掺杂浓度依赖的发射光谱中观察到显著不同的浓度猝灭现象。" } ] }, { "name": "fig", "data": { "id": "F8", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图8" } ], "title": [ { "name": "text", "data": "Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "6-3" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "1-2" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "E" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777313&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777320&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777317&type=" } } } ] }, { "name": "text", "data": "P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "17" } ] }, { "name": "text", "data": "的室温发射光谱(插图所示为其中4个掺杂浓度样品在300 nm激发下的实物照片和相应的CIE坐标图)" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } }, { "name": "text", "data": "]" } ] } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 8" } ], "title": [ { "name": "text", "data": "Photoluminescence emission spectra of Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "6-3" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "1-2" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "E" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777322&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777330&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777324&type=" } } } ] }, { "name": "text", "data": "P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "17" } ] }, { "name": "text", "data": " at room temperature. The inset shows the CIE chromaticity coordinates of four phosphors and corresponding luminescence images under 300 nm excitation" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777331&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777337&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777333&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "但当激活剂离子在多个格位中的掺杂倾向性一致或非常接近时，其在多个格位中的浓度猝灭现象将几乎一样而无法分辨。实际上，" }, { "name": "xref", "data": { "text": "图8", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8" } ] } }, { "name": "text", "data": "所示的低能侧较宽的发射带来自于同时占据Ca(1)和Ca(2)两个格位的Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。晶体结构精修结果表明，不同浓度掺杂时Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子在这两个Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "格位的占位率一致。因此，如" }, { "name": "xref", "data": { "text": "图9", "type": "fig", "rid": "F9", "data": [ { "name": "text", "data": "图9" } ] } }, { "name": "text", "data": "所示，该低能发射带随着Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂浓度的增加虽然表现出有规律的浓度猝灭效应，但从其归一化光谱可见，半高宽和峰值波长都没有发生变化，表现出与Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "占据单一格位时相同的演变行为。因此，当激活剂离子占据多个格位但其占位倾向性一致时，难以通过浓度猝灭效应来判断其是单一格位占据还是多格位占据。" } ] }, { "name": "fig", "data": { "id": "F9", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图9" } ], "title": [ { "name": "text", "data": "Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "6-3" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "1-2" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Eu" }, { "name": "sub", "data": [ { "name": "text", "data": "5" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "17" } ] }, { "name": "text", "data": "的室温发射光谱(a)和归一化发射光谱(b)" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } }, { "name": "text", "data": "]" } ] } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 9" } ], "title": [ { "name": "text", "data": "Photoluminescence emission spectra of Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "6-3" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "1-2" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "E" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777341&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777349&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777346&type=" } } } ] }, { "name": "text", "data": "P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "17" } ] }, { "name": "text", "data": "(a) at room temperature and the corresponding normalized emission spectra(b)" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } }, { "name": "text", "data": "]" } ] } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777354&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777363&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777358&type=" } ] } } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2.2" } ], "title": [ { "name": "text", "data": "结构分析法" } ], "level": "2", "id": "s2b" } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2.2.1" } ], "title": [ { "name": "text", "data": "晶体结构精修" } ], "level": "3", "id": "s2b1" } }, { "name": "p", "data": [ { "name": "text", "data": "很多荧光粉都是一种离子掺杂型固溶体；激活剂离子掺杂入基质晶格后，由于其具有与被取代离子不同的离子半径和相对原子质量，且对入射X射线的衍射能力也不同，因此将造成掺杂后荧光粉的X射线衍射谱(XRD)与未掺杂基质物相的XRD有所不同。多数情况下，实验所合成荧光粉为多晶粉体，利用粉晶结构精修方法如Rietveld方法，可将激活剂离子分别放入不同的可能晶体学掺杂格位，通过比较其理论所得XRD与实测XRD之间的异同而确定激活剂离子在不同格位的掺杂占据情况。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "相对于绝大多数基质中所含离子而言，稀土激活剂离子Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "和Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "具有更大的相对原子质量，为通过Rietveld等晶体结构精修过程分析Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "/Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "在荧光粉中的格位占据及占位率提供了有利条件；但受浓度猝灭效应制约，荧光粉中激活剂离子的掺杂浓度一般不高，使得通过晶体结构精修方法精确分析激活剂离子的格位占据和占位率具有一定困难。因此，在文献中该方法也常与前文所述光谱学方法联用，用于分析激活剂离子的掺杂格位。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2019年，夏志国等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "10", "type": "bibr", "rid": "R10", "data": [ { "name": "text", "data": "10" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "报道了Rb" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "YSi" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "7" } ] }, { "name": "text", "data": "∶Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "荧光粉中对Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子进行选择性格位占据以获得蓝光激发下的宽带红光发射(" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "=450 nm," }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "em,max" } ] }, { "name": "text", "data": "=622 nm)。在Rb" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "YSi" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "7" } ] }, { "name": "text", "data": "晶体结构(空间群" }, { "name": "italic", "data": [ { "name": "text", "data": "P" } ] }, { "name": "text", "data": "6" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "/" }, { "name": "italic", "data": [ { "name": "text", "data": "mmc" } ] }, { "name": "text", "data": ")中存在形成[Rb1O" }, { "name": "sub", "data": [ { "name": "text", "data": "9" } ] }, { "name": "text", "data": "]、[Rb2O" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "]和[YO" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "]三种配位多面体的阳离子格位可供Eu离子占据。利用TOPAS软件尝试通过结构精修确定Eu离子的占据格位。精修初始模型中设置Eu可同时占据上述三种阳离子格位，但精修结果表明只有Y" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "格位有Eu离子占据，而其他阳离子格位Eu的占位率为零，见" }, { "name": "xref", "data": { "text": "表1", "type": "table", "rid": "T1", "data": [ { "name": "text", "data": "表1" } ] } }, { "name": "text", "data": "。但作者指出上述精修结果不能排除少量Eu离子占据Rb" }, { "name": "sup", "data": [ { "name": "text", "data": "+" } ] }, { "name": "text", "data": "格位的可能性:如" }, { "name": "xref", "data": { "text": "表1", "type": "table", "rid": "T1", "data": [ { "name": "text", "data": "表1" } ] } }, { "name": "text", "data": "所示，Eu离子占位率精修结果的标准偏差为0.000 8(0.08%)，因此Rietveld精修不能给出Eu占位率低于0.24%(3倍标准偏差，即0.24%)的占位率精修结果" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "24", "type": "bibr", "rid": "R24", "data": [ { "name": "text", "data": "24" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。荧光光谱结果表明该荧光粉表现出基于Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子4f→5d跃迁的宽带激发与发射特征。如" }, { "name": "xref", "data": { "text": "表2", "type": "table", "rid": "T2", "data": [ { "name": "text", "data": "表2" } ] } }, { "name": "text", "data": "所示，根据不同阳离子在不同配位数时的有效离子半径对比推测，占据Y" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "离子格位的Eu离子应为Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "，而占据Rb" }, { "name": "sup", "data": [ { "name": "text", "data": "+" } ] }, { "name": "text", "data": "离子(如果有)的Eu离子应为Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "。Eu-" }, { "name": "italic", "data": [ { "name": "text", "data": "L" } ] }, { "name": "text", "data": "3边X射线吸收近边结构谱结果表明，该样品中所含Eu离子价态同时表现为3+(占主要)和2+(占次要)。进一步采用密度泛函理论计算方法探究Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的占据格位，表明Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "倾向于多数占据Rb(2)" }, { "name": "sup", "data": [ { "name": "text", "data": "+" } ] }, { "name": "text", "data": "格位，少量占据Y" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "格位。" } ] }, { "name": "table", "data": { "id": "T1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "表1" } ], "title": [ { "name": "text", "data": "Rb" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "YSi" }, 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"name": "sub", "data": [ { "name": "text", "data": "3.97" } ] }, { "name": "text", "data": "Eu" }, { "name": "sub", "data": [ { "name": "text", "data": "0.03" } ] }, { "name": "text", "data": "](Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "0.955" } ] }, { "name": "text", "data": "Eu" }, { "name": "sub", "data": [ { "name": "text", "data": "0.045" } ] }, { "name": "text", "data": ")P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "17" } ] } ] } ] ], "foot": [] } ] } }, { "name": "p", "data": [ { "name": "text", "data": "上述结果对比表明，Rietveld结构精修在表征较低掺杂浓度掺杂离子的占据格位及占位率方面具有一定的局限性，在表征一系列从低掺杂浓度到高掺杂浓度样品中激活剂离子占据格位与占位率方面具有可参考性。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2.2.2" } ], "title": [ { "name": "text", "data": "扩展X射线吸收谱技术" } ], "level": "3", "id": "s2b2" } }, { "name": "p", "data": [ { "name": "text", "data": "扩展X射线吸收谱技术是另一种可用以分析激活剂离子配位结构的手段。物质对X射线的吸收系数与入射X射线的能量有关，在一种原子吸收边(吸收系数突变处，内层电子被激发到外层而引起)高能侧几百电子伏范围内，吸收系数呈振荡变化。离吸收边30~50 eV直到近1 000 eV范围内的振荡被称为扩展X射线吸收精细结构(EXAFS)，其形状与近邻原子结构状态即近邻配位原子种类、原子间距、配位数、无序度因子等有关，因而通过分析EXAFS谱可获得原子近邻结构信息" }, { "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": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "Pawik等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "26", "type": "bibr", "rid": "R26", "data": [ { "name": "text", "data": "26" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "报道采用X射线吸收近边结构谱来证明不同压力条件下所合成SrSi" }, { "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": "∶Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "荧光粉中Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "已完全还原为+2价，并采用EXAFS谱研究Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "在基质中的格位占据，发现Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "优先占据Sr2格位(占60%左右)，剩余Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "占据Sr4格位。Akai等" }, { "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": "报道采用EXAFS谱研究Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "在Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "Sc" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Si" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "12" } ] }, { "name": "text", "data": "中的格位占据，在Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "Sc" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Si" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "12" } ] }, { "name": "text", "data": "中存在八配位的Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "和六配位的Sc" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "两种格位可供Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "占据。但如" }, { "name": "xref", "data": { "text": "图11", "type": "fig", "rid": "F11", "data": [ { "name": "text", "data": "图11" } ] } }, { "name": "text", "data": "所示，在" }, { "name": "italic", "data": [ { "name": "text", "data": "k" } ] }, { "name": "text", "data": "=26~107 nm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "范围进行傅里叶转换后可见，Ce—O的峰值位置与Ca—O的一致，而与Sc—O的差异明显，因此推断Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "占据Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "格位。此外，Zhu等" }, { "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": "通过EXAFS谱证明了在Mg" }, { "name": "sub", "data": [ { "name": "text", "data": "14" } ] }, { "name": "text", "data": "Ge" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "24" } ] }, { "name": "text", "data": "∶Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "荧光粉中引入F" }, { "name": "sup", "data": [ { "name": "text", "data": "-" } ] }, { "name": "text", "data": "和Ti" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "离子后增强了其对蓝光的吸收效率的原因在于Mn—F键的形成。因此，EXAFS手段不仅可以确定激活剂离子的格位占据情况，还能判断其占位率；其对激活剂离子格位占据和占位率的判断(尤其是低浓度掺杂时)的精确度要远高于前述晶体结构精修手段。" } ] }, { "name": "fig", "data": { "id": "F11", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图11" } ], "title": [ { "name": "text", "data": "Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "Sc" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Si" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "12" } ] }, { "name": "text", "data": "∶Ce中Sc、Ca和Ce的K边EXAFS谱的傅里叶转换" }, { "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": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 11" } ], "title": [ { "name": "text", "data": "Fourier Transform of Sc, Ca, Ce K-edge EXAFS spectra of Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "Sc" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Si" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "12" } ] }, { "name": "text", "data": "∶Ce" }, { "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": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777400&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777409&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777405&type=" } ] } } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2.3" } ], "title": [ { "name": "text", "data": "计算光谱学方法" } ], "level": "2", "id": "s2c" } }, { "name": "p", "data": [ { "name": "text", "data": "采用理论计算如从头计算等第一原理计算方法分析Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "/Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "激活荧光粉中掺杂格位时，将从头计算所得到激活剂离子在不同格位占据时的4f→5d跃迁能量与荧光粉在低温下实测所得激发光谱进行对比，可确定Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "/Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "在荧光粉中的占据格位；另外，不同占据构型计算所得的形成能也用于辅助判断格位占据。相比于Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "掺杂复杂体系，Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂复杂体系的从头计算更加困难，因为Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子激发态4f" }, { "name": "sup", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "5d" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "所涉及的能级数量远大于Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "离子激发态4f" }, { "name": "sup", "data": [ { "name": "text", "data": "0" } ] }, { "name": "text", "data": "5d" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "所涉及的能级数量" }, { "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": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "SrAl" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "∶Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "是一种可发射宽带绿光长余辉的荧光粉，且其在共掺Dy" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "离子后表现出超长余辉，目前是商业化的重要长余辉荧光粉材料。在过去数十年中，关于其荧光性质的研究很多，但有关其绿光发光的来源及长余辉机制众说纷纭。SrAl" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "在低于923 K时为单斜晶系结构，空间群为" }, { "name": "italic", "data": [ { "name": "text", "data": "P" } ] }, { "name": "text", "data": "2" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "，含有两个不同的Sr" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子格位。掺杂Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "后，在室温中发射主峰波长为520 nm的绿光；而在低温下，还发射主峰为445 nm的蓝光。宁利新等" }, { "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": "以SrAl" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "∶Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "绿光长余辉荧光粉为研究对象，首次在Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂复杂体系中进行从头计算，通过基于波函数的CASSCF/CASPT2计算4f" }, { "name": "sup", "data": [ { "name": "text", "data": "7" } ] }, { "name": "text", "data": "和4f" }, { "name": "sup", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "5d" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "电子组态中与4f→5d跃迁相关的自旋多重态能级。如" }, { "name": "xref", "data": { "text": "图12", "type": "fig", "rid": "F12", "data": [ { "name": "text", "data": "图12" } ] } }, { "name": "text", "data": "所示，在4f" }, { "name": "sup", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "5d" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "电子组态时，E" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777414&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777423&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777418&type=" } } } ] }, { "name": "text", "data": "的计算得到的最低能级高于E" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777427&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777436&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777433&type=" } } } ] }, { "name": "text", "data": "的最低能级；从实测激发光谱看，监测445 nm蓝光发光的激发光谱的起始端在监测520 nm绿光发光的激发光谱起始端的高能量一侧(如" }, { "name": "xref", "data": { "text": "图12(a)", "type": "fig", "rid": "F12", "data": [ { "name": "text", "data": "图12(a)" } ] } }, { "name": "text", "data": "所示)。实测激发光谱的第一个峰值的15%~20%处可认为是4f" }, { "name": "sup", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "5d" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "电子组态的最低能级，将其与计算结果进行对比可见，尽管由实测光谱得到的最低激发态能级与计算得到的最低激发态能级间差值达660~1 000 cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "，但对比可明显看出该荧光粉的蓝光和绿光发光分别来自于E" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777442&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777452&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777447&type=" } } } ] }, { "name": "text", "data": "和E" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777457&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777467&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777462&type=" } } } ] }, { "name": "text", "data": "。此外，从振子强度方面来看，实测光谱中监测蓝光发光所得激发光谱在33 000 cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "有一段下凹(如" }, { "name": "xref", "data": { "text": "图12(a)", "type": "fig", "rid": "F12", "data": [ { "name": "text", "data": "图12(a)" } ] } }, { "name": "text", "data": "所示)，而监测绿光发光所得激发光谱没有；该特征在计算所得振子强度的结果中也存在(如" }, { "name": "xref", "data": { "text": "图12(b)", "type": "fig", "rid": "F12", "data": [ { "name": "text", "data": "图12(b)" } ] } }, { "name": "text", "data": "所示33 000 cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "处)。因此，可将无下凹特征的、监测绿光发光的激发光谱归因于占据Sr2格位的Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子。其他基于密度泛函理论计算(优先)格位占据的经典实例还有关于B" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777472&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777482&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777477&type=" } } } ] }, { "name": "text", "data": "Sr" }, { "name": "sub", "data": [ { "name": "italic", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "∶Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "固溶体荧光粉中在中间组分" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=1时获得更高热猝灭性的解释:在" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=1前后，Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的占据格位不同而晶体场劈裂不同，导致其5d" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "能级与基质导带间的能隙" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "dC" } ] }, { "name": "text", "data": "在" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=1时达到最大，此时有效抑制了Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子5d电子的热激发离子化而使" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=1组分荧光粉表现出优于其他组分的热猝灭性能" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "31", "type": "bibr", "rid": "R31", "data": [ { "name": "text", "data": "31" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "fig", "data": { "id": "F12", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图12" } ], "title": [ { "name": "text", "data": "SrAl" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "中Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "占据Sr1和Sr2格位时其4f→5d跃迁(从4f" }, { "name": "sup", "data": [ { "name": "text", "data": "7" } ] }, { "name": "text", "data": "(" }, { "name": "sup", "data": [ { "name": "text", "data": "8" } ] }, { "name": "text", "data": "S" }, { "name": "sub", "data": [ { "name": "text", "data": "7/2" } ] }, { "name": "text", "data": ")基态到4f" }, { "name": "sup", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "5d" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "电子组态的自旋八重态能级)的计算能量位置和相对振子强度示意图，同时给出归一化实测激发光谱用于对比" }, { "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": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 12" } ], "title": [ { "name": "text", "data": "Schematic diagram for the calculated energies and relative oscillator strengths of the 4f→5d transitions from the 4f" }, { "name": "sup", "data": [ { "name": "text", "data": "7" } ] }, { "name": "text", "data": "(" }, { "name": "sup", "data": [ { "name": "text", "data": "8" } ] }, { "name": "text", "data": "S" }, { "name": "sub", "data": [ { "name": "text", "data": "7/2" } ] }, { "name": "text", "data": ") ground level to the spin-octet levels in the 4f" }, { "name": "sup", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "5d" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": " configuration of E" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777486&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777494&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777490&type=" } } } ] }, { "name": "text", "data": " and E" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777497&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777502&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777501&type=" } } } ] }, { "name": "text", "data": " in SrAl" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": ". The experimental normalized excitation spectra are also included for comparison" }, { "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": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777506&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777510&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777509&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "此外，当激活剂离子在基质晶格中进行不等价取代时将会因电荷平衡方式不同而出现多种微观配位多面体，也可通过理论计算方法将不同微观配位多面体与实测光谱进行归属对应。在Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "AlO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "F∶Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "荧光粉中，一方面，Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "可能同时占据两个不同的Sr" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "格位或只占据其中一个；另一方面，Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "取代Sr" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "时的电荷平衡机制可能是Na'" }, { "name": "sub", "data": [ { "name": "text", "data": "Sr" } ] }, { "name": "text", "data": "，也可能是O'" }, { "name": "sub", "data": [ { "name": "text", "data": "F" } ] }, { "name": "text", "data": "。因此，Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "AlO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "F∶Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "的光谱归属相对困难。宁利新等" }, { "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": "用密度泛函理论首先计算了几种可能微观配位情况(C" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777511&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777513&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777512&type=" } } } ] }, { "name": "text", "data": "-Na'" }, { "name": "sub", "data": [ { "name": "text", "data": "Sr1" } ] }, { "name": "text", "data": "、C" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777514&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777516&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777515&type=" } } } ] }, { "name": "text", "data": "-Na'" }, { "name": "sub", "data": [ { "name": "text", "data": "Sr2" } ] }, { "name": "text", "data": "、C" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777517&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777519&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777518&type=" } } } ] }, { "name": "text", "data": "-Na'" }, { "name": "sub", "data": [ { "name": "text", "data": "Sr1" } ] }, { "name": "text", "data": "、C" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777520&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777523&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777521&type=" } } } ] }, { "name": "text", "data": "-Na'" }, { "name": "sub", "data": [ { "name": "text", "data": "Sr2" } ] }, { "name": "text", "data": "、C" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777527&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777532&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777529&type=" } } } ] }, { "name": "text", "data": "-O'" }, { "name": "sub", "data": [ { "name": "text", "data": "F" } ] }, { "name": "text", "data": "、C" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777534&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777536&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777535&type=" } } } ] }, { "name": "text", "data": "-O'" }, { "name": "sub", "data": [ { "name": "text", "data": "F" } ] }, { "name": "text", "data": "、C" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777537&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777542&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777539&type=" } } } ] }, { "name": "text", "data": "-2O'" }, { "name": "sub", "data": [ { "name": "text", "data": "F" } ] }, { "name": "text", "data": "、C" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777545&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777551&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777548&type=" } } } ] }, { "name": "text", "data": "-2O'" }, { "name": "sub", "data": [ { "name": "text", "data": "F" } ] }, { "name": "text", "data": "、)的总形成能，其中C" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777558&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777563&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777560&type=" } } } ] }, { "name": "text", "data": "-" }, { "name": "italic", "data": [ { "name": "text", "data": "i" } ] }, { "name": "text", "data": "O'" }, { "name": "sub", "data": [ { "name": "text", "data": "F" } ] }, { "name": "text", "data": "(" }, { "name": "italic", "data": [ { "name": "text", "data": "i" } ] }, { "name": "text", "data": " =1,2)的总形成能较低而更易形成；接着采用基于波函数的CASSCF/CASPT2计算不同微观配位情况下Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "离子的4f" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "和5d" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "能级。从" }, { "name": "xref", "data": { "text": "图13", "type": "fig", "rid": "F13", "data": [ { "name": "text", "data": "图13" } ] } }, { "name": "text", "data": "所示计算能级位置与实测激发光谱对比可知，激发光谱中的A峰(~440 nm)和B峰(~404 nm)分别可归属于C" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777569&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777573&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777572&type=" } } } ] }, { "name": "text", "data": "-2O'" }, { "name": "sub", "data": [ { "name": "text", "data": "F" } ] }, { "name": "text", "data": "和C" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777577&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777583&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777579&type=" } } } ] }, { "name": "text", "data": "-O'" }, { "name": "sub", "data": [ { "name": "text", "data": "F" } ] }, { "name": "text", "data": "的4f" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "→5d" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "跃迁，且A峰相比于B峰强度较低，说明更易形成C" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777590&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777597&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777595&type=" } } } ] }, { "name": "text", "data": "-O'" }, { "name": "sub", "data": [ { "name": "text", "data": "F" } ] }, { "name": "text", "data": "这种电荷平衡配位体。因此，光谱学方法仅能证明荧光粉中存在单一或多种微观配位多面体，结合计算光谱学方法可进一步对微观配位多面体加以明确。" } ] }, { "name": "fig", "data": { "id": "F13", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图13" } ], "title": [ { "name": "text", "data": "Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "AlO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "F中C" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777605&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777612&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777606&type=" } } } ] }, { "name": "text", "data": "-O'" }, { "name": "sub", "data": [ { "name": "text", "data": "F" } ] }, { "name": "text", "data": "、和C" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777616&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777626&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777620&type=" } } } ] }, { "name": "text", "data": "-2O'" }, { "name": "sub", "data": [ { "name": "text", "data": "F" } ] }, { "name": "text", "data": "(" }, { "name": "italic", "data": [ { "name": "text", "data": "i" } ] }, { "name": "text", "data": "=1,2)配位中心的4f" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "→5d" }, { "name": "sub", "data": [ { "name": "italic", "data": [ { "name": "text", "data": "i" } ] } ] }, { "name": "text", "data": "(" }, { "name": "italic", "data": [ { "name": "text", "data": "i" } ] }, { "name": "text", "data": " =1~5)能级跃迁的计算能量位置和相对振子强度示意图，同时给出实测激发光谱用于对比" }, { "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": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 13" } ], "title": [ { "name": "text", "data": "Schematic diagram for the calculated energies and relative oscillator strengths of 4f" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "→5d" }, { "name": "sub", "data": [ { "name": "italic", "data": [ { "name": "text", "data": "i" } ] } ] }, { "name": "text", "data": "(" }, { "name": "italic", "data": [ { "name": "text", "data": "i" } ] }, { "name": "text", "data": "=1-5) transitions(in order of increasing energy) of C" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777630&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777643&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777637&type=" } } } ] }, { "name": "text", "data": "-O'" }, { "name": "sub", "data": [ { "name": "text", "data": "F" } ] }, { "name": "text", "data": " and C" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777646&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777658&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777650&type=" } } } ] }, { "name": "text", "data": "-2O'" }, { "name": "sub", "data": [ { "name": "text", "data": "F" } ] }, { "name": "text", "data": "(" }, { "name": "italic", "data": [ { "name": "text", "data": "i" } ] }, { "name": "text", "data": "=1, 2) centers in Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "AlO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "F. The experimental excitation spectrum is also included for comparison" }, { "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": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777663&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777671&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777667&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "而关于以Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "为代表的过渡金属离子能级的计算，Tartu大学Brik教授等发表的诸多相关论著中利用电荷交换模型(Exchange charge model)计算包含点群对称性等信息的晶体场参数" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "graphicsData": { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777672&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777681&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777677&type=" } } } ] }, { "name": "text", "data": "并用于进行哈密尔顿算符的对角化和能级位置计算" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "32", "type": "bibr", "rid": "R32", "data": [ { "name": "text", "data": "32" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "离子d→d跃迁受电子云膨胀效应影响显著，在不同基质(尤其是氧化物基质)或同一基质的不同格位中发射能量差异显著；通过计算Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "在不同格位中的各能级位置，并与实测激发光谱对比，可推断Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "离子在基质晶格中的占据格位。Brik等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "33", "type": "bibr", "rid": "R33", "data": [ { "name": "text", "data": "33" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "报道采取电荷交换模型确定Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "在Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Al" }, { "name": "sub", "data": [ { "name": "text", "data": "14" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "25" } ] }, { "name": "text", "data": "晶体结构中的(优先)占据格位。在Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Al" }, { "name": "sub", "data": [ { "name": "text", "data": "14" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "25" } ] }, { "name": "text", "data": "晶体结构中Al1、Al2和Al3格位形成[AlO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "]四面体配位，而Al4、Al5和Al6格位形成[AlO" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "]八面体配位，因此，Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "离子理论上可以占据Al4、Al5和Al6格位。如" }, { "name": "xref", "data": { "text": "图14(a)", "type": "fig", "rid": "F14", "data": [ { "name": "text", "data": "图14(a)" } ] } }, { "name": "text", "data": "所示，理论计算所得Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "的能级位置(用竖线给出)与实验测得的Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Al" }, { "name": "sub", "data": [ { "name": "text", "data": "14" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "25" } ] }, { "name": "text", "data": "∶0.1%Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "荧光粉的激发与发射光谱吻合较好。Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "离子" }, { "name": "sup", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "A" }, { "name": "sub", "data": [ { "name": "text", "data": "2g" } ] }, { "name": "text", "data": "→" }, { "name": "sup", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "T" }, { "name": "sub", "data": [ { "name": "text", "data": "1g" } ] }, { "name": "text", "data": "跃迁为自旋允许跃迁，荧光强度显著高于" }, { "name": "sup", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "A" }, { "name": "sub", "data": [ { "name": "text", "data": "2g" } ] }, { "name": "text", "data": "→" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "T" }, { "name": "sub", "data": [ { "name": "text", "data": "1g" } ] }, { "name": "text", "data": "等自旋禁戒跃迁。计算结果表明Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "占据Al4、Al5和Al6格位时，最低能量的" }, { "name": "sup", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "A" }, { "name": "sub", "data": [ { "name": "text", "data": "2g" } ] }, { "name": "text", "data": "→" }, { "name": "sup", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "T" }, { "name": "sub", "data": [ { "name": "text", "data": "1g" } ] }, { "name": "text", "data": "跃迁分别位于332,326,444 nm；而实测激发光谱中320~330 nm波长范围强度最高。故推断Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "优先占据共价键性更高的Al4和Al5格位，而较少占据Al6格位(示于" }, { "name": "xref", "data": { "text": "图14(b)", "type": "fig", "rid": "F14", "data": [ { "name": "text", "data": "图14(b)" } ] } }, { "name": "text", "data": ")。因此，通过计算所得激活剂离子的能级位置，与实测荧光光谱对比，可推断激活剂离子的(优先)占据格位。" } ] }, { "name": "fig", "data": { "id": "F14", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图14" } ], "title": [ { "name": "text", "data": "(a)Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Al" }, { "name": "sub", "data": [ { "name": "text", "data": "14" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "25" } ] }, { "name": "text", "data": "∶0.1%Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "荧光粉的激发(黑线)与发射(红线)光谱，其中理论计算所得Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "的能级位置用竖线给出(长竖线，自旋四重态；短竖线，自旋二重态);(b)在Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Al" }, { "name": "sub", "data": [ { "name": "text", "data": "14" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "25" } ] }, { "name": "text", "data": "晶体结构中Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "倾向于占据Al4和Al5格位而不倾向于占据Al6格位示意图" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "33", "type": "bibr", "rid": "R33", "data": [ { "name": "text", "data": "33" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 14" } ], "title": [ { "name": "text", "data": "(a)Photoluminescence excitation(black line) and emission(red line) spectra of Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Al" }, { "name": "sub", "data": [ { "name": "text", "data": "14" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "25" } ] }, { "name": "text", "data": "∶0.1%Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": ". The calculated energy levels of Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": " are shown by the vertical lines(long lines, spin-quartet states. short lines, spin-doublet states). (b)Schematic of the site occupancy preference of Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": " ions to Al4 and Al5 sites over Al6 sites in AlO" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": " layer of Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Al" }, { "name": "sub", "data": [ { "name": "text", "data": "14" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "25" } ] }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "33", "type": "bibr", "rid": "R33", "data": [ { "name": "text", "data": "33" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777686&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777691&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23777687&type=" } ] } } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "3" } ], "title": [ { "name": "text", "data": "总结与展望" } ], "level": "1", "id": "s3" } }, { "name": "p", "data": [ { "name": "text", "data": "白光LED用荧光粉中激活剂离子如Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "、Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "和Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "在基质中时常出现多格位占据现象，如何表征其多格位占据问题对于分析相应荧光粉的发光特性具有重要意义。本文综述了8种研究占据格位的方法，列于" }, { "name": "xref", "data": { "text": "表4", "type": "table", "rid": "T4", "data": [ { "name": "text", "data": "表4" } ] } }, { "name": "text", "data": "。这8种方法可归为三类:光谱学方法、结构分析法和计算光谱学方法。其中，光谱学方法包括以下5种谱图的测试分析:激发波长依赖的发光光谱与监测波长依赖的激发光谱、波长依赖的荧光衰减曲线、时间分辨发射光谱、变温发射光谱与变温荧光衰减曲线以及掺杂浓度依赖的发射光谱。" } ] }, { "name": "table", "data": { "id": "T4", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "表4" } ], "title": [ { "name": "text", "data": "各种激活剂离子格位占据(和/或占位率)分析方法的特点及优劣势比较" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Tab. 4" } ], "title": [ { "name": "text", "data": "Pros/cons of the various methods for analyzing the site-occupation and/or occupancy of the activator" } ] } ], "note": [], "table": [ { "head": [ [ { "colspan": "1", "rowspan": "1", "align": "center", "style": "border-top:1px solid #000;border-bottom:1px solid #000;", "data": [ { "name": "text", "data": "分类" } ] }, { "colspan": "1", "rowspan": "1", "align": "center", "style": "border-top:1px solid #000;border-bottom:1px solid #000;", "data": [ { "name": "text", "data": "方法" } ] }, { "colspan": "1", "rowspan": "1", "align": "center", "style": "border-top:1px solid #000;border-bottom:1px solid #000;", "data": [ { "name": "text", "data": "特点与优劣势比较" } ] } ] ], "body": [ [ { "colspan": "1", "rowspan": "5", "align": "center", "data": [ { "name": "text", "data": "光谱学方法(1~5)" } ] }, { "colspan": "1", "rowspan": "1", "align": "left", "data": [ { "name": "text", "data": "(1)激发波长依赖的发射光谱与监测波长依赖的激发光谱" } ] }, { "colspan": "1", "rowspan": "1", "align": "left", "data": [ { "name": "text", "data": "可证明激活剂离子在基质中形成一种还是多种微观配位多面体；根据晶体场理论可定性推测激活剂离子所占据格位。虽然可证明荧光粉中存在一种或多种微观配位多面体，但无法区分其来自于激活剂离子占据不同格位还是占据同一格位但形成了多种微观配位多面体。" } ] } ], [ { "colspan": "1", "rowspan": "1", "align": "left", "data": [ { "name": "text", "data": "(2)波长依赖的荧光衰减曲线" } ] }, { "colspan": "1", "rowspan": "1", "align": "left", "data": [ { "name": "text", "data": "当激活剂离子占据多种不同晶体学格位时，荧光衰减曲线表现出依赖于监测荧光波长的特点。但与方法1一样，无法区分其来自于激活剂离子占据不同晶体学格位还是占据一种格位但形成了多种微观配位多面体。" } ] } ], [ { "colspan": "1", "rowspan": "1", "align": "left", "data": [ { "name": "text", "data": "(3)时间分辨发射光谱" } ] }, { "colspan": "1", "rowspan": "1", "align": "left", "data": [ { "name": "text", "data": "当激活剂离子占据多种不同晶体学格位时，随延迟时间增加，时间分辨发射光谱将宽化或峰值波长发生移动。不仅能证明激活剂离子在基质中所占据掺杂格位数，还能区分其发射能量并证明占据多个格位的激活剂离子间存在能量传递。但激活剂离子同时占据多个阳离子格位时，发射能量非常接近时能否区分，有待商榷。" } ] } ], [ { "colspan": "1", "rowspan": "1", "align": "left", "data": [ { "name": "text", "data": "(4)变温发射光谱与变温荧光衰减曲线" } ] }, { "colspan": "1", "rowspan": "1", "align": "left", "data": [ { "name": "text", "data": "根据激活剂离子在所占据的多个格位中所表现热猝灭行为的不同，可判断其所占据格位数，但无法判断具体占据格位。此外，当激活剂离子在所占据多个格位中表现出同样热猝灭行为时，则无法判断其多格位占据情况。" } ] } ], [ { "colspan": "1", "rowspan": "1", "align": "left", "data": [ { "name": "text", "data": "(5)掺杂浓度依赖的发射光谱" } ] }, { "colspan": "1", "rowspan": "1", "align": "left", "data": [ { "name": "text", "data": "可确定激活剂离子的优先占据格位；可根据其发生浓度猝灭现象的不同定性判断占据多个格位。但当激活剂离子在多个格位中占据的倾向性一致时，其在多个格位中占据的浓度猝灭现象同时发生，将难以区分其占据格位数。" } ] } ], [ { "colspan": "1", "rowspan": "2", "align": "left", "data": [ { "name": "text", "data": "结构分析法 (6~7)" } ] }, { "colspan": "1", "rowspan": "1", "align": "left", "data": [ { "name": "text", "data": "(6)Rietveld等方法进行晶体结构精修" } ] }, { "colspan": "1", "rowspan": "1", "align": "left", "data": [ { "name": "text", "data": "可确定激活剂离子所占据格位数及其在各个格位中的占位率。在表征一系列从低掺杂浓度到高掺杂浓度样品中激活剂离子占据格位与占位率方面具有可参考性，可半定量获得激活剂离子在某一格位的占位率。但掺杂格位和占位率结果的准确性依赖于精修过程。此时可有意提高激活剂的掺杂浓度而不考虑浓度猝灭，只为使通过结构精修方法获得激活剂格位占据的结果更加可靠，然后再推测激活剂低浓度掺杂的情况(不过要留意激活剂在低浓度与高浓度掺杂时格位占据与占位率是否一致)。" } ] } ], [ { "colspan": "1", "rowspan": "1", "align": "left", "data": [ { "name": "text", "data": "(7)EXAFS技术" } ] }, { "colspan": "1", "rowspan": "1", "align": "left", "data": [ { "name": "text", "data": "可研究晶体物质，也可研究非晶态、准晶态和液态物质中激活剂离子的配位结构。利用强X射线源可对样品中含量很少(如百万分之一含量)的原子进行分析。可同时分析激活剂离子的格位占据及占位率且准确性(尤其是较低浓度掺杂时)要远高于晶体结构精修手段。因为同步辐射X射线具有强度高、能量范围宽、分辨率好，并具有偏振性等优点，绝大部分EXAFS测试在同步辐射光源上进行；但同步辐射光源测试机时较难获得，对EXAFS谱的分析也需要经验。" } ] } ], [ { "colspan": "1", "rowspan": "1", "align": "center", "style": "border-bottom:1px solid #000;", "data": [ { "name": "text", "data": "计算光谱学方法(8)" } ] }, { "colspan": "1", "rowspan": "1", "align": "left", "style": "border-bottom:1px solid #000;", "data": [ { "name": "text", "data": "(8)密度泛函理论与电荷交换模型等方法进行理论计算" } ] }, { "colspan": "1", "rowspan": "1", "align": "left", "style": "border-bottom:1px solid #000;", "data": [ { "name": "text", "data": "采用密度泛函理论与电荷交换模型等计算激活剂离子占据不同格位时的能级位置或跃迁能量，与实测荧光光谱的谱型和强度对比，推断激活剂离子所占据格位数与优先占据格位。但根据所选取基质晶胞参数、计算模型与参数等的不同，计算所得能级位置的绝对误差可高达上千波数，因此在计算模型的选取和优化方面需要经验。" } ] } ] ], "foot": [] } ] } }, { "name": "p", "data": [ { "name": "text", "data": "首先，上述方法在区分激活剂离子所占格位数方面各有优劣势。比如对不同延迟时间时测得的时间分辨发射光谱进行高斯分峰拟合，可区分激活剂离子在不同格位的发射能量并证明占据不同格位的激活剂离子间存在能量传递；而从掺杂浓度依赖的发射光谱中可以推断激活剂离子的优先占据格位，但需要制备一系列不同掺杂浓度的样品且激活剂离子在多个格位中的占据倾向性一致时，无法根据浓度猝灭现象区分占据单一格位还是多个格位。此外，当激活剂离子与基质被取代格位离子属于不等价取代时，尤其要区分激活剂离子是占据了不同晶体学格位还是占据同一格位但形成了多种微观配位多面体。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "其次，值得强调的是，合成纯相样品是分析荧光粉中激活剂离子格位占据的前提。在荧光粉合成过程中，有时即使采取了多种方法对制备过程进行优化却依然难以去除杂相(如硼酸盐体系中非常容易产生稀土硼酸盐" }, { "name": "italic", "data": [ { "name": "text", "data": "Ln" } ] }, { "name": "text", "data": "BO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "杂相且难以去除" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "34", "type": "bibr", "rid": "R34", "data": [ { "name": "text", "data": "34" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "；其他类似情况还有硅酸盐体系中易产生" }, { "name": "italic", "data": [ { "name": "text", "data": "Ln" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Si" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "7" } ] }, { "name": "text", "data": "∶Ce和/或" }, { "name": "italic", "data": [ { "name": "text", "data": "Ln" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "∶Ce杂相，碱土硅酸盐体系中易产生(Ba,Sr,Ca)" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "∶Eu/Ce，以及磷酸盐体系中易产生稀土磷酸盐" }, { "name": "italic", "data": [ { "name": "text", "data": "Ln" } ] }, { "name": "text", "data": "PO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "∶Ce等)。尽管杂相的含量很少，但其发光却可能很强，若未加认真辨识分析，将会对激活剂离子在主相中的格位占据判断产生非常大的误导。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "第三，激活剂离子掺杂进入基质后出现或选择性地仅占据某一格位、或占据多个格位但占据优先性显著不同、或几乎均匀地占据多个格位的这种现象的驱动力，很可能来自掺杂离子与基质中被取代格位的(平均)离子半径间的差异。梁宏斌等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "34", "type": "bibr", "rid": "R34", "data": [ { "name": "text", "data": "34" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "报道，在未掺杂Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "La" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "(BO" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": ")" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "基质中，Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "和La" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "是有序分布的，但当掺杂Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "后，Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "的离子半径介于Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "和La" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "之间，其同时占据Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "和La" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "两个阳离子格位但优先占据La" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "格位，因为其与La" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "离子的离子半径更加接近；此外，Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "占据Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "格位时还造成一定程度的反占位缺陷(即少量Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "占据La" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "/Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "格位)，用于电荷平衡补偿。而在其关于Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "1.995-" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Sr" }, { "name": "sub", "data": [ { "name": "italic", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "∶0.005Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "中Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "格位占据分析的论文中报道" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "31", "type": "bibr", "rid": "R31", "data": [ { "name": "text", "data": "31" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，在" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "≤1时，Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "仅占据(平均)离子半径较小的AE2格位；当1" }, { "name": "text", "data": "<" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "<" }, { "name": "text", "data": "2时，Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "除占据AE2格位外也占据(平均)离子半径更大的AE1格位。因此，由于Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子半径小于Ba" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "，其在Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "中掺杂时首先占据较小格位，而Sr" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "(离子半径稍大于Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "但小于Ba" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": ")在Ba" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "中逐渐固溶将改变AE1和AE2格位的平均离子半径，进而改变Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的格位占据。此外，宁利新等" }, { "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": "采用从头计算方法研究了Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "在SrAl" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "基质中两个Sr" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子格位的占据情况，发现尽管[Sr1O" }, { "name": "sub", "data": [ { "name": "text", "data": "9" } ] }, { "name": "text", "data": "]和[Sr2O" }, { "name": "sub", "data": [ { "name": "text", "data": "9" } ] }, { "name": "text", "data": "]多面体的形状和多面体畸变程度不一，但将一个Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子放置在Sr1或Sr2格位并经优化超晶格后所得密度泛函理论总形成能仅相差0.5 meV，几乎可忽略。因此认为，相比于Sr" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "格位所形成的微观配位多面体，在九配位时Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "(0.130 nm)与Sr" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "(0.131 nm)非常接近才是促使Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "均匀占据两个Sr" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "格位的主要原因。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "最后，在实际研究中，采用多种方法联用对准确分析激活剂离子的(优先)占据格位具有很大优势。比如，将计算光谱学方法与实验光谱学方法结合，可以推断出对应于实测激发光谱的具体微观配位多面体。再如，将结构分析方法与多种光谱学方法联用，不仅可以确定激活剂离子所占格位数，还能确定其优先占据格位及半定量占位率。此外，如" }, { "name": "xref", "data": { "text": "表4", "type": "table", "rid": "T4", "data": [ { "name": "text", "data": "表4" } ] } }, { "name": "text", "data": "中所述，EXAFS手段在表征激活剂离子格位占据及占位率方面有独特优势，相信随着我国同步辐射光源的建设，将会催生更多相关研究。" } ] }, { "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:http://cjl.lightpublishing.cn/thesisDetails#10.37188/CJL.20210309." } ] } ] } ], "footnote": [], "reflist": { "title": [ { "name": "text", "data": "参考文献:" } ], "data": [ { "id": "R1", "label": "[1]", "citation": [ { "lang": "en", "text": [ { "name": "text", "data": "DORENBOS P" }, { "name": "text", "data": ". 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