Cd²⁺-Doped Cs₂ZnCl₄ Yellow-Emitting Phosphor and Its Optical Properties Enhanced Publication

{ "defaultlang": "zh", "titlegroup": { "articletitle": [ { "lang": "zh", "data": [ { "name": "text", "data": "Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "黄光荧光粉及其光学性能" } ] }, { "lang": "en", "data": [ { "name": "text", "data": "Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "-Doped Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": " Yellow-Emitting Phosphor and Its Optical Properties" } ] } ] }, "contribgroup": { "author": [ { "name": [ { "lang": "zh", "surname": "张", "givenname": "伟", "namestyle": "eastern", "prefix": "" }, { "lang": "en", 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E-mail： " }, { "name": "text", "data": "xchen@fjirsm.ac.cn" } ] ] } ], "email": "xchen@fjirsm.ac.cn", "deceased": false } ], "aff": [ { "id": "aff1", "intro": [ { "lang": "zh", "label": "1", "text": "中国科学院福建物质结构研究所 中国科学院功能纳米结构设计与组装重点实验室 福建省纳米材料重点实验室， 福建 福州 350108", "data": [ { "name": "text", "data": "中国科学院福建物质结构研究所 中国科学院功能纳米结构设计与组装重点实验室 福建省纳米材料重点实验室， 福建 福州 350108" } ] }, { "lang": "en", "label": "1", "text": "CAS Key Laboratory of Design and Assembly of Functional Nanostructures and Fujian Key Laboratory of Nanomaterials， Fujian Institute of Research on the Structure of Matter， Chinese Academy of Sciences， Fuzhou， Fujian 350108， China", "data": [ { "name": "text", "data": "CAS Key Laboratory of Design and Assembly of Functional Nanostructures and Fujian Key Laboratory of Nanomaterials， Fujian Institute of Research on the Structure of Matter， Chinese Academy of Sciences， Fuzhou， Fujian 350108， China" } ] } ] }, { "id": "aff2", "intro": [ { "lang": "zh", "label": "2", "text": "福州大学 材料科学与工程学院 先进材料技术重点实验室， 福建 福州 350108", "data": [ { "name": "text", "data": "福州大学 材料科学与工程学院 先进材料技术重点实验室， 福建 福州 350108" } ] }, { "lang": "en", "label": "2", "text": "Key Laboratory of Advanced Materials Technologies， College of Materials Science and Engineering， Fuzhou University， Fuzhou， Fujian 350108， China", "data": [ { "name": "text", "data": "Key Laboratory of Advanced Materials Technologies， College of Materials Science and Engineering， Fuzhou University， Fuzhou， Fujian 350108， China" } ] } ] }, { "id": "aff3", "intro": [ { "lang": "zh", "label": "3", "text": "中国福建光电信息科学与技术创新实验室（闽都创新实验室）， 福建 福州 350108", "data": [ { "name": "text", "data": "中国福建光电信息科学与技术创新实验室（闽都创新实验室）， 福建 福州 350108" } ] }, { "lang": "en", "label": "3", "text": "Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China， Fuzhou， Fujian 350108， China", "data": [ { "name": "text", "data": "Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China， Fuzhou， Fujian 350108， China" } ] } ] } ] }, "abstracts": [ { "lang": "zh", "data": [ { "name": "p", "data": [ { "name": "text", "data": "全无机零维金属卤化物因其独特的光学性能和可溶液法加工的特点，有望成为替代铅卤钙钛矿的新一代发光材料在固态照明和光电探测等领域发挥重要作用。本文报道了一种Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂的Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "新型黄光荧光粉。该材料在270 nm紫外光激发下，呈现565 nm的宽带、长寿命（11.4 ms）发光，荧光量子产率达到46.0%。通过变温高分辨光谱测试分析，证明了其发光来源于Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "E → " }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "A" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "禁戒跃迁，并且在低温下（" }, { "name": "text", "data": "<" }, { "name": "text", "data": "170 K）还观测到局域态激子的发光及其到Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的高效能量传递过程。此外，该材料还展现出优异的抗热猝灭性能，150 °C温度下的发光强度依然保持室温时的90.0%。本工作为Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂金属卤化物的激发态动力学提供了新发现，也为新型高效零维金属卤化物发光材料的设计开发提供了新思路。" } ] } ] }, { "lang": "en", "data": [ { "name": "p", "data": [ { "name": "text", "data": "All-inorganic zero-dimensional （0D） metal halides， owing to their intriguing optical properties and easy solution processibility， are emerging as a new generation of luminescent materials and as an alternative to lead halide perovskites for various applications such as solid-state lighting and photodetectors. Herein， a new yellow phosphor is developed based on Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "-doped Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "， which exhibits intense broadband and long-lived （11.4 ms） photoluminescence （PL） at 565 nm upon 270 nm excitation， with a PL quantum yield up to 46.0%. Temperature-dependent PL spectroscopic analyses reveal that the broadband PL originates from the forbidden " }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "E → " }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "A" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": " transition of Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": ". Specifically， localized exciton emission is observed at low temperatures below 170 K， in parallel with efficient energy transfer from the localized excitons to Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": ". Besides， the phosphor displays an excellent anti-thermal quenching property， remaining 90% PL intensity at 150 °C in comparison with that at room temperature. These findings provide not only new insights into the excited-state dynamics of Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " in metal halides， but also a new avenue for the exploration of novel and efficient luminescent materials based on 0D metal halides." } ] } ] } ], "keyword": [ { "lang": "zh", "data": [ [ { "name": "text", "data": "金属卤化物" } ], [ { "name": "text", "data": "Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] } ], [ { "name": "text", "data": "镉掺杂" } ], [ { "name": "text", "data": "光致发光" } ], [ { "name": "text", "data": "激发态动力学" } ] ] }, { "lang": "en", "data": [ [ { "name": "text", "data": "metal halide" } ], [ { "name": "text", "data": "Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] } ], [ { "name": "text", "data": "cadmium doping" } ], [ { "name": "text", "data": "photoluminescence" } ], [ { "name": "text", "data": "excited-state dynamics" } ] ] } ], "highlights": [], "body": [ { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "1　引 言" } ], "level": "1", "id": "s1" } }, { "name": "p", "data": [ { "name": "text", "data": "全无机零维金属卤化物因其优异的光学性能和可溶液法加工的特点，在光电和光伏领域受到了广泛关注" }, { "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": "5", "type": "bibr", "rid": "R5", "data": [ { "name": "text", "data": "5" } ] } } ], "rid": [ "R1", "R2", "R3", "R4", "R5" ], "text": "1-5", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。与CsPbX" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": " (X = Cl, Br, I)钙钛矿等三维金属卤化物相比，零维金属卤化物的结构基元彼此孤立、B位阳离子之间的电子相互作用相对较弱，因此表现出与CsPbX" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "截然不同的物化性能如更好的结构稳定性、更大的激子结合能和更强的电–声子相互作用" }, { "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": "。由于这种零维结构限域效应，该类材料在X射线、紫外或可见光激发下，可以产生独特的自限激子发光，因此有望成为替代CsPbX" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "钙钛矿的新一代发光材料，在LED照明显示、光电探测、X射线闪烁体等领域发挥重要作用" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "10", "type": "bibr", "rid": "R10", "data": [ { "name": "text", "data": "10" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "15", "type": "bibr", "rid": "R15", "data": [ { "name": "text", "data": "15" } ] } } ], "rid": [ "R10", "R11", "R12", "R13", "R14", "R15" ], "text": "10-15", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。然而，零维金属卤化物通常存在着缺陷容忍度低、间接带隙或直接带隙禁戒跃迁的局限性，导致其本征的自限激子发光效率低" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "16", "type": "bibr", "rid": "R16", "data": [ { "name": "text", "data": "16" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "19", "type": "bibr", "rid": "R19", "data": [ { "name": "text", "data": "19" } ] } } ], "rid": [ "R16", "R17", "R18", "R19" ], "text": "16-19", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。如何实现零维金属卤化物在不同波段的高效、稳定发光，是该类材料能否获得实际应用的关键，也是目前该领域的一个研究热点。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "离子掺杂是调控金属卤化物光、电、磁性能的一种非常有效的手段" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "20", "type": "bibr", "rid": "R20", "data": [ { "name": "text", "data": "20" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "24", "type": "bibr", "rid": "R24", "data": [ { "name": "text", "data": "24" } ] } } ], "rid": [ "R20", "R21", "R22", "R23", "R24" ], "text": "20-24", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。近年来，人们通过在不同的金属卤化物中掺杂过渡金属离子(如Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "、Cu" }, { "name": "sup", "data": [ { "name": "text", "data": "+" } ] }, { "name": "text", "data": "、Cr" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "等)、稀土离子(如Tb" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "、Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "、Yb" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "、Er" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "等)或主族元素ns" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "电子组态离子(如Bi" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "、Sb" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "、Te" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "、Sn" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "等)，开发出了一系列从紫外/可见到近红外不同波段高效发光的新型发光材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "25", "type": "bibr", "rid": "R25", "data": [ { "name": "text", "data": "25" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "38", "type": "bibr", "rid": "R38", "data": [ { "name": "text", "data": "38" } ] } } ], "rid": [ "R25", "R26", "R27", "R28", "R29", "R30", "R31", "R32", "R33", "R34", "R35", "R36", "R37", "R38" ], "text": "25-38", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。例如，通过在零维Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "或Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnBr" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "中掺杂Cu" }, { "name": "sup", "data": [ { "name": "text", "data": "+" } ] }, { "name": "text", "data": "、Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "、Te" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "、Sn" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "和Sb" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "，可分别实现这些离子的蓝光、绿光、黄光、红光和近红外发射" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "39", "type": "bibr", "rid": "R39", "data": [ { "name": "text", "data": "39" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "47", "type": "bibr", "rid": "R47", "data": [ { "name": "text", "data": "47" } ] } } ], "rid": [ "R39", "R40", "R41", "R42", "R43", "R44", "R45", "R46", "R47" ], "text": "39-47", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。但是，由于Te" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "与Zn" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的离子半径和价态差异大，导致基于Te" }, { "name": "sup", "data": [ { "name": "text", "data": "4+" } ] }, { "name": "text", "data": "掺杂的Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnX" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "黄光材料稳定性差、发光效率低。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "本文报道了一种Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂的Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "黄光材料。该材料在270 nm紫外光激发下，呈现565 nm的宽带、长寿命发光，荧光量子产率达到了46.0%。通过X射线粉末衍射、扫描电镜、荧光光谱和荧光寿命等测试手段对不同浓度Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂的Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "样品的晶体结构和光学性能进" } ] }, { "name": "p", "data": [ { "name": "text", "data": "行了详细分析。利用变温高分辨光谱对Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": ": Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的发光机理和激发态动力学进行了深入研究。最后，证明了该材料具有良好的结构和发光稳定性，有望作为一类新型、高效的黄光荧光粉应用于固态照明。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2　实验部分" } ], "level": "1", "id": "s2" } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.1　化学试剂" } ], "level": "2", "id": "s2a" } }, { "name": "p", "data": [ { "name": "text", "data": "氯化铯CsCl (99.999%)、氯化锌ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": " (99.99%)和氯化镉CdCl" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": " (99.99%)购自阿拉丁试剂有限公司(中国上海)。盐酸(分析纯)和无水乙醇(分析纯)购自国药集团化学试剂公司(中国上海)。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.2　Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： " }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "样品制备" } ], "level": "2", "id": "s2b" } }, { "name": "p", "data": [ { "name": "text", "data": "实验中采用溶剂热法制备了不同浓度Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂的Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "样品，Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的掺杂浓度通过改变前驱体Cd/Zn投料量来调控。以合成Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": ": 20%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " (投料浓度)为例，按化学计量比称取2 mmol CsCl、0.8 mmol ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "和0.2 mmol CdCl" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "至25 mL聚四氟乙烯高压反应釜中，然后加入5 mL盐酸，随后将其置于电热鼓风箱内180 °C反应12 h，待反应结束冷却至室温，3000 转/分钟离心收集沉淀样品，并用无水乙醇洗涤三次，最后60 °C鼓风干燥12 h得到粉末样品。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.3　结构形貌表征和光学性能测试" } ], "level": "2", "id": "s2c" } }, { "name": "p", "data": [ { "name": "text", "data": "采用X射线粉末衍射仪(XRD, Rigaku, Miniflex600, Cu K" }, { "name": "sub", "data": [ { "name": "text", "data": "α" } ] }, { "name": "text", "data": ", " }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "text", "data": " = 0.154187 nm)分析物相。使用扫描电子显微镜(SEM, JEOL, JSM-7600F)对样品进行显微形貌和元素分析。Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的实际掺杂浓度由等离子发射光谱仪(ICP–AES, Ultima2, Jobin Yvon)测试确定。X射线光电子能谱(XPS)由型号为ESCALAB 250Xi (Thermo Fisher)的XPS仪器测试。热重曲线采用型号为STA449-F5的同步热分析仪在N" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "气氛下测试，升温速率为10 °C/分钟。漫反射光谱由Lambda 950 (Perkin-Elmer) 紫外-可见-近红外分光光度计测得。粉末发光照片用华为Nova 5手机拍照。荧光激发、发射光谱和荧光寿命通过FLS980 (Edinburgh)荧光光谱仪测试，450 W连续和微秒脉冲氙灯作为激发光源。对比测试激发和发射光谱时，需将样品充分研磨，并称量等量的样品进行测试；测试过程中，利用带卡槽的石英片保证样品厚度一致，且光斑被样品完全覆盖，确保所有样品的测试条件严格一致。样品的绝对荧光量子产率(PLQYs)采用涂覆硫酸钡的标准积分球(直径为150 mm, Edinburgh)在FLS980上测试。测试变温光谱时，将样品放置在冷热台上(77–873 K, THMS 600, Linkam Scientific Instruments)控温。除另有说明，所有光谱数据均采用粉末样品在室温下采集，并对光谱仪和积分球做光谱校正。" } ] } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3　结果与讨论" } ], "level": "1", "id": "s3" } }, { "name": "p", "data": [ { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "a为Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "的晶体结构示意图，它属于t正交晶系，空间群为Pnma，由彼此孤立的[ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "]" }, { "name": "sup", "data": [ { "name": "text", "data": "2–" } ] }, { "name": "text", "data": "四面体结构单元和处于间隙位置的Cs" }, { "name": "sup", "data": [ { "name": "text", "data": "+" } ] }, { "name": "text", "data": "组成，形成一种分子层面的零维结构" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "39", "type": "bibr", "rid": "R39", "data": [ { "name": "text", "data": "39" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。实验中采用溶剂热法合成了不同浓度Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂的Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": ": " }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "样品。由于Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "与Zn" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "价态相同、离子半径差异小，因此Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "主要占据四面体Zn" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "格位(D" }, { "name": "sub", "data": [ { "name": "text", "data": "2h" } ] }, { "name": "text", "data": "对称性)。Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的实际掺杂浓度由ICP–AES确定，结果显示Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "投料浓度为5、10、15、20和25 mol%的样品Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的实际掺杂浓度分别为0.9、3.2、5.7、9.8和14.1 mol%。" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "b为Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": ": " }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的粉末XRD谱图，所有样品的衍射峰与正交相Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "标准卡片(JCPDS No. 70-1965)一一对应，且没有多余杂峰，表明所制备样品为Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "纯相，低浓度(" }, { "name": "text", "data": "<" }, { "name": "text", "data": "14.1 mol%)的Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂对物相没有影响。另外，随着Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂浓度的增加，XRD衍射峰向小角度发生了微弱偏移，这是由于Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " (4配位，0.078 nm)的离子半径大于Zn" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " (4配位，0.060 nm)，当Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "取代Zn" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "后，晶格膨胀所致。但需要注意的是，当Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的投料浓度高于30 mol%时，则产生CsCdCl" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "杂相。扫描电镜显示样品的尺寸约300–400 μm (" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "c)。元素分析面扫表明Cs、Zn、Cl和Cd元素在Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": ": Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "中均匀分布(" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "d-h)。XPS表征显示Cs 3d、Zn 2p、Cl 2p以及掺杂样品中Cd" }, { "name": "sup", "data": [ { "name": "text", "data": " " } ] }, { "name": "text", "data": "3d (404.9和411.7 eV)的光电子信号(" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "i-l)。掺杂Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "后，Zn 2p的XPS峰(1021.8和1044.9 eV)发生了微小偏移，Cl 2p的XPS峰(198.2和199.8 eV)显著展宽，表明Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "占据了四面体Zn" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "格位从而引起Zn" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "与Cl" }, { "name": "sup", "data": [ { "name": "text", "data": "–" } ] }, { "name": "text", "data": "周围的电子云密度发生改变" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "48", "type": "bibr", "rid": "R48", "data": [ { "name": "text", "data": "48" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "fig", "data": { "id": "F1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图1" } ], "title": [ { "name": "text", "data": "（a） Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "和Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的晶体结构示意图及其对应粉末样品的发光照片（" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": " = 254 nm）；（b） Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： " }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的粉末XRD谱图，红色竖线代表正交相Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "标准卡片（JCPDS No. 70-1965）；Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的（c）扫描电镜照片和（d-h） 元素分析面扫照片（Cs、Zn、Cd、Cl）；（i-l） Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": " （上）与Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " （下）的高分辨XPS谱图（Cs 3d、Zn 2p、Cd 3d、Cl 2p）及相应的分峰拟合。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 1" } ], "title": [ { "name": "text", "data": "（a） Crystal structures and PL photographs （" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": " = 254 nm） of Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": " and Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "； （b） Power XRD patterns of Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： " }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " with different Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " concentrations， and the bottom lines represent the standard XRD pattern of orthorhombic Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": " （JCPDS No. 70-1965）； （c） SEM image and （d-h） EDS elemental mappings （Cs， Zn， Cd， Cl， and merge） of Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "； （i-l） High-resolution XPS spectra of Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": " （top） and Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " （bottom） in the energy regions typical for Cs 3d， Zn 2p， Cd 3d， and Cl 2p and the corresponding fitting." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36455609&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36455615&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36455612&type=", "width": "154.55200195", "height": "127.30000305", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "a和b分别为不同浓度Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": ": " }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "粉末样品的漫反射光谱的Tauc plot曲线及漫反射光谱。不掺杂的Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "在紫外波段235 nm处存在一个宽带吸收峰，其吸收边拓展至300 nm，归属于Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "基质价带到导带的电子跃迁" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "41", "type": "bibr", "rid": "R41", "data": [ { "name": "text", "data": "41" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。随着Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂浓度从0升高到9.8 mol%，材料的吸收逐渐增强，进一步增加Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的掺杂浓度，吸收强度略有减弱。吸收的变化是由于Cd 3d与Cl 2p轨道杂化改变了导带中的电子态密度分布引起。通过Kubelka-Munk公式，可以计算得到不同浓度Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": ": " }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "样品的带隙，公式如下" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "49", "type": "bibr", "rid": "R49", "data": [ { "name": "text", "data": "49" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "：" } ] }, { "name": "fig", "data": { "id": "F2", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图2" } ], "title": [ { "name": "text", "data": "Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "：" }, { "name": "italic", "data": [ { "name": "text", "data": " x" } ] }, { "name": "text", "data": "%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的（a）紫外-可见漫反射光谱的Tauc plot曲线及（b）漫反射光谱、（c）激发（" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "em" } ] }, { "name": "text", "data": " = 565 nm）和发射（" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": " = 270 nm）光谱、（d）荧光衰减曲线（" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "em" } ] }, { "name": "text", "data": " = 565 nm）；（e）监测Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "不同波段发光的荧光衰减曲线。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 2" } ], "title": [ { "name": "text", "data": "（a） Tauc plots of the UV/Vis diffuse reflectance spectra and （b） the reflectance spectra， （c） PL excitation （" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "em" } ] }, { "name": "text", "data": " = 565 nm） and emission spectra （" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": " = 270 nm）， and （d） PL decay curves （" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "em" } ] }, { "name": "text", "data": " = 565 nm） of Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "：" }, { "name": "italic", "data": [ { "name": "text", "data": " x" } ] }, { "name": "text", "data": "%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " with different Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " concentrations； （e） PL decay curves of Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " by monitoring the broadband emission at different wavelengths." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36455618&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36455624&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36455622&type=", "width": "151.76499939", "height": "96.15000153", "fontsize": "" } ] } }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（1）" } ], "data": [ { "name": "text", "data": "F（R） = （1 – R）" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": " / 2R" } ], "id": "DF1" } }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（2）" } ], "data": [ { "name": "text", "data": "［F（R） × " }, { "name": "italic", "data": [ { "name": "text", "data": "hυ" } ] }, { "name": "text", "data": "］" }, { "name": "sup", "data": [ { "name": "text", "data": "1/2" } ] }, { "name": "text", "data": " = A（" }, { "name": "italic", "data": [ { "name": "text", "data": "hυ " } ] }, { "name": "text", "data": "– E" }, { "name": "sub", "data": [ { "name": "text", "data": "g" } ] }, { "name": "text", "data": "）" }, { "name": "italic", "data": [ { "name": "text", "data": " " } ] }, { "name": "text", "data": " " } ], "id": "DF2" } }, { "name": "p", "data": [ { "name": "text", "data": "其中，R为漫反射系数(%)，" }, { "name": "italic", "data": [ { "name": "text", "data": "hυ" } ] }, { "name": "text", "data": "代表光子能量，A为吸收系数。结果表明，当Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的掺杂浓度从0增加到14.1 mol%，材料的带隙从4.31 eV减小到3.92 eV，说明Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂对材料的带隙产生了较大影响。" } ] }, { "name": "p", "data": [ { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "c为Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": ": " }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的常温激发和发射光谱。常温下，Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "基质几乎不发光，而Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂的样品在270 nm紫外光激发下呈现明亮的宽带黄光发射，发射峰位于565 nm，半高宽为312 meV。随着Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂浓度增加，发光逐渐增强，当Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的掺杂浓度为9.8 mol%时发光最强，荧光量子产率达到46.0%，继续增加Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的掺杂浓度导致发光减弱。通过监测565 nm的荧光发射，可以观测到270 nm的激发峰，归属于材料的基质吸收以及Cl" }, { "name": "sup", "data": [ { "name": "text", "data": "–" } ] }, { "name": "text", "data": "→Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "荷移跃迁吸收" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "39", "type": "bibr", "rid": "R39", "data": [ { "name": "text", "data": "39" } ] } }, { "name": "text", "data": ", " }, { "name": "xref", "data": { "text": "50", "type": "bibr", "rid": "R50", "data": [ { "name": "text", "data": "50" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "d为Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": ": " }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的荧光衰减曲线，所有样品的荧光衰减一致，呈近单指数衰减，荧光寿命约11.4 ms。毫秒级的荧光寿命表明材料的发光来源于Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的4d" }, { "name": "sup", "data": [ { "name": "text", "data": "9" } ] }, { "name": "text", "data": "5s组态(" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "E能级)到4d" }, { "name": "sup", "data": [ { "name": "text", "data": "10" } ] }, { "name": "text", "data": "组态(" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "A" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "能级)电子的禁戒跃迁" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "51", "type": "bibr", "rid": "R51", "data": [ { "name": "text", "data": "51" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "55", "type": "bibr", "rid": "R55", "data": [ { "name": "text", "data": "55" } ] } } ], "rid": [ "R51", "R52", "R53", "R54", "R55" ], "text": "51-55", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，与此前Chen Ou等报道的CsPbCl" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": ": Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "发光来源相近" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "53", "type": "bibr", "rid": "R53", "data": [ { "name": "text", "data": "53" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。考虑到浓度猝灭的发生必然伴随发光中心离子荧光寿命的缩短，因此，不同浓度Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂样品的荧光寿命不变，可以排除浓度猝灭对发光的影响。" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "b显示，当Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂浓度" }, { "name": "text", "data": ">" }, { "name": "text", "data": "9.8 mol%时，材料的吸收有所减弱，因此，可以推断Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": ": " }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "样品的荧光强度随着Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂浓度的增加(" }, { "name": "text", "data": ">" }, { "name": "text", "data": "9.8 mol%)而减弱的原因在于光学吸收的减小，而非浓度猝灭。此外，不同波段的荧光衰减也保持高度的一致性(" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "e)，表明Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": ": Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "在565 nm的宽带发射来自Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的同一激发态且Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "处在一个均匀的晶体场环境" }, { "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": "为了深入理解Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": ": Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的激发态动力学过程，我们对材料开展了低温和变温高分辨光谱测试分析。" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "a为Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": ": 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "与Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "的10 K激发和发射光谱。在10 K低温下，Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": ": 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "呈现两个交叠的宽包发射，发射峰位于515 nm和565 nm。其中，565 nm的发射峰与常温光谱很好的吻合，来源于Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "离子发光。通过分别监测515 nm和565 nm的发射，得到几乎一致的激发谱，激发峰位于270 nm和298 nm，分别归属于材料的基质吸收与Cl" }, { "name": "sup", "data": [ { "name": "text", "data": "–" } ] }, { "name": "text", "data": "→Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "荷移跃迁吸收" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "39", "type": "bibr", "rid": "R39", "data": [ { "name": "text", "data": "39" } ] } }, { "name": "text", "data": ", " }, { "name": "xref", "data": { "text": "56", "type": "bibr", "rid": "R56", "data": [ { "name": "text", "data": "56" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。值得注意的是，515 nm的荧光寿命" }, { "name": "text", "data": "<" }, { "name": "text", "data": "1 μs。通过与Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "基质的激发、发射光谱以及荧光寿命对比，可以推测515 nm的发光来源于Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "基质本身局域态受限激子(trapped exciton, TE)的单线态发光" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "57", "type": "bibr", "rid": "R57", "data": [ { "name": "text", "data": "57" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "60", "type": "bibr", "rid": "R60", "data": [ { "name": "text", "data": "60" } ] } } ], "rid": [ "R57", "R58", "R59", "R60" ], "text": "57-60", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "fig", "data": { "id": "F3", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图3" } ], "title": [ { "name": "text", "data": "（a） Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " （实线）与Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": " （虚线）的10 K激发和发射光谱；（b） Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的变温发射光谱（" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": " = 270 nm）；（c） Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： 9.8% Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "中TE （515 nm）与Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " （565 nm）的荧光积分强度随温度变化关系；（d） Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的变温荧光衰减曲线（" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "em" } ] }, { "name": "text", "data": " = 565 nm）；（e） Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "中的能量传递与发光机理示意图以及Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的基态和激发态。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 3" } ], "title": [ { "name": "text", "data": "（a） PL excitation and emission spectra of Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " （solid curve） and Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": " （dashed curve）； （b） Temperature-dependent PL emission spectra （" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": " = 270 nm） of Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "； （c） Integrated PL intensities of the TE emission （515 nm） and the Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " emission （565 nm） in Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " as a function of temperature； （d） Temperature-dependent PL decay curves of Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " （" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "em" } ] }, { "name": "text", "data": " = 565 nm）； （e） Schematic of the energy transfer processes and the PL mechanism in Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "， and the corresponding ground state （GS） and excited state （ES） configurations of Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " dopants." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36455626&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36455633&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36455630&type=", "width": "152.25900269", "height": "96.97899628", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "b为Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": ": 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "在270 nm激发下，从10 K到410 K的变温发射光谱。如图" }, { "name": "xref", "data": { "text": "3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "3" } ] } }, { "name": "text", "data": "b和" }, { "name": "xref", "data": { "text": "3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "3" } ] } }, { "name": "text", "data": "c所示，随着温度升高，TE (515 nm)的发光逐渐减弱，170 K时完全猝灭；与此同时，Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " (565 nm)的发光逐渐增强，350 K时达到最高值，随后随温度升高发光开始减弱，说明存在着TE到Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的声子辅助能量传递过程。随着温度升高，一方面，TE到Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的能量传递速率提升，使得Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "发光增强；另一方面，由于电–声子耦合加剧，无辐射弛豫加快，导致Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的发射谱展宽、发光减弱、荧光寿命缩短" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "61", "type": "bibr", "rid": "R61", "data": [ { "name": "text", "data": "61" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "63", "type": "bibr", "rid": "R63", "data": [ { "name": "text", "data": "63" } ] } } ], "rid": [ "R61", "R62", "R63" ], "text": "61-63", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。当温度从10 K升高到290 K，Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "(" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "E能级)的荧光寿命从35.1 ms缩短到16.0 ms(" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "d)。另外，因为TE与Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的发射谱存在较大的光谱交叠，所以当温度低于170 K时，在荧光衰减曲线的初始端可以观测到来自TE的快衰减(" }, { "name": "text", "data": "<" }, { "name": "text", "data": "1 μs)。由于TE到Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的能量传递弥补了Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的无辐射弛豫能量损失，因此，Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": ": 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "表现出了优异的抗热猝灭性能，其热猝灭温度(T" }, { "name": "sub", "data": [ { "name": "text", "data": "50" } ] }, { "name": "text", "data": ")高于410 K。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "根据上述分析，Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": ": Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的激发态动力学过程可以用位形坐标图定性地描述(" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "e)：在270 nm紫外光激发下，电子从价带被激发到导带，形成自由激子(FE)。在低温下，一部分自由激子被Cl" }, { "name": "sup", "data": [ { "name": "text", "data": "–" } ] }, { "name": "text", "data": "空位缺陷捕获形成局域态的受限激子(TE)，TE的辐射复合产生515 nm的绿光发射；另一部分自由激子将能量传递给Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "，引起Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "E能级电子布居，" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "E → " }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "A" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "的电子跃迁产生Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的565 nm黄光发射。同时，TE与Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "E能级的位形坐标交叠，而且势垒(ΔE)小，因此随着温度升高，TE突破势垒将能量传递给Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "，在光谱上表现为TE的发光减弱，Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的发光增强。因为ΔE足够小，所以TE到Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的能量传递非常高效，170 K时能量传递效率达到100%，TE发光完全猝灭，导致在常温下只能观测到Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的发光。考虑到Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的最外层d轨道处于电子全充满的稳定状态(电子组态：[Kr]4d" }, { "name": "sup", "data": [ { "name": "text", "data": "10" } ] }, { "name": "text", "data": ")，激发Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "(四面体配位)需要将t" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "轨道上的一个电子转移到更高能量的分子轨道(a" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "，主要来源于Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的5s轨道)，形成第一激发态" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "E" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "53", "type": "bibr", "rid": "R53", "data": [ { "name": "text", "data": "53" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "55", "type": "bibr", "rid": "R55", "data": [ { "name": "text", "data": "55" } ] } } ], "rid": [ "R53", "R54", "R55" ], "text": "53-55", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。根据跃迁选择定则，" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "E到基态" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "A的电子跃迁是宇称和自旋禁戒的，所以Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的发光表现出ms量级的荧光寿命。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "稳定性是评估材料能否获得实际应用的重要指标。为此，我们测试了Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": ": 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "样品的结构、空气、光和热稳定性。热重分析显示Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": ": 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的初始失重温度达到了507 °C(" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "a)，表明该材料具有良好的结构热稳定性。XRD测试显示Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": ": 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "粉末在空气中保存12个月后，其物相保持不变，XRD衍射峰与正交相Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "标准卡片一一对应 (" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "b)，说明材料具有良好的空气稳定性。保存12个月后，材料的发射光谱和发光强度与新合成样品相比基本不变(" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "c)，荧光量子产率为45.5%，保持了新合成样品(46.0%)的98.9%。另外，在270 nm紫外光(20 W)持续辐照90分钟后，样品的发光强度也基本保持不变(" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "d)，表明材料优异的发光稳定性。特别地，该材料还表现出优异的抗热猝灭性能。在150 °C温度下，其发光强度依然保持室温时的90.0%(" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "e和f)。这些结果表明，Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": ": Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "具有良好的结构、空气、光和热稳定性，有望作为新型的黄光材料应用于固态照明、光电探测以及防伪编码等技术领域。" } ] }, { "name": "fig", "data": { "id": "F4", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图4" } ], "title": [ { "name": "text", "data": "（a） Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "粉末样品的热重曲线；Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "在空气中保存12个月前后的（b）粉末XRD谱图及（c）荧光发射光谱（" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": " = 270 nm）对比；（d）在270 nm紫外光持续照射90分钟，Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的发光强度（" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "em" } ] }, { "name": "text", "data": " = 565 nm）随时间变化关系；Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的（e）变温发射光谱（298–468 K， " }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": " = 270 nm）及（f）对应的荧光积分强度随温度变化关系。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 4" } ], "title": [ { "name": "text", "data": "（a） Thermogravimetric curve of Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " powder； （b） Powder XRD patterns and （c） PL emission spectra （" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": " = 270 nm） of Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " before and after their storage in ambient air for 12 months； （d） Time-dependent integrated PL intensity of Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " recorded at different time intervals under continuous illumination with an UV lamp （" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": " = 270 nm） for 90 min； （e） Temperature-dependent PL emission spectra （298–468 K， " }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": " = 270 nm） and （f） the corresponding integrated PL intensity of Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "： 9.8%Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": " as a function of temperature." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36455635&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36455640&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36455637&type=", "width": "152.87600708", "height": "97.17299652", "fontsize": "" } ] } } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "4　结 论" } ], "level": "1", "id": "s4" } }, { "name": "p", "data": [ { "name": "text", "data": "本文通过溶剂热法合成一系列不同浓度Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "掺杂的Cs" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "ZnCl" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "粉体材料，并对其光学性能进行了深入研究。该材料在270 nm紫外光激发下，呈现565 nm的宽带(半高宽：312 meV)黄光发射，荧光寿命达到了11.4 ms，荧光量子产率为46.0%。通过变温光谱等测试分析，证明了其发光来源于Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的4d" }, { "name": "sup", "data": [ { "name": "text", "data": "9" } ] }, { "name": "text", "data": "5s → 4d" }, { "name": "sup", "data": [ { "name": "text", "data": "10" } ] }, { "name": "text", "data": " (" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "E → " }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "A" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": ")自旋和宇称禁戒的电子跃迁。特别地，在低温下(" }, { "name": "text", "data": "<" }, { "name": "text", "data": "170 K)还观测到局域态受限激子(TE)的单线态发光(515 nm)以及TE到Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的高效能量传递过程。最后，验证了该材料良好的结构和光稳定性以及优异的抗热猝灭性能。这些结果为零维金属卤化物发光材料的光学性能设计提供了很好的理论和实验基础。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "本文(补充文件及)专家审稿意见和作者回复内容下载地址：" }, { "name": "extlink", "data": { "text": [ { "name": "text", "data": "http://cjl.lightpublishing.cn/thesisDetails#10.37188/CJL.20220" } ], "href": "http://cjl.lightpublishing.cn/thesisDetails#10.37188/CJL.20220" } }, { "name": "text", "data": "***(20220***为文章稿号)." } ] } ] } ], "footnote": [], "reflist": { "title": [ { "name": "text", "data": "参考文献" } ], "data": [ { "id": "R1", "label": "1", 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