Synthesis and Luminescent Properties of Self-activated LiSr₂Ca₂（BN₂）₃ Phosphor Enhanced Publication

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"stringName": [], "aff": [ { "rid": "aff1", "text": "1" }, { "rid": "aff2", "text": "2" } ], "role": [], "deceased": false }, { "name": [ { "lang": "zh", "surname": "朝", "givenname": "克夫", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "CHAO", "givenname": "Ke-fu", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "1" }, { "rid": "aff2", "text": "2" }, { "rid": "aff3", "text": "3" } ], "role": [ "corresp" ], "corresp": [ { "rid": "cor1", "lang": "en", "text": "E-mail： phyerick@imnu.edu.cn", "data": [ { "name": "text", "data": "E-mail： phyerick@imnu.edu.cn" } ] } ], "bio": [ { "lang": "zh", "text": [ "朝克夫（1979-），男（蒙古族），内蒙古呼和浩特人，博士，副教授，硕士生导师，2007年于中国科学院长春光学精密机械与物理研究所获得博士学位，主要从事稀土掺杂微纳米发光材料的研究。 E-mail： phyerick@imnu.edu.cn" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865342&type=", "small": 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"text", "data": "内蒙古师范大学 物理与电子信息学院， 内蒙古 呼和浩特 　010022" } ] }, { "lang": "en", "label": "1", "text": "School of Physics and Electronic Information， Inner Mongolia Normal University， Hohhot 010022， China", "data": [ { "name": "text", "data": "School of Physics and Electronic Information， Inner Mongolia Normal University， Hohhot 010022， China" } ] } ] }, { "id": "aff2", "intro": [ { "lang": "zh", "label": "2", "text": "内蒙古师范大学 内蒙古自治区功能材料物理与化学重点实验室， 内蒙古 呼和浩特　010022", "data": [ { "name": "text", "data": "内蒙古师范大学 内蒙古自治区功能材料物理与化学重点实验室， 内蒙古 呼和浩特　010022" } ] }, { "lang": "en", "label": "2", "text": "Inner Mongolia Key Laboratory for Physics and Chemistry of Functional Materials， Inner Mongolia Normal University， Hohhot 010022， China", "data": [ { "name": "text", "data": "Inner Mongolia Key Laboratory for Physics and Chemistry of Functional Materials， Inner Mongolia Normal University， Hohhot 010022， China" } ] } ] }, { "id": "aff3", "intro": [ { "lang": "zh", "label": "3", "text": "内蒙古自治区新能源储能材料工程研究中心， 内蒙古 呼和浩特　010022", "data": [ { "name": "text", "data": "内蒙古自治区新能源储能材料工程研究中心， 内蒙古 呼和浩特　010022" } ] }, { "lang": "en", "label": "3", "text": "Inner Mongolia Engineering Research Center of New Energy Storage Materials， Inner Mongolia， Hohhot 010022， China", "data": [ { "name": "text", "data": "Inner Mongolia Engineering Research Center of New Energy Storage Materials， Inner Mongolia， Hohhot 010022， China" } ] } ] } ] }, "abstracts": [ { "lang": "zh", "data": [ { "name": "p", "data": [ { "name": "text", "data": "自激活发光受到了研究人员的广泛关注，其中硼氮化物缺陷发光材料因毒性低、合成简单、结构多样性等优点，具有成为新一代LED用荧光粉的潜力，但是低热稳定性限制了其实际应用。本文采用高温固相一步法，通过部分取代LiSr" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（LSBN）中的Sr，合成了一种新的LiSr" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（LSCBN）发光材料。采用X射线衍射仪、扫描电子显微镜和荧光光谱仪对荧光粉的相组成、形貌和光学性质进行了表征。结果表明，所制备的样品LSBN为立方晶系，空间群" }, { "name": "italic", "data": [ { "name": "text", "data": "Im‐3m" } ] }, { "name": "text", "data": "。在紫外区域有较宽的激发带，发射光谱峰值位于561 nm，半峰宽度（FWHM）约为4 504 cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "。LSCBN的发光强度是LSBN的的2倍。解释了LSCBN的发光机理，LSCBN荧光粉中存在替代式缺陷，在光激励下形成发光中心。变温光谱显示，150 ℃时，LSBN的发光强度为初始强度的17%，LSCBN的发光强度为初始强度的57%，超过了已报道的其他硼氮化物荧光粉。这种离子取代的方法能有效调控发光波长和增强荧光强度，改善热稳定性，为硼氮化物缺陷材料发光性能的改善提供了新的思路和应用前景。" } ] } ] }, { "lang": "en", "data": [ { "name": "p", "data": [ { "name": "text", "data": "Self-activated phosphors have received a lot of attention from researchers， among which nitridoborate defect phosphors have the potential to become a new generation of phosphors for LEDs due to low toxicity， simple synthesis， and structural diversity， but low thermal stability limits their practical applications. In this paper， a new LiSr" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（LSCBN） phosphor was synthesized by partially replacing Sr in LiSr" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（LSBN） using a high-temperature solid-phase one-step method. The phase composition， morphology， and optical properties of the phosphor were characterized by X-ray diffraction， scanning electron microscopy， and fluorescence spectrometry. The results show that the prepared sample LSBN is a cubic crystal system with the space group " }, { "name": "italic", "data": [ { "name": "text", "data": "Im‐3m" } ] }, { "name": "text", "data": ". It has a wide excitation band in the UV region， the peak of the emission spectrum is located at 561 nm， and the full width at half maximum（FWHM） is about 4 504 cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": ". The luminescence intensity of a LSCBN is twice that of a LSBN. In LSCBN， the partial replacement of Sr by Ca introduces substitutional defects that form new luminescence centers. In the temperature dependence PL spectra， the intensity of LSBN at 150 ℃ is 17% of the initial value， and LSCBN can maintain 57% of the initial intensity at 150 ℃， which exceeds other nitridoborate phosphors that have been reported. This ion-substitution method can effectively regulate the luminescence wavelength and enhance the luminous intensity， improve the thermal stability， and provide a new idea and application prospect for the improvement of the luminescence performance of defect-related nitridoborate phosphors." } ] } ] } ], "keyword": [ { "lang": "zh", "data": [ [ { "name": "text", "data": "硼氮化物" } ], [ { "name": "text", "data": "缺陷发光材料" } ], [ { "name": "text", "data": "阳离子取代" } ], [ { "name": "text", "data": "发光机理" } ] ] }, { "lang": "en", "data": [ [ { "name": "text", "data": "nitridoborate" } ], [ { "name": "text", "data": "defect-related phosphor" } ], [ { "name": "text", "data": "cation substitution" } ], [ { "name": "text", "data": "luminescence mechanism" } ] ] } ], "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": "近年来，由于白光LED（WLED）具有亮度高、使用寿命长、能耗低和安全环保等优点，已逐渐取代传统光源，成为了新一代固态光源" }, { "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": "。目前，商用的WLED荧光粉主要有YAG∶Ce" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "6", "type": "bibr", "rid": "R6", "data": [ { "name": "text", "data": "6" } ] } }, { "name": "text", "data": "] " } ] }, { "name": "text", "data": "、CaAlSiN" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "∶Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "7", "type": "bibr", "rid": "R7", "data": [ { "name": "text", "data": "7" } ] } }, { "name": "text", "data": "]" } ] }, { "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": "∶Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "2", "type": "bibr", "rid": "R2", "data": [ { "name": "text", "data": "2" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "等，都需要用到稀土材料。但是，由于稀土材料需要高成本的分离、精制和提纯技术，它们大多价格昂贵" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "8", "type": "bibr", "rid": "R8", "data": [ { "name": "text", "data": "8" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，且稀土储备有限，不利于可持续发展。所以研究人员对无稀土掺杂的荧光粉进行了大量探索。其中，与缺陷有关的发光材料因成本低、毒性小、效率高、无稀土离子掺杂和制备简单等突出优点而受到了广泛关注。例如，BCNO" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "9", "type": "bibr", "rid": "R9", "data": [ { "name": "text", "data": "9" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、多孔氧化铝膜" }, { "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": "、SnO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "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": "，以及Zn" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "V" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "7" } ] }, { "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": "、Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "KZn" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "（VO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "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": "、Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "italic", "data": [ { "name": "text", "data": "M" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "（VO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "（" }, { "name": "italic", "data": [ { "name": "text", "data": "M" } ] }, { "name": "text", "data": "=Mg, Zn）" }, { "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": "等一系列钒酸盐化合物。这些材料以氧化物材料为主且需要近紫外高能量激发，发光效率低，热稳定性差。因此，有必要寻找新的缺陷相关发光材料。另外，LED芯片的工作温度约为150 ℃，这将导致涂覆在芯片上的荧光粉材料因受热而出现不可逆转的劣化。因此，发光材料具备良好的热稳定性是固态照明具有优异性能的关键。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "氮化物材料因具有优异的热稳定性、高量子效率以及丰富的结构而被应用在LED照明、显示、防伪和生物标记领域。其中，带有[BN]" }, { "name": "italic", "data": [ { "name": "sup", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "sup", "data": [ { "name": "text", "data": "-" } ] }, { "name": "text", "data": "、[BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "]" }, { "name": "sup", "data": [ { "name": "text", "data": "3-" } ] }, { "name": "text", "data": "、[BN" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "]" }, { "name": "sup", "data": [ { "name": "text", "data": "6-" } ] }, { "name": "text", "data": "、[B" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "N" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "]" }, { "name": "sup", "data": [ { "name": "text", "data": "8-" } ] }, { "name": "text", "data": "和[B" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "N" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "]" }, { "name": "sup", "data": [ { "name": "text", "data": "9-" } ] }, { "name": "text", "data": "离子的硼氮化物可以通过B和N离子实现不同的阴离子基团。设想当B和N不按既定化学比成键时很容易形成空位缺陷，因此硼氮化物相对于铝氮化物和硅氮化物是非常适合缺陷发光材料的基质" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "15", "type": "bibr", "rid": "R15", "data": [ { "name": "text", "data": "15" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "16", "type": "bibr", "rid": "R16", "data": [ { "name": "text", "data": "16" } ] } } ], "rid": [ "R15", "R16" ], "text": "15-16", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。王育华课题组报道了Mg" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "BN" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "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": "、α, β‑Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "B" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "N" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "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": "和CaMg" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "N" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "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": "自激活发光材料，并应用在了白光LED照明器件上。然而，据我们了解，目前已知的硼氮化物自激活荧光粉的热稳定性普遍较低，难以满足LED用荧光粉的需求。所以研究提高硼氮化物热稳定性是一个非常有意义的课题。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "含有线性[N=B=N]" }, { "name": "sup", "data": [ { "name": "text", "data": "3-" } ] }, { "name": "text", "data": "的" }, { "name": "italic", "data": [ { "name": "text", "data": "AM" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "[BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "]" }, { "name": "sub", "data": [ { "name": "text", "data": "3 " } ] }, { "name": "text", "data": "（" }, { "name": "italic", "data": [ { "name": "text", "data": "A" } ] }, { "name": "text", "data": "=Li, Na, 1/2Mg；" }, { "name": "italic", "data": [ { "name": "text", "data": "M" } ] }, { "name": "text", "data": "=Ca,Sr,Ba,Eu）" }, { "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": "四元化合物具有稳定的立方结构，" }, { "name": "italic", "data": [ { "name": "text", "data": "A" } ] }, { "name": "text", "data": "原子、" }, { "name": "italic", "data": [ { "name": "text", "data": "M" } ] }, { "name": "text", "data": "原子与N原子形成了坚固的八面体配位环境，可以容纳大量包括阳离子和阴离子的取代，具有复杂多变的晶体场环境，通过在阳离子或阴离子位点上进行不同程度的取代或形成固溶体结构，从而实现光学性能的调控" }, { "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": "。迄今为止，还没有关于LiSr" }, { "name": "sub", "data": [ { "name": "text", "data": "4-" } ] }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Ca" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "系列荧光粉发光特性的报道。本文采用高温固相法合成 了一系列LiSr" }, { "name": "sub", "data": [ { "name": "text", "data": "4-" } ] }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Ca" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "荧光粉。重点研究了LSCBN荧光粉的晶体结构、光致发光光谱、变温光谱等光学性能，分析了自激活发光的机理。通过Ca部分取代Sr实现了光谱调控。研究开发性能优异的硼氮化物发光材料对发展新型自激活荧光粉及其性能调控具有重要意义。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2　实　　验" } ], "level": "1", "id": "s2" } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.1　样品制备" } ], "level": "2", "id": "s2a" } }, { "name": "p", "data": [ { "name": "text", "data": "通过高温固相反应法合成了一系列LiSr" }, { "name": "sub", "data": [ { "name": "text", "data": "4-" } ] }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Ca" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "⁃" } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=0,1,2,3,4）样品。原料为Li" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "N（Materion, 99.5%）、Sr" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "N" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "（Materion,99.9%）、Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "N" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "（Materion, 99.9%）、h-BN（Alfa Aesar,99.9%）。首先，在99.99%的氩气氛手套箱中按化学计量比例称量原料，并在手套箱中研磨6 min，使原料充分混合；然后放入BN坩埚；最后，在箱式电阻炉中进行升温反应。升温前，用高纯度氮气对电阻炉洗气两次，在流动氮气的条件下，以5 ℃/min的升温速率加热到1 200 ℃，保温4 h，自然冷却至室温后，取出样品并磨成粉末，等待下一步测试。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.2　测量和表征" } ], "level": "2", "id": "s2b" } }, { "name": "p", "data": [ { "name": "text", "data": "采用Panalytical Empyrean型（Philips公司）Ｘ射线衍射仪对样品进行晶体结构分析，该仪器采用Cu靶，Kα射线（" }, { "name": "italic", "data": [ { "name": "text", "data": "λ=" } ] }, { "name": "text", "data": "0.154 06 nm）。在10°~90°范围内采集X射线衍射（XRD）数据，计数时间为0.1 s/step，步长为0.03°。用S-3400N型（Hitachi公司）扫描电子显微镜（SEM）以及配备的能谱仪（EDS）设备分析粉末的形貌及元素。采用FS5稳态瞬态荧光光谱仪（Edinburgh, UK），配合450 W氙光源和双激发单色仪，对样品的激发、发射光谱、衰减曲线及热稳定性进行了测量。采用CASTEP程序的DFT方法对LSCBN和LSBN进行了结构优化，交换关联（XC）函数选择局域密度近似（LDA）。" } ] } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3　结果与讨论" } ], "level": "1", "id": "s3" } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.1　晶体结构与相鉴定" } ], "level": "2", "id": "s3a" } }, { "name": "p", "data": [ { "name": "text", "data": "对制备获得的LiSr" }, { "name": "sub", "data": [ { "name": "text", "data": "4-" } ] }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Ca" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=0, 1, 2, 3, 4）样品进行了X射线衍射（XRD）测试，并与LSBN和LiCa" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "标准卡片进行了对比。" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "显示了LiSr" }, { "name": "sub", "data": [ { "name": "text", "data": "4-" } ] }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Ca" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=0, 1, 2, 3, 4）荧光粉的XRD图像。结果表明，样品与标准卡片PDF#98‐040‐2173和PDF#98‐040‐0339的特征峰匹配良好。除了LSBN样品外，其他样品中都含有少量的CaO杂质，O是在制备过程中引入的。LSBN样品中几乎没有检测到SrO杂质。随着Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "替代Sr" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "浓度的增加，衍射峰向大角度移动。这是因为半径小的Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "（CN = 6, " }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "text", "data": " = 0.114 nm）逐渐替代了半径较大的Sr" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "（CN=6, " }, { "name": "italic", "data": [ { "name": "text", "data": "R" } ] }, { "name": "text", "data": " =0.132 nm）。根据布拉格方程，衍射峰的移动证明Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "已经成功地进入了主晶格，形成了一系列连续固溶体。" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "中显示" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=3时的衍射光谱出现了明显的展宽，这是由于粒径尺寸的不均匀性和粒径尺寸较小导致的。另外，根据XRD峰的强度可以推断LiSrCa" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "样品相对于其他样品，晶格畸变变大，导致结构对称性下降。因此产生XRD谱峰的显著展宽。通过XRD分析以及合成出来样品的表面形态，以下我们重点研究了LSBN和LSCBN样品的性能。" } ] }, { "name": "fig", "data": { "id": "F1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图1" } ], "title": [ { "name": "text", "data": "LiSr" }, { "name": "sub", "data": [ { "name": "text", "data": "4-" } ] }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Ca" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=0，1，2，3，4）样品的XRD图像，LSBN和LiCa" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "的PDF标准卡片作为参考。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.1" } ], "title": [ { "name": "text", "data": "XRD spectra of LiSr" }, { "name": "sub", "data": [ { "name": "text", "data": "4-" } ] }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Ca" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=0， 1， 2， 3， 4） phosphors. As a reference， the standard XRD pattern of LSBN and LiCa" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865349&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865352&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865350&type=", "width": "76.33081055", "height": "58.38425446", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "利用SEM分析了LSBN和LSCBN样品的形貌和元素组成。" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "（a）、（b）分别为LSBN和LSCBN样品的SEM照片。从图中可以看出样品表面光滑，晶体结晶比较完整，说明结晶性良好。样品形貌不规则，不团聚，具有较好的分散性。LSCBN样品的能量色散X射线光电子能谱（EDS）分析如" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "（c）所示，表明样品主要由Sr、Ca、B、N、O组成。由于Li元素较轻，无法利用EDS测试到。" } ] }, { "name": "fig", "data": { "id": "F2", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图2" } ], "title": [ { "name": "text", "data": "LSBN（a）和LSCBN（b）样品的SEM照片；（c）LSCBN样品的EDS图谱；（d）LSBN与LSCBN荧光粉的晶体结构。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.2" } ], "title": [ { "name": "text", "data": "SEM photos of LSBN（a） and LSCBN（b）. （c）EDS spectrum of LSCBN. （d）Crystal structure of LSBN and LSCBN" }, { "name": "sub", "data": [ { "name": "text", "data": " " } ] }, { "name": "text", "data": "phosphors." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865354&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865358&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865356&type=", "width": "156.27383423", "height": "129.49484253", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "为了进一步分析LSCBN与LSBN的晶格结构，采用CASTEP程序的DFT方法进行了结构优化。采用已经被报道的LSBN晶体结构" }, { "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": "作为LSBN的初始模型。基于已知的LSBN晶体结构，按照化学计量比，以1/2、1/4、3/4的比例用Ca对Sr进行替代，建立了多个晶胞模型，并进行结构优化。平面波的截止能量设为700 eV，布里渊区k点采样设为6×6×6。以1/4和3/4的比例用Ca对Sr进行替代建立LiSr" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "Ca（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "和LiSr" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "Ca" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "的晶胞模型，由于破坏了晶胞中原子的对称性，在结构优化后产生了晶格畸变。以1/2的比例建立的LSCBN晶胞，通过结构优化，没有产生晶格畸变。这个结果与LSCBN的XRD良好结晶度相匹配。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "结构优化后LSBN和LSCBN的三维结构如" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "（d）所示，二者均为" }, { "name": "italic", "data": [ { "name": "text", "data": "Im" } ] }, { "name": "text", "data": "-3" }, { "name": "italic", "data": [ { "name": "text", "data": "m" } ] }, { "name": "text", "data": "结构，呈立方相。较小半径的Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "的引入使得晶胞参数减小。8" }, { "name": "italic", "data": [ { "name": "text", "data": "c" } ] }, { "name": "text", "data": "（1/4, 1/4, 1/4）位置的Sr和Ca与6个最近邻N原子连接，分别组成了无序的SrN" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "和CaN" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "八面体。SrN" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "八面体与CaN" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "八面体通过共享面相互连接。2" }, { "name": "italic", "data": [ { "name": "text", "data": "a" } ] }, { "name": "text", "data": "（0, 0, 0; 1/2, 1/2, 1/2）位置的Li与周围的6个最近邻的N原子组成了LiN" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "正八面体。LiN" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "八面体与SrN" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "和CaN" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "两种八面体通过面共享相互连接。LSCBN的晶胞由（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sup", "data": [ { "name": "text", "data": "3-" } ] }, { "name": "text", "data": "、LiN" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "、SrN" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "和CaN" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "组成。根据鲍林规则，由于面共享而产生的两个紧密的阳离子位点会使晶格不稳定，但与2" }, { "name": "italic", "data": [ { "name": "text", "data": "a" } ] }, { "name": "text", "data": "位置碱土离子共线连接的[N=B=N]" }, { "name": "sup", "data": [ { "name": "text", "data": "3-" } ] }, { "name": "text", "data": "的刚性键形成了稳定的立方框架结构，使得晶胞形成了稳定的立方结构。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.2　自激活发光特性" } ], "level": "2", "id": "s3b" } }, { "name": "p", "data": [ { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "（a）～（c）显示了LiSr" }, { "name": "sub", "data": [ { "name": "text", "data": "4-" } ] }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Ca" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=0, 1, 2, 3, 4） 的激发光谱（PLE）和发射光谱（PL）。如" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "（a）所示，样品都具有较宽的激发带。随着Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "取代Sr" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "比例的增大（从" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=0至" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=4），样品的激发光谱逐渐变窄，位于360 nm处的最强峰也不断减弱，同时最有效激发峰蓝移到了306 nm处。如" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "（b）、（c）所示，从" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=0至" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=4，样品的光谱不断蓝移，发射相对强度先增加后减小。LSCBN的相对荧光强度最高，约为LSBN的2倍。对应的最强发射波长为561 nm，为黄光发射，半峰宽度（FWHM）约为4 504 cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "，比LSBN的596 nm（FWHM=4 116 cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "）最强发射峰蓝移了38 nm（1 047 cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "）。" } ] }, { "name": "fig", "data": { "id": "F3", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图3" } ], "title": [ { "name": "text", "data": "LiSr" }, { "name": "sub", "data": [ { "name": "text", "data": "4-" } ] }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Ca" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=0，1，2，3，4）的归一化激发光谱（a）、发射光谱（b）、归一化发射光谱（c）；（d）LSCBN的发光原理。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.3" } ], "title": [ { "name": "text", "data": "（a）-（c）Normalized PLE spectra， PL spectra， Normalized PL spectra of LiSr" }, { "name": "sub", "data": [ { "name": "text", "data": "4-" } ] }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Ca" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=0， 1， 2， 3， 4）. （d）Luminescence diagrams LSCBN." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865362&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865367&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865364&type=", "width": "161.32464600", "height": "127.79148102", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "我们尝试着利用简略" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "（d）解释了LiSr" }, { "name": "sub", "data": [ { "name": "text", "data": "4-" } ] }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Ca" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "‐" } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "系列样品的发光原理。根据文献报道，硼氮化物的自激活发光主要是来自于碱土金属离子的空位" }, { "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": "，属于本征缺陷。由于热振动，原子会离开晶格，向外扩散形成空位（过程②和③），即产生肖特基缺陷" }, { "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": "。在紫外光照射时，部分能量被晶格振动吸收（过程①），而其他的电子则被Sr和Ca的空位形成的发光中心捕获。在晶格弛豫之后，多余的能量以光的形式（过程④和⑤）从晶格被释放出来。此外，对于LSCBN，Ca取代了部分Sr后，因为Ca的电负性大于Sr，因此需要更高的激发光能量，激发光峰位蓝移。发射光谱蓝移说明Ca取代Sr，产生了新的Ca空位（V" }, { "name": "sub", "data": [ { "name": "text", "data": "Ca" } ] }, { "name": "text", "data": "），发射光谱包含了两个空位的发光，导致光谱宽化。所以我们认为Ca取代Sr，在原有本征缺陷的基础上又形成了新的替代式的缺陷" }, { "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": "。另外，未见到关于在360 nm激发下CaO发光的报道。结合LSBN和LSCBN的XRD数据和上述光谱数据，我们认为CaO杂质不对样品的发光产生影响。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "进一步，我们发现LSCBN样品具有余辉发光现象。" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "（a）插图中的样品从左到右分别是LiSr" }, { "name": "sub", "data": [ { "name": "text", "data": "4-" } ] }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Ca" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=0, 1, 2, 3, 4） 样品的实物图。从图中可以看出，样品在日光下均呈现白色的体色。在254 nm的激发下，LSCBN样品的发光最亮。" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=1、" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=2和" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=3时样品具有余辉现象；" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=0时LSBN样品没有余辉现象。接着我们测量了LSCBN样品的余辉衰减曲线。如" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "（a）所示，用紫外灯对样品激发大约30 s，确保缺陷达到饱和状态，然后关闭激发源，并记录样品在561 nm处的发射强度。从图中可以清晰地观察到样品的发射强度变化，样品在30 s处发光最强，500 s处样品的发射强度基本降到最低。设备可探测的持续发光时间为470 s。" } ] }, { "name": "fig", "data": { "id": "F4", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图4" } ], "title": [ { "name": "text", "data": "（a）LSCBN样品的余辉衰减曲线，插图为LiSr" }, { "name": "sub", "data": [ { "name": "text", "data": "4-" } ] }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Ca" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=0，1，2，3，4） 样品的实物图，（ⅰ） 日光照射，（ⅱ） 254 nm紫外光照射，（ⅲ）停止紫外光照射；（b）LSCBN样品的发光原理。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.4" } ], "title": [ { "name": "text", "data": "（a）Afterglow decay curve of LSCBN phosphor，the inset presents the physical diagram of LiSr" }, { "name": "sub", "data": [ { "name": "text", "data": "4-" } ] }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Ca" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": " =0， 1， 2， 3， 4） samples， （ⅰ） under daylight irradiation； （ⅱ） under 254 nm UV irradiation； （ⅲ）after stopping UV irradiation. （b）Luminescence schematic of LSCBN phosphor." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865369&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865376&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865375&type=", "width": "161.28564453", "height": "63.67138672", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "众所周知，阴离子空位能级是阳离子指向阴离子空位的空轨道，它是阳离子-阴离子键断裂的结果。这些能级位于导带（CB）底部以下。同样，阳离子空位能级是围绕阳离子空位的阴离子的孤对轨道，它是阳离子-阴离子键断裂的结果。这些能级位于价带（VB）顶部之上。与这些能级相关的陷阱深度（ET）随着宿主晶格的阳离子-阴离子键的强度增加而变大" }, { "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": "。样品在紫外光激发下，根据电荷补偿原理，正负电荷空位（V" }, { "name": "sub", "data": [ { "name": "text", "data": "Sr" } ] }, { "name": "text", "data": "、V" }, { "name": "sub", "data": [ { "name": "text", "data": "Ca" } ] }, { "name": "text", "data": "、V" }, { "name": "sub", "data": [ { "name": "text", "data": "N" } ] }, { "name": "text", "data": "）同时产生，如式（" }, { "name": "xref", "data": { "text": "1", "type": "disp-formula", "rid": "DF1", "data": [ { "name": "text", "data": "1" } ] } }, { "name": "text", "data": "）、（" }, { "name": "xref", "data": { "text": "2", "type": "disp-formula", "rid": "DF2", "data": [ { "name": "text", "data": "2" } ] } }, { "name": "text", "data": "）、（" }, { "name": "xref", "data": { "text": "3", "type": "disp-formula", "rid": "DF3", "data": [ { "name": "text", "data": "3" } ] } }, { "name": "text", "data": "）所示：" } ] }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（1）" } ], "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865385&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865381&type=", "width": "23.36800003", "height": "4.06400013", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF1" } }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（2）" } ], "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865391&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865388&type=", "width": "24.55333328", "height": "4.06400013", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF2" } }, { "name": "dispformula", "data": { "label": [ { "name": "text", "data": "（3）" } ], "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865397&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865395&type=", "width": "22.26733208", "height": "4.06400013", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF3" } }, { "name": "p", "data": [ { "name": "text", "data": "结合上述缺陷形成的理论和余辉发光现象，我们认为，Ca的电负性更强，Ca—N键的强度大于Sr—N键，形成Ca空位的陷阱深度大于Sr空位的陷阱深度，因此就需要更高的能量激发，对应激发光谱蓝移。" } ] }, { "name": "p", "data": [ { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "（b）解释了LSCBN样品的发光原理，受到紫外光激发时，电子从价带被激发到导带能级（过程①），被导带附近的缺陷能级捕获后，可以继续向下跃迁到Sr空位和Ca空位形成的发光中心（过程④和⑤），电子和发光中心的空穴复合后产生发光。另外，Ca离子取代Sr离子后，它们与周围环境的相互作用，因其电负性和电离势的不同而不同于它们所替代的宿主阳离子" }, { "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": "，在晶格中产生了替代式缺陷" }, { "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": "。根据电荷补偿原理，Ca替代缺陷的引入使得能级中产生了新的N空位能级" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865403&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865400&type=", "width": "3.97933316", "height": "4.06400013", "fontsize": "" } } } ] }, { "name": "text", "data": "，即有部分电子被" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865408&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865406&type=", "width": "3.97933316", "height": "4.06400013", "fontsize": "" } } } ] }, { "name": "text", "data": "捕获，经历一段时间之后它们才逃逸出来，到达Ca的缺陷能级，产生余辉（过程⑥）。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "通常，LED芯片稳定工作时放热导致发光材料环境温度高达150 ℃，所以荧光粉的热稳定性对于实际应用中的荧光粉很重要。测试了LSBN与LSCBN的发射光谱的温度依赖性曲线。从" }, { "name": "xref", "data": { "text": "图 5", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图 5" } ] } }, { "name": "text", "data": "（a）~（d）中可以看出，温度从25 ℃升高到了225 ℃，LSBN发射光谱的形状和峰值几乎不变，发射强度逐渐下降，150 ℃时发射强度约为室温下初始强度的17%，荧光热猝灭比较严重。LSCBN样品的发射强度先略微升高，在100 ℃后才逐渐降低，光谱的形状基本不变，峰位逐渐蓝移。这可能是在高温下发生了热激活声子的隧穿" }, { "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": "，导致在较高能级下发生电子跃迁，因此发生短波长发射，主峰位置蓝移。在150 ℃时，LSCBN发射强度约为室温下初始强度的57%。对于LSCBN样品，我们认为，一方面，基质材料的晶体结构更加稳定，晶体的刚性变强使其具有更好的热稳定性。这一点从下面热猝灭的活化能分析也能看出。" } ] }, { "name": "fig", "data": { "id": "F5", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图5" } ], "title": [ { "name": "text", "data": "（a）～（b）LSBN和LSCBN光致发光光谱的温度依赖性；（c）～（d）LiSr" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "和LSCBN相对强度的温度依赖性。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.5" } ], "title": [ { "name": "text", "data": "（a）-（b）Temperature dependence of the photoluminescence spectra of LSBN and LSCBN. （c）-（d）Temperature dependence of the relative intensities of LSBN and LSCBN." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865412&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865418&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865414&type=", "width": "127.97412109", "height": "96.09348297", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "使用Arrhenius方程拟合了LSBN和LSCBN的热猝灭数据。活化能Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "text", "data": "可由下式计算" }, { "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": "dispformula", "data": { "label": [ { "name": "text", "data": "（4）" } ], "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865423&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865421&type=", "width": "46.14333344", "height": "5.16466665", "fontsize": "" } } }, { "name": "text", "data": "，" } ], "id": "DF4" } }, { "name": "p", "data": [ { "name": "text", "data": "其中" }, { "name": "italic", "data": [ { "name": "text", "data": "I" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "0" } ] }, { "name": "text", "data": "是室温下的发射强度，" }, { "name": "italic", "data": [ { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "T" } ] } ] }, { "name": "text", "data": "是不同温度下的发射强度，" }, { "name": "italic", "data": [ { "name": "text", "data": "K" } ] }, { "name": "text", "data": "是玻尔兹曼常数（8.629×10" }, { "name": "sup", "data": [ { "name": "text", "data": "-5" } ] }, { "name": "text", "data": " eV），" }, { "name": "italic", "data": [ { "name": "text", "data": "c" } ] }, { "name": "text", "data": "是与晶格相关的常数，Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "text", "data": "是热猝灭的活化能。LSBN和LSCBN样品的" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865430&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865426&type=", "width": "20.15066719", "height": "5.41866684", "fontsize": "" } } } ] }, { "name": "text", "data": "与" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865435&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865432&type=", "width": "10.92199993", "height": "3.13266683", "fontsize": "" } } } ] }, { "name": "text", "data": "的线性关系的斜率分别为-1.736和-5.544。根据" }, { "name": "xref", "data": { "text": "公式（4）", "type": "disp-formula", "rid": "DF4", "data": [ { "name": "text", "data": "公式（4）" } ] } }, { "name": "text", "data": "，LSBN的活化能Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "为0.149 8 eV，LSCBN的活化能Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "为0.440 5 eV。电子在紫外光的激发下，从基态转移到激发态，经过自旋晶格弛豫后，电子可以辐射跃迁的方式分别返回LSBN和LSCBN的基态，分别发出橙色和黄色光。部分电子也可以通过吸收活化能Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "和Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "以无辐射跃迁的方式返回基态，这就导致了热猝灭。活化能Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "text", "data": "是一个势垒，Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "text", "data": "越大意味着电子越难以无辐射跃迁的方式返回基态，这就导致了良好的热稳定性。根据上述计算，Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": ">" }, { "name": "text", "data": "Δ" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "，所以LSCBN的热稳定性优于LSBN。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "另一方面，随着温度升高，晶格热振动增加。距离导带近的" }, { "name": "inlineformula", "data": [ { "name": "math", "data": { "math": "", "graphicsData": { "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865441&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35865438&type=", "width": "3.97933316", "height": "4.06400013", 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"title": [ { "name": "text", "data": "4　结　　论" } ], "level": "1", "id": "s4" } }, { "name": "p", "data": [ { "name": "text", "data": "本文通过高温固相反应法合成了一系列LiSr" }, { "name": "sub", "data": [ { "name": "text", "data": "4-" } ] }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "Ca" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "text", "data": "（BN" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（" }, { "name": "italic", "data": [ { "name": "text", "data": "x" } ] }, { "name": "text", "data": "=0, 1, 2, 3, 4）样品。实验和结构优化结果表明LSCBN具有良好的结晶性和稳定的立方结构。LSCBN样品发光相对强度提高到了LSBN的2倍。LSCBN荧光粉在" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "=306 nm处发出峰值波长为561 nm的黄光。与LSBN相比，LSCBN的激发光谱变窄蓝移。同时，LSCBN具有余辉现象，设备可探测的持续发光时间为470 s。在LSBN基质中，本征缺陷引起了自激活发光；而在同样晶体结构的LSCBN中，Ca部分取代Sr时引入了替代式的缺陷，形成了新的发光中心，导致光谱性能的变化。值得一提的是，LSCBN样品在150 ℃时，发射强度约为室温下初始强度的57%，优于已报道的其他硼氮化物发光材料。本文采取阳离子取代的方法，成功改善了荧光粉的性能。这种方法不仅为优化发光材料的性能（尤其是热稳定性能方面）提供了实验依据，也为探索新的、优异的缺陷发光材料提供了实验依据。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "本文专家审稿意见及作者回复内容的下载地址：" }, { "name": "extlink", "data": { "text": [ { "name": "text", "data": "http://cjl.lightpublishing.cn/thesisDetails#10.37188/CJL.20220217." } ], "href": "http://cjl.lightpublishing.cn/thesisDetails#10.37188/" } } ] } ] } ], "footnote": [], "reflist": { "title": [ { "name": "text", "data": "参考文献" } ], "data": [ { "id": "R1", "label": "1", "citation": [ { "lang": "zh", "text": [ { "name": "text", "data": "沈超" }, { "name": "text", "data": "， " }, { "name": "text", "data": "邵起越" }, { "name": "text", "data": "， " }, { "name": "text", "data": "韩学林" }, { "name": "text", "data": "， " }, { 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