Sulfide Boosting Near-Unity Photoluminescence Quantum Yield of Silver Nanocluster
Sulfide Boosting Near-Unity Photoluminescence Quantum Yield of Silver Nanocluster
复制标题
硫化物提高银纳米团簇近乎一致的光致发光量子产率
DOI：
10.1021/jacs.2c06093
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发表时间：
2022
影响因子：
15
通讯作者：
Di Sun
中科院分区：
文献类型：
--
作者：
Shan-Shan Zhang;Shana Havenridge;Chengkai Zhang;Zhi Wang;Lei Feng;Zhi-Yong Gao;Christine M. Aikens;Chen-Ho Tung;Di Sun
银纳米团簇已成为光电应用的最有前途的候选材料，但其室温光致发光量子产率（PLQY）远不能达到尖端器件的性能。ideal.to本文中，通过用多个VO 43-和E2-阴离子作为结构导向剂在内部支撑核并用PhC-43-和Ph 2 PE 2-（E = S，Ag 64-S; E = Se，. Ag 64-Se）的刚性配体壳外部保护核，在室温下在未脱气溶液中构建了两个具有高PLQY的超四面体银纳米团簇。这两个团簇具有相似的外部Ag 58四面体笼和[Ag 6E4 @（VO 4）4]核，形成一对可比较的核，clusters.to解密了如此高PLQY的起源，特别是在Ag 64-S中，其中PLQY高达97%。内硫化物对非辐射衰变的较强抑制作用是使PLQY接近1的关键。用瞬态吸收光谱证实了磷光的性质。通过碰撞诱导解离研究，还建立了Ag_（36）截角四面体上包含Ag_7二级结构单元的四重帽组装机制。本工作不仅为高发光量子效率的银纳米团簇的可控合成提供了一种核工程策略，而且揭示了近统一发光量子效率的来源，为今后制备高发光银纳米团簇奠定了基础.
Silver nanoclusters have emerged as promising.candidates for optoelectronic applications, but their room-temperature photoluminescence quantum yield (PLQY) is far from ideal.to access cutting-edge device performance. Herein, two supertetrahedral silver nanoclusters with high PLQY in non-degassed.solution at room temperature were constructed by interiorly.supporting the core with multiple VO43− and E2− anions as.structure-directing agents and exteriorly protecting the core with a.rigid ligand shell of PhC≡C− and Ph2PE2− (E = S, Ag64-S; E = Se,.Ag64-Se). Both clusters have similar outer Ag58 tetrahedral cages.and [Ag6E4@(VO4)4] cores, forming a pair of comparable clusters.to decrypt the origin of such a high PLQY, particularly in Ag64-S,.where the PLQY reached up to 97%. The stronger suppression.effect of inner sulfides for nonradiative decay is critical to boost the PLQY to near unity. Transient absorption spectroscopy is.employed to confirm the phosphorescence nature. The quadruple-capping assembly mechanism involving Ag7 secondary building.units on a Ag36 truncated tetrahedron was also established by collision-induced dissociation studies. This work not only provides a.strategy of core engineering for the controlled syntheses of silver nanoclusters with high PLQY but also deciphers the origin of a.near-unity PLQY, which lays a foundation for fabricating highly phosphorescent silver nanoclusters in the future.