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中国物理学会期刊

类富勒烯团簇发光性能的理论研究

First-principles study of luminescence of fullerene-like clusters

CSTR: 32037.14.aps.71.20212426
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  • 热激活延迟荧光(TADF)作为一种特殊的分子荧光机制, 对于提高发光效率有着重要意义. 以C60和C70为代表的碳富勒烯具有高对称结构和离域π电子, 被广泛证明具有显著的TADF效应; 相比之下, 其他类富勒烯团簇的光物理性质尚不清楚. 本文利用含时密度泛函理论探索了一系列类富勒烯团簇的激发态性质, 包括实验合成的具有不同尺寸的氮化硼笼型团簇B12N12, B24N24和B36N36, 以及与B12N12结构相同、元素组成不同的B12P12, Al12N12和Ga12N12. 计算结果表明, 这些类富勒烯化合物团簇具有2.83—6.54 eV的能隙, 主要吸收紫外光, 荧光发射波长在可见光区间, 包括红光、橙光、蓝光和紫光. 它们的第一激发单重态和三重态的能量差较小(ΔEST < 0.29 eV), 因此可能通过系间窜越和反系间窜越发生TADF过程. 导致ΔEST较低的原因是这些化合物团簇的最高占据分子轨道和最低未占据分子轨道分布在不同的元素上, 使得二者重叠度较低. 这些理论结果揭示了类富勒烯团簇的发光性质和可能的荧光机理, 为寻找和设计稳定高效的发光材料提供了重要指导.

     

    Thermally activated delayed fluorescence (TADF), a unique molecular fluorescence mechanism, plays a key role in designing emitters of high efficiency. Carbon fullerenes such as C60 and C70 exhibit strong TADF with intensity even higher than that of the prompt fluorescence, owing to their long lifetimes of triplet state and modest singlet-triplet energy gaps. Thus, there arises the intriguing question whether other fullerene-like clusters can also have fluorescence and host the TADF effect. In this work, by time-dependent density functional theory (TD-DFT) calculations, we explore the excited-states of the experimentally reported boron nitride cage clusters B12N12, B24N24 and B36N36, as well as compound clusters B12P12, Al12N12 and Ga12N12 with the same geometry as B12N12. Using the HSE06 hybrid functional, the predicted energy gaps of these fullerene-like clusters are obtained to range from 2.83 eV to 6.54 eV. They mainly absorb ultraviolet light, and their fluorescence spectra are all in the visible range from 405.36 nm to 706.93 nm, including red, orange, blue, and violet emission colors. For the boron nitride cages, the energy gap of excited states increases with the cluster size increasing, accompanied by a blue shift of emission wavelength. For the clusters with B12N12 geometry and different elemental compositions, the excited energy gap decreases as the atomic radius increases, resulting in a red shift of emission wavelength. In addition, the highest occupied molecular orbitals (HOMOs) and lowest unoccupied molecular orbitals (LUMOs) of these compound cage clusters are distributed separately on different elements, resulting in small overlap between HOMO and LUMO wavefunctions. Consequently, these fullerene-like clusters exhibit small singlet-triplet energy differences below 0.29 eV, which is beneficial for the intersystem crossing between the excited singlet state and triplet state, and hence promoting the TADF process. Our theoretical results unveil the fluorescence characteristics of cage clusters other than carbon fullerenes, and provide important guidance for precisely modulating their emission colors by controlling the cluster sizes and elemental compositions. These experimentally feasible fullerene-like compound clusters possess many merits as fluorophors such as outstanding stabilities, non-toxicity, large energy gap, visible-light fluorescence, and small singlet-triplet energy gap. Therefore, they are promising luminescent materials for applications in display, sensors, biological detection and labelling, therapy, and medicine.

     

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