National Laboratory of Solid State Microstructures and Department of Physics, Nanjing University, Nanjing, 210093, P. R. China.
School of Physics, Southeast University, Nanjing, 211189, P. R. China.
Small. 2018 Nov;14(48):e1803132. doi: 10.1002/smll.201803132. Epub 2018 Oct 11.
Although 2D black phosphorus (BP) shows excellent optical and electronic properties, there are few reports on the photoluminescence (PL) properties of BP nanostructures because of the low yield of mechanical exfoliation, instability in water, and relatively weak emission. Herein, liquid exfoliation is combined with surface passivation to produce fluorescent BP quantum dots (BPQDs) with a high yield. The BPQDs exhibit strong PL in both ethanol and water and the absolute fluorescent quantum yield in water reaches 70%. Moreover, the BPQD solution exhibits stable PL for 150 d under ambient conditions and better photostability than conventional organic dyes and heavy-metal semiconducting nanostructures with intense fluorescence. The experiments and theoretical calculation reveal that the intense and stable PL originates from the intrinsic band-to-band excitation states and two surface states related to the POH and POCH CH bonding structures introduced by passivation. The polar water molecules remove many nonradiative centers and simultaneously increase the P-related fluorescent groups on the surface of BPQDs. Therefore, PL from the BPQDs in water is enhanced largely. The excellent fluorescent properties of BPQDs in an aqueous solution bode well for bioimaging and the negligible biotoxicity and distinct cell images suggest large potential in the biomedical and display fields.
尽管二维黑磷(BP)表现出优异的光学和电子性能,但由于机械剥落的产率低、在水中不稳定以及相对较弱的发射,关于 BP 纳米结构的光致发光(PL)特性的报道很少。在此,通过液相剥离并结合表面钝化来制备具有高产率的荧光 BP 量子点(BPQDs)。BPQDs 在乙醇和水中均表现出强 PL,并且在水中的绝对荧光量子产率达到 70%。此外,BPQD 溶液在环境条件下可稳定地发出 PL 达 150 天,并且具有比传统有机染料和强荧光重金属半导体纳米结构更好的光稳定性。实验和理论计算表明,强烈而稳定的 PL 源于本征的带带激发态以及与钝化引入的 POH 和 POCH CH 键合结构相关的两个表面态。极性水分子去除了许多非辐射中心,同时增加了 BPQDs 表面上与 P 相关的荧光基团。因此,水中的 BPQDs 的 PL 得到了极大的增强。BPQDs 在水溶液中的优异荧光性能有望应用于生物成像,而且其可忽略的生物毒性和明显的细胞成像表明其在生物医学和显示领域有很大的应用潜力。