van der Waals solid solution crystals for highly efficient in-air photon upconversion under subsolar irradiance
van der Waals solid solution crystals for highly efficient in-air photon upconversion under subsolar irradiance
复制标题
DOI：
10.1039/d1mh01542g
复制
发表时间：
2021-10-28
影响因子：
13.3
通讯作者：
Murakami, Yoichi
中科院分区：
文献类型：
--
作者：
Enomoto, Riku;Hoshi, Megumi;Murakami, Yoichi
三重态敏化光子上转换(UC)具有广泛的应用前景。然而，由于结晶度低、晶区小和三重态敏化剂的聚集而导致的激子输运不良，对高性能固体材料的追求受到了挑战。在这里，我们展示了范德瓦尔斯固溶体概念在生产具有非凡性能的分子晶体方面的巨大优势。0.001级的卟啉增敏剂在重结晶过程中溶解在含有大量侧基的蓝色荧光碳氢化合物消光剂9-(2-naphthyl)-10-[4-(1-naphthyl)phenyl]anthracene(ANNP)的分子晶体中。这一尝试产生了毫米大小、颜色均匀、透明的固溶体晶体，解决了长期以来存在的感光剂聚集问题。这种晶体在空气中表现出前所未有的光致发光性能(量子产率达到16%，最高定义为50%；激发强度阈值为0.175太阳；光稳定性超过15万S)，这证明了这一概念在寻找优质的光致发光固体材料方面是非常有效的。
Triplet-sensitized photon upconversion (UC) has been proposed for broad applications. However, the quest for superior solid materials has been challenged by the poor exciton transport often caused by low crystallinity, a small crystal domain, and aggregation of triplet sensitizers. Here, we demonstrate substantial advantages of the van der Waals solid solution concept to yield molecular crystals with extraordinary performance. A 0.001%-order porphyrin sensitizer is dissolved during recrystallization into the molecular crystals of a blue-fluorescent hydrocarbon annihilator, 9-(2-naphthyl)-10-[4-(1-naphthyl)phenyl]anthracene (ANNP), which contains bulky side groups. This attempt yields millimeter-sized, uniformly colored, transparent solid solution crystals, which resolves the long-standing problem of sensitizer aggregation. After annealing, the crystals exhibit unprecedented UC performance (UC quantum yield reaching 16% out of a maximum of 50% by definition; excitation intensity threshold of 0.175 sun; and high photostability of over 150 000 s) in air, which proves that this concept is highly effective in the quest for superior UC solid materials.