Chen Jindong, Wu Qingchen, Tian Haotian, Jiang Xiaotian, Xu Feng, Zhao Xin, Lin Zheshuai, Luo Min, Ye Ning
Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences Fuzhou, Fujian, 350002, China.
University of Chinese Academy of Sciences, Beijing, 100049, China.
Adv Sci (Weinh). 2022 May;9(14):e2105787. doi: 10.1002/advs.202105787. Epub 2022 Mar 31.
Pnictides are superior infrared (IR) nonlinear optical (NLO) material candidates, but the exploration of NLO pnictides is still tardy due to lack of rational material design strategies. An in-depth understanding structure-performance relationship is urgent for designing novel and eminent pnictide NLO materials. Herein, this work unravels a vital band gap mechanism of pnictides, namely P atom with low coordination numbers (2 CN) will cause the decrease of band gap due to the delocalization of non-bonding electron pairs. Accordingly, a general design paradigm for NLO pnictides, ionicity-covalency-metallicity regulation is proposed for designing wide-band gap NLO pnictides with maintained SHG effect. Driven by this idea, millimeter-level crystals of MgSiP2 are synthesized with a wide band gap (2.34 eV), a strong NLO performance (3.5 x AgGaS ), and a wide IR transparency range (0.53-10.3 µm). This work provides an essential guidance for the future design and synthesis of NLO pnictides, and also opens a new perspective at Zintl chemistry important for other material fields.
磷化物是优异的红外（IR）非线性光学（NLO）材料候选物，但由于缺乏合理的材料设计策略，NLO磷化物的探索仍然滞后。深入理解结构-性能关系对于设计新型卓越的磷化物NLO材料至关重要。在此，这项工作揭示了磷化物的一个重要带隙机制，即低配位数（2配位）的P原子会由于非键电子对的离域而导致带隙减小。因此，提出了一种NLO磷化物的通用设计范式，即离子性-共价性-金属性调控，用于设计具有维持的倍频效应的宽带隙NLO磷化物。受此想法驱动，合成出了毫米级的MgSiP2晶体，其具有宽带隙（2.34 eV）、强NLO性能（3.5×AgGaS）和宽红外透明范围（0.53 - 10.3 µm）。这项工作为未来NLO磷化物的设计和合成提供了重要指导，也为对其他材料领域重要的Zintl化学开辟了新视角。
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