Hu Cong, Cheng Meng, Jin Wenqi, Han Jian, Yang Zhihua, Pan Shilie
Research Center for Crystal Materials, CAS Key Laboratory of Functional Materials and Devices for Special Environments, Xinjiang Technical Institute of Physics & Chemistry, CAS, 40-1 South Beijing Road, Urumqi 830011, China.
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China.
Research (Wash D C). 2023;6:0053. doi: 10.34133/research.0053. Epub 2023 Mar 9.
The design of new materials with special performances is still a great challenge, especially for the deep-ultraviolet nonlinear optical materials in which it is difficult to balance large bandgaps and strong second harmonic generation responses due to their inverse relationship. Cation variation not only influences the whole structure frameworks but also directly participates in the formation of electronic structures, both of which could lead to the uncontrollability of the properties of the designed materials. Here, a novel approach, aiming at purposeful and foreseeable material designs, is proposed to characterize the role of cations. By the verification of several series of borates, the influences of cation variation on property changes are explored systematically. Accordingly, a feasible strategy of designing deep-ultraviolet nonlinear optical materials by substituting barium for lead has been concluded, which could obviously blue-shift the ultraviolet cutoff edge and maintain the relatively strong second harmonic generation response (more than 2 times of KHPO), achieving the property optimization, and especially works efficiently in fluorooxoborates. The property optimization design strategy and the cation characterization method are not only helpful in exploring nonlinear optical materials but also enlightening in material design and selection.
设计具有特殊性能的新材料仍然是一项巨大的挑战，特别是对于深紫外非线性光学材料而言，由于其带隙和二次谐波产生响应之间存在反比关系，因此很难在两者之间取得平衡。阳离子的变化不仅会影响整个结构框架，还会直接参与电子结构的形成，这两者都可能导致所设计材料性能的不可控性。在此，提出了一种旨在进行有目的和可预见材料设计的新方法，以表征阳离子的作用。通过对几系列硼酸盐的验证，系统地探索了阳离子变化对性能变化的影响。据此，得出了一种用钡替代铅来设计深紫外非线性光学材料的可行策略，该策略可使紫外截止边明显蓝移，并保持相对较强的二次谐波产生响应（大于磷酸二氢钾的2倍），实现性能优化，尤其在氟氧化硼酸盐中效果显著。该性能优化设计策略和阳离子表征方法不仅有助于探索非线性光学材料，而且对材料设计和选择也具有启发性。
