He Wenyu, Zhu Xianchao, Hu Zhanggui, Wang Jiyang, Wu Yicheng
Tianjin Key Laboratory of Functional Crystal Materials, Institute of Functional Crystals, Tianjin University of Technology, Tianjin 300384, China.
Inorg Chem. 2024 Oct 7;63(40):19023-19029. doi: 10.1021/acs.inorgchem.4c03422. Epub 2024 Sep 22.
A new deep-ultraviolet (DUV) nonlinear optical (NLO) material KRbBPO (KRBPO) has been designed and synthesized by adjusting the B/P molar ratio to 8:1. The KRBPO crystals were synthesized by a flux method and crystallized in noncentrosymmetric (NCS) and polar space group This compound exhibits a double-layer structure in which the A layer is composed of [BO] and [BO] units and the B layer is formed by interconnected [BO] and [BO] groups, and the two layers are connected by [PO] tetrahedron. The theoretical calculations and experiments show that the synergistic interaction of π-conjugated and non-π-conjugated units leads to relatively well-balanced NLO properties of the title compound, including moderated SHG (0.7 × KDP), short UV cutoff edge (λ < 190 nm), and a large band gap of 6.16 eV. Specifically, the coplanar arrangement of B-O groups in double-layer makes the KRBPO display a large birefringence (0.075@532 nm) and enables the shortest phase-matched wavelength to reach an important laser output wavelength of 266 nm.
通过将硼/磷摩尔比调整为8:1，设计并合成了一种新型深紫外（DUV）非线性光学（NLO）材料KRbBPO（KRBPO）。KRBPO晶体通过助熔剂法合成，并结晶于非中心对称（NCS）极性空间群中。该化合物呈现双层结构，其中A层由[BO]和[BO]单元组成，B层由相互连接的[BO]和[BO]基团形成，两层通过[PO]四面体连接。理论计算和实验表明，π共轭单元和非π共轭单元的协同相互作用导致标题化合物具有相对平衡的NLO性质，包括适度的倍频效应（0.7×KDP）、短的紫外截止边（λ<190nm）和6.16eV的大带隙。具体而言，双层中B-O基团的共面排列使KRBPO表现出大的双折射（532nm处为0.075），并使最短的相位匹配波长达到重要的激光输出波长266nm。
