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Design and Synthesis of a Deep-Ultraviolet Nonlinear Optical Crystal KRb3B6Ge3O17 Composed of [B3O8] Units and [GeO4]
Ziqi Guo1, Xianchao Zhu1, Zhanggui Hu1
1State Key Laboratory of Crystal Materials, Tianjin Key Laboratory of Functional Crystal Materials, Institute of Functional Crystals, Tianjin University of Technology, Tianjin 300384, China.
Abstract:
Alkali metal borogermanates have emerged as promising candidates for ultraviolet (UV) and deep-ultraviolet (DUV) nonlinear optical (NLO) crystals due to their excellent comprehensive performance of a short absorption edge and moderate second harmonic response in the UV regions. A new DUV borogermanate KRb3B6Ge3O17 (KRBG) has been successfully synthesized by a high-temperature solid-state method using a boron-rich B/Ge molar ratio of 2:1. KBRG has a noncentrosymmetric structure and crystallizes in the polar space group Cc. The structure consists of two-dimensional (2D) infinite layers formed by the interconnection and coplanar arrangement of the [B3O8] groups and [GeO4] tetrahedra. The layers are alternately connected by isolated [GeO4] tetrahedra bridging and [GeO4] tetrahedra sharing O atom connections, effectively eliminating the dangling bonds of [B3O8] units and shifting the UV cutoff edge to the DUV region. Experimental and theoretical calculations show that KRBG has a DUV cutoff edge (λcutoff < 200 nm), a large bandgap (6.11 eV), and a moderate second harmonic generation (SHG) effect (1.1 × KDP). The above findings reveal that KRBG is a highly potential NLO crystal in UV and even DUV regions, enriching the structural variety of borogermanate.
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