Noncentrosymmetric versus Centrosymmetric: Influence of the Na⁺ Substitution on Structural Transition and Second-Harmonic Generation Property

Abstract

A series of K 3– x Na x B 6 O 10 Br (0.5 ≤ x ≤ 1.2) polycrystalline samples have been synthesized by the standard solid-state reaction method. Four stoichiometric crystals K 3– x Na x B 6 O 10 Br ( x = 0.13, 0.67, 1.30, 2.20) have been successfully grown from the high-temperature solution, and the crystal structures were determined by single-crystal X-ray diffraction. Interestingly, the Na + concentration plays a profound role to influence the crystal structure. Up to about 23% ( x = 0.7) K + ions can be substituted by Na + ions with the same noncentrosymmetric (NCS) crystal structure of K 3 B 6 O 10 Br (space group R 3 m ) being retained, while a higher Na concentration would lead to it crystallizing in the centrosymmetric (CS) space group Pnma . Meanwhile, the second-harmonic generation (SHG) response of K 3– x Na x B 6 O 10 Br ( x ≤ 0.7) is about 2.8 times that of KDP, while the SHG response decreases sharply when x > 0.7 (the SHG response is zero at x = 1.3). After careful structural analysis, we believe that the different Br-M (M = K/Na, K, or Na) lattices, which are influenced by the coordination environments of the cations, are responsible for the structural changes from NCS to CS.