A Sharp Improvement of Sulfate's Birefringence Induced by the Synergistic Effect of Heteroleptic and Dimeric Strategies

Abstract

As for tetrahedron-based ultraviolet nonlinear optical crystals, it is so difficult to achieve a sufficient birefringence to satisfy the phase-matching condition. Thereover, it is necessary to greatly increase the polarizability anisotropy of tetrahedra. Meanwhile, the tetrahedra should be arranged as uniformly as possible. Based on these ideas, a new strategy that dimerizes the heteroleptic tetrahedra with heteroleptic atoms as bridges is proposed and implemented, resulting in a new compound, Na₂S₃O₆, which crystallizes in a centrosymmetric monoclinic phase (phase-I) and a non-centrosymmetric orthorhombic one (phase-II). In the phase-I, a large birefringence of 0.103 @ 546 nm comparable to those of many triangle-based crystals is confirmed experimentally, indicating the ability of [S₃O₆] group in improving the birefringence. Besides, the phase-II exhibits an improved birefringence of 0.056 @ 546 nm and a moderate second harmonic generation response of 1.4 × KH₂PO₄. In particular, the phase-II exhibits a typical phase-matching behavior under the irradiation of 532 nm laser. Moreover, the excellent optical properties of [S₃O₆] group are further verified by theoretical calculations. These results completely illustrate the validity of the design strategy. Therefore, this work lights a new route for exploring novel ultraviolet nonlinear optical crystals.