HgB2S4: A d10 Metal Thioborate with Giant Birefringence and Wide Band Gap

Birefringent crystals are important optical devices in various advanced optical systems because they can create and control polarized light. In this work, the capability of planar [B3S6] to produce large birefringence was theoretically studied for the first time. Moreover, the first d10 metal thioborate HgB2S4 (HBS) has been synthesized successfully, which was constructed by the π-conjugated [B3S6] and [HgS2] units. Notably, HBS shows great potential to be an infrared birefringent material due to its large birefringence, Δn = 0.52 @ 1064 nm (∼4.3 × α-BaB2O4 and ∼10.4 × AgGaS2 @ 1064 nm), wide band gap of 3.36 eV, and wide transparent window (∼0.37–25 μm). To the best of our knowledge, both the birefringence and the band gap of HBS are the largest among mercury sulfides. Structure-performance analyses reveal that the π-conjugated [B3S6] units are the main birefringence contributor and could be regarded as a good unit for designing IR birefringent materials. This work will provide direct guidance to design high performance birefringent crystals in the future.