Halogen-Ion-Induced Structural Phase Transition Giving a Polymorph of HgBr2 with Balanced Nonlinear Optical Properties.

The key to developing new infrared nonlinear optical (NLO) materials is balancing second-order nonlinear optical effects and the laser-induced damage threshold (LIDT). In this paper, a new polymorph of HgBr2 (P212121) was synthesized by a "halogen-ion-induced effect" in solution, which features a crystal structure different from that of the original phase (Cmc21) and exhibits better NLO properties. Its powders show a strong SHG effect (9 × KDP), a high LIDT (30 × AgGaS2), a wide infrared transparent range, and stability in air, making it a prospective NLO material in the IR region. In addition, the above excellent NLO characteristics are well illustrated in DFT theoretical calculations. More importantly, experimental results show that the new infrared NLO polymorph with excellent comprehensive properties could be controllably obtained by using the halogen-ion-induced strategy.