Syntheses, structure and properties of a new series of organic–inorganic Hg-based halides: adjusting halogens resulted in huge performance mutations

Abstract

Three new organic–inorganic hybrid perovskite (OIHP) halides, [N(CH₃)₄]HgCl_0.63Br_2.37 (I), [N(CH₃)₄]HgBrI₂ (II) and [N(CH₃)₄]HgCl_0.45I_2.55 (III), were synthesized by a hydrothermal reaction. They feature different crystal structures, in which both II and III are isomorphic and contain a one-dimensional chain with organic cation [N(CH₃)₄]⁺ interspersed in the space, whereas II has a similar one-dimensional chain but significantly different spatial arrangement due to the enhanced hydrogen bond interaction. The experimental results show that the divergent second-order nonlinear optical (NLO) effect from Br(Cl) to I and the arrangement of anion groups change dramatically from the presence of hydrogen bonds to the absence of hydrogen bonds, leading to a sharply increased NLO response of II and III (18 and 25 times that of I) compared with that of I. Moreover, the phase matching ability disappeared and the band gap decreased significantly. Meanwhile, a high temperature phase transition was observed in II and III, which is rare in common OIHPs. All these results indicate that the regulation of halogen bonds plays a crucial role in the structural and property mutations of OIHP halides.