Symmetry breaking of A 3 M 2 X 9 -type perovskite derivatives induced by polar quaternary ammonium cations: achieving efficient nonlinear optical properties.

Low-dimensional organic-inorganic metal halides, especially lead-free perovskites, are attracting increasing attention because of their environmentally friendly processing, flexible structures, chemical stability, and promising nonlinear optical properties. Herein, we report a new stable polar 0D lead-free hybrid bismuth chloride to enable the second-harmonic generation (SHG) active material (BTA) 3 Bi 2 Cl 9 (BTA = benzyltriethylammonium, C 6 H 5 CH 2 N(C 2 H 5 ) 3 + ) that was obtained by the antisolvent vapor diffusion method and crystallized in the polar Cc space group. Its structure features organic cations surrounded by face-sharing [Bi 2 Cl 9 ] 3- dimers. (BTA) 3 Bi 2 Cl 9 exhibits a wide direct bandgap (3.21 eV) and a strong phase-matchable SHG conversion efficiency (1.39 × KDP). Theoretical calculation reveals that the SHG response is owing to the synergistic effect of distorted inorganic [Bi 2 Cl 9 ] 3- anions and polar organic BTA + cations. This work not only enriches the family of organic-inorganic A 3 M 2 X 9 (A = monovalent cations; M = trivalent metal ions; and X = halide ions) NLO crystals but also provides the possibilities for further designing novel lead-free semiconducting piezoelectric, pyroelectric and ferroelectric materials.