ZIF-8 as nonlinear optical material: influence of structure and synthesis

Journal article (2016)

Authors

S van Cleuvenbergen Katholieke Universiteit Leuven

Ivo Stassen Katholieke Universiteit Leuven

E Gobechiya Katholieke Universiteit Leuven

Y. Zhang University of Namur

K Markey Katholieke Universiteit Leuven

Dirk E. De Vos Katholieke Universiteit Leuven

CEA Kirschhock Katholieke Universiteit Leuven

Benoit Champagne University of Namur

T Verbiest Katholieke Universiteit Leuven

M.A. van der Veen

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Published Date

2016

Language

English

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Abstract

Metal–organic framework ZIF-8, from the zeolitic imidazolate framework family, shows a large intrinsic second-order nonlinear optical (NLO) response. In addition, ZIF-8 is a stable, inexpensive material that is transparent in the visible (vis) and near-infrared (NIR) window. This is crucial for NLO applications. The second-order NLO activity is due to the noncentrosymmetric octupolar symmetry of the material. We found that fast syntheses lead to a lower second-order NLO response. Consistent with polarized second-harmonic generation (SHG) microscopy measurements, we ascribe this to defects that create local centers of centrosymmetry but do not affect the orientation of the crystal lattice. Syntheses with slow nucleation lead to quasi-perfect crystals with a large average second-order NLO coefficient ⟨deff⟩ of 0.25 pm/V, which is explained and supported by ab initio theoretical calculations.