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Two-stage evolution from phosphate to sulfate of new KTP-type family members as UV nonlinear optical materials through chemical cosubstitution-oriented design

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Abstract

KTiOPO4 (KTP) is a classic commercial nonlinear optical (NLO) crystal, but its narrow bandgap (3.52 eV) prevents its practical application in the ultraviolet (UV) region. Many trials to widen the narrow bandgap of KTP have failed in the past few decades. A chemical cosubstitution strategy was implemented to design new members of the KTP-type family as potential UV NLO materials. First, a novel centrosymmetric KTP-type compound NH4SbFPO4·H2O with a sharply enlarged bandgap (5.01 eV) was obtained through three-site aliovalent substitution. Second, the noncentrosymmetric NH4SbF2SO4 was synthesized by the introduction of more F anions to destroy the crystal symmetry and SO42− to replace PO43− for balancing the charge in NH4SbFPO4·H2O, which realized the transformation from a visible phosphate system to solar blind UV sulfate system for KTP-type family NLO materials. The preliminary experimental results indicated that NH4SbF2SO4 is a promising solar blind UV NLO material. The first-principles calculations revealed that the sharply enlarged bandgap resulted from the substitution of the transition metal cations with the main group metal cations and the introduction of F anions with high electronegativity.

Graphical abstract: Two-stage evolution from phosphate to sulfate of new KTP-type family members as UV nonlinear optical materials through chemical cosubstitution-oriented design

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Supplementary files

Article information


Submitted
06 Mar 2020
Accepted
26 Mar 2020
First published
26 Mar 2020

Dalton Trans., 2020, Advance Article
Article type
Paper

Two-stage evolution from phosphate to sulfate of new KTP-type family members as UV nonlinear optical materials through chemical cosubstitution-oriented design

F. He, Y. Ge, X. Zhao, J. He, L. Huang, D. Gao, J. Bi, X. Wang and G. Zou, Dalton Trans., 2020, Advance Article , DOI: 10.1039/D0DT00846J

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