Intense <i>d‐p</i> Hybridization in Nb₃O₁₅ Tripolymer Induced the Largest Second Harmonic Generation Response and Birefringence in Germanates

Abstract

We herein report two asymmetric germanate crystals, KNbGe₃ O₉ and K₃ Nb₃ Ge₂ O₁₃ , with different structures and optical properties derived from divergent polymerized forms of GeO₄ and NbO₆ groups. Remarkably, K₃ Nb₃ Ge₂ O₁₃ achieved a rare combination of the strongest second harmonic generation (SHG) response of 17.5×KDP @ 1064 nm and the largest birefringence of 0.196 @ 546 nm in germanates. It features unique [Nb₃ O₁₂ ]_∞ tubular chains constructed by circular Nb₃ O₁₅ tripolymers. Theoretical calculations reveal that the d-p interactions in the Nb₃ O₁₅ group are responsible for outstanding optical properties. This work emphasizes the significance of the polymerizable functional units in obtaining high-performance nonlinear optical (NLO) crystals.