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Intense d-p Hybridization in Nb3 O15 Tripolymer Induced the Largest Second Harmonic Generation Response and
Kaichuang Chen1,2, Chensheng Lin1, Jindong Chen3
1Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002, Fuzhou, Fujian, China.
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.
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