Traditional fluorides are rarely reported as candidates for nonlinear optical (NLO) materials featuring deep-ultraviolet (DUV) cutoff edge. Theoretical investigations suggest that the ZrF8 dodecahedron shows large polarizability anisotropy and benefits for large birefringence. Herein, a new fluorine-rich fluoride, K3Ba2Zr6F31, was synthesized by coupling ZrF8 group and features the acentric cis-[Zr6F34]10‒ clusters with the 63-screw axis. Significantly, K3Ba2Zr6F31 exhibits short UV cutoff edge (below 200 nm) and moderate second-harmonic generation response (0.5 × KH2PO4 (KDP)). It also possesses a relatively large birefringence (0.08@1064 nm), together with a broad transparency window (2.5‒21.1 μm). First-principles calculations suggest that the cis-[Zr6F34]10‒ cluster built by ZrF8 dodecahedra are the dominant contributor to the large band gap (7.89 eV, cal.) and SHG response simultaneously. Such a systematic work declares that Zr-based fluorides afford a new paradigm for the development of efficient NLO materials with short UV cutoff edge.

This article is Open Access

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