Small Changes,Big Impact: Tungsten Bronzes with Extremely Large Second Harmonic Generation Achieved by the Transition Metal Doping on the B-Site

Two novel transition metal-doped tungsten bronze oxides, Pb_2.15Li_0.85Nb_4.85Ti_0.15O₁₅ (PLNT) and Pb_2.15Li_0.55Nb_4.85W_0.15O₁₅ (PLNW), are synthesized by high-temperature solid-state reactions. The Rietveld method using the high-resolution synchrotron radiation indicates that PLNT and PLNW crystallize in the orthorhombic polar noncentrosymmetric space group, Pmn2₁ (no. 31). As a class of tungsten bronze oxide, PLNT and PLNW retain a unique rigid framework composed of d⁰ transition metal cation (Ti⁴⁺ or W⁶⁺)-doped highly distorted NbO₆ octahedra along with the subsequently generated Pb/LiO₁₂ and PbO₁₅ polyhedra. Interestingly, the d⁰ transition metal-doped tungsten bronzes, PLNT and PLNW, exhibit extremely large second-harmonic generation (SHG) responses of 56 and 67 × KH₂PO₄, respectively. The observed immeasurably strong SHG is mainly attributed to a net polarization originating from the alignment of highly distorted NbO₆ octahedra with doped transition metals in the frameworks. It is believed that doping transition metal cations at the B-site of the tungsten bronze structures should be an innovative strategy to develop novel high-performance nonlinear optical materials.