A(3)A(3)' Zn6Te4O24 (A = Na, A ' = Rare Earth) Garnets: A-Site Ordered Noncentrosymmetric Structure, Photoluminescence, and Na-Ion Conductivity

A large number of oxides that adopt the centrosymmetric (CS) garnet-type structure (space group Ia (3) over bard) have been widely studied as promising magnetic and host materials. Hitherto, no noncentrosymmetric (NCS) garnet has been reported yet, and a strategy to NCS garnet design is therefore significant for expanding the application scope. Herein, for the series A(3)A(3)'Zn6Te4O24 (A = Na, A' = La, Eu, Nd, Y, and Lu), we demonstrated that the structural symmetry evolution from CS Ia (3) over bard (A' = La) to NCS I4(1)22 (A' = Eu, Nd, Y, and Lu) could be achieved due to the A-site cationic ordering-driven inversion symmetry breaking. Na(3)A(3)'Zn6Te4O24 (A' = rare earth) are the first garnets that possess NCS structures with A-site cationic ordering. Diffuse reflectance spectra and theoretic calculations demonstrated that all these NCS garnets are indirect semiconductors. Moreover, their potential applications as host materials for red phosphors and Na-ion conductors were also investigated in detail, which firmly confirmed the NCS structure and A-site cationic ordering. Our findings have paved the way to design NCS or even polar garnets that show intriguing functional properties, such as ferroelectricity, multiferroicity, and second harmonic generation.