Details

Autor(en) / Beteiligte

• Zhou, Sheng-Hua
• Ran, Mao-Yin
• Wei, Wen-Bo
• Wang, A-Yang
• Wu, Xin-Tao
• Lin, Hua
• Zhu, Qi-Long

Titel

Heteroanion-introduction-driven birefringence enhancement in oxychalcogenide BaMGeOS (M = Mn, Cd)

Ist Teil von

• Inorganic chemistry frontiers, 2023-10, Vol.1 (2), p.5997-64

Erscheinungsjahr

2023

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Birefringent crystals play a crucial role in regulating the polarization of light and are widely used in optoelectronic fields. However, the effective design of novel infrared (IR) birefringent crystals with large birefringence (Δ n ) still face significant challenges. In this study, we present the rational design and successful synthesis of two novel quinary oxychalcogenides with the formula Ba 3 M II Ge 3 O 2 S 8 (M II = Mn, Cd), employing a heteroanion-introduction strategy via high-temperature solid-state reactions. Ba 3 M II Ge 3 O 2 S 8 (M II = Mn, Cd) crystallized in the monoclinic space group P 2 1 / n (no. 14) and the structures comprised one-dimensional (1D) [M II Ge 3 S 8 O 2 ] 6− chains arranged in an antiparallel manner and separated by Ba 2+ cations. The coexistence of multiple heteroanionic ligands ([M II OS 5 ] octahedra, [GeOS 3 ], and [GeO 2 S 2 ] tetrahedra) in one material was surprisingly discovered for the first time in the realm of oxychalcogenides. It was revealed that the heteroanion-introduction strategy not only leads to a reduction in the structural dimensionality but also enhances the optical anisotropy significantly. Notably, Ba 3 M II Ge 3 O 2 S 8 (M II = Mn, Cd) demonstrated large Δ n values of 0.11 and 0.14, which represent a remarkable improvement compared to the three-dimensional (3D) parent AE 3 M II M IV 2 Q 8 system (Δ n = 0). Furthermore, theoretical calculations suggest that the significant Δ n of Ba 3 M II Ge 3 O 2 S 8 (M II = Mn, Cd) resulted primarily from the combination of polarizabilities from the various heteroanionic groups. Overall, these results highlight the potential of the heteroanion-introduction strategy for designing novel IR birefringent materials for optoelectronic applications. Two novel 1D quinary oxychalcogenides, Ba 3 M II Ge 3 O 2 S 8 (M II = Mn, Cd), were designed using a heteroanion-introduction strategy, which exhibit a significant enhancement in birefringence compared to the known 3D framework AE 3 M II M IV 2 Q 8 .