Ultraviolet

Anisotropy

Materials science

Optical anisotropy

Band gap

Physics

Optics

Tetrahedron

Crystallography

Chemistry

Birefringence

Optoelectronics

Advanced Science

Understanding and exploring the functional modules (FMs) consisting of local atomic groups can promote the development of the materials with functional performances. Oxygen‐containing tetrahedral modules are popular in deep‐ultraviolet (DUV) optical materials, but their weak optical anisotropy is adverse to birefringence. Here, the fluorooxosulfate group is proved as a new birefringence‐enhanced FM for the first time. The birefringence of fluorooxosulfates can be 4.8–15.5 times that of sulfates with the same metal cations while maintaining a DUV band gap. The polarizing microscope measurement confirms the birefringence enhancement by using the millimeter crystals experimentally. The theoretical studies from micro and macro levels further reveal a novel universal strategy that the fluorine induced anisotropic electronic distribution in fluorooxo–tetrahedral group is responsible for the enhancement of birefringence. This study will guide the future discovery of DUV optical materials with enlarged birefringence.

Fluorine‐Driven Enhancement of Birefringence in the Fluorooxosulfate: A Deep Evaluation from a Joint Experimental and Computational Study