Deep‐Ultraviolet Nonlinear‐Optical van‐der‐Waals Beryllium Borates**

Following our ab initio nonlinear optical (NLO) materials design guidelines, in this Letter, we discovered a novel type of structure to realize potential deep-ultraviolet (DUV) NLO performance in the classical beryllium borate system. By densely stacking the NLO-active layered frameworks, the key design scheme for the structural evolution from the (Be2BO3F2) layers in KBe2BO3F2 (KBBF) to the novel (Be2BO5H3) layers in berborite is illustrated. Based on available experimental results and systematical theoretical evaluation from first principles, the NLO properties of berborite are further obtained as comparable as the only pratical DUV NLO crystal KBBF. It is demonstrated that berborite can achieve available DUV phase-matched output with strong NLO effect for the practically important 177.3 nm and 193.7 nm lasers. Once obtained with sizable single crystal, it can be applied as a promising DUV NLO crystal.