Pushing KTiOPO4-like Nonlinear Optical Sulfates into the Deep-Ultraviolet Spectral Region

Accurately designing and synthesizing new deep-ultraviolet (deep-UV) nonlinear optical (NLO) crystals that are limited by the so-called 200 nm wall on their transparency windows remain challenging. On the basis of a bandgap-directed computer-aided material design approach, two new NLO sulfates, KMgSO4F and KZnSO4F, are designed and successfully synthesized. They feature three-dimensional frameworks closely related to the commercial NLO crystal, KTiOPO4 (KTP). Remarkably, the transmittance spectrum based on a single crystal indicates that the transparency window of KZnSO4F is significantly blue-shifted to <190 nm from 350 nm for KTP. The microscopic origin of this significant transparent window blue shift is illustrated well by first-principles calculations. This work pushes the transparency windows of KTP-like NLO sulfates into the deep-UV spectral region for the first time and will pave a prospective way to the accurate design and synthesis of new deep-UV NLO materials.

Automated summary

This study successfully designed and synthesized two new deep-ultraviolet nonlinear optical crystals by using a bandgap-directed computer-aided material design approach. The transmittance spectrum of one of the crystals, KZnSO4F, showed a significant blue-shifted transparency window to <190 nm, which was explained by first-principles calculations. This work pushes the transparency windows of KTP-like NLO sulfates into the deep-UV spectral region for the first time and will pave a prospective way to the accurate design and synthesis of new deep-UV NLO materials.