Toward Large Second-Harmonic Generation and Deep-UV Transparency in Strongly Electropositive Transition Metal Sulfates

Chao Wu; Chunbo Jiang; Guangfeng Wei; Xingxing Jiang; Zujian Wang; Zheshuai Lin; Zhipeng Huang; Mark G Humphrey; Chi Zhang

doi:10.1021/jacs.2c11645

Toward Large Second-Harmonic Generation and Deep-UV Transparency in Strongly Electropositive Transition Metal Sulfates

J Am Chem Soc. 2023 Feb 8;145(5):3040-3046. doi: 10.1021/jacs.2c11645. Epub 2023 Jan 12.

Authors

Chao Wu¹, Chunbo Jiang¹, Guangfeng Wei¹, Xingxing Jiang², Zujian Wang², Zheshuai Lin², Zhipeng Huang¹, Mark G Humphrey³, Chi Zhang¹

Affiliations

¹ China-Australia Joint Research Center for Functional Molecular Materials, School of Chemical Science and Engineering, Tongji University, Shanghai 200092, China.
² Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
³ Research School of Chemistry, Australian National University, Canberra, ACT 2601, Australia.

PMID: 36634002
DOI: 10.1021/jacs.2c11645

Abstract

The development of deep-ultraviolet (DUV)/solar-blind UV nonlinear optical (NLO) crystals simultaneously possessing wide UV transparency, strong second-harmonic generation (SHG) response, and suitable birefringence is a major challenge in advanced laser technology. We herein propose a "cation compensation" strategy for strong optical nonlinearity in inorganic solids that is exemplified by the introduction of strongly electropositive transition metals (TMs). Following this strategy, the first d⁰ TM UV-transparent NLO sulfates, MF₂(SO₄) (M = Zr (ZFSO), Hf (HFSO)), have been synthesized. Short UV cutoff edges of 206 nm and below 190 nm are observed for bulk ZFSO and HFSO crystals, respectively, together with the strongest powder SHG responses (3.2 × (ZFSO) and 2.5 × KDP (HFSO)) for solar-blind UV/DUV NLO sulfates, as well as suitable birefringence. This work provides a new and efficient approach to the development of urgently needed high-performance NLO materials for applications in the short-wavelength UV region.