Non-π-Conjugated Deep-Ultraviolet Nonlinear Optical Crystal K2Zn3(SO4)(HSO4)2F4

Yang Zhou; Xingyu Zhang; Zheyao Xiong; Xifa Long; Yanqiang Li; Yangxin Chen; Xin Chen; Sangen Zhao; Zheshuai Lin; Junhua Luo

doi:10.1021/acs.jpclett.1c01533

Non-π-Conjugated Deep-Ultraviolet Nonlinear Optical Crystal K₂Zn₃(SO₄)(HSO₄)₂F₄

J Phys Chem Lett. 2021 Sep 2;12(34):8280-8284. doi: 10.1021/acs.jpclett.1c01533. Epub 2021 Aug 23.

Authors

Yang Zhou^{1

2}, Xingyu Zhang³, Zheyao Xiong^{1

2}, Xifa Long^{1

2}, Yanqiang Li^{1

2

4}, Yangxin Chen^{1

2}, Xin Chen^{1

2}, Sangen Zhao^{1

2

4}, Zheshuai Lin^{3

2}, Junhua Luo^{1

2

4}

Affiliations

¹ State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.
² University of the Chinese Academy of Sciences, Beijing 100049, China.
³ Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
⁴ Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou, Fujian 350108, China.

PMID: 34425677
DOI: 10.1021/acs.jpclett.1c01533

Abstract

Deep-ultraviolet (deep-UV) (wavelengths of <200 nm) nonlinear optical (NLO) materials are playing an increasingly important role because of their significant technological applications in advanced scientific instruments. In recent years, the non-π-conjugated systems have received extensive attention as new emerging sources of deep-UV NLO materials. Here, a new non-π-conjugated deep-UV NLO material, K₂Zn₃(SO₄)(HSO₄)₂F₄, has been successfully obtained by the hydrothermal method. It has a layered structure formed by [Zn₃(SO₄)(HSO₄)₂F₃]_∞ layers bridged via K-O and K-F bonds. Powder second-harmonic generation shows that K₂Zn₃(SO₄)(HSO₄)₂F₄ can achieve phase matching, and the response is ∼0.3 times that of KH₂PO₄. Remarkably, the single-crystal transmittance spectrum confirms that the absorption edge of K₂Zn₃(SO₄)(HSO₄)₂F₄ is below 200 nm, and the experimentally measured birefringence is 0.0126 at λ = 546 nm. In-depth first-principles calculations illustrate well the microscopic origin of the optical properties. This work enriches the structrual diversity of non-π-conjugated deep-UV NLO materials.