Solid-State Nonlinear Optical Switch with the Widest Switching Temperature Range Owing to Its Continuously Tunable Tc

Chun-Ya Pan; Xin-Rui Yang; Lin Xiong; Zhong-Wei Lu; Bo-Yu Zhen; Xin Sui; Xue-Bin Deng; Ling Chen; Li-Ming Wu

doi:10.1021/jacs.0c01741

Solid-State Nonlinear Optical Switch with the Widest Switching Temperature Range Owing to Its Continuously Tunable T_c

J Am Chem Soc. 2020 Apr 1;142(13):6423-6431. doi: 10.1021/jacs.0c01741. Epub 2020 Mar 18.

Authors

Chun-Ya Pan¹, Xin-Rui Yang¹, Lin Xiong², Zhong-Wei Lu¹, Bo-Yu Zhen², Xin Sui², Xue-Bin Deng¹, Ling Chen¹, Li-Ming Wu²

Affiliations

¹ Beijing Key Laboratory of Energy Conversion and Storage Materials, College of Chemistry, Beijing Normal University, Beijing 100875, People's Republic of China.
² Key Laboratory of Theoretical and Computational Photochemistry of Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875, People's Republic of China.

PMID: 32160462
DOI: 10.1021/jacs.0c01741

Abstract

Interest on the nonlinear optical (NLO) switches that turn on/off the second-harmonic generation (SHG) triggered by the external stimulus (such as heat) have continuously grown, especially on the solid-state NLO switches showing superior stability, reversibility, and reproducibility. Herein, we discover (NH₄)₂PO₃F, as an entirely new solid-state NLO switch showing outstanding switch contrast and reversibility as well as strong SHG intensity (1.1 × KH₂PO₄ (KDP)) and high laser-induced damage threshold (2.0 × KDP), undergoes a unique first-order phase transition that originates from a reversible hydrogen-bond rearrangement and needs to overcome an energy barrier. Accordingly, we put forward a strategy to continuously modify such an energy barrier by reducing the number of hydrogen bonds per unit cell via an isoelectronic replacement of NH₄⁺ by K⁺ with a similar size yet incapability of providing any hydrogen bond. Consequently, K_x(NH₄)_2-xPO₃F (x = 0-0.3) exhibiting excellent switching performance are obtained. Remarkably, K_x(NH₄)_2-xPO₃F not only realizes a continuously tunable T_c spanning from 270 to 150 K, representing the widest NLO switching temperature range ever known but also indicates the first solid-state NLO switch example with continuous T_c. Intrinsically, such a T_c decline depends on the weakening degree of the hydrogen-bonding interactions in the unit cell. These new insights will shed useful light on the future material design and open new application possibilities.