Issue 9, 2022

Unprecedented mid-infrared nonlinear optical materials achieved by crystal structure engineering, a case study of (KX)P2S6 (X = Sb, Bi, Ba)

Abstract

Three acentric type-I phase-matchable infrared nonlinear optical materials KSbP2S6, KBiP2S6, and K2BaP2S6, showing excellent balance between the second harmonic generation coefficient, bandgap, and laser damage threshold, were synthesized via a high-temperature solid-state method. KSbP2S6 is isostructural to KBiP2S6, which both crystallize in the β-KSbP2Se6 structure type. K2BaP2S6 was discovered for the first time, which crystallizes in a new structure type. KSbP2S6 and KBiP2S6 exhibit close structural similarity to the parent compound, centrosymmetric Ba2P2S6. The [P2S6] motifs, isotypic to ethane, exist in Ba2P2S6, KSbP2S6, KBiP2S6, and K2BaP2S6. The mixed cations, K/Sb pair, K/Bi pair, and K/Ba pair, play a dual-role of aligning the [P2S6] structure motifs, contributing to a high SHG coefficient, as well as enlarging the bandgap. KSbP2S6, KBiP2S6, and K2BaP2S6 are direct bandgap semiconductors with a bandgap of 2.9(1) eV, 2.3(1) eV and 4.1(1) eV, respectively. KSbP2S6, KBiP2S6, and K2BaP2S6 exhibit a high second harmonic response of 2.2× AgGaS2, 1.8× AgGaS2, and 2.1× AgGaS2, respectively, coupled with a high laser damage threshold of 3× AgGaS2, 3× AgGaS2, and 8× AgGaS2, respectively. The DFT calculations also confirm that the large SHG coefficient mainly originates from [P2S6] anionic motifs.

Graphical abstract: Unprecedented mid-infrared nonlinear optical materials achieved by crystal structure engineering, a case study of (KX)P2S6 (X = Sb, Bi, Ba)

Supplementary files

Article information

Article type
Edge Article
Submitted
07 Dec 2021
Accepted
02 Feb 2022
First published
02 Feb 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2022,13, 2640-2648

Unprecedented mid-infrared nonlinear optical materials achieved by crystal structure engineering, a case study of (KX)P2S6 (X = Sb, Bi, Ba)

V. Nguyen, B. Ji, K. Wu, B. Zhang and J. Wang, Chem. Sci., 2022, 13, 2640 DOI: 10.1039/D1SC06849K

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