Breaking through the “3.0 eV wall” of energy band gap in mid-infrared nonlinear optical rare earth chalcogenides by charge-transfer engineering

Dajiang Mei; Wangzhu Cao; Naizheng Wang; Xingxing Jiang; Jun Zhao; Weikang Wang; Junhui Dang; Shiyan Zhang; Yuandong Wu; Pinhua Rao; Zheshuai Lin

doi:10.1039/D1MH00562F

Breaking through the “3.0 eV wall” of energy band gap in mid-infrared nonlinear optical rare earth chalcogenides by charge-transfer engineering†

Dajiang Mei,*^ac Wangzhu Cao,^a Naizheng Wang,

^bd Xingxing Jiang,*^b Jun Zhao,

^a Weikang Wang,

^a Junhui Dang,^a Shiyan Zhang,^a Yuandong Wu,^a Pinhua Rao

^a and Zheshuai Lin

*^bd

Author affiliations

* Corresponding authors

^a College of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, Shanghai 201620, China
E-mail: meidajiang718@pku.edu.cn

^b Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China
E-mail: xxjiang@mail.ipc.ac.cn, zslin@mail.ipc.ac.cn

^c State Key Laboratory of Crystal Materials and Institute of Crystal Materials, Shandong University, Jinan, 250100, China

^d University of Chinese Academy of Sciences, Beijing 100049, China

Abstract

Increasing the energy band gap under the premise to maintain a large nonlinear optical (NLO) response is a challenging issue for the exploration and molecular design of mid-infrared nonlinear optical crystals. Utilizing a charge-transfer engineering method, we designed and synthesized a rare earth chalcogenide, KYGeS₄. With an NLO effect as large as that in AgGaS₂, KYGeS₄ breaks through the limitation of energy band gap, i.e., the “3.0 eV wall”, in NLO rare earth chalcogenides, and thus exhibits an excellent comprehensive NLO performance. First-principles electronic structure analysis demonstrates that the large band gap in KYGeS₄ is ascribed to the decreased covalency of Y–S bonds by transferring charge from [YS₇] to [GeS₄] polyhedra. The charge-transfer engineering strategy would have significant implications for the exploration of good-performance NLO crystals.

This article is part of the themed collection: Materials Horizons Lunar New Year collection 2022

Materials Horizons

Breaking through the “3.0 eV wall” of energy band gap in mid-infrared nonlinear optical rare earth chalcogenides by charge-transfer engineering†

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Breaking through the “3.0 eV wall” of energy band gap in mid-infrared nonlinear optical rare earth chalcogenides by charge-transfer engineering

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