BaCdSnS4 and Ba3CdSn2S8: syntheses, structures, and non-linear optical and photoluminescence properties.
Two non-centrosymmetric metal chalcogenides, BaCdSnS4 and Ba3CdSn2S8, were synthesized using a high temperature solid-state reaction in an evacuated silica tube. Although the two compounds have the same building units in their structures, namely CdS4, SnS4 and BaS8 units, both of them have different structures. BaCdSnS4 crystallizes in the orthorhombic space group Fdd2 and its structure can be characterized by the two-dimensional ∞[Cd-Sn-S] layers composed of corner- and edge-sharing CdS4 and SnS4 tetrahedra with Ba atoms located between the two adjacent ∞[Cd-Sn-S] layers. Ba3CdSn2S8 crystallizes in the space group I4[combining macron]3d of the orthorhombic system and the CdS4 and SnS4 groups are connected with each other via corner-sharing to form a three-dimensional framework, which is different from the 2D ∞[Cd-Sn-S] layer structure in BaCdSnS4. The UV-vis-NIR diffuse-reflectance spectra show that the experimental band gaps are about 2.30 eV for BaCdSnS4 and 2.75 eV for Ba3CdSn2S8, respectively. IR and Raman measurement results indicate that their transparent ranges are up to 25 μm. Second-order NLO measurements show that BaCdSnS4 exhibits strong powder second-harmonic generation (SHG) intensities at 2.09 μm laser pumping that are ∼5 and 0.7 times that of AgGaS2 in the particle size 38-55 and 150-200 μm, respectively, whereas Ba3CdSn2S8 only exhibits SHG intensities of about 0.8 and 0.1 times that of AgGaS2 at the same particle sizes. The origin of the NLO response in BaCdSnS4 may originate from the macroscopic arrangement of the SnS4 and CdS4 tetrahedra. Furthermore, the photoluminescence properties of the two compounds have also been investigated and show obvious blue and green light emission.
Key Laboratory of Functional Materials and Devices for Special Environments, Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences, Xinjiang Key Laboratory of Electronic Information Materials and Devices, 40-1 South Beijing Road, Urumqi 830011, China. slpan@ms.xjb.ac.cn wukui@ms.xjb.ac.cn and School of Physics Science and Technology, Xinjiang University, Urumqi, Xinjiang 830046, China.
Ni
N
Zhen
Key Laboratory of Functional Materials and Devices for Special Environments, Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences, Xinjiang Key Laboratory of Electronic Information Materials and Devices, 40-1 South Beijing Road, Urumqi 830011, China. slpan@ms.xjb.ac.cn wukui@ms.xjb.ac.cn.
Kui
K
Wu
Key Laboratory of Functional Materials and Devices for Special Environments, Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences, Xinjiang Key Laboratory of Electronic Information Materials and Devices, 40-1 South Beijing Road, Urumqi 830011, China. slpan@ms.xjb.ac.cn wukui@ms.xjb.ac.cn.
Ying
Y
Wang
School of Physics Science and Technology, Xinjiang University, Urumqi, Xinjiang 830046, China.
Qiang
Q
Li
Key Laboratory of Functional Materials and Devices for Special Environments, Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences, Xinjiang Key Laboratory of Electronic Information Materials and Devices, 40-1 South Beijing Road, Urumqi 830011, China. slpan@ms.xjb.ac.cn wukui@ms.xjb.ac.cn.
Wenhui
W
Gao
Key Laboratory of Functional Materials and Devices for Special Environments, Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences, Xinjiang Key Laboratory of Electronic Information Materials and Devices, 40-1 South Beijing Road, Urumqi 830011, China. slpan@ms.xjb.ac.cn wukui@ms.xjb.ac.cn.
Dianwei
D
Hou
Key Laboratory of Functional Materials and Devices for Special Environments, Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences, Xinjiang Key Laboratory of Electronic Information Materials and Devices, 40-1 South Beijing Road, Urumqi 830011, China. slpan@ms.xjb.ac.cn wukui@ms.xjb.ac.cn.
Zhihua
Z
Yang
Shandong University, Jinan 250100, China.
Huaidong
H
Jiang
Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800, China.
Yongjun
Y
Dong
Key Laboratory of Functional Materials and Devices for Special Environments, Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences, Xinjiang Key Laboratory of Electronic Information Materials and Devices, 40-1 South Beijing Road, Urumqi 830011, China. slpan@ms.xjb.ac.cn wukui@ms.xjb.ac.cn.
Shilie
S
Pan