Syntheses, Structures, Optical and Magnetic Properties of Ba₂MLnSe₅(M = Ga, In;Ln= Y, Nd, Sm, Gd, Dy, Er)

Abstract

The twelve quaternary rare-earth selenides Ba(2)MLnSe5 (M = Ga, In; Ln = Y, Nd, Sm, Gd, Dy, Er) have been synthesized for the first time. The compounds Ba(2)GaLnSe(5) (Ln = Y, Nd, Sm, Gd, Dy, Er) are isostructural and crystallize in a new structure type in the centrosymmetric space group P ̅1 of the triclinic system while the isostructural compounds Ba(2)InLnSe(5) (Ln = Y, Nd, Sm, Gd, Dy, Er) belong to the Ba(2)BiInS(5) structure type and crystallize in the noncentrosymmetric space group Cmc2(1) of the orthorhombic system. The structures contain infinite one-dimensional anionic chains (1)(∞)[GaLnSe(5)](4-) and (1)(∞)[InLnSe(5)](4-), and both chains are built from LnSe(6) octahedra and MSe(4) (M = Ga, In) tetrahedra in the corresponding selenides. As deduced from the diffuse reflectance spectra, the band gaps of most Ba(2)MLnSe(5) (M = Ga, In; Ln = Y, Nd, Sm, Gd, Dy, Er) compounds are around 2.2 eV. The magnetic susceptibility measurements on Ba(2)GaGdSe(5) and Ba(2)InLnSe(5) (Ln = Nd, Gd, Dy, Er) indicate that they are paramagnetic and obey the Curie-Weiss law, while the magnetic susceptibility of Ba(2)InSmSe(5) deviates from the Curie-Weiss law as a result of the crystal field splitting. Furthermore, Ba(2)InYSe(5) exhibits a strong second harmonic generation response close to that of AgGaSe(2), when probed with the 2090 nm laser as fundamental wavelength.

K2Sn2ZnSe6, Na2Ge2ZnSe6, and Na2In2GeSe6: a new series of quaternary selenides with intriguing structural diversity and nonlinear optical properties

“…Examples include BaGa 4 S 7 , 8 BaGa 4 Se 7 , 9 BaGa 2 MSe 6 (M = Si, Ge; Q = S, Se), 10 Pb 4 Ga 4 GeQ 12 (Q = S, Se), 11 Ba 23 Ga 8 Sb 2 S 38 , 12 Cs 5 BiP 4 Se 12 , 13 Ln 4 GaSbS 9 (Ln = Pr, Nd, Sm, Gd−Ho), 14 and Ba 2 InYQ 5 (Q = Se, Te), 15,16 LiGaS 2 , 17 LiGaSe 2 , 18 Li 2 In 2 MS 6 (M = Si, Ge), 19 SnGa 4 Q 7 (Q = S, Se), 20 AAsQ 2 (A = Li,Na; Q = S,Se), 21 AZrPSe 6 (A = K, Rb, Cs) 1 and Na 4 MgM 2 Se 6 (M = Si, Ge). 22 Generally speaking, a large macroscopic NLO response originates from the cooperative arrangement of the microscopic NLO building units, including the MX 4 tetrahedra (M = Ga, In, Si, Ge, Sn etc.…”

Syntheses, crystal structures, and NLO properties of the quaternary sulfides RE3Sb0.33SiS7 (RE=La, Pr)

“…Tetrahedrally coordinated triel or tetrel metal chalcogenides have drawn considerable attentions not only for their diverse structural features but also for their second-order nonlinear optical (NLO) activity, such as: AgGaS 2 (AGS) [1], LiGaQ 2 (Q = S, Se, Te) [2], LiInQ 2 (Q = S, Se) [3], BaGa 4 Q 7 [4], K 2 Hg 3 Ge 2 S 8 [5], Li 2 Ga 2 GeS 6 [6], Li 2 In 2 MQ 6 (M = Si, Ge) [7], BaGa 2 MS 6 (M = Si, Ge) [8], Ba 2 BiInS 5 [9], Ba 2 InYSe 5 [10], Ba 4 CuGa 5 Q 12 (Q = S, Se) [11], Li 2 CdGeS 4 [12], Y 3 Zn 0.5 SiS 7 [13], Eu 2 Ga 2 GeS 7 [14], Pb 4 Ga 4 GeQ 12 (Q = S, Se) [15], Ba 3 AGa 5 Se 10 Cl 2 (A = K, Rb, Cs) [16], and ACd 4 Ga 5 Q 12 (A = K, Rb, Cs; Q = S, Se) [17]. Among them, AgGaS 2 is the well-known middle-infrared (mid-IR) benchmark NLO material exhibiting a high second-harmonic generation (SHG) coefficient and a wide transparent range.…”

Synthesis, Crystal Structure, and Optical Property of the Quaternary Semiconductor La4Cd4In2S13

“…In recent years, rare-earth chalcogenides in combination with a triel element have attracted a great deal of attention not only because they can form a large number of structure types but also because of their excellent IR NLO performance, [6][7][8] (RE = Pr, Nd, Sm, Gd -Ho) [6] and Ba 2 InYSe 5 [7] with strong SHG effects in the IR region and RE 4 InSbS 9 (RE = La, Pr, Nd) [8] exhibiting strong Kleinman forbidden NLO coefficients in type I phase-matchable behavior. On the other hand, binary CdS, CdSe, and CdTe are also interesting for their semiconducting, photoconducting, and light-emitting properties, which made them some of the most important members of the II-VI family of solids.…”

“…Moreover, InQ 4 (Q = S, Se) tetrahedra is a typical functional unit for a number of applications such as NLO properties. [7,8] In this paper, our synthetic attempt, intended for Cd analogous of RE 3 MInS 7 (M = Fe, Co, Ni; RE = rare-earth metal), [10] resulted in the isolation of single crystals of another new quaternary rare-earth sulfide, La 4 Cd 4 In 2 S 13 with two-dimensional structure, which represents the example of chalcogenides in quaternary RE/M/N/Q (RE = rare-earth metal; M = Zn, Cd; N = Ga, In; Q = chalcogenides) system. Herein, we report its synthesis, crystal structure, and optical property.…”