A Series of New Infrared NLO Semiconductors, ZnY₆Si₂S₁₄, Al_xDy₃(Si_yAl_1−y)S₇, and Al_0.33Sm₃SiS₇

Abstract

Four new quaternary isostructural rare-earth thiosilicates, ZnY(6)Si(2)S(14) (1), Al(0.50)Dy(3)(Si(0.50)Al(0.50))S(7) (2), Al(0.38)Dy(3)(Si(0.85)Al(0.15))S(7) (3), and Al(0.33)Sm(3)SiS(7) (4), crystallized in the chiral and polar space group P6(3), have been prepared by a facile synthetic routine. Compounds 1-3 show strong second harmonic generation effects at 2.1 um with the intensities of 1, 2, and 3 being about 2, 2, and 1 times that of KTP (KTiOPO(4)), respectively. The calculated band structure of 1 implies that the optical absorptions of BLn(6)M(2)Q(14) and ALn(3)MQ(7) family compounds are mainly ascribed to the charge transitions from Q-p to Ln-4f (4d for Y) states. Compounds 2-4 exhibit antiferromagnetic-like interactions.

Syntheses, structures and properties of five chiral quaternary sulfides, Al x Ln3(Si y Al1−y )S7 (Ln = Y, Gd, Dy) and In0.33Sm3SiS7

“…Compounds 1-4, Al 0.50 Dy 3 (Si 0.50 Al 0.50 )S 7 and Al 0.38 -Dy 3 (Si 0.85 Al 0.15 )S 7 [29] have the same type of disorders as mentioned above, which are the first ones with Si and Al atoms jointly occupying the E site in ALn 3 EQ 7 compounds. Their formulae can be concluded as Al x Ln 3 -(Al y Si z )S 7 with y + z = 1 and 3x + 3y + 4z = 5.…”

“…The five compounds were synthesized by a new solid-state reaction routine [28][29][30][31] . Unlike the traditional synthetic approach for multinary chalcogenides, where binary metal chalcogenide or metal element as metal source are used, and it is necessary that the operations are done in drybox since most of the reactants are unstable in the air, we used rare-earth oxides Ln 2 O 3 and In 2 O 3 as the Ln and In source, respectively, meanwhile, oxytropic boron was added to the reactive system to extract oxygen from metal oxides as well as prevent the air, water and silica tubes' disadvantageous influences on the syntheses, which ensures the successful operation in the air.…”

“…Generally, the A sites in ALn 3 MQ 7 compounds are occupied by monovalent alkali or coinage metal cations Na + , Ag + and Cu + , or divalent main-group metal cations Mg 2+ . Only three compounds, Al 0.33 Sm 3 SiS 7 [29] , Al 0.44 -La 3 Si 0.93 S 7 [22] and In 0.67 La 6 Si 2 S 14 [23] , have trivalent ions on the A sites. Interestingly, the A sites in 1-5 are occupied by trivalent Al 3+ or In 3+ ions, respectively, indicating that trivalent ions are easy to be introduced to the ALn 3 MQ 7 compounds by our synthetic approach.…”

Novel 3-D network SeS /NCPAN composites prepared by one-pot in-situ solid-state method and its electrochemical performance as cathode material for lithium-ion battery

“…Here, it has to be clarified that the quartz tube's crack had no influence on the muffle furnace, not to mention on human beings, which just made the experiments failed. In fact, many multinary metal chalcogenides were obtained by us using this method [50][51][52][53][54]. After these unsuccessful attempts, a successful method was proposed as we described in the experimental section, while only SeS x /NCPAN (x = 0 or 0.1) composites can be obtained.…”

Carborane tuning on iridium complexes: redox-switchable second-order NLO responses

“…Notably, Valore et al [21,22] reported that the presence of various charge transfer (CT) processes between the Ir(III) metal center and phenanthrolines ligands also produced a promising NLO response. Meanwhile, inorganic materials have attracted considerable attention as candidates for secondorder NLO materials [23][24][25]. In this context, carboranes are known for their extraordinary molecular architecture, remarkable thermal stability, steric groups, and complex overall electronic structure, and can be regarded as efficient building blocks with which to construct excellent luminescent and electronic materials in organic and polymeric fields [26][27][28][29].…”