New Members of SHG Active Dugganite Family, A₃BC₃D₂O₁₄ (A = Ba, Pb; B = Te, Sb; C = Al, Ga, Fe, Zn; D = Si, Ge, P, V): Synthesis, Structure, and Materials Properties

Abstract

A family of compounds, A3BC3D2O14 (A = Ba, Pb; B = Te, Sb; C = Al, Ga, Fe, Zn; D = Si, Ge, P, V), with the Dugganite structure was prepared employing traditional solid-state chemistry methods. PXRD and Rietveld refinement studies indicate that the compounds are stabilized in P321 space group (no. 150). The compounds are found to be SHG active with values ranging from 1.9 to 15.0 × KDP. The compounds exhibit high dielectric constants and low loss in our studies. The noncentrosymmetry related properties of the new Dugganites were understood by band structure calculations. We also explored the present Dugganite-structured oxides for the development of new inorganic colored materials by substituting Co2+, Ni2+, Cu2+, and Fe3+ in place of Zn2+. Thus, substitution of Co2+ and Fe3+ together tunes the blue color of the cobalt compound to blue-green color arising from metal-to-metal charge transfer (MMCT) of Fe3+ and Co2+ ions. The tetrahedrally coordinated Ni2+ in the Dugganite imparts a magenta color.

Stuffed Tridymite Structures: Synthesis, Structure, Second Harmonic Generation, Optical, and Multiferroic Properties

“…Normally, Ni‐containing compounds do not exhibit bright purple color and the observation of such a color in our present compounds for a tetrahedral Ni 2+ is interesting. Similar purplish (magenta) color has been seen in Ni‐doped α‐LiZnBO 3 , [41] Ba 3 TeGa 2 NiSi 2 O 14 [40d] …”

“…Although three spin‐allowed transitions are known for Ni 2+ in tetrahedral coordination, only one transition [ 3 T 1 (F)→ 3 T 1 (P)], which is spin‐allowed and observed in the visible region. The doublet absorption observed at approximately 1.95 and 2.30 eV in BaZn 1− x Ni x SiO 4 (0< x ≤0.25) may be due to the 3 T 1 (F)→ 3 T 1 (P) transition within the tetrahedral symmetry [40d] . The small shoulder at 1.55 eV could be due to the spin‐orbit coupling, which is known for d 8 ions such as Ni 2+ in the tetrahedral symmetry [40] .…”

“…We determined the CIE 1931 chromaticity coordinates for all the compounds (Figure 10, Table 2). The color coordinates ( L *, a *, and b * parameters) for BaCoSiO 4 was compared with other known blue‐colored compounds: CoAl 2 O 4 , [39c] LiZn 0.5 Co 0.5 BO 3 , [41] Ca 3 Sb 2 Ga 2 CoO 12 , [40d] and YIn 0.9 Mn 0.1 O 3 [44] (Table 3). The color coordinates of BaCoSiO 4 compares favorably with the reported blue‐colored compounds.…”

Alignment of Polar Moieties Leading to Strong Second Harmonic Response in KCsMoP2O9

“…), stereoactive lone pair cations (I 5+ , Pb 2+ , Sn 2+ , etc. ), and d 10 cations (Zn 2+ , Cd 2+ , and Hg 2+ ) with large polar displacement. − To the best of our knowledge, in recently discovered alkali- or alkaline-earth metal molybdates, LiNa 5 Mo 9 O 30 exhibits the largest SHG responses (experimental 2 × KDP; calculated d 32 = 11 × d 36 (KDP)). As Te 4+ was introduced into alkali- or alkaline-earth metal molybdates, some compounds with large SHG response were produced, such as β-BaTeMo 2 O 9 with the impressive SHG response (600 × SiO 2 ); however, the simultaneous presence of Mo and Te caused considerable red shift of the cutoff edge.…”

Structural evolution of transition metal orthoborates (Zn3B2O6−Co3B2O6) with the Kotoite mineral structure: Synthesis, structure and properties

“…[5][6][7][8][9][10] We have been exploring mineral structures over the years with a specific goal to achieve new colored inorganic compounds. Thus, spiroffite, [11] lyonsite, [12] garnet, [13] corundum, [14] dugganite, [15] paganoite, [16] tridymite [17] and langasite [18] mineral structures were explored. In continuation of this theme, we have been exploring the kotoite structure.…”