Bi12(Bi0.5IIITl0.5III)O19.50

Radaev, Sergei; Trömel, M.; Kargin, Yu. F.; Marin, A. A.; Rider, E. E.; Sarin, V. A.

doi:10.1107/s0108270193011205

Cited by 11 publications

(5 citation statements)

References 2 publications

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“…The structural formula for the sillenites saturated with M 3+ ions can be written as As in the case of M 2+ sillenites, the stoichoimetry of the comprehensively investigated M 3+ sillenites also matches the structural formulas 3 and 4. The Bi 12 (Bi 1/2 M 3+ 1/2 )O 19.5 composition is reported for M 3+ = Ga 3+ , Fe 3+ , Cr 3+ and Tl 3+ . ,, Earlier works on gallium and iron sillenites , proposed the same cation ratio while mistakenly assuming the presence of Bi 5+ . If we do not consider the studies that were later disproved, such as ref , there are only a few reports about compositions that deviate from formula 4.…”

Section: Resultsmentioning

confidence: 97%

“…The Bi 12 (Bi 1/2 M 3+ 1/2 )O 19.5 composition is reported for M 3+ ) Ga 3+ , Fe 3+ , Cr 3+ and Tl 3+ . 8, 25,26 Earlier works on gallium and iron sillenites 6,27 proposed the same cation ratio while mistakenly assuming the presence of Bi 5+ . If we do not consider the studies that were later disproved, such as ref 19, there are only a few reports about compositions that deviate from formula 4.…”

Section: Resultsmentioning

confidence: 99%

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A Stoichiometric Model for Sillenites

2002

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A critical review of crystallographic studies on sillenite compounds has allowed us to develop a general structural formula for the stoichiometric sillenites: Bi 12 (Bi 4/5-nx M n+ 5x )O 19.2+nx . We defined the stoichiometric sillenites as those with an oxygen sublattice that is fully occupied by either oxygen ions or lone electron pairs of Bi 3+ ions. Nonstoichiometric groups of sillenites were identified as being either substoichiometric, with a deficient oxygen sublattice, or superstoichiometric, with an excess of oxygen. The compositions of the sillenites reported in the literature agree well with the proposed stoichiometric model. Two sillenites, Al and Zn, that were found to deviate from this model were experimentally investigated using X-ray diffraction, scanning electron microscopy, and wavelength-dispersive spectroscopy. The composition was found to be different from that reported previously and to correspond to the proposed stoichiometric model.

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Section: Resultsmentioning

confidence: 97%

Section: Resultsmentioning

confidence: 99%

A Stoichiometric Model for Sillenites

2002

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“…14 Sillen as early as in 1937 16 proposed the possibility of stabilizing metastable γ-Bi 2 O 3 with the incorporation of small amount of other cations. The prediction can be well judged from the follow-up studies on sillenite-type structures with numerous M n+ cations (e.g., Al 3+ , Si 4+ , P 5+ , Ti 4+ , V 5+ , Mn 4+ , Fe 3+ , Zn 2+ , Ge 4+ , As 5+ , Cd 2+ , and Tl 3+ ) 11,14,15,[17][18][19][20][21][22][23] mainly on the 2a site. Craig et al, 24 however, proposed the presence of Bi 5+ on the 2a site although Bi 5+ is known to be unstable at high temperatures.…”

Section: Introductionmentioning

confidence: 97%

“…The centroid of both Bi 3+ O 3 E tetrahedra and Bi 3+ O 5 E octahedra keeps a stereochemically active 6s 2 lone electron pair (LEP; E in formula) instead of one ligand oxygen. The crystal structure 10,11 and the appearances of different polyhedra are depicted in Figure 1. The Bi 3+ cations locate on both 24f and 2a sites comprising of BiO 5 E nido-octahedra and BiO 3 E nido-tetrahedra, respectively.…”

Section: Introductionmentioning

confidence: 99%

Indium containing sillenite semiconductor: Synthesis, structural, spectroscopic, and thermogravimetric analysis

2023

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Sillenite-type ceramics are non-centrosymmetric phases of ongoing research interest because of their structural defects and optoelectronic properties. We report a series of sillenite compounds with a general composition Bi 12 (Bi 3+ 4/5−3x In 3+ 5x □ 1/5−2x )O 19.2+3x □ 0.8−3x for x = 0.03-0.27 to understand how the crystal-physicochemical properties change with a successive filling of empty Bi 3+ positions in the tetrahedral site by In 3+ cation. Conventional solidstate synthesis method is used to prepare the microcrystalline samples. Each sample is characterized by X-ray diffraction, Raman, UV/Vis diffuse reflectance spectroscopy, and thermogravimetry (TG/DSC). X-ray powder data Rietveld refinement reveals that phase-pure samples can be obtained for x = 0.03-0.08 in the space group I23. Appearance of starting In 2 O 3 as minor phases with the final products for 0.10 < x < 0.27 suggests for x max = 0.08. The successive decrease of the lattice parameter indicates the incorporation of smaller In 3+ cations in the structure. The effect of the lone electron pairs of Bi 3+ and the structural cation vacancies lead to the modification of the interatomic bond lengths. At least one Raman active phonon mode shows hardening for decreasing cation vacancy concentration in the system. The bandgap energy increases with increasing indium content. An additional absorption band at lower energy for x = 0.03-0.08 complements the theoretical study, which completely disappears for x > 0.08. The stronger In-O bonds play pivotal roles in the thermal stability of the phases studied by TGA/DSC analysis.

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“…Later, the crystal structure of sillenites was studied extensively [16][17][18][19][20][21][22]. Bi 12 M x O 20 ± δ crystals have a cubic structure of pentagontritetrahedral symmetry (sp.…”

Section: Introductionmentioning

confidence: 99%

Growth of Sillenite-Structure Single Crystals

et al. 2005

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The main processes for preparing bulk single crystals and films of photorefractive and piezoelectric Bi 12 M x O 20 ± δ (M = Group II-VIII elements) sillenite compounds are considered. Experimental data are summarized on the crystal growth of Bi 12 M x O 20 ± δ from the melt and under hydrothermal conditions, and the key morphological features of sillenites are analyzed. Various types of macroscopic growth defects in sillenite-type crystals are described, and their origin is discussed. The compositions of second-phase inclusions in undoped and doped (Group I-VIII elements) Bi 12 SiO 20 , Bi 12 GeO 20 , and Bi 12 TiO 20 single crystals are presented, and the main physicochemical properties of various Bi 12 M x O 20 ± δ crystals are summarized.

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Bi12(Bi0.5IIITl0.5III)O19.50

Cited by 11 publications

References 2 publications

A Stoichiometric Model for Sillenites

A Stoichiometric Model for Sillenites

Indium containing sillenite semiconductor: Synthesis, structural, spectroscopic, and thermogravimetric analysis

Growth of Sillenite-Structure Single Crystals

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