Tetrahedral Mn4+ as chromophore in sillenite-type compounds

Medina, Elena A.; Pathirana, Vidhara H.; Li, Jun; Ramirez, A. P.; Subramanian, M. A.

doi:10.1016/j.jssc.2020.121463

Cited by 7 publications

(8 citation statements)

References 35 publications

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“…12 Mn 4+doped crystalline host materials are actively developed as red phosphors 13 or cool green pigments. 14 Mn 5+ -Containing compounds are promising materials for cool pigments 15 or laser applications. 16 Co 2+ /Co 3+ /Co 4+ are active centers with catalytic activity for various applications.…”

Section: Introductionmentioning

confidence: 99%

Revealing the peculiar local behavior of manganese and cobalt in diffusion-doped calcium orthovanadate Ca₃(VO₄)₂

et al. 2022

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Section: Introductionmentioning

confidence: 99%

Revealing the peculiar local behavior of manganese and cobalt in diffusion-doped calcium orthovanadate Ca₃(VO₄)₂

et al. 2022

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“…The darker color of ZTO-0.1M prepared at higher temperatures (800–1000 °C) implies the possible presence of Mn–Mn CT (Mn 2+ → Mn 4+ ) in the Mn singly doped case (Figure S5). , ZTO-0.1M (yellow), ZTO-0.1ML (gray-violet), and MTO-0.1ML (violet) were processed in acid and base solutions to examine the chemical stability. Table S6 shows their CIE ( L *, a *, b *) values before and after processing.…”

Section: Resultsmentioning

confidence: 99%

“…Intense color in inorganic solids can arise through d–d electron transitions, charge transfer (CT), or intervalence CT within a chromophore. − Manganese (Mn) is an extraordinary chromophore in that its unfilled 3 d electron shell and variable oxidation states can render rich color regions from specific electronic transitions. − Mn 2+ doping into ZnO 4 tetrahedra of α-Zn 2 SiO 4 yields a yellowish glass . Mn 3+ displays an intense bright blue or violet color when it is hosted in trigonal-bipyramidal 5-coordination in Y(Ga, In)O 3 and melilite structured LaAlGe 2 O 7 . ,, Mn 4+ in a different host could be green, red, or brown. , Mn 5+ in a tetrahedral coordination is reported to be turquoise or sky blue. , In these pigments, monovalent Mn is required to avoid color impurity and low chromogenic efficiency. Most previous reports have taken efforts to stabilize the desired Mn valence state by controlling the Mn concentration and/or reaction conditions.…”

Section: Introductionmentioning

confidence: 99%

Robust Yellow-Violet Pigments Tuned by Site-Selective Manganese Chromophores

et al. 2021

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The rational design of multifunctional inorganic pigments relies on the manipulation of ionic valence and local surroundings of a chromophore in structurally and chemically habitable hosts. To date, the development of environmentally benign and intense violet/purple pigments is still a challenge. Here we report a family of A 3−x Mn x TeO 6 and A 3−2x Mn x Li x TeO 6 (A = Zn, Mg; x = 0.01−0.15) pigments colored by site-selective Mn 2+ O 4 yellow and Mn 3+ O 5−6 violet chromophores. Zn 2.9 Mn 0.1 TeO 6 is intense bright yellow, comparable with commercial BiVO 4 , and has better near-infrared reflectivity (∼89%) in comparison to commercial TiO 2 . The codoped Li + "activator" generates holes and chargebalanced Mn 3+ (Mn 3+ O 5−6 ), realizing a color transformation from yellow to the bright violet pigments of A 3−2x Mn x Li x TeO 6 . The most vivid Mg 2.8 Mn 0.1 Li 0.1 TeO 6 is probably the best violet pigment known to date, exhibits excellent chemical and thermodynamic stability, and demonstrates pressure-dependent stability up to 5−7 GPa, before a (reversible) phase transition to pink. Theoretical calculations revealed the correlation between site-preference occupancy and chromophore motifs and predicted a wide color gamut of pigments in Zn 3 TeO 6 -hosted 3d transition-metal ions other than manganese.

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“…[3][4][5] This, along with the absence of inversion symmetry, is the source of outstanding electrical and optical properties suitable for photorefractive applications. [1][2][3][4][5] Among sillenites, bismuth silicate (Bi 12 SiO 20 , BSO) is a technologically important material as it exhibits large electro-optic and photoconductive effects, which make it suitable for optical switches, optics-based electric field sensors, holographic storage, and photorefractive devices. [6][7][8][9][10][11][12][13][14] It is used for two-wave mixing, four-wave mixing, phase conjugation, real-time holography, optical data storage, optical computing, and electro-optical modulation.…”

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Crystal Interface Control at Low Thermal Gradient and Investigation of the Effect of Cr on the Crystal Structure and Optical Properties of Bismuth Silicate

Bhaumik

Viswanathan

Bhatt

et al. 2021

Physica Status Solidi (b)

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Sillenite structure crystals (general composition Bi 12 XO 20 , X ¼ Si, Ge, and Ti with space group I23) posses a number of properties important for practical applications. [1,2] They are characterized by XO 4 tetrahedra located at the center and corners of its cubic unit cell. These XO 4 tetrahedra are linked with stereochemically active 6s 2 lone electron pair of Bi 3þ via BiO 5 octahedra. [3][4][5] This, along with the absence of inversion symmetry, is the source of outstanding electrical and optical properties suitable for photorefractive applications. [1][2][3][4][5] Among sillenites, bismuth silicate (Bi 12 SiO 20 , BSO) is a technologically important material as it exhibits large electro-optic and photoconductive effects, which make it suitable for optical switches, optics-based electric field sensors, holographic storage, and photorefractive devices. [6][7][8][9][10][11][12][13][14] It is used for two-wave mixing, four-wave mixing, phase conjugation, real-time holography, optical data storage, optical computing, and electro-optical modulation. [7,8] It has been reported that the photorefractive property of BSO is enhanced significantly on doping with metals like Cr, Fe, Mg, Ru, etc. [8,[15][16][17][18][19][20][21][22][23][24][25][26][27] Though most of these dopants make material sensitive to photorefraction in the visible region, especially around 500 nm, that is, 2.5 eV, practical feasibility prefers the region near the infrared (1.5À2 eV), mainly because of the availability of compact laser diodes in this region. [28] Cr doping shifts the photorefractive sensitivity of BSO to the near-infrared region and therefore makes it a potential material for applications like optical image processing, holographic interferometry, optical storage, and phase conjugation. In literature, there are reports on the growth of Cr-doped BSO crystal and investigations on the photorefractive effect, dielectric property, optical activity, Faraday effect, etc. [15][16][17][18][19][20][21][22][23][24] For the growth of the crystal, Czochralski technique has been used as BSO is a congruently melting compound. [25,26] It is known that the devices mentioned earlier require crystals with a low dislocation density and high optical homogeneity. [29] One of the important aspects of growth of crystals having low dislocation density is to grow the crystal with a flat-ish crystalÀmelt interface. [26] A few studies have been reported on undoped BSO for relatively higher thermal gradient. [30,31] However, to obtain large-sized good quality crystal of BSO, a lower thermal gradient is favorable. [32] In view of this, one of the objectives of the work is investigate the effect of the growth condition on the interface shape control of the Cr:BSO crystal when grown along 〈110〉 in the lower axial

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Tetrahedral Mn4+ as chromophore in sillenite-type compounds

Cited by 7 publications

References 35 publications

Revealing the peculiar local behavior of manganese and cobalt in diffusion-doped calcium orthovanadate Ca₃(VO₄)₂

Revealing the peculiar local behavior of manganese and cobalt in diffusion-doped calcium orthovanadate Ca₃(VO₄)₂

Robust Yellow-Violet Pigments Tuned by Site-Selective Manganese Chromophores

Crystal Interface Control at Low Thermal Gradient and Investigation of the Effect of Cr on the Crystal Structure and Optical Properties of Bismuth Silicate

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Tetrahedral Mn4+ as chromophore in sillenite-type compounds

Cited by 7 publications

References 35 publications

Revealing the peculiar local behavior of manganese and cobalt in diffusion-doped calcium orthovanadate Ca3(VO4)2

Revealing the peculiar local behavior of manganese and cobalt in diffusion-doped calcium orthovanadate Ca3(VO4)2

Robust Yellow-Violet Pigments Tuned by Site-Selective Manganese Chromophores

Crystal Interface Control at Low Thermal Gradient and Investigation of the Effect of Cr on the Crystal Structure and Optical Properties of Bismuth Silicate

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Revealing the peculiar local behavior of manganese and cobalt in diffusion-doped calcium orthovanadate Ca₃(VO₄)₂

Revealing the peculiar local behavior of manganese and cobalt in diffusion-doped calcium orthovanadate Ca₃(VO₄)₂