Elucidation of Codoping Effects on the Solubility Enhancement of Er<sup>3+</sup> in SiO<sub>2</sub> Glass:  Striking Difference between Al and P Codoping

Saitoh, Akira; Matsuishi, Satoru; Se-Weon, Choi; Nishii, Junji; Oto, Masanori; Hirano, Masahiro; Hosono, Hideo

doi:10.1021/jp060702w

Cited by 59 publications

(62 citation statements)

References 24 publications

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“…Monteil et al 71 72) proposed that the oxygen coordination number of Al should be 6 based on the coordination in alkali-free aluminosilicate crystals and glasses. 73),74) Saitoh et al 75) elucidated the local structure around an Er 3+ ion using electron spin echo envelope modulation (ESEEM) spectroscopy. ESEEM spectroscopy is a powerful tool because it can determine the distance and coordination number of ligands in a mediumrange structure because very fine interference signals, which are unresolved in conventional continuous wave (CW)-electron paramagnetic resonance (EPR) spectroscopy, are observable by time domain measurements; i.e., it provides information on the medium-range structure around a specific paramagnetic species and quantitative results are obtained by a simulation of the spectrum shape.…”

Section: Mechanism Of Codoping Effectmentioning

confidence: 99%

“…On the other hand, the formation of CeB complex was not observed, and, instead, the segregation of CeO 2 was enhanced. Saitoh et al 75) applied ESEEM spectroscopy and elucidated that a Ce ion was preferentially surrounded by four PO 4 units in the CeP-codoped silica glass while a Ce ion was surrounded by 0.8 BO 3 unit as speculated from the chemical composition of CeB-codoped silica glass. 79) They concluded that the coordination selectivity of the PO 4 unit to Ce is ³10 times larger than that of the SiO 4 unit, whereas the BO 3 unit has no selectivity (³1).…”

Section: Mechanism Of Codoping Effectmentioning

confidence: 99%

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Doping effects in amorphous oxides

Funabiki

Kamiya

Hosono

2012

J. Ceram. Soc. Japan

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Impurity doping of crystalline Si is one of the most striking techniques in semiconductor technology. A rigid and perfect crystalline lattice is prerequisite for effective doping. However, it has been reported to date that introducing a small amount of impurities drastically improves also the properties of amorphous materials. This paper reviews three pronounced doping effects on optical and electrical properties of amorphous oxides; i.e., (i) F-doping of silica glass to improve the vacuum-ultraviolet optical transmission and radiation toughness, (ii) codoping effects on solubility enhancement of rare earth ions in silica glass melt, and (iii) electron-carrier generation in transparent amorphous oxide semiconductors. It is emphasized that effectiveness of electron doping is determined by the magnitude of electron affinity and stabilization energy of a dopant. Importance of the local structure formed around a dopant ion and the location of conduction band minimum measured from the vacuum level is addressed to understand the doping effects in amorphous oxides.

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Section: Mechanism Of Codoping Effectmentioning

confidence: 99%

Section: Mechanism Of Codoping Effectmentioning

confidence: 99%

Doping effects in amorphous oxides

Funabiki

Kamiya

Hosono

2012

J. Ceram. Soc. Japan

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“…3)18) Most of RE-Al codoped silica glasses for optical application have been synthesized by vapor phase methods, such as the vapor-phase axial deposition and chemical vapor deposition (CVD), 3),4),12), 16) because these methods are suitable to suppress the incorporation of metallic impurities. However, the vapor pressure of RE compounds is often low, making the direct vapor-phase loading of RE ions into silica glass difficult.…”

Section: Introductionmentioning

confidence: 99%

Cosolvent-free sol–gel synthesis of rare-earth and aluminum codoped monolithic silica glasses

Kaneko

Kajihara

Kanamura

2013

J. Ceram. Soc. Japan

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A cosolvent-free solgel method to synthesize monolithic silica glasses containing both of rare-earth and aluminum ions has been studied. Fracture during drying and bloating during sintering are significantly suppressed by forming macroporous wet gels via macroscopic phase separation in parallel with gelation. The resultant rare-earth and aluminum codoped silica glasses exhibit good visible transparency, suggesting an improvement of dispersion of rare-earth ions in these glasses. The aluminum codoping increases the photoluminescence efficiency in glasses doped with Nd 3+ ions.

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“…Small changes in composition of crystalline materials can lead to large changes in their electronic properties, such as optical absorption and electrical conductivity (1). Similarly, a small concentration of (co)dopants in amorphous materials can be used to control their optical properties (2,3). Glass properties are typically controlled by varying composition or processing conditions (4).…”

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confidence: 99%

Electron anions and the glass transition temperature

Johnson

Sushko

Tomota

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

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Properties of glasses are typically controlled by judicious selection of the glass-forming and glass-modifying constituents. Through an experimental and computational study of the crystalline, molten, and amorphous [Ca 12 Al 14 O 32 ] 2+ · (e -) 2 , we demonstrate that electron anions in this system behave as glass modifiers that strongly affect solidification dynamics, the glass transition temperature, and spectroscopic properties of the resultant amorphous material. The concentration of such electron anions is a consequential control parameter: It invokes materials evolution pathways and properties not available in conventional glasses, which opens a unique avenue in rational materials design.amorphous materials | glass transition | electrides | molecular dynamics | density functional theory O ne of the key challenges in materials design is identification of degrees of freedom that ensure robust control of the properties of interest. Small changes in composition of crystalline materials can lead to large changes in their electronic properties, such as optical absorption and electrical conductivity (1). Similarly, a small concentration of (co)dopants in amorphous materials can be used to control their optical properties (2, 3). Glass properties are typically controlled by varying composition or processing conditions (4). However, delicate control of viscosity and glass transition temperature in multicomponent materials (T g ) has remained elusive due to the collective origin of these properties. Substitution of atomic anions with electron anions in materials to form electrides (5, 6) introduces an additional degree of freedom. Here we demonstrate that electron anions dramatically change dynamics of atoms in an inorganic amorphous material, which strongly affects its T g . Extending the concept of electron anions to other amorphous materials would provide a powerful instrument for the design of glasses with finely tuned characteristics.Calcium aluminates (CA), composed of CaO and Al 2 O 3 , represent a common family of oxide glasses. Whereas pure Al 2 O 3 is a poor glass former, blending it with CaO leads to the formation of stable glasses composed of AlO 4 tetrahedra with strong and directional covalent bonds instead of nondirectional ionic bonds in bulk Al 2 O 3 (7). In contrast, Ca-O bonds retain their ionic character; they are weaker than Al-O bonds and lack a preferred orientation, which enables motion of the AlO 4 tetrahedra relative to each other. Hence, the T g of stoichiometric CA systems decreases by ∼50 K as the CaO content increases from 57 mol% to 70 mol% (Fig. 1). This relatively narrow interval of T g variation with composition is typical of multicomponent glasses (8, 9). The T g for stoichiometric [Ca 12 (5,14,15). In crystalline C12A7:e -, the electrons occupy the cage conduction band (CCB) states associated with the lattice cages (16, 17), leading to polaron-type conduction at x < ∼0.5 and metallic conduction at x > 0.5 (13, 16). The exceptionally low work function of crystalline C12A7:e -...

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Elucidation of Codoping Effects on the Solubility Enhancement of Er³⁺ in SiO₂ Glass: Striking Difference between Al and P Codoping

Cited by 59 publications

References 24 publications

Doping effects in amorphous oxides

Doping effects in amorphous oxides

Cosolvent-free sol–gel synthesis of rare-earth and aluminum codoped monolithic silica glasses

Electron anions and the glass transition temperature

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Elucidation of Codoping Effects on the Solubility Enhancement of Er3+ in SiO2 Glass: Striking Difference between Al and P Codoping

Cited by 59 publications

References 24 publications

Doping effects in amorphous oxides

Doping effects in amorphous oxides

Cosolvent-free sol–gel synthesis of rare-earth and aluminum codoped monolithic silica glasses

Electron anions and the glass transition temperature

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Product

Resources

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Elucidation of Codoping Effects on the Solubility Enhancement of Er³⁺ in SiO₂ Glass: Striking Difference between Al and P Codoping