Sathravada Balaji

Efficient ~2.0 μm emission from Ho 3+ doped tellurite glass sensitized by Yb 3+ ions: Judd-Ofelt analysis and energy transfer mechanism [Invited]

The ~2.0μm emission characteristics of Ho3+ both by direct excitation and through Yb3+ sensitization in barium-tellurite glass are reported. The radiative properties of active ions have been evaluated by applying Judd-Ofelt theory on the measured absorption spectrum. A significant enhancement of Ho3+ emission (2.0μm) observed with 12 fold decrease of Yb3+ emission (1008nm) in co-doped sample entrenched the efficient energy transfer from Yb3+:2F5/2→Ho3+:5I6. The host phonon assistance in the energy transfer process has been conferred by using Dexter model. Comparatively better emission properties (Arad, Δλeff, σem) reveal that, the present material could be promising for laser emission at ~2.0μm.

Yb 3+ ion concentration effects on ∼1 μm emission in tellurite glass

The effects of Yb3+ ion concentration on physical, optical, and spectroscopic properties have been studied in a low phonon (∼590  cm−1) barium-lanthanum-tellurite glass. Due to the unfeasibility of Judd-Ofelt theory Yb3+-doped systems, the oscillator strength of absorption transition, F27/2→F5/22 has been evaluated by using the Smakula equation. The nature of emission from F25/2→F7/22 transition of Yb3+ ions is described theoretically by using a rate equation in comparison with experimental results. By applying reciprocity (RM) and Fuchtbauer-Ladenburg methods on emission spectra as well as the excitation random walk model on measured fluorescence lifetimes, the radiation trapping and concentration quenching effects have been discussed. Considering all the spectroscopic and laser performance parameters, an optimum Yb-ion doping concentration (YT1) has been determined, and the gain measurements performed on the sample revealed a flat gain over a broad wavelength range could be achieved even with a low (∼20%) excitation population density. A comparative study with other hosts revealed the potentiality of the present glass for ∼1 micron emission.

Role of Yb(3+) ions on enhanced ~2.9 μm emission from Ho(3+) ions in low phonon oxide glass system.

The foremost limitation of an oxide based crystal or glass host to demonstrate mid- infrared emissions is its high phonon energy. It is very difficult to obtain radiative mid-infrared emissions from these hosts which normally relax non-radiatively between closely spaced energy levels of dopant rare earth ions. In this study, an intense mid-infrared emission around 2.9 μm has been perceived from Ho3+ ions in Yb3+/Ho3+ co-doped oxide based tellurite glass system. This emission intensity has increased many folds upon Yb3+: 985 nm excitation compared to direct Ho3+ excitations due to efficient excited state resonant energy transfer through Yb3+: 2F5/2 → Ho3+: 5I5 levels. The effective bandwidth (FWHM) and cross-section (σem) of measured emission at 2.9 μm are assessed to be 180 nm and 9.1 × 10−21 cm2 respectively which are comparable to other crystal/glass hosts and even better than ZBLAN fluoride glass host. Hence, this Ho3+/Yb3+ co-doped oxide glass system has immense potential for the development of solid state mid-infrared laser sources operating at 2.9 μm region.

Experimental evidence for quantum cutting co-operative energy transfer process in Pr3+/Yb3+ ions co-doped fluorotellurite glass: dispute over energy transfer mechanism

Pr3+/Yb3+ doped materials have been widely reported as quantum-cutting materials in recent times. However, the question of the energy transfer mechanism in the Pr3+/Yb3+ pair in light of the quantum-cutting phenomenon still remains unanswered. In view of that, we explored a series of Pr3+/Yb3+ co-doped low phonon fluorotellurite glass systems to estimate the probability of different energy transfer mechanisms. Indeed, a novel and simple way to predict the probability of the proper energy transfer mechanism in the Pr3+/Yb3+ pair is possible by considering the donor Pr3+ ion emission intensities and the relative ratio dependence in the presence of acceptor Yb3+ ions. Moreover, the observed results are very much in accordance with other estimated results that support the quantum-cutting phenomena in Pr3+/Yb3+ pairs, such as sub-linear power dependence of Yb3+ NIR emission upon visible ∼450 nm laser excitation, integrated area of the donor Pr3+ ions visible excitation spectrum recorded by monitoring the acceptor Yb3+ ions NIR emission, and the experimentally obtained absolute quantum yield values using an integrating sphere setup. Our results give a simple way of estimating the probability of an energy transfer mechanism and the factors to be considered, particularly for the Pr3+/Yb3+ pair.

Al2O3 influence on structural, elastic, thermal properties of Yb3+ doped Ba–La-tellurite glass: Evidence of reduction in self-radiation trapping at 1 μm emission

Ba-La-tellurite glasses doped with Yb(3+) ions have been prepared through melt quenching technique by modifying their composition with the inclusion of varied concentration of Al2O3 to elucidate its effects on glass structural, elastic, thermal properties and Yb(3+) ion NIR luminescence performance. The FTIR spectral analysis indicates Al2O3 addition is promoting the conversion of BOs from NBOs which have been generated during the process of depolymerisation of main glass forming TeO4 units. The elastic properties of the glass revealed an improved rigidity of the glass network on addition of Al2O3. In concurrence to this, differential thermal analysis showed an increase in glass transition temperature with improved thermal stability factor. Also, Yb(3+) fluorescence dynamics demonstrated that, Al2O3 inclusion helps in restraining the detrimental radiation trapping of ∼1μm emission.

Understanding the Formation of CaAl2Si2O8 in Melilite-Based Glass-Ceramics: Combined Diffraction and Spectroscopic Studies

An assessment is undertaken for the formation of anorthite crystalline phase in a melilite-based glass composition (CMAS: 38.7CaO–9.7MgO–12.9Al2O3–38.7SiO2 mol %), used as a sealing material in solid oxide fuel cells, in view of the detrimental effect of anorthite on the sealing properties. Several advanced characterization techniques are employed to assess the material after prolonged heat treatment, including neutron powder diffraction (ND), X-ray powder diffraction (XRD), 29Si and 27Al magic-angle spinning nuclear magnetic resonance (MAS-NMR), and in situ Raman spectroscopy. ND, 29Si MAS-NMR, and 27Al MAS-NMR results revealed that both Si and Al adopt tetrahedral coordination and participate in the formation of the network structure. In situ XRD measurements for the CMAS glass demonstrate the thermal stability of the glass structure up to 850 °C. Further heat treatment up to 900 °C initiates the precipitation of melilite, a solid solution of akermanite/gehlenite crystalline phase. Qualitative XRD data for glass-ceramics (GCs) produced after heat treatment at 850 °C for 500 h revealed the presence of anorthite along with the melilite crystalline phase. Rietveld refinement of XRD data indicated a high fraction of glassy phase (∼67%) after the formation of crystalline phases. The 29Si MAS-NMR spectra for the CMAS-GC suggest the presence of structural units in the remaining glassy phase with a polymerization degree higher than dimer units, whereas the 27Al MAS-NMR spectra revealed that most Al3+ cations exhibit a 4-fold coordination. In situ Raman spectroscopy data indicate that the formation of anorthite crystalline phase initiated after 240 h of heat treatment at 850 °C owing to the interaction between the gehlenite crystals and the remaining glassy phase.

Quantum cutting induced multifold enhanced emission from Cr3+-Yb3+-Nd3+ doped zinc fluoroboro silicate glass—Role of host material

Energy transfer induced multifold enhanced emission from Yb3+ is realized in a new series of Cr3+-Yb3+ co-doped as well as Cr3+-Yb3+-Nd3+ triply doped zinc fluoroboro silicate glass system. The observed multifold enhancement of Yb3+ emission under Cr3+ excitation is attributed to probable occurrence of the quantum cutting process that is credited to the present host matrix where emission of Cr3+ is red shifted to 920 nm, which is resonant with Yb3+ absorption. The sensitized luminescence of Yb3+ in the Cr3+-Yb3+ system has further been enhanced upon inclusion of Nd3+, thus demonstrating bridging action of Nd3+ ions in this energy transfer process. The energy transfer efficiency from Cr → Yb is enhanced from 38% to 54% in the presence of Nd3+ ions. The absolute quantum yield of Yb3+ ions under Cr3+ excitation for the optimized Cr-Yb sample is found to be more than double of the Cr3+ singly doped sample and increased further in Cr-Yb-Nd doped glass confirming the contribution of quantum cutting in the energ...

Internal stress induced metallization of single-walled carbon nanotubes in a nanotube/glass conducting composite

Single-walled carbon nanotubes (SWCNTs) have been incorporated into a (Pb, Zn)-phosphate glass host by a melt-quenching technique. Studies of the optical and electronic properties show that the nanotubes in the composite have suffered conformational deformations and attained a band structure of quasimetallic type, making the composite a good electrical conductor. Possible strains in the nanotubes of the composite such as radial compression, torsion and bending have been considered and their role in modulating the band structures has been analyzed by judging the change in band gap energies (ΔE) of the deformed SWCNTs using an equation which is based on the π-electron tight binding model. The effect of σ*-π* hybridization due to the radial compression in generating the metallicity is also discussed. The carrier transport in the composite above room temperature has been shown to be dominated by fluctuation induced tunneling.

Structural elucidation of NASICON (Na3Al2P3O12) based glass electrolyte materials: effective influence of boron and gallium

Understanding the conductivity variations induced by compositional changes in sodium super ionic conducting (NASICON) glass materials is highly relevant for applications such as solid electrolytes for sodium (Na) ion batteries. In the research reported in this paper, NASICON-based NCAP glass (Na2.8Ca0.1Al2P3O12) was selected as the parent glass. The present study demonstrates the changes in the Na+ ion conductivity of NCAP bulk glass with the substitution of boron (NCABP: Na2.8Ca0.1Al2B0.5P2.7O12) and gallium (NCAGP: Na2.8Ca0.1Al2Ga0.5P2.7O12) for phosphorus and the resulting structural variations found in the glass network. For a detailed structural analysis of NCAP, NCABP and NCAGP glasses, micro-Raman and magic angle spinning-nuclear magnetic resonance (MAS-NMR) spectroscopic techniques (for 31P, 27Al, 23Na, 11B and 71Ga nuclei) were used. The Raman spectrum revealed that the NCAP glass structure is more analogous to the AlPO4 mesoporous glass structure. The 31P MAS-NMR spectrum illustrated that the NCAP glass structure consists of a high concentration of Q0 (3Al) units, followed by Q0 (2Al) units. The 27Al MAS-NMR spectrum indicates that alumina exists at five different sites, which include AlO4 units surrounded by AlO6 units, Al(OP)4, Al(OP)5, Al(OAl)6 and Al(OP)6, in the NCAP glass structure. The 31P, 27Al and 11B MAS-NMR spectra of the NCABP glass revealed the absence of B–O–Al linkages and the presence of B3–O–B4–O–P4 linkages which further leads to the formation of borate and borophosphate domains. The 71Ga MAS-NMR spectrum suggests that gallium cations in the NCAGP glass compete with the alumina cations and occupy four (GaO4), five (GaO5) and six (GaO6) coordinated sites. The Raman spectrum of NCAGP glass indicates that sodium cations have also been substituted by gallium cations in the NCAP glass structure. From impedance analysis, the dc conductivity of the NCAP glass (∼3.13 × 10−8 S cm−1) is slightly decreased with the substitution of gallium (∼2.27 × 10−8 S cm−1) but considerably decreased with the substitution of boron (∼1.46 × 10−8 S cm−1). The variation in the conductivity values are described based on the structural changes of NCAP glass with the substitution of gallium and boron.

Structure and Crystallization of Alkaline-Earth Aluminosilicate Glasses: Prevention of the Alumina-Avoidance Principle

Aluminosilicate glasses are considered to follow the Al-avoidance principle, which states that Al-O-Al linkages are energetically less favorable, such that, if there is a possibility for Si-O-Al linkages to occur in a glass composition, Al-O-Al linkages are not formed. The current paper shows that breaching of the Al-avoidance principle is essential for understanding the distribution of network-forming AlO4 and SiO4 structural units in alkaline-earth aluminosilicate glasses. The present study proposes a new modified random network (NMRN) model, which accepts Al-O-Al linkages for aluminosilicate glasses. The NMRN model consists of two regions, a network structure region (NS-Region) composed of well-separated homonuclear and heteronuclear framework species and a channel region (C-Region) of nonbridging oxygens (NBOs) and nonframework cations. The NMRN model accounts for the structural changes and devitrification behavior of aluminosilicate glasses. A parent Ca- and Al-rich melilite-based CaO-MgO-Al2O3-SiO2 (CMAS) glass composition was modified by substituting MgO for CaO and SiO2 for Al2O3 to understand variations in the distribution of network-forming structural units in the NS-region and devitrification behavior upon heat treating. The structural features of the glass and glass-ceramics (GCs) were meticulously assessed by advanced characterization techniques including neutron diffraction (ND), powder X-ray diffraction (XRD), 29Si and 27Al magic angle spinning (MAS)-nuclear magnetic resonance (NMR), and in situ Raman spectroscopy. ND revealed the formation of SiO4 and AlO4 tetrahedral units in all the glass compositions. Simulations of chemical glass compositions based on deconvolution of 29Si MAS NMR spectral analysis indicate the preferred formation of Si-O-Al over Si-O-Si and Al-O-Al linkages and the presence of a high concentration of nonbridging oxygens leading to the formation of a separate NS-region containing both SiO4 and AlO4 tetrahedra (Si/Al) (heteronuclear) in addition to the presence of Al[4]-O-Al[4] bonds; this region coexists with a predominantly SiO4-containing (homonuclear) NS-region. In GCs, obtained after heat treatment at 850 °C for 250 h, the formation of crystalline phases, as revealed from Rietveld refinement of XRD data, may be understood on the basis of the distribution of SiO4 and AlO4 structural units in the NS-region. The in situ Raman spectra of the GCs confirmed the formation of a Si/Al structural region, as well as indicating interaction between the Al/Si region and SiO4-rich region at higher temperatures, leading to the formation of additional crystalline phases.