Spectroscopic properties and Judd-Ofelt analysis of Dy3+ ions in molybdenum borosilicate glasses

doi:10.1016/j.jlumin.2017.12.041

Journal of Luminescence

Volume 196, April 2018, Pages 477-484

https://doi.org/10.1016/j.jlumin.2017.12.041 Get rights and content

Abstract

Borosilicate glasses containing MoO₃ and Dy₂O₃ were prepared by the melt quenching technique. The structure and the thermal properties of these glasses have been performed by using infrared (IR) technique at room temperature and DTA. The mechanical properties have been experimentally determined and calculated according to Makishima–Mackenzie model. The optical properties of the prepared glasses have been studied using the UV – Spectroscopy. The glass transition temperature and the optical band gap decrease with increasing the MoO₃ content. The values of the optical band gap lie between 2.25–3.22 eV. The optical properties of the Dy³⁺ ion have been investigated using the Judd-Ofelt approach. The oscillator strengths and optical intensity parameters, Ω_t = 2, 4 and 6 have been evaluated. An interesting behavior of the calculated lifetime versus total angular momentum, J, has been observed, where, the lifetime values of the ⁶F_J states show an exponential increase versus J.

Introduction

At the present time, several optical devices are used extensively in the activities of human beings. Permanently, new light source devices have been studied and developed to get a good performance and fair light emission. It was originated that glasses doped with rare earth oxides (REO) are now very interesting materials for the development of optical fibers, optical amplifiers, sensors and laser [1]. Optical studies disclose the radiative properties of REO doped glasses; these properties strongly depend on the host matrix and can be modified by proper network formers as well as modifiers. In addition, the borate based glasses provide interesting optical and structural properties. REO doped glasses are potential candidates for lasers, waveguide, optical fibers, solar concentrators and optical detectors [2]. Dy₂O₃ doped lead phosphate glasses have various possible applications in several fields, such as solar cells and were characterized by IR, photoluminescence and UV–visible measurements [3]. The glasses containing Dy₂O₃ can be considered as good paramagnetic materials, which can be utilized as storage media. The principal of this probable use is based on the spread of a unidirectional light in optical materials, which results in high Verdet constant. The concentration of Dy₂O₃ is largely influenced the values of Verdet constant [4]. Moreover, trivalent dysprosium (Dy⁺³) ion, in particular, act as a potential candidate to absorb UV light and emit light mainly in the blue spectral region (460–500 nm) and yellow region (560–600 nm). The origin of these emissions was due to the 5d-4 f transitions and its 5d state can be easily affected by the crystal field environment. Thus, it is feasible to obtain white light from Dy³⁺ doped single phosphor by adjusting the yellow to blue emission intensity ratio (Y/B). Several hosts were reported to develop white light, namely molybdates-, borates-, phosphates-, vanadates- based glasses [5]. The presence of ⁶F_11/2, ⁶H_9/2 → ⁶H_15/2 transitions in Dy³⁺ at about 1.3 µm may be useful for optical amplification and visible up conversion emission required for solid state laser [6]. Furthermore, Dy³⁺ ions reveal very strong emission in the visible and NIR regions by providing lasing transitions.

Moreover, glasses containing transition metal oxides (TMO) such as MoO₃ have been studied because of their stimulating semi-conducting properties, which are owing to the springing of “polarons” from the higher to lower valence states, i.e., from Mo⁵⁺ to Mo³⁺ [4]. When these glasses are mixed with alkaline earth ions, their chemical resistance and optical transparency, increased at the excitation and lasing wavelengths. They are most compatible with the manufacture process in the development of optical devices [7], [8], [9].

The purpose of the current investigation is the study of the effect of the network of alkali borosilicate glasses containing different concentrations of MoO₃ on the optical absorption and the fluorescence spectra of Dy³⁺ ions. The characterization of these glasses has been performed by using IR, thermal and ultrasonic techniques along with an application of Judd-Ofelt theory.

Section snippets

Experimental procedures

In order to prepare glass samples having the listed nominated chemical compositions in Table 1, appropriate amounts of analytically pure grade chemicals SiO₂, MoO₃, Na₂B₄O₇ and Dy₂O₃ were thoroughly mixed in an agate mortar and melted in a platinum crucible in an electric furnace at 1150 °C for about 1 h until a bubble free liquid was formed. The melt was revolved in the crucible every 20 min to achieve homogeneity. Then, the resultant melt has been casted in a brass mold and subsequently annealed

X-ray diffraction measurements

The XRD of the studied glasses (not shown) present no discrete lines, no sharp peaks, and indicate that the glass samples have a high degree of glassy state.

IR spectroscopy

IR spectra of the prepared glass samples are shown in Fig. 1. The spectra reveal five mean absorption broadbands. Manifestation of the broadband indicates that a wide distribution of the structural units within the glasses. The most intense bands of the base glass lie within 777–1118 cm⁻¹ region and the moderate intensive bands lie between

Conclusions

The Dy³⁺ doped molybdenum borosilicate glasses have been prepared with different concentration of MoO₃. The density and the refractive index decrease while the molar volume increases with the increase of MoO₃. Both of longitudinal (v_L) and shear ultrasonic (v_T) velocities of the glass system with different mol% of MoO₃ concentration are decreased. Both of bulk modulus (K and K_Th.) and Young's modulus (Y_, and Y_Th) decrease with increasing of MoO₃ concentration. The decrease in the mechanical

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Lead phosphate glasses within system [40PbO–50P₂O₅-(10-x) WO₃- xTm₂O₃] doped with diﬀerent concentration of xTm₂O₃ ions are equipped and used the rapid cooling mechanism. Produced sets are noticed to soak up highly in the UV domain and ascribed to the concerted aided impurities of iron and participation of lead Pb²⁺ ions. Subsisting of WO₃ exposed clear absorption patterns which are ascribed to appear of W⁵⁺ pentavalent ions. Physical parameters such as density (ρ), molar volumes (V_m), refractive index (n), an optical energy gap (E_g) and Urbach energy (ΔE) values of prepared glasses were evaluated. In addition to, the Judd–Ofelt coefficients of the transformation form of oscillator probabilities, f_exp., f_th, branching ratio, β and radiative lifespans, τ, of many excited sites of Tm³⁺ have also been computed. Gain cross-section laser transformation stage from ³H₆ → ³F₃, ³H₆ → ³H₄, ³H₆ → ³H₅ and ³H₆ →³F₄ and induced emission cross-section determined at specific concentrate of Tm₂O₃ ions across all current glasses. Thus, their spectroscopic characteristics suggest that such Tm³⁺ doped glasses are an excellent choice for optical purposes.
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The effect of Dysprosium concentration has been studied in glasses of the system 30 SiO₂ + 30 Li₂O + (40−x) B₂O₃ + x Dy₂O₃ glass system where x = 0.5, 1, 2.5, 5 and 10 mol%. FT-IR studies were performed to understand the functional groups of the network involved in the host glass. The optical band gap is found in the range of 3.84–3.5 eV. From the absorption spectra, the experimental data were compared with the theoretical data computed by Judd–Ofelt theory. Nephelauxetic ratio (β) and bonding parameters (δ) computed using the absorption spectrum. The Judd–Ofelt parameters (Ω2, Ω4, and Ω6) obtained demonstrates the covalent and asymmetric nature of dysprosium ions. From the visible emission spectra, the intensity ratios were calculated from yellow to blue and the relative differences were discussed based on the concentration of Dy³⁺ ions. CIE chromaticity coordinates were calculated for all glass samples. A CIE chromatogram shows a glass containing 0.5 mol% Dy₂O₃ with color coordinates X = 0.32 and Y = 0.33 with the highest emission intensity. These glasses have great potentials for lasers and white LEDs (Light-Emitting Diode) applications.
Se ha estudiado el efecto de la concentración de disprosio en vidrios del sistema 30 SiO₂ + 30 Li₂O + (40-x) B₂O₃ + x Dy₂O₃, donde x = 0,5%, 1%, 2,5%, 5% y 10% en moles. Los estudios de FT-IR se realizaron para investigar y entender los grupos funcionales de la red que compone el vidrio. La banda prohibida óptica se encuentra entre 3,84 y 3,5 eV.
Observando los espectros de absorción, los datos experimentales se compararon con los cálculos teóricos computados con la teoría de Judd-Ofelt. El nephelauxetic ratio (β) y los parámetros de unión (δ) se calcularon utilizando los espectros de absorción. Los parámetros (Ω2, Ω4 y Ω6), obtenidos mediante Judd-Ofelt, demuestran el carácter covalente y asimétrico de los iones de disprosio. A partir de los espectros de emisión visible se calcularon las relaciones de intensidad desde amarillo hasta azul, y se discutieron las diferencias relativas, basándose en la concentración de iones Dy³⁺. Se calcularon las coordenadas de cromaticidad CIE para todas las muestras de vidrio. El cromatograma CIE correspondiente a un vidrio que contiene 0,5% en moles de Dy₂O₃ muestra coordenadas de color X = 0,32 y Y = 0,33, con la mayor intensidad de emisión. Este conjunto de vidrios tiene un gran potencial para su posible uso en aplicaciones como láseres y LED blancos.

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Spectroscopic properties and Judd-Ofelt analysis of Dy3+ ions in molybdenum borosilicate glasses

Abstract

Introduction

Section snippets

Experimental procedures

X-ray diffraction measurements

IR spectroscopy

Conclusions

J. Alloy. Compd.

J. Taibah Univ. Sci.

J. Dyes Pigments

J. Non-Cryst. Solids

J. Non-Cryst. Solids

J. Mater. Sci. Eng. B

J. Non-Cryst. Solids

Physica B

J. Non-Cryst. Solids

J. Non-Cryst. Solids

J. Non-Cryst. Solids

Physica B

J. Proc. Eng.

J. Non-Cryst. Solids

J. Mol. Struct.

J. Lumin.

J. Mol. Struct.

J. Alloy. Compd.

Ceram. Int.

J. Lumin.

J. Lumin.

J. Alloy. Compd.

Spectrochim. Acta A

J. Quant. Spectrosc. Radiat. Transf.

Spectroscopic properties and Judd-Ofelt analysis of Dy³⁺ ions in molybdenum borosilicate glasses