Academic Editor:Fei Meng
Physics Department, Faculty of Science, University Putra Malaysia (UPM), 43400 Serdang, Selangor, Malaysia
Received 28 July 2015; Revised 29 September 2015; Accepted 8 October 2015; 16 November 2015
This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
1. Introduction
Judd-Ofelt theory was first introduced by Judd and Ofelt in 1962 to explore the spectral intensities at 4f-4f transitions of the rare earth ions [1, 2]. In present years, Judd-Ofelt analysis has become a very important tool to estimate the luminescence and laser efficiency of materials. Rare earth ions consist of very strong intensities and sharp spectral characteristic in 4f transitions [3]. Based on this characteristic, rare earth ions become the most needed materials to develop excellent luminescence and laser applicability. Judd-Ofelt analysis consists of three parameters which are [figure omitted; refer to PDF] , [figure omitted; refer to PDF] , and [figure omitted; refer to PDF] [1, 2]. The three Judd-Ofelt intensity parameters are determined empirically from the room temperature (RT) absorption spectrum by minimizing the differences between calculated and experimental transition line (or oscillator) strengths of a series of excited multiplets by standard least-squares or chi square method [4]. Lately, the luminescence and upconversion properties of Er3+ ions have been considered due to their intense green and red emission [5, 6]. These emissions provide an excellent application in many areas from high density optical storage and optoelectronics to medical applications.
Tellurite based glass is widely being used as the main host materials to attain excellent optical and dielectric properties. It is well known that tellurite based glass possesses a high quality of glass forming ability, wide transmission band, fast optical switches, excellent linear and nonlinear optical properties, and exceptional optical fibers for fiber-optical communications. Based on these properties, it is of interest to investigate the new tellurite glass system with various compositions. The formation of tellurite glass system acquires glass stabilizer to obtain stable and reliable glass system. Borate oxide is the most interesting compound to be used as glass stabilizer which is due to its low melting temperature and good rare earth ion solubility. Furthermore, borate matrix consists of BO3 (trigonal structure) and BO4 (tetrahedra structure) which generate 4 stable borate groups such as diborate and triborate. The insertion of zinc oxide in the glass system provides low rates of crystallization and contributes to a significant growth of glass forming ability. Moreover, tellurite based glass has a good compatibility with rare earth ions since they provide low phonon energy (700-800 cm-1 ) environment to minimize the nonradiative losses which are lower compared to the other oxide glass such as silicates, borates, phosphates, and germinates [7-9].
Tellurite glass containing nanoparticles system has a great attraction, especially to study the effect of nanosize particles on optical behavior. Nowadays, special attention has been given to enhance the luminescence properties of materials by using silver and gold nanoparticles [10-13]. However, the investigations on the tellurite glass containing rare earth nanoparticles have not been well explored. Erbium oxide has very special properties, especially in luminescence and laser applications. Lately, the investigations of luminescence and spectral intensity of tellurite glass containing erbium oxide system have been extensively studied [14, 15]. Nevertheless, the research on tellurite glass system containing erbium oxide NPs seems not to be available. Nanoparticles are very useful to improve the quantum efficiency of laser materials. Awang et al., 2013, stated that nanoparticles may enhance the weak optical transitions by generation of intense electric fields upon electromagnetic excitation where plasmonic metal nanostructures in the vicinity of the rare earth (RE) ions alter their free space spectroscopic properties [12]. Hence, it is extremely demanding to further explore the spectral intensity and green emission of tellurite based glass containing erbium oxide NPs.
2. Experimental Methodology
The tellurite based glass containing Er3+ NPs was prepared by using melt-quenching method with chemical composition of [figure omitted; refer to PDF] . The high purity of raw materials (99.99%, purity grade) of erbium (III) oxide nanoparticles, Er2 O3 NPs (20-30 nm, Nanostructured and Amorphous Materials Inc.), tellurium (IV) oxide, TeO2 (Puratronic, Alfa Aesar), zinc oxide, ZnO (Assay, Alfa Aesar), and boron oxide, B2 O3 (Assay, Alfa Aesar), was used to fabricate the glass sample. The chemical composition of about 13 g was weighted and mixed thoroughly and placed in alumina crucible. The homogenous mixture was then transferred to the electrical furnace of 400°C in about 1 hour to remove the excess water molecule.
The mixture was transferred to the electrical furnace of 900°C in about 2 hours for the melting process. The melt was poured onto a preheated stainless steel split mould. The mould was kept in an electrical furnace of 400°C in about 1 hour to remove strain and improve the mechanical strength. After that, the furnace was turned off to cool down at room temperature. The glass sample was cut by using Isomet, Buehler, low speed saw machine to obtain 2 mm thickness of the glass sample. The sample was polished with various types of sand papers, 1500 grit, 1200 grit, and 1000 grit, to obtain flat and smooth surface. The density of the glass sample was measured through Archimedes principle by using acetone as immersion liquid. The FTIR, XRD, and EDX analysis were performed by using EDX-720/800 HS Shimadzu, Xpert Highscore PANalytical X-ray diffractometers and PerkinElmer Spectrum 100 Series FT-IR spectrometers. The refractive index of the glass sample was carried out by using EL X-02C high precision ellipsometer with the angle of the incident at 70° and wavelength of the beam laser, [figure omitted; refer to PDF] nm. The absorption analysis of the glass sample was measured by using UV-1650PC UV-Vis Spectrophotometer (Shimadzu) with the wavelength of 190-1100 nm.
3. Result and Discussions
3.1. Transmission Electron Microscopy (TEM)
Figure 1 illustrates the TEM image for erbium oxide NPs before and after the glass formation. It is clear from the figure that the pure erbium oxide nanoparticles exhibit three-dimensional spherical-shaped structures. The average size of nanoparticles before the glass formation is found in the range 18 nm. It can be seen from Figure 1 that the erbium oxide NPs exist after the glass formation. The average size of the nanoparticles is found in the range 28 nm with three-dimensional spherical-shaped structures. It can be seen that the average size of nanoparticles is increased after the glass formation. This may be due to the particle sintering and grain growth as a result of the high-temperature thermal treatment in which the smaller particles tend to form larger particles.
Figure 1: TEM image of erbium oxide NPs before (a) and after (b) the glass formation.
(a) [figure omitted; refer to PDF]
(b) [figure omitted; refer to PDF]
3.2. X-Ray Diffraction and EDX Analysis
The noncrystallinity of the glass system was confirmed by using X-ray diffraction (XRD) method. The X-ray diffraction pattern of the tellurite based glass containing Er3+ NPs was recorded at room temperature in the range of [figure omitted; refer to PDF] . The XRD spectra are shown in Figure 2 and it is clear from the figure that the spectra possess broad diffusion at lower scattering angle indicating the long range disorder arrangement. This is in accordance with the characteristic of glass materials which possess amorphous structural arrangement. The absence of sharp peaks recommends that the glass sample exhibit noncrystalline phase. The energy dispersion X-ray (EDX) analysis was performed to determine the exact composition of the glass materials. The EDX spectra are shown in Figure 3 and the measured weight composition of the glass sample is tabulated in Table 1. It can be seen from Figure 3 that all the elements of zinc, erbium oxide NPs, boron, and tellurite exist in the glass system. There is no sign of foreign elements in the EDX spectra which indicates that the glass sample is free from contamination.
Table 1: Calculated and EDX-measured weight of oxides of [figure omitted; refer to PDF] [(TeO2 )0.70 (B2 O3 )0.30 ]0.7 (ZnO)0.3 [figure omitted; refer to PDF] 0.95 (Er2 O3 )0.05 .
Oxides | Experimental weight% | Calculated weight% |
TeO2 | 58.062 | 56.929 |
B2 O3 | 17.073 | 17.772 |
ZnO | 8.806 | 10.643 |
Er2 O3 | 16.059 | 14.656 |
Figure 2: XRD spectra of [figure omitted; refer to PDF] [(TeO2 )0.70 [figure omitted; refer to PDF] (ZnO)0.3 [figure omitted; refer to PDF] (Er2 O3 )0.05 .
[figure omitted; refer to PDF]
Figure 3: EDX spectra of [figure omitted; refer to PDF] [(TeO2 )0.70 (B2 O3 )0.30 ]0.7 (ZnO)0.3 [figure omitted; refer to PDF] (Er2 O3 )0.05 .
[figure omitted; refer to PDF]
3.3. Fourier Transform Infrared Analysis
Fourier transform infrared analysis (FT-IR) is used to understand the characteristic of the local structure and functional groups for particular materials. The transmission spectra were recorded at room temperature in the range of 280-2400 cm-1 . The obtained data of transmission spectra were plotted in Figure 4 and tabulated in Table 2. It can be seen from Figure 4 that the existence of intense absorption bands was centered at 645 cm-1 , 1223 cm-1 , and 1331 cm-1 . The transmission band of the local structure of pure TeO2 glass was centered at 640 cm-1 [22]. Tellurite oxide containing glass possesses two types of structural arrangement which are trigonal pyramidal TeO3 and trigonal bipyramidal TeO4 . These two types of structural arrangements can be identified through the transmission band at 600-700 cm-1 . The transmission band centered at 600-650 cm-1 is due to the formation of trigonal bipyramidal TeO4 while that at 650-700 cm-1 corresponds to the formation of trigonal pyramidal TeO3 , respectively. Based on Figure 4, the existence of transmission band located at 656-664 cm-1 correlates to the formation of trigonal pyramidal TeO3 structural arrangement. This is the indication of the formation of nonbridging oxygen in the glass network, which contributes to the high frequency position of TeO3 compared to TeO4 .
Table 2: Assignment of infrared transmission bands of [figure omitted; refer to PDF] [(TeO2 )0.70 (B2 O3 )0.30 ]0.7 (ZnO)0.3 [figure omitted; refer to PDF] 0.95 (Er2 O3 )0.05 .
Number | Position (cm-1 ) | Assignments |
1 | 1331 | Trigonal B-O bond stretching vibrations in isolated trigonal BO3 units |
| ||
2 | 1223 | Trigonal B-O bond stretching vibrations of BO3 units from boroxyl groups |
| ||
3 | 645 | TeO3 group exists in tellurite containing glass |
Figure 4: FTIR spectrum of [figure omitted; refer to PDF] [(TeO2 )0.70 (B2 O3 )0.30 ]0.7 (ZnO)0.3 [figure omitted; refer to PDF] (Er2 O3 )0.05 .
[figure omitted; refer to PDF]
Borate glass, B2 O3 , possesses boroxyl ring structural arrangement located at 806 cm-1 . However, this band disappeared after the glass formation which indicates the absence of boroxyl ring in the glass system. Furthermore, the trigonal BO3 and tetrahedral BO4 are taking place after the glass formation. Previous research reported that the transmission band of borate network is mainly active in only three spectral regions [23, 24]. The first band of borate network is located in the range of 1200-1600 cm-1 . This correlates with the asymmetric stretching vibration of the B-O band in trigonal BO3 units [25]. The second band of borate network lies in the range of 800-1200 cm-1 which corresponds to the stretching vibrations of B-O band in tetrahedral BO4 units. The third group of borate network is positioned in the range of 700 cm-1 which correlates to bending vibrations of B-O-B in trigonal BO3 units. It can be seen from Figure 4 that the intense absorption bands of borate network are located at 1233 cm-1 and 1343 cm-1 . These two bands are attributed to the symmetric stretching vibrations of B-O in trigonal BO3 units.
The characteristic of ZnO4 unit is located at 418 cm-1 . However, the ZnO4 unit is absent from the present glass system. This indicates that the zinc lattice is completely broken down and may be formulated as ZnB4 O7 [26]. It can be seen from Figure 4 that no sign of erbium unit appeared. This is due to the low concentration of erbium ions that could not be detected by the instrument.
3.4. Optical Density and Extinction Coefficient
The optical absorption studies give information to understand the electronic transitions of the materials. The absorption spectra of tellurite based glass containing erbium oxide NPs recorded at room temperature in the UV-Vis region are shown in Figure 5. It can be seen from the figure that the absorption spectra consist of several bands which is due to the characteristic of Er3+ ions. Furthermore, erbium ions consist of 4f electrons which are shielded by the outer 5s and 5p bonding electrons which result from the sharp absorption bands. These bands correspond to the 10 transitions originating from the [figure omitted; refer to PDF] ground state. The transitions arise from the intraconfigurational (f-f) transitions from the ground state [figure omitted; refer to PDF] to the excited states [figure omitted; refer to PDF] [27]. The absorption band below 300 nm could not be determined which is due to the rapid increases of the electronic absorption edge. The absorption coefficient [figure omitted; refer to PDF] has been obtained by using the following relation: [figure omitted; refer to PDF] where [figure omitted; refer to PDF] is the absorbance and [figure omitted; refer to PDF] is the thickness of the glass sample. The obtained value of absorption coefficient is presented in Table 3. The absence of clear sharp absorption coefficient edge recommends that the glass sample is amorphous in nature. Besides that, the absorption edge depends on the oxygen bond strength of the glass sample. The variety of oxygen bond strength will affect the absorption characteristic of the materials.
Table 3: Optical coefficient and extinction coefficient of [figure omitted; refer to PDF] [(TeO2 )0.70 (B2 O3 )0.30 ]0.7 (ZnO)0.3 [figure omitted; refer to PDF] 0.95 (Er2 O3 )0.05 .
Samples | Absorption coefficient (cm-1 ) | Extinction coefficient ( [figure omitted; refer to PDF] ) 10-8 |
0.05 | 1.3359 | 66.110 |
Figure 5: Optical density spectra of [figure omitted; refer to PDF] .
[figure omitted; refer to PDF]
The hallmark of the Er3+ -ligand bonds can be determined through the nephelauxetic ratio and bonding parameters [figure omitted; refer to PDF] of the glass sample. The value of nephelauxetic ratio can be expressed by the following relation: [figure omitted; refer to PDF] where [figure omitted; refer to PDF] correspond to the wavenumber (in cm-1 ) for the single excited states transition of Er3+ and [figure omitted; refer to PDF] is the wavenumber (in cm-1 ) for the same position of excited states transitions in aquo-ion [27]. The bonding parameter [figure omitted; refer to PDF] of the glass sample can be determined by considering the average values of [figure omitted; refer to PDF] through the following formula: [figure omitted; refer to PDF] The obtained values of nephelauxetic ratio and bonding parameter for the title glass were tabulated in Table 4. The ionic or covalent characteristic of the materials can be predicted by negative or positive sign value of the bonding parameter. It can be seen from the table that the bonding parameter is in negative sign which indicates that the glass sample is ionic in nature. The ionic nature of the metal-ligand is affected by the chemical composition of the glass materials. The existence of trivalent electron of erbium oxide NPs contributes to the strong ionic characteristic of the glass sample. Previous research on glass containing erbium oxide reported the same ionic behavior with this work [28].
Table 4: Band positions and bonding parameters of [figure omitted; refer to PDF] [(TeO2 )0.70 (B2 O3 )0.30 ]0.7 (ZnO)0.3 [figure omitted; refer to PDF] 0.95 (Er2 O3 )0.05 .
Transition(from [figure omitted; refer to PDF] ) | Wavenumber (cm-1 ) | Wavenumber in aquo-ion (cm-1 ) [16] |
[figure omitted; refer to PDF] | 22,201 | 22,300 |
[figure omitted; refer to PDF] | 20,435 | 20,600 |
[figure omitted; refer to PDF] | 19,120 | 19,270 |
[figure omitted; refer to PDF] | 18,349 | 18,550 |
[figure omitted; refer to PDF] | 15,291 | 15390 |
[figure omitted; refer to PDF] | 12,516 | 12,400 |
[figure omitted; refer to PDF] | 2.4830 |
|
[figure omitted; refer to PDF] | -59.726 |
|
3.5. Judd-Ofelt Analysis
The introduction of Judd-Ofelt theory [2, 16] provides the information of transition behaviour between 4f-4f electronic configuration and calculation of transition probabilities, branching ratio, oscillator strength, and intensity parameters ( [figure omitted; refer to PDF] , [figure omitted; refer to PDF] , and [figure omitted; refer to PDF] ). Judd-Ofelt theory is an important approach to analyze and investigate the spectral properties of tellurite glass system containing erbium ions. The Judd-Ofelt analysis acquires the precise integrated absorption cross section measurement over the range of wavelength and transition state of excitation. The experimental oscillator strength for each transition state of excitation can be expressed by the following relation: [figure omitted; refer to PDF] where [figure omitted; refer to PDF] is the concentration of Er3+ ions in cm-1 and [figure omitted; refer to PDF] is the molar absorptivity in L/(mol·cm) obtained from the measured absorbance of the glass system. The molar absorptivity [figure omitted; refer to PDF] at a given energy is computed from Beer-Lambert Law as shown in the following: [figure omitted; refer to PDF] where [figure omitted; refer to PDF] is the concentration of Er3+ ion (mol%), [figure omitted; refer to PDF] is the thickness of the glass sample (cm), and [figure omitted; refer to PDF] is the optical density (OD). According to the Judd-Ofelt theory, the estimation of theoretical oscillator strength of an electric dipole transition from [figure omitted; refer to PDF] to [figure omitted; refer to PDF] is determined by the following expression: [figure omitted; refer to PDF] where [figure omitted; refer to PDF] is Plank's constant, [figure omitted; refer to PDF] is the refractive index, and [figure omitted; refer to PDF] is the doubly reduced matrix elements of the unit tensor operator. The obtained values of experimental and calculated oscillator strength were tabulated in Table 5. The Judd-Ofelt parameter is computed by using least-square fitting procedure which gives the best fit between experimental and calculated oscillator strength. Meanwhile, according to the Judd-Ofelt theory, the line strength [figure omitted; refer to PDF] can be found from an integrated absorption cross section by the following expression [29]: [figure omitted; refer to PDF] where [figure omitted; refer to PDF] is the total angular momentum of the lower state, [figure omitted; refer to PDF] is the mean wavelength, and [figure omitted; refer to PDF] is the optical density over the range of wavelength. The theoretical expression of electric dipole line strength is given by [figure omitted; refer to PDF] where [figure omitted; refer to PDF] is the Judd-Ofelt parameters. The reduced matrix element [figure omitted; refer to PDF] can be calculated in the intermediate-coupling approximation and is invariant of environment. A Judd-Ofelt analysis minimizes the square of the difference between [figure omitted; refer to PDF] and [figure omitted; refer to PDF] with [figure omitted; refer to PDF] as adjustable parameters [29]. The validity of fitting has been obtained by comparing the experimental and calculated line strength which is listed in Table 5. Using the least-square fitting method, the Judd-Ofelt parameters [figure omitted; refer to PDF] ( [figure omitted; refer to PDF] ) of erbium oxide NPs together with various types of glass system from earlier reported literature [17-21] were summarized in Table 6. The data of Judd-Ofelt parameters from previous literature will be used for comparison with the present glass. It can be seen from Table 6 that the obtained values of Judd-Ofelt parameters are as follows: [figure omitted; refer to PDF] , 0.400, and 0.07, respectively, in units of 10-20 cm2 .
Table 5: Integrated areas, dipole line strengths [figure omitted; refer to PDF] , oscillator strength [figure omitted; refer to PDF] , and calculated JO intensity parameters of [figure omitted; refer to PDF] [(TeO2 )0.70 (B2 O3 )0.30 ]0.7 (ZnO)0.3 [figure omitted; refer to PDF] 0.95 (Er2 O3 )0.05 .
Transition | [figure omitted; refer to PDF] | [figure omitted; refer to PDF] | Line strength [figure omitted; refer to PDF] (×10-20 cm2 ) | Oscillator strengths [figure omitted; refer to PDF] (×10-20 cm2 ) | ||
(from [figure omitted; refer to PDF] ) | (nm) | (10-7 ) cm | Measured [figure omitted; refer to PDF] | Calculated [figure omitted; refer to PDF] | Measured [figure omitted; refer to PDF] | Calculated [figure omitted; refer to PDF] |
[figure omitted; refer to PDF] | 452 | 5.05 | 0.051 | 0.051 | 0.144 | 0.144 |
[figure omitted; refer to PDF] | 489 | 11.60 | 0.108 | 0.066 | 0.285 | 0.173 |
[figure omitted; refer to PDF] | 527 | 21.97 | 0.191 | 0.202 | 0.473 | 0.499 |
[figure omitted; refer to PDF] | 654 | 25.97 | 0.180 | 1.037 | 0.354 | 2.039 |
[figure omitted; refer to PDF] | 800 | 10.80 | 0.061 | 0.075 | 0.096 | 0.119 |
[figure omitted; refer to PDF] | 977 | 14.71 | 0.069 | 0.008 | 0.091 | 0.011 |
Ω2 = (1.223 ± 0.021) × 10-20 cm2 , Ω4 = (0.400 ± 0.104) × 10-20 cm2 , Ω6 = (0.037 ± 0.112) × 10-20 cm2 , and [figure omitted; refer to PDF] = 0.0537 × 10-20 cm2 .
Table 6: JO intensity parameters [figure omitted; refer to PDF] for various glass systems.
Glass system | [figure omitted; refer to PDF] (×10-21 cm2 ) | References | ||
Ω2 | Ω4 | Ω6 | ||
TeO2 -ZnO-Na2 O-B2 O3 -GeO2 -Er2 O3 | 5.75 | 5.02 | 1.11 | [17] |
TeO2 -B2 O3 -CdO-Li2 O-Er2 O3 | 5.21 | 1.93 | 1.05 | [18] |
B2 O3 -TeO2 -MgO-Er2 O3 | 3.74 | 2.74 | 1.86 | [19] |
PbBr2 -TeO2 -Er2 O3 | 3.13 | 1.25 | 0.73 | [20] |
Er/Yb-GeO2 -PbO-Bi2 O3 | 3.29 | 1.34 | 3.02 | [21] |
Er2 O3 (NPs)-ZnO-B2 O3 -TeO2 | 1.223 | 0.400 | 0.037 | This work |
The values of [figure omitted; refer to PDF] and [figure omitted; refer to PDF] parameters correspond to the asymmetry of the local environment of Er3+ ions sites which depends on the covalency between Er3+ ions and ligand anions. Meanwhile, the value of [figure omitted; refer to PDF] parameter is linked to the local basicity of Er3+ ions and inversely proportional to the covalency of the Er-O bond. It can be seen that the Judd-Ofelt parameters behavior of most of the glass system is following the trend of [figure omitted; refer to PDF] . The relatively small value of [figure omitted; refer to PDF] and [figure omitted; refer to PDF] was found for tellurite glass containing erbium oxide NPs compared to the other glass system. According to the Judd-Ofelt theory, the [figure omitted; refer to PDF] and [figure omitted; refer to PDF] parameters are strongly sensitive to the local environment symmetry of rare earth ions. The small value of [figure omitted; refer to PDF] and [figure omitted; refer to PDF] indicates that the glass system possesses the lower asymmetric nature of the local environment around Er3+ sites. This has also shown the ionic nature of the chemical bond between Er3+ ions and the ligands. Furthermore, this effect is reflected to the inorganic ligand field character of the glass matrix [30].
Compared with [figure omitted; refer to PDF] and [figure omitted; refer to PDF] parameters, [figure omitted; refer to PDF] parameter does not depend on the local structure. It can be seen from Table 6 that the obtained value of [figure omitted; refer to PDF] parameter of present glass is lower compared to the other glass system containing erbium oxide. This indicates that the prepared glass system possesses a high number in Er-O covalency compared to the other glass system. The high number of covalency is due to the high number of nonbridging oxygen ions (NBOs) around the host matrix. In addition, the presence of a high number of NBOs leads to producing higher number of electron density of the ligand ions. It can be concluded that the tellurite glass containing Er3+ (NPs) possesses a relatively strong covalency and lower asymmetry around Er3+ sites.
The Judd-Ofelt parameters ( [figure omitted; refer to PDF] , [figure omitted; refer to PDF] ) can be used to compute the radiative transition probability [figure omitted; refer to PDF] (electric dipole transition probability [figure omitted; refer to PDF] and magnetic dipole transition probability [figure omitted; refer to PDF] ), fluorescence branching ratio β , and radiative lifetime [figure omitted; refer to PDF] of Er3+ (NPs) ions [31]. The radiative transition probability [figure omitted; refer to PDF] (also called Einstein coefficient for spontaneous emission) for any excited transition state can be expressed by the following relation: [figure omitted; refer to PDF] The magnetic dipole line strength [figure omitted; refer to PDF] is neglected since the excitation bands are essentially electric dipole in nature. The calculated radiative transition probabilities were tabulated in Table 7. It can be seen that the radiative probability [figure omitted; refer to PDF] of Er3+ : [figure omitted; refer to PDF] transition possesses a high value which is beneficial to the green emission.
Table 7: Calculated transition probabilities and branching ratio of [figure omitted; refer to PDF] [(TeO2 )0.70 (B2 O3 )0.30 ]0.7 (ZnO)0.3 [figure omitted; refer to PDF] 0.95 (Er2 O3 )0.05 .
Transition | λ (nm) | [figure omitted; refer to PDF] (S-1 ) | [figure omitted; refer to PDF] (S-1 ) | β | Lifetime (ms) | |
[figure omitted; refer to PDF] | [figure omitted; refer to PDF] | 1535 | 17.063 | 11.77 | 1.000 | 13.070 |
| ||||||
[figure omitted; refer to PDF] | [figure omitted; refer to PDF] | 2680 |
| 3.070 | 0.443 |
|
[figure omitted; refer to PDF] | 976 |
| 22.25 | 0.557 | 25.014 | |
| ||||||
[figure omitted; refer to PDF] | [figure omitted; refer to PDF] | 4406 | 10.02 | 0.190 | 0.037 |
|
[figure omitted; refer to PDF] | 1666 |
| 3.370 | 0.051 |
| |
[figure omitted; refer to PDF] | 799 |
| 60.26 | 0.912 | 15.136 | |
| ||||||
[figure omitted; refer to PDF] | [figure omitted; refer to PDF] | 3604 | 11.99 | 1.710 | 0.016 |
|
[figure omitted; refer to PDF] | 1982 | 4.791 | 8.910 | 0.049 |
| |
[figure omitted; refer to PDF] | 1139 |
| 23.38 | 0.056 |
| |
[figure omitted; refer to PDF] | 654 |
| 368.65 | 0.879 | 2.384 | |
| ||||||
[figure omitted; refer to PDF] | [figure omitted; refer to PDF] | 1714 |
| 9.27 | 0.090 |
|
[figure omitted; refer to PDF] | 1234 |
| 2.83 | 0.027 |
| |
[figure omitted; refer to PDF] | 845 |
| 26.96 | 0.261 |
| |
[figure omitted; refer to PDF] | 545 |
| 64.17 | 0.622 | 9.688 | |
| ||||||
[figure omitted; refer to PDF] | [figure omitted; refer to PDF] | 2611 |
| 10.64 | 0.003 |
|
[figure omitted; refer to PDF] | 1514 |
| 34.76 | 0.011 |
| |
[figure omitted; refer to PDF] | 1127 |
| 27.39 | 0.009 |
| |
[figure omitted; refer to PDF] | 793 |
| 43.26 | 0.014 |
| |
[figure omitted; refer to PDF] | 523 |
| 2986.46 | 0.963 | 0.322 | |
| ||||||
[figure omitted; refer to PDF] | [figure omitted; refer to PDF] | 1938 |
| 2.36 | 0.003 |
|
[figure omitted; refer to PDF] | 1260 |
| 21.78 | 0.031 |
| |
[figure omitted; refer to PDF] | 980 |
| 68.67 | 0.099 |
| |
[figure omitted; refer to PDF] | 718 |
| 201.15 | 0.289 |
| |
[figure omitted; refer to PDF] | 489 |
| 402.70 | 0.578 | 1.435 | |
| ||||||
[figure omitted; refer to PDF] | [figure omitted; refer to PDF] | 2532 |
| 4.57 | 0.007 |
|
[figure omitted; refer to PDF] | 1894 |
| 7.72 | 0.011 |
| |
[figure omitted; refer to PDF] | 1098 |
| 7.27 | 0.010 |
| |
[figure omitted; refer to PDF] | 841 |
| 17.15 | 0.024 |
| |
[figure omitted; refer to PDF] | 707 |
| 121.87 | 0.174 |
| |
[figure omitted; refer to PDF] | 559 |
| 432.97 | 0.617 |
| |
[figure omitted; refer to PDF] | 410 |
| 110.25 | 0.157 | 1.425 |
The quality of the fitting between [figure omitted; refer to PDF] and [figure omitted; refer to PDF] was performed by the following expression [30]: [figure omitted; refer to PDF] where [figure omitted; refer to PDF] is the number of the spectral bands analyzed and [figure omitted; refer to PDF] is the number of JO parameters calculated. The obtained value of rms deviation was 0.0537 × 10-20 cm2 , which shows a good agreement with calculated and experimental data and consequently a good precision in the determination of intensity parameters. The branching ratio [figure omitted; refer to PDF] and radiative lifetime [figure omitted; refer to PDF] of Er3+ can be evaluated by using the following equation: [figure omitted; refer to PDF] The obtained results for fluorescence branching ratio β and radiative lifetime [figure omitted; refer to PDF] of Er3+ (NPs) ions are tabulated in Table 7. The lifetime is an important information for optical amplifiers and lasers application, especially at the 1.5 μ m band. The longer lifetime at transition of [figure omitted; refer to PDF] level gives advantage to the population inversion between [figure omitted; refer to PDF] and [figure omitted; refer to PDF] levels [32].
3.6. Green Photoluminescence
Figure 6 shows the room temperature photoluminescence spectra of zinc borotellurite glass system containing erbium oxide NPs under 385 nm excitation wavelength. Two main peaks were observed at 559 nm and 539 nm, which are attributed to [figure omitted; refer to PDF] and [figure omitted; refer to PDF] levels to the ground state at [figure omitted; refer to PDF] . The observed bands are due to the stark splitting effects which correspond to the low symmetry of the local environment around Er3+ sites [33]. This can be proved by the previous data of [figure omitted; refer to PDF] intensity parameter at the lower number. The electronic configuration schematic diagram is shown in Figure 7 to determine the mechanism of emission and energy transfer. The emission peaks at 559 nm and 539 nm can be ascribed to the visible light emissions by transitions of excited optical centers in the deep levels [33].
Figure 6: Green emission spectrum of [figure omitted; refer to PDF] .
[figure omitted; refer to PDF]
Figure 7: The schematic diagram of [figure omitted; refer to PDF] and possible mechanism for visible emissions.
[figure omitted; refer to PDF]
It can be seen from Figure 7 that the excitation occurs from the ground state ( [figure omitted; refer to PDF] ) by absorbing a photon (25 974 cm-1 ) from the excitation beam (GSA (ground state absorption) 385 nm) and makes a transition to [figure omitted; refer to PDF] level. The electrons at [figure omitted; refer to PDF] decay nonradiatively (NR) by multiphonon relaxation to populate [figure omitted; refer to PDF] , [figure omitted; refer to PDF] , and [figure omitted; refer to PDF] levels. The electrons at [figure omitted; refer to PDF] level were then relaxed nonradiatively and populate level [figure omitted; refer to PDF] , while the latest state ( [figure omitted; refer to PDF] ) is in thermal equilibrated population with [figure omitted; refer to PDF] excitation levels [34]. The electrons at the excited states of [figure omitted; refer to PDF] then decay radiatively to the ground states, [figure omitted; refer to PDF] , and produce green emission. The mechanism of red emission could be also explained by the energy transfer (ET) process between two adjacent Er3+ electrons through this process:
: ET1 : [figure omitted; refer to PDF] ,
: ET2 : [figure omitted; refer to PDF] .
The energy transfer rate strongly depends on the distance of two Er3+ ions which means that the concentration of Er3+ affects the efficiency of energy transfer. Furthermore, the emission peaks of red emission are strongly influenced by energy transfer process. However, there is absence of red emission peak of the graph in the present glass system which is due to the low concentration of Er3+ ions.
4. Conclusion
In summary, the quaternary composition of TeO2 -B2 O3 -ZnO-Er2 O3 NPs glass was successfully prepared and analyzed for structural and optical properties. The noncrystallinity of the glass sample was confirmed by XRD analysis. The existence of all glass elements with their exact composition was proved by EDX analysis. FT-IR analysis revealed the formation of TeO3 indicating the existence of nonbridging oxygen. The bands of BO3 units at 1233 and 1343 cm-1 were also shown which correspond to the symmetric stretching vibrations of B-O in trigonal BO3 units. The absorption spectra consist of 10 transitions originating from the ground state [figure omitted; refer to PDF] to the excited states [figure omitted; refer to PDF] . The extinction coefficient is found to be decreased with increasing wavelength due to the decreasing number of absorption coefficient. The obtained value of nephelauxetic ratio and bonding parameter suggest that the present glass system is ionic in nature. The Judd-Ofelt parameter was shown to follow the trend of [figure omitted; refer to PDF] . The obtained value of Judd-Ofelt parameter recommends that the present glass system possesses a relatively strong covalency and lower asymmetry around Er3+ sites. The quenched green emission of the present glass system is shown by the photoluminescence spectra. The existence of green emission peaks at 559 nm and 539 nm, which are attributed to 4 S3/2 and 2 H11/2 , is observed which is due to the stark splitting effect. The obtained result of Judd-Ofelt and photoluminescence shows that the glass sample is very useful in green laser application with high lifetime and strong spectral intensity.
Acknowledgment
The authors appreciate the financial support for the work from the Ministry of Higher Education of Malaysia through GPIBT (9411800).
Conflict of Interests
The authors declare that there is no conflict of interests regarding the publication of this paper.
[1] B. R. Judd, "Optical absorption intensities of rare-earth ions," Physical Review , vol. 127, no. 3, pp. 750-761, 1962.
[2] G. S. Ofelt, "Intensities of crystal spectra of rare-earth ions," The Journal of Chemical Physics , vol. 37, no. 3, pp. 511-520, 1962.
[3] B. G. Wybourne, "The fascination of the rare earths - then, now and in the future," Journal of Alloys and Compounds , vol. 380, no. 1-2, pp. 96-100, 2004.
[4] W. Luo, J. Liao, R. Li, X. Chen, "Determination of Judd-Ofelt intensity parameters from the excitation spectra for rare-earth doped luminescent materials," Physical Chemistry Chemical Physics , vol. 12, no. 13, pp. 3276-3282, 2010.
[5] A. F. da Silva, D. S. Moura, A. S. Gouveia-Neto, E. A. Silva Jr., L. A. Bueno, E. B. Costa, E. N. Azevedo, "Intense red upconversion fluorescence emission in NIR-excited erbium-ytterbium doped laponite-derived phosphor," Optics Communications , vol. 284, no. 19, pp. 4501-4503, 2011.
[6] A. Egatz-Gomez, O. G. Calderon, S. Melle, F. Carreño, M. A. Anton, E. M. Gort, "Homogeneous broadening effect on temperature dependence of green upconversion luminescence in erbium doped fibers," Journal of Luminescence , vol. 139, pp. 52-59, 2013.
[7] F. Chen, T. Xu, S. Dai, Q. Nie, X. Shen, J. Zhang, X. Wang, "Linear and non-linear characteristics of tellurite glasses within TeO2 -Bi2 O3 -TiO2 ternary system," Optical Materials , vol. 32, no. 9, pp. 868-872, 2010.
[8] M. J. Weber From Galileo's 'Occhialino' to Optoelectronics , of edited by P. Mazzoldi, World Scientific, Singapore, 1993.
[9] G. Lakshminarayana, R. Vidya Sagar, S. Buddhudu, "NIR luminescence from Er3+ /Yb3+ , Tm3+ /Yb3+ , Er3+ /Tm3+ and Nd3+ ions-doped zincborotellurite glasses for optical amplification," Journal of Luminescence , vol. 128, no. 4, pp. 690-695, 2008.
[10] M. Reza Dousti, S. Raheleh Hosseinian, "Enhanced upconversion emission of Dy3+ -doped tellurite glass by heat-treated silver nanoparticles," Journal of Luminescence , vol. 154, pp. 218-223, 2014.
[11] M. R. Dousti, M. R. Sahar, M. S. Rohani, A. Samavati, Z. A. Mahraz, R. J. Amjad, A. Awang, R. Arifin, "Nano-silver enhanced luminescence of Eu3+ -doped lead tellurite glass," Journal of Molecular Structure , vol. 1065-1066, no. 1, pp. 39-42, 2014.
[12] A. Awang, S. K. Ghoshal, M. R. Sahar, M. Reza Dousti, R. J. Amjad, F. Nawaz, "Enhanced spectroscopic properties and Judd-Ofelt parameters of Er-doped tellurite glass: effect of gold nanoparticles," Current Applied Physics , vol. 13, no. 8, pp. 1813-1818, 2013.
[13] R. de Almeida, D. M. da Silva, L. R. P. Kassab, C. B. de Araújo, "Eu3+ luminescence in tellurite glasses with gold nanostructures," Optics Communications , vol. 281, no. 1, pp. 108-112, 2008.
[14] M. S. Figueiredo, F. A. Santos, K. Yukimitu, J. C. S. Moraes, J. R. Silva, M. L. Baesso, L. A. O. Nunes, L. H. C. Andrade, S. M. Lima, "Luminescence quantum efficiency at 1.5 μ m of Er3+ -doped tellurite glass determined by thermal lens spectroscopy," Optical Materials , vol. 35, no. 12, pp. 2400-2404, 2013.
[15] Y. Ma, Y. Guo, F. Huang, L. Hu, J. Zhang, "Spectroscopic properties in Er3+ doped zinc- and tungsten-modified tellurite glasses for 2.7 μ m laser materials," Journal of Luminescence , vol. 147, pp. 372-377, 2014.
[16] B. R. Judd, "Optical absorption intensities of rare-earth ions," Physical Review , vol. 127, no. 3, pp. 750-761, 1962.
[17] F. Ren, Y.-Z. Mei, C. Gao, L.-G. Zhu, A.-X. Lu, "Thermal stability and Judd-Ofelt analysis of optical properties of Er3+ -doped tellurite glasses," Transactions of Nonferrous Metals Society of China (English Edition) , vol. 22, no. 8, pp. 2021-2026, 2012.
[18] K. V. Raju, C. N. Raju, S. Sailaja, B. S. Reddy, "Judd-Ofelt analysis and photoluminescence properties of RE3+ (RE = Er & Nd): cadmium lithium boro tellurite glasses," Solid State Sciences , vol. 15, pp. 102-109, 2013.
[19] K. Selvaraju, K. Marimuthu, "Structural and spectroscopic studies on concentration dependent Er3+ doped boro-tellurite glasses," Journal of Luminescence , vol. 132, no. 5, pp. 1171-1178, 2012.
[20] R. Rolli, M. Montagna, S. Chaussedent, A. Monteil, V. K. Tikhomirov, M. Ferrari, "Erbium-doped tellurite glasses with high quantum efficiency and broadband stimulated emission cross section at 1.5 μ m," Optical Materials , vol. 21, no. 4, pp. 743-748, 2003.
[21] H.-R. Bahari Poor, H. A. A. Sidek, R. Zamiri, "Ultrasonic and optical properties and emission of Er3+ /Yb3+ doped lead bismuth-germanate glass affected by Bi+ /Bi2+ ions," Journal of Luminescence , vol. 143, pp. 526-533, 2013.
[22] D. Souri, "DSC and FTIR spectra of tellurite-vanadate glasses containing molybdenum," Middle-East Journal of Scientific Research , vol. 5, no. 1, pp. 44-48, 2010.
[23] B. Karthikeyan, R. Philip, S. Mohan, "Optical and non-linear optical properties of Nd3+ -doped heavy metal borate glasses," Optics Communications , vol. 246, no. 1-3, pp. 153-162, 2005.
[24] B. Karthikeyan, S. Mohan, "Structural, optical and glass transition studies on Nd3+ -doped lead bismuth borate glasses," Physica B: Condensed Matter , vol. 334, no. 3-4, pp. 298-302, 2003.
[25] M. Farouk, A. Samir, F. Metawe, M. Elokr, "Optical absorption and structural studies of bismuth borate glasses containing Er3+ ions," Journal of Non-Crystalline Solids , vol. 371-372, pp. 14-21, 2013.
[26] M. E. Zayas, H. Arizpe, S. J. Castillo, F. Medrano, G. C. Diaz, J. M. Rincon, M. Romero, Beltran, F. J. Espinoza, "Glass formation area and structure of glassy materials obtained from the ZnO-CdO-TeO2 ternary system," Physics and Chemistry of Glasses , vol. 46, no. 1, pp. 46-57, 2005.
[27] W. T. Carnall, P. R. Fields, K. Rajnak, "Spectral intensities of the trivalent lanthanides and actinides in solution. II. Pm3+ , Sm3+ , Eu3+ , Gd3+ , Tb3+ , Dy3+ , and Ho3+ ," The Journal of Chemical Physics , vol. 49, article 4424, 1968.
[28] K. Maheshvaran, S. Arunkumar, V. Sudarsan, V. Natarajan, K. Marimuthu, "Structural and luminescence studies on Er3+ /Yb3+ co-doped boro-tellurite glasses," Journal of Alloys and Compounds , vol. 561, pp. 142-150, 2013.
[29] B. M. Walsh, N. P. Barnes, D. J. Reichle, S. Jiang, "Optical properties of Tm3+ ions in alkali germanate glass," Journal of Non-Crystalline Solids , vol. 352, no. 50-51, pp. 5344-5352, 2006.
[30] S. O. Baki, L. S. Tan, C. S. Kan, H. M. Kamari, A. S. M. Noor, M. A. Mahdi, "Structural and optical properties of Er3+ -Yb3+ codoped multicomposition TeO2 -ZnO-PbO-TiO2 -Na2 O glass," Journal of Non-Crystalline Solids , vol. 362, no. 1, pp. 156-161, 2013.
[31] D. Yin, Y. Qi, S. Peng, S. Zheng, F. Chen, G. Yang, X. Wang, Y. Zhou, "Er3+ /Tm3+ codoped tellurite glass for blue upconversion-structure, thermal stability and spectroscopic properties," Journal of Luminescence , vol. 146, pp. 141-149, 2014.
[32] Y. Fang, L. Hu, M. Liao, L. Wen, "Effect of bismuth oxide on the thermal stability and Judd-Ofelt parameters of Er3+ /Yb3+ co-doped aluminophosphate glasses," Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy , vol. 68, no. 3, pp. 542-547, 2007.
[33] P. Ren, X. Liu, K. Zhang, P. Zhang, F. Teng, Z. Zhang, E. Xie, P. Yan, "Green photoluminescence from erbium-doped molybdenum trioxide," Materials Letters , vol. 122, pp. 320-322, 2014.
[34] Z. Ashur Said Mahraz, M. R. Sahar, S. K. Ghoshal, M. R. Dousti, R. J. Amjad, "Silver nanoparticles enhanced luminescence of Er3+ ions in boro-tellurite glasses," Materials Letters , vol. 112, pp. 136-138, 2013.
You have requested "on-the-fly" machine translation of selected content from our databases. This functionality is provided solely for your convenience and is in no way intended to replace human translation. Show full disclaimer
Neither ProQuest nor its licensors make any representations or warranties with respect to the translations. The translations are automatically generated "AS IS" and "AS AVAILABLE" and are not retained in our systems. PROQUEST AND ITS LICENSORS SPECIFICALLY DISCLAIM ANY AND ALL EXPRESS OR IMPLIED WARRANTIES, INCLUDING WITHOUT LIMITATION, ANY WARRANTIES FOR AVAILABILITY, ACCURACY, TIMELINESS, COMPLETENESS, NON-INFRINGMENT, MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE. Your use of the translations is subject to all use restrictions contained in your Electronic Products License Agreement and by using the translation functionality you agree to forgo any and all claims against ProQuest or its licensors for your use of the translation functionality and any output derived there from. Hide full disclaimer
Copyright © 2015 Azlan Muhammad Noorazlan et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Abstract
Investigation on green emission and spectral intensity of tellurite based glass containing erbium oxide NPs is one of the crucial issues. Tellurite based glass containing erbium oxide NPs with the composition of {[(TeO2)0.70(B2O3)0.30]0.7(ZnO)0.3}0.95(Er2O3)0.05 has been prepared by using conventional melt-quenching method. The structural and optical properties of the glass sample were characterized by using XRD, FTIR, UV-Vis absorption, and PL spectroscopy. The amorphous structural arrangement was proved through XRD method. The formation of TeO3 and BO3 units was revealed by FTIR analysis. Five transition states of excitation were shown in UV-Vis spectra which arise from the ground state 4I15/2 to the excited states 4G11/2 + 2H9/2 + 4F5/2 + 4F7/2 + 2H11/2 + 4S3/2 + 4F9/2 + 4I9/2 + 4I11/2. The intensity parameters [subscript]Ωt[/subscript] (t=2, 4, 6) are calculated and follow the trend of [subscript]Ω2[/subscript] >[subscript]Ω4[/subscript] >[subscript]Ω6[/subscript] . Broad green emission at 559 nm under 385 nm excitation was obtained.
You have requested "on-the-fly" machine translation of selected content from our databases. This functionality is provided solely for your convenience and is in no way intended to replace human translation. Show full disclaimer
Neither ProQuest nor its licensors make any representations or warranties with respect to the translations. The translations are automatically generated "AS IS" and "AS AVAILABLE" and are not retained in our systems. PROQUEST AND ITS LICENSORS SPECIFICALLY DISCLAIM ANY AND ALL EXPRESS OR IMPLIED WARRANTIES, INCLUDING WITHOUT LIMITATION, ANY WARRANTIES FOR AVAILABILITY, ACCURACY, TIMELINESS, COMPLETENESS, NON-INFRINGMENT, MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE. Your use of the translations is subject to all use restrictions contained in your Electronic Products License Agreement and by using the translation functionality you agree to forgo any and all claims against ProQuest or its licensors for your use of the translation functionality and any output derived there from. Hide full disclaimer