- Open Access
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- Authors : Siti Maisarah Aziz , Nurulhuda Mohammad Yusoff, Roslan Umar , M.R. Sahar, Salmiah Jamal Mat Rosid , Siti Noor Syuhada Mohd, Muhammad Amin, S.N.S. Yaacob
- Paper ID : IJERTV8IS060572
- Volume & Issue : Volume 08, Issue 06 (June 2019)
- Published (First Online): 08-07-2019
- ISSN (Online) : 2278-0181
- Publisher Name : IJERT
- License: This work is licensed under a Creative Commons Attribution 4.0 International License
Structural and Electron Spin Resonance Analysis of Eu3+ Doped Borotellurite Glass Containing Manganese Oxide Nanoparticles
1Siti Maisarah Aziz (corresponding author)
1Nurulhuda Mohammad Yusoff
1Salmiah Jamal Mat Rosid
1Siti Noor Syuhada Mohd @ Muhammad Amin
1UniSZA Science and Medicine Foundation Centre, Universiti Sultan Zainal Abidin, Gong Badak Campus, 21300 Kuala Nerus, Terengganu, Malaysia
2East Coast Environmental Research Institute (ESERI), Universiti Sultan Zainal Abidin, Gong Badak Campus, 21300 Kuala Nerus, Terengganu, Malaysia
3Advanced Optical Material Research Group, Department of Physics, Faculty Science, Universiti Teknologi Malaysia, 81310, Skudai, Johor Bahru, Johor, Malaysia
Abstract:- Structural properties of 30B2O3-(59-x)TeO2-10MgO-xEu2O3-1Mn3O4 glass are prepared via melt quenching method. The glass samples are characterized by X-ray Diffraction (XRD), Fourier Transform Infrared (FTIR) Spectroscopy and Electron Spin Resonance (ESR) Spectroscopy. The glass nature is confirmed by XRD pattern. FTIR spectra display a shift in vibrational modes of TeO4 and TeO3 units thus indicate an alteration in the glass network structure due to an incorporation of Eu2O3. Influence which varies Eu2O3 concentrations on the structural due to the nature of spin-spin interaction are determined. Both g value and resonance magnetic field (Hr) are found to be in the range of (189-198) and (211-226) Oe respectively. The obtained g value of glass samples will modify the structural of europium doped magnesium borotellurite glass due to this presence of manganese oxide nanoparticles (Mn3O4 NPs) which may be useful for developing efficient photonic devices.
KeywordsBorotellurite glass, structural properties, nanoparticles, ESR analysis (key words)
Glasses are unique materials that have been benefitted years ago. Glass has been extensively investigated due to its high temperature resistance, high dielectric constant and good mechanical strength [1-3]. Furthermore, glass is not only known because of its excellent thermal and mechanical properties  but also of its potential in becoming a good medium for luminescence due to its enhancement of absorption efficiency of rare earth ions [5,6]. This excellent property has motivated researcher to further the study in optimizing luminescent thus develop to a more suitable material specifically in the development of laser and solid state device. To this day, rare earth ions (REIs) doped glass materials turn out to be an interesting topic in luminescence material.
Dehelean et al.  acknowledged that REIs doped glasses exhibit high brightness and improved efficiency thus are very prospective for broad array of technological applications . Trivalent Eu3+ ion is a well-known activator with simple electronic transitions . The Eu3+ ions possess prominent laser emissions in the orange or red region  and narrow band emission  with longer lifetime. Both synthesis and characterizations of REIs doped binary and ternary glasses are intensively performed due to its advantages in . Combination of TeO2 and B2O3 is an intrinsically interesting subject of study due to the stability of borotellurite (BT) compound . BT glasses have promising optical materials due to its high refractive index, low phonon energy and higher transparency in the infrared spectrum [14,15]. Further, BT glass needs another element known as glass modifier such as alkaline earth metal oxide and transition metal oxide  to improve the network connectivity then produce a stable BT glass with increasing non-bridging oxygen (NBO). The substitution of network modifier such as MgO would produce stable BT glass . The addition of such modifiers would modify and increase the NBO, consequently open up the glass structure . BT glass is emerged as a favorable host for accommodating large amount of REIs. Maheshvaran et al.  reported that Eu3+ doped BT glass has potential for red-emitting glass due to excellent luminescent properties and can be used as optical materials. Hence, Eu3+ doped glass has drawn much interest in technological applications especially for optoelectronic materials [21-23]. Luminescence properties of BT glass is one of the important characteristic which can be used as a strong indicator to hunt for a new functional material. Incorporation of nanoparticles in BT glass shows remarkable changes in optical properties of lanthanides . Synthesis and characterization of magnetic Mn3O4 NPs have ever-growing interest. The incorporation of Mn3O4 in glass has paramount importance due to its excellent physical and structural properties . However, not many efforts are dedicated
towards the incorporation of europium in this glass system. This motivated an investigation of the REIs doped glasses containing Mn3O4 NPs. In this paper, a new series of Mn3O4 NPs embedded BT glass doped with different concentrations of trivalent europium have been prepared and its structural studies are performed and reported.
Raw materials for the glass preparation of magnesium BT glasses embedded Mn3O4 NPs are commercially obtained in powder form. Analytical grade glass constituents of B2O3 (purity 98.94%), Te2O (purity 99%), MgO (purity 99%), Eu2O3 (purity 99%) and Mn3O4 (purity 99.7%) in powder form are well-mixed with nominal glass compositions of (59-x)TeO2-30B2O3-10MgO-xEu2O3-1Mn3O4 (where x = 0.5,
, 1.5 and 2.0 mol %). Required proportion of B2O3, Te2O, MgO, Eu2O3 and Mn3O4 powders are weighed using an electronic balance (Precisa 205 A SCS). Then the total of batched mixture is placed in a platinum crucible before being melted at 900 oC for 1 hrs in an electric furnace. The melt is then transferred to an annealing furnace and poured into the brass mould before being annealed at 350 oC for 3 hrs to reduce the mechanical and thermal stress that causes embrittlement . The melt is then cooled down to room temperature. Synthesized glasses are characterized using X-ray Diffraction (XRD), Fourier Transform Infrared (FTIR) Spectroscopy and Electron Spin Resonance (ESR) measurements.
RESULT AND DISCUSSION
Fig. 1 shows XRD patterns of the synthesized glass sample. The XRD pattern of the glass recorded in the range of 10 90 as shown in Fig. 1.
A broad hump is exhibits in the range of 15o-40o, which confirms the characteristic of amorphous nature of the glass [27, 28]. Conversely, peaks that indicate the existence of Mn3O4 NPs were hardly detected by XRD due to its fairly low concentration compared with host and modifier.
FTIR spectra of prepared glasses in the range of 400 cm-1 – 4000 cm-1 are shown in Fig. 2 and the corresponding peak positions with the assignments of vibrational modes are listed in Table 1.
The FTIR spectra in Fig. 2 clearly comprise of main sharp distinctive and characteristic absorption bands. These bands are due to main BT network group vibration. From Fig. 2, it is noticed that the peak at 665-682 cm-1 is referred to the TeO4 tbp group in the present glass . It is observed that, as the amount of Eu2O3 is increased, the peak of TeO4 tbp is displaced from 665 cm-1 toward a higher wavenumber and reaches 682 cm-1 at 1.0 mol % of Eu2O3. This is attributed to the formation of more TeO3 units at the expense of TeO4 units . Formation of large number of Te-O bonds in TeO3 units has strengthened the glass network. However, as the amount of Eu2O3 is beyond 1.0 mol %, the vibration peaks slightly shifted toward alower wavenumber. This shift might indicate structural alteration.
Electron Spin Resonance (ESR) studies of Eu3+ doped BT glasses embedded with various concentrations of Eu2O3 have
been investigated and represented in Fig. 3 at room temperature. ESR is used to detect paramagnetic behaviour and to provide information on the coordination of isolated sites . The calculated values of magnetic parameters such as resonance magnetic field (Hr), peak-to-peak line width (Hpp) and g value which can be obtained from ESR spectra are presented in Table 2.
For various concentrations of Eu2O3, it is observed that the intensity of the signal g value at 4.3 is more intense compared to g value that close to 2. It pointed out that Mn2+ center is present dominantly in a rhombic environment. Additionally, a positive shift in the g value as concentration of Eu2O3 increase would indicate that the Mn2+ is in a covalent environment . The value of g = 1.89 is the minimum amount where the bond is in covalence environment as shown by BTME1.0Mn sample. Meanwhile, variations of line width (Hpp = peak to peak distance) with concentration of Eu2O3 is another sensitive indicator of changes in the environment of Mn ions . Overall, the ESR strongly indicates that Mn2+ centers are in asymmetric sites and the nature of the bonding is dominantly covalent bond.
BTME1.0Mn BTME1.5Mn BTME2.0Mn
10 20 30 40 50 60 70 80 90
% Transmittance (a.u.)
% Transmittance (a.u.)
Fig. 1 X-Ray Diffraction (XRD) patterns of glass system
3600 3000 2400 1800 1200 600
Fig.2. Fourier Transform Infrared (FTIR) spectra of the prepared glass system
Relative intensity (a.u.)
Relative intensity (a.u.)
g = 4.3
g = 1.9
BTME0.5Mn BTME1.0Mn BTME1.5Mn BTME2.0Mn
quenching technique. The amorphous nature of glasses is confirmed by XRD. The FTIR spectra are strongly influenced by the variations of Eu2O3 concentration. For the ESR spectra, manganese ions exhibit two resonance signals at g values 1.9 and 4.3. ESR spectra strongly indicated that Mn2+ centers were in asymmetric sites (octahedral) and the nature of the bonding is dominantly covalent type.
The authors gratefully acknowledge the financial support
0 200 400 600
The structural and magnetic properties of Eu3+:Mn doped BT glass has successfully been studied and prepared by melt Fig.3. Electron Spin Resonance (ESR) spectra of prepared glass samples
from RMC, UTM through the research grant (VOTE: 4F752, 4L657, 16H41 and 13J81) and thank Faculty of Science UTM for providing the measurement facilities are gratefully acknowledged.
TABLE 1. The IR peak positions and band assignments of the present glass systems
Assignments IR Band (cm-1)
TABLE 2. Magnetic properties of prepared BT glasses at various concentration of Eu2O3
Sahar, M.R, Fizik Bahan Amorfus, (1st ed.),UTM Skudai:DBP, 2000
Meyer, K, Characterization of the Structure of Binary Zinc Ultraphosphate Glasses by Infrared and Raman Spectroscopy, Journal of Non-Crystalline Solids, vol. 209, pp. 227-239,1997.
Gandhi, Y., Kityk, I. V., Brik, M.G., Rao, P.R., Veeraiah, N, Influence of tungsten on the emission features of Nd3+ , Sm3+ and Eu3+ ions in ZnF2-WO3-TeO2 glasses, Journal Alloys Compound, vol. 508, pp.278-291, 2010.
Stambouli, W., Elhouichet, H., Gelloz, B., Fe, M, Optical and spectroscopic properties of Eu-doped tellurite glasses and glass ceramics, Journal Luminescence, vol. 138, pp. 201-208, 2013.
Khafagy, A.H., El-Adawy, A.A., Higazy, A.A., El-Rabaie, S., Eid, A.S, The glass transition temperature and infrared absorption spectra of: (70-x)TeO2+15B2O3+15P2O5 +xLi2O glasses, Journal Non-Crystalline Solids, vol. 354, pp.1460-1466, 2008.
Neov, S., Kozhukharov, V., Gerasimova, I., Krezhov, K., Sidzhimov, B, A model for structural recombination in tellurite glasses, Journal Physics C: Solid State Physics, vol. 12, pp.715-718, 1979.
Dehelean, A., Culea, E. Magnetic behaviour of europium ions in some tellurite glasses obtained by the sol-gel method. Journal Physics Conference Series 182, pp.12064, 2009.
Sazali, E.S., Sahar, M.R., Ghoshal, S.K, Influence of Europium Ion on Structural, Mechanical and Luminescence Behavior of Tellurite Nanoglass. Journal Physics Conference Series 431, pp. 12008, 2013.
Akamatsu, H., Fujita, K., Nakatsuka, Y., Murai, S., Tanaka, K. Magneto-optical properties of Eu2+ -containing aluminoborosilicate glasses with ferromagnetic interactions, Optical Mater. vol. 35, pp. 1997-2000, 2013.
Bo., P., Teturo, I., The Fluorescence Properties of Eu3+ in Various Glasses and the Energy Transfer Between Eu3+ and Sm3+ in Borosilico-phosphate Glass, Review of Laser Engineering. vol. 22, pp.16-27,1994.
Rehana, P., Ravi, O., Ramesh, B., Dillip, G.R, Photoluminescence studies of Eu3+ ions doped calcium zinc niobium borotellurite glasses, Advance Mater. Letter, vol. 7, pp.170-174, 2016.
Arunkumar, S., Marimuthu, K, Structural and luminescence studies on Eu3+: B2O3-Li2O-MO-LiF (M=Ba, Bi2, Cd, Pb, Sr2 and Zn) glasses, Journal Luminescence, vol.139, pp.6-15, 2013.
Elkhoshkhany, N., El-Mallawany, R, Optical and kinetics parameters of lithium boro-tellurite glasses, Ceramic International. vol. 41, pp. 561-3567, 2015.
Sudhakar Reddy, B., Hwang, H.-Y., Jho, Y.-D., Seung Ham, B. Optical properties of Nd3+-doped and Er 3+-Yb3+ codoped borotellurite glass for use in NIR lasers and fiber amplifiers, Ceramic International. vol. 41, pp.3684-3692, 2015.
Lakshminarayana, G., Kaky, K.M., Baki, S.O., Lira, A, Physical,structural, thermal, and optical spectroscopy studies of TeO2-B2O3-MoO3-ZnO-R2O (R = Li, Na, and K)/MO (M = Mg, Ca, and Pb) glasses, Journal Alloys Compound, vol. 690, pp. 799-816, 2017.
Said Mahraz, Z.A., Sahar, M.R., Ghoshal, S.K, Band gap and polarizability of boro-tellurite glass: Influence of erbium ions, Journal Molecule Structure, vol. 1072, pp.238-241, 2014.
Gaafar, M.S., Marzouk, S.Y., Zayed, H.A., Soliman, L.I., Serag El-Deen, A.H, Structural studies and mechanical properties of some borate glasses doped with different alkali and cobalt oxides, Current Applied Physics, vol. 13, pp.152-158, 2013.
K. Doweidar, H., El-Damrawi, G., Mansour, E., Fetouh, R.E, Structural role of MgO and PbO in MgO-PbO-B2 O3 glasses as revealed by FTIR; A new approach, J. Non-Crystalline Solids, vol. 358, pp 941-946, 2012.
Smith, C.E., Brow, R.K. The properties and structure of zinc magnesium phosphate glasses. Journal Non-Crystalline Solids, vol. 390, pp 51-58, 2014.
Maheshvaran, K., Marimuthu, K, Concentration dependent Eu3+ doped boro-tellurite glasses-Structural and optical investigations, Journal Luminescence,vol. 132, pp. 2259-2267, 2012.
Babu, A.M., Jamalaiah, B.C., Suhasini, T., Rao, T.S., Moorthy,
L.R. Optical properties of Eu3+ ions in lead tungstate tellurite glasses. Solid State Science, vol. 13, pp. 574-578, 2011.
Maheshvaran, K., Veeran, P.K., Marimuthu, K., Structural and optical studies on Eu3+ doped boro-tellurite glasses. Solid State Sci. 2013, 17, 5462.
Rehana, P., Ravi, O., Ramesh, B., Dillip, G.R. Photoluminescence studies of Eu3+ ions doped calcium zinc niobium borotellurite glasses. Advance Material Letter, vol. 7, 170-174, 2016.
Ashur Said Mahraz, Z., Sahar, M.R., Ghoshal, S.K., Dousti, M.R., Amjad, R.J, Silver nanoparticles enhanced luminescence of Er3+ ions in boro-tellurite glasses, Mater Letter, vol. 112, pp.136-138, 2013
Manzan, R.S., Donoso, J.P., Magon, C.J., Silva, I. dAnciÃ£es A, Optical and Structural Studies of Mn2+ Doped SbPO4 -ZnO-PbO Glasses, Journal of the Brazilian Chemical Society vol. 26, pp. 2607-2614, 2015.
N.M. Yusoff, M.R. Sahar, The incorporation of silver nanoparticles in samarium doped magnesium tellurite glass: Effect on the characteristic of bonding and local structure, Physica B,vol. 470-471,pp. 6-14, 2015.
S.Y. Moustafa, M.R. Sahar, S.K. Ghoshal, Comprehensive thermal and structural characterization of antimony-phosphate glass Results in Physics vol.7 pp.13961411, 2017.
Widanarto, W., Sahar, M.R., Ghoshal, S.K., Arifin, R., Rohani,
M.S. Hamzah, K, Effect of Natural Fe3O4 Nanoparticles on Structural and Optical Properties of Er3+ doped tellurite Glass, Journal of Magnetism and Magnetic Materials, vol. 326, pp. 123-128, 2013.
R.S. Kundu Sunil Dhankhar, R. Punia Kirti Nanda N. Kishore, Bismuth modified physical, structural and optical properties of mid-IR transparent zinc boro-tellurite glasses, Journal of Alloys and Compounds, vol. 587, pp. 66-73, 2014.
Swapna, G. Upender & M. Prasad, Raman, FTIR, thermal and optical properties of TeO2-Nb2O5-B2O3-V2O5 quaternary glass system journal of Taibah, University for Science, vol. 11, pp. 583-592, 2017.
P.Gayathri Pavani, K.Sadhana, V.Chandra Mouli, Optical, physical and structural studies of boro-zinc tellurite glasses Physica B: Condensed Matter, vol. 406, pp. 1242-1247, 2011.
K.Selvaraju, K.Marimuthu ,Structural and spectroscopic studies on concentration dependent Er3+ doped boro-tellurite glasses, Journal of Luminescence, vol. 132, pp.1171-1178, 2012.
Nirmal Kaur Atul Khanna, Structural characterization of borotellurite and alumino-borotellurite glasses, Journal of Non-Crystalline Solids, vol. 404, pp.116-123, 2014
M. Anand Pandarinath, G. Upender, K. Narasimha Rao, D. Suresh Babu, Thermal, optical and spectroscopic studies of boro-tellurite glass system containing ZnO Journal of Non-Crystalline Solids, vol. 433, pp. 60-67, 2016.
Naseri, M.G., Saion, E.B., Hashim, M., Shaari, A.H., Ahangar, H.A, Synthesis and characterization of zinc ferrite nanoparticles by a thermal treatment method. Solid State Communication, vol. 151, pp. 1031-1035, 2011.
Nicolae, E., Pascuta, P., Pustan, M., Tamas-gavrea, D.R, Effects of Eu:Ag codoping on structural, magnetic and mechanical properties of lead tellurite glass ceramics, J. Non-Crystalline Solids, vol. 408, pp. 18-25, 2015.
Wang, M.-C., Cheng, H.-Z., Lin, H.-J., Wang, C.-F., Hsi, C.-S, Crystallization and magnetic properties of a 10Li2O-9MnO2-16Fe2O3-25CaO-5P2O5-35SiO2 glass, Material Chemistry Physics, vol. 140, pp.16-23, 2013.