Structural and Electron Spin Resonance Analysis of Eu3+ Doped Borotellurite Glass Containing Manganese Oxide Nanoparticles

Structural and Electron Spin Resonance Analysis of Eu3+ Doped Borotellurite Glass Containing Manganese Oxide Nanoparticles

1Siti Maisarah Aziz (corresponding author)

2Roslan Umar

1Nurulhuda Mohammad Yusoff

1Salmiah Jamal Mat Rosid

1Siti Noor Syuhada Mohd @ Muhammad Amin

3M.R. Sahar

3S.N.S. Yaacob

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)

1. INTRODUCTION

   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 [4] 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. [7] acknowledged that REIs doped glasses exhibit high brightness and improved efficiency thus are very prospective for broad array of technological applications [8]. Trivalent Eu3+ ion is a well-known activator with simple electronic transitions [9]. The Eu3+ ions possess prominent laser emissions in the orange or red region [10] and narrow band emission [11] with longer lifetime. Both synthesis and characterizations of REIs doped binary and ternary glasses are intensively performed due to its advantages in [12]. Combination of TeO2 and B2O3 is an intrinsically interesting subject of study due to the stability of borotellurite (BT) compound [13]. 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 [16] to improve the network connectivity then produce a stable BT glass with increasing non-bridging oxygen (NBO)[17]. The substitution of network modifier such as MgO would produce stable BT glass [18]. The addition of such modifiers would modify and increase the NBO, consequently open up the glass structure [19]. BT glass is emerged as a favorable host for accommodating large amount of REIs. Maheshvaran et al. [20] 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 [24]. 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 [25]. 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.

2. EXPRIMENTAL

   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. , 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 [26]. 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.

3. 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 [29]. 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 [30]. 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 [35]. 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 [36]. 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 [37]. Overall, the ESR strongly indicates that Mn2+ centers are in asymmetric sites and the nature of the bonding is dominantly covalent bond.

Intensity (a.u.)

Intensity (a.u.)

BTME0.5Mn

BTME1.0Mn BTME1.5Mn BTME2.0Mn

10 20 30 40 50 60 70 80 90

2 (degree)

% Transmittance (a.u.)

% Transmittance (a.u.)

BO3

BO3

BO4

BO4

O-H

O-H

H-O-H

H-O-H

TeO

TeO

3

3

TeO

TeO

4

4

Fig. 1 X-Ray Diffraction (XRD) patterns of glass system

BTME0.5Mn

BTME1.0Mn BTME1.5Mn

BTME2.0Mn

3600 3000 2400 1800 1200 600

Wavenumber (cm-1)

Fig.2. Fourier Transform Infrared (FTIR) spectra of the prepared glass system

Relative intensity (a.u.)

Relative intensity (a.u.)

1500

1000

500

0

-500

-1000

-1500

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.

ACKNOWLEDGEMENTS

The authors gratefully acknowledge the financial support

0 200 400 600

H (Oe)

VI. CONCLUSIONS

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

TABLE 2. Magnetic properties of prepared BT glasses at various concentration of Eu2O3

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