Structural and luminescence properties of Eu3+ and Dy3+-doped Magnesium Boro-Tellurite ceramics

Nur Zu Ira Bohari1, a, R. Hussin1, b, Zuhairi Ibrahim1, c, M. H. Haji Jumali2, d,

Royston Uning1, e, Aliff Rohaizad1, f

1Phosphor Research Group, Department of Physics, Faculty of Science, University Teknologi Malaysia, 81310, UTM, Skudai, Johor Bahru, Malaysia

2Centre for Applied Physics Studies, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600, Bangi, Selangor, Malaysia

anurzuira@yahoo.com, broslihussin@utm.my, czuhairi@utm.my, dhafizhj@ukm.my, euningroyston@gmail.com, faliffrohaizad@yahoo.com

Keywords: Magnesium boro-tellurite ceramic, luminescence, structure

Abstract. Boro-tellurite ceramics with the composition of 60B2O3-10TeO2-30MgO-1Eu2O3-

1Dy2O3 in mol % were prepared by solid-state reaction method. The samples were characterized by

x-ray diffraction (XRD), photoluminescence (PL) and FTIR spectroscopy. The XRD studies have

revealed the presence of MgTe2O5 and MgB6O10.7H2O crystalline as the major and minor phases in

these samples. The FTIR spectra reveal the presence of B-O vibrations of B-O-B, BO3 and BO4

bridging oxygen and Te-O stretching modes of Te2O, TeO3 and TeO4 units in the prepared

ceramics. The PL peaks were assigned to the Eu3+

transitions 5D0→

7F0 at 580 nm,

5D0→

7F1 at 591

nm and 596 nm, 5D0→

7F2 at 612, 618 and 621 nm,

5D0→

7F3 at 651 nm, and

5D0→

7F4 at 692 nm and

702 nm when excited at 394 nm.

INTRODUCTION

Ceramic based on alkali boro-tellurite doped with rare earth have tremendous applications for

lasers, optical amplifier, photo sensitivity, optical storage, and bio-ceramics materials [1-8].

Currently, a great deal of research has been focused on rare earth (RE) doped glasses owing to their

extensive applications [9, 10]. But, the investigation on the luminescence properties of RE doped

ceramic is not many due to the opacity limited their applications in optical transmission devices.

However, such opaque characteristic can improve the absorption efficiency, which increases the

luminous efficiency of the RE ions. Based on this point, ceramic are more competitive than glasses

in the development of white lighting and sensor. Tanabe and co-workers have predicted a

Ce:YAG(Y3Al5O12) opaque glass ceramic phosphor, is a promising material for realization of long-

life white LED devices [11].

Over the past several years, the use of tellurite as a host material has attached a great deal of

attention, both in fundamental research and in optical device fabrication. In fact, TeO2 host show

relatively low phonon energy. Furthermore, they exhibit high refractive indices, good transparency,

low melting point, high dielectric constant as well as their good UV and IR transmission. Hence,

TeO2 are very attractive and interesting for a range of different applications [12, 13]. Borate has

importance due to its special physical properties like high transparency, low melting point, high

thermal stability and good rare earth ions solubility [14]. Addition of alkali oxides (such as Li2O)

and chalcogen (TeO2) to pure B2O3 induces changes in the network and results in the creation of

anionic sites that accommodate the tellurite ions. Therefore, an important family of luminescent

material, boro-tellurite has been paid intense attention because of their good chemical durability,

good thermal stability, high refractive index, good transparency in the mid-infrared region (0.35-

6µm), low phonon energy values (700-800 cm-1

) and also high solubility for rare earth ions [15].

The aim of the present study is to determine the structure through X-Ray diffraction (XRD) and

Advanced Materials Research Vol. 895 (2014) pp 269-273Online available since 2014/Feb/13 at www.scientific.net© (2014) Trans Tech Publications, Switzerlanddoi:10.4028/www.scientific.net/AMR.895.269

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identify the local structural groups through Fourier Transform Infrared spectroscopy (FTIR) spectra.

Finally, luminescence spectra were measured using photoluminescence spectroscopy.

EXPERIMENTAL

The sample based on alkali Boro-Tellurite doped with rare earth ions were synthesized using solid

state reaction method. High purity of H3BO3 (Aldrich, 99.99%), TeO2 (99.99%), MgO (Aldrich,

99.99%), Eu2O3 (Aldrich, 99.99%), Dy2O3 (Aldrich, 99.99%) were employed as the raw materials.

The compositions of 60B2O3-10TeO2-30MgO-1Eu2O3-1Dy2O3 were prepared. Analytical grade

reagents of H3BO3, TeO2, MgO, Eu2O3 and Dy2O3 powders in appropriate amounts (mol %) were

thoroughly mixed and heat treated at 650oC for 5 hours. The crystalline phases in the ceramic

samples were identified using Siemen Diffraction D500 diffractometer with CuKα radiation. A

FLS980 fluorescence spectrometer was used to record the excitation and emission spectra. The

FTIR spectra of the ceramics were recorded using Perkin-Elmer spectrometer (Spectrum 100) in the

wavenumber range 400-4000 cm−

1.

RESULTS AND DISCUSSION

The XRD pattern of the Eu3+

and Dy3+

doped magnesium boro-tellurite ceramic in the range of 10o

≤ θ ≤ 80o was shown in Fig. 1. The X-ray diffraction patterns reveal that the composition of the

ceramics was found to consist mainly of the MgTe2O5, MgB4O7, B7Mg, MgO(B2O3)2 and

MgB6O10.7H2O crystalline phase, indicating that the doping ions Eu3+

and Dy3+

did not form any

new phases in the synthesis process. The infrared spectra of the 60B2O3-10TeO2-30MgO-1Eu2O3-

1Dy2O3 ceramic was shown in Fig. 2. The FTIR spectra contain a number of peaks which seem to

be broad or moderate in band width [16]. The 400-600 cm-1

band is assigned the bending vibrations

of Te-O-Te or O-Te-O linkages [17, 18]. The next bands at 600-640 cm-1

have been attributed to the

stretching vibrations of the [TeO4] trigonal bipyramid units and respectively, and 680-760 cm-1

[TeO3] trigonal pyramid units [19]. The peaks located in the range of 800-1200cm-1

are assigned to

[BO4] units while at 1200-1600 cm-1

are assigned to B-O stretching vibrations in BO3 units [20].

The peaks observed around 1082 cm-1

and 1258 cm-1

are due to the stretching of the BO4 and BO3

units. The intensive B-O-B bending linkage vibrations were observed around 700 cm-1

.

Symmetrical stretching vibration of Te-O bond in trigonal bipyramids (TeO4) and Te-O bending

vibrations in trigonal pyramids(TeO3) in the tellurium network were observed around 612 cm-1

and

686 cm-1

[20].

Fig. 1: X-ray diffraction patterns for 60B2O3-10TeO2-30MgO-1Eu2O3-1Dy2O3 ceramic

2θ

10 20 30 40 50 60 70 80

Inte

nsi

ty

▼MgB4O7

■ MgO(B2O3)2

● MgB6O10.7H2O

▲B7Mg

♦ MgTe2O5

270 Solid State Science and Technology IV

340 360 380 400 420 440 460 480

0.0

3.0x105

6.0x105

9.0x105

1.2x106

1.5x106

5D

2

7F

0

5D

3

7F

0

5L

6

7F

0

5L

7

7F

0

5G

2

7F

0

5D

4

7F

0

5D

4

wavelength(nm)

7F

0

(b)

500 550 600 650 700 750 800

0.0

2.0x104

4.0x104

6.0x104

8.0x104

1.0x105

1.2x105

1.4x105

1.6x105

7F

4

5D

0

7F

3

5D

0

7F

2

5D

0

7F

1

5D

0

5D

0

7F

0

inte

nsi

ty(a

.u)

wavelength(nm)

(a)

Fig. 2: Infrared spectra of the Eu3+

and Dy3+

doped magnesium boro-tellurite ceramic

The excitation spectrum of the Eu3+

and Dy3+

doped magnesium boro-tellurite ceramic was shown

in Fig. 3. The excitation transitions such as 7F0→

5D4,

7F0→

5G2,

7F0→

5L7,

7F0→

5L6,

7F0→

5D3, and

7F0→

5D2 corresponding to the band positions at 362, 366, 376, 381, 394, 398, 401, 414 and 464 nm

were observed from the spectrum. The 7F0→

5L6 transition possess higher intensity compared to all

other transitions. This transitions have been used as the excitation wavelength (394 nm) to record

the emission spectrum for the Eu3+

and Dy3+

doped boro-tellurite as shown in Fig. 3. The emission

transitions such as 5D0→

7F0,

5D0→

7F1,

5D0→

7F2,

5D0→

7F3 and

5D0→

7F4 corresponding to the band

position at 580, 591, 596, 612, 618, 651, 692 and 702 nm were observed from the spectrum. PL

emissions from 580 to 702 nm are due to the 5D0-7Fj (j=0, 1, 2, 3, 4) transitions of Eu

3+ as shown in

Fig. 4 in agreement with other reported values [21, 22]. From the emission spectra it was observed

that, the 5D0→

7F2 transition is more intense more than the other transitions as reported in the other

Eu3+

[23-25]. The special Dy3+

emission peaks are not present, showing that Dy3+

acts as trap

centers that cause long afterglow characteristics, rather than the luminescent centers in the host

lattice [26]. Fig. 4 presents the energy level for emission and excitation transitions of Eu3+

doped

boro-tellurite ceramic.

Fig. 3: (a) Emission and (b) excitation spectrum of Eu3+

and Dy3+

doped boro-tellurite ceramic

BO

4

BO

3

Wavenumbers,cm-1

1800 1600 1400 1200 1000 800 600 400

Tra

nsm

issi

on

%

BO

B

BO

4

Te

O3

Te

2O

Te

O4

Advanced Materials Research Vol. 895 271

0

5

10

15

20

25

30

702nm

692nm

651nm

621nm

618nm

612nm

596nm

591nm

5G

25L

65D

35D

2

5D

15D

0

7F

2

7F

3

7F

4

7F

5

7F

6

7F

0

Energ

y (

10

3 c

m-1)

Eu3+

7F

1

580nm

emission

Fig. 4: Energy level diagram for emission and excitation bands of Eu3+

and Dy3+

doped magnesium

boro-tellurite ceramic

CONCLUSION

Eu3+

and Dy3+

doped boro-tellurite ceramic have been prepared and their structural and

spectroscopic behavior were studied and reported. The experimental results indicate that the role of

Eu3+

in 60B2O3-10TeO2-30MgO ceramic showed the luminescence center and Dy3+

play an

important role as trap centers. The Eu3+

and Dy3+

doped magnesium boro-tellurite ceramic have

shown a strong emission at 618 nm (5D0→

7F2).

ACKNOWLEDGEMENT

We would like to acknowledge the financial supports from Fundamental Research Grant Scheme

(FRGS) under research grant Project Number: R.J130000.7826.4F140 and the authors thank Faculty

of Science UTM and Department of Physics UKM for providing the measurement facilities.

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Advanced Materials Research Vol. 895 273

Solid State Science and Technology IV 10.4028/www.scientific.net/AMR.895 Structural and Luminescence Properties of Eu3+ and Dy3+-Doped Magnesium Boro-Tellurite Ceramics 10.4028/www.scientific.net/AMR.895.269

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