Optik 127 (2016) 80768081

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Optik
journal homepage: www.elsevier.de/ijleo

Low cost phosphors: Structural and photoluminescence

properties of Mn2+ -doped willemite glass-ceramics
Nur Farhana Samsudin a , Khamirul Amin Matori a,b, , Zaidan Abdul Wahab b ,
Josephine Ying Chi Liew b , Yap Wing Fen a,b , Sidek Hj. Ab Aziz b ,
Mohd Haz Mohd Zaid b
a
Materials Synthesis and Characterization Laboratory, Institute of Advanced Technology, Universiti Putra Malaysia, 43400 UPM
Serdang, Selangor, Malaysia
b
Department of Physics, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia

a r t i c l e

i n f o

Article history:
Received 12 April 2016
Accepted 4 June 2016
Keywords:
Manganese
Willemite
Phosphors
Optical
Photoluminescence

a b s t r a c t
In this study, Mn2+ -doped willemite glass-ceramics were prepared from conventional meltquenching method derived MnO-ZnO-SLS precursor glass by an isothermal heat-treatment
process where waste SLS glass bottle are used as a silicon source. The structure, phase
morphology and luminescent properties of the Mn2+ -doped willemite phosphors were
characterized using X-ray diffraction (XRD), eld emission scanning electron microscopy
(FESEM) and photoluminescence (PL) spectroscopy. The XRD pattern revealed the phase
transformation of zinc orthosilicate (-Zn2 SiO4 ) with the progression of heat treatment
temperature. The FESEM images showed the aggregated and irregularity in shape morphology of the samples. Meanwhile, the emission intensity of the samples exhibit a green
emission centered at about 527 nm while the yellow emission centered at 585 nm and
red emission centered at 600 nm resulted from 4 T1 6 A1 energy transition of Mn2+ ions,
respectively.
2016 Elsevier GmbH. All rights reserved.

1. Introduction
In recent years, a number of scholars proposed an interest on synthesizing method and various properties of variety oxide
based phosphors [13]. Among them, Manganese doped willemite (Zn2 SiO4 :Mn2+ ) has been distinguished as a competent
host matrix for numerous transition metal and rare earth dopant ions for efcient luminescence in the red, yellow and green
spectral zones [4,5]. Zn2 SiO4 :Mn2+ is a signicant material that has been used in Cathode Ray Tubes (CRT), Plasma Displays
Panels (PDP) and lamps due to its high saturated color, strong luminescence, long life span, lack of moisture sensitivity
and chemical stability [68]. Zn2 SiO4 :Mn2+ is a polymorphic that exist , and other phases where stable -Zn2 SiO4
emits green luminescence, while metastable -Zn2 SiO4 emits yellow emission under photoluminescence measurements
[911]. The yellow and green emission come from the same sources, which the energy transition from 4 T1 -6 A1 of the Mndoping ions, substituted into the Zn sites of the Zn2 SiO4 host lattices [12]. It appears to be that -Zn2 SiO4 can only occur

Corresponding author at: Materials Synthesis and Characterization Laboratory, Institute of Advanced Technology, Universiti Putra Malaysia, 43400
UPM Serdang, Selangor, Malaysia.
E-mail addresses: nfarhanasamsudin@gmail.com (N.F. Samsudin), khamirul@upm.edu.my (K.A. Matori), zaidan@upm.edu.my (Z.A. Wahab),
josephine@upm.edu.my (J.Y.C. Liew), yapwingfen@gmail.com (Y.W. Fen), sidek@upm.edu.my (S.Hj.A. Aziz), mhmzaid@gmail.com (M.H.M. Zaid).
http://dx.doi.org/10.1016/j.ijleo.2016.06.019
0030-4026/ 2016 Elsevier GmbH. All rights reserved.

N.F. Samsudin et al. / Optik 127 (2016) 80768081

8077

Fig. 1. XRD pattern of 1 wt.% Mn-doped Zn2 SiO4 sintered at different temperatures.

under certain condition. Previous researcher synthesized Mn-doped -Zn2 SiO4 by melting and rapidly cooling mixtures of
Zn2 SiO4 composition from 1500 C [13]. It is noted that the preparation condition were being responsible for the formation
of -Zn2 SiO4 and -Zn2 SiO4 [14].
Over the time, numerous researchers have reported that Zn2 SiO4 :Mn2+ shows strong green emission under an ultraviolet
light [1519]. Surprisingly, very little information is observed on the effects of transition metals doped zinc silicate towards
soda lime silica (SLS) waste bottle as a source of silica, SiO2 . Most of them use pure SiO2 as a starting material in the synthesis
process. Instead of using pure SiO2 as a source of silica, the using of SLS in the production of Zn2 SiO4 can reduce the cost
of production and also has advantages as an attractive host matrix for transition metal ions because of its ne optical and
mechanical properties, such as good chemical stability, high transparency, low melting point and high thermal stability [20].
In the present study, Zn2 SiO4 :Mn2+ have been prepared from conventional melt-quenching method derived MnO-ZnO-SLS
precursor glass by an isothermal heat-treatment process and the effect of sintering temperature towards its structural and
photoluminescence properties also been investigated.

2. Experimental
1 wt.% Mn-doped willemite glass ceramics were prepared from a 30 g batch with the starting materials, i.e. ZnO (99.99%,
Alfa Aesar), SLS waste glass powder and MnO (99.99%, Alfa Aesar) by using the conventional melt-quenching method. All
chemicals were mixed via milling process up to 24 h using the ball milling jar to obtain the homogenous batch. Then, the
chemical batch was melted in an alumina crucible at 1400 C in air with heating rate of 10 C min1 for 2 h in an electrical
furnace. Later, the molten mixture was poured into the water to get the transparent of glass fritz. The glass frits were cooled to
room temperature and then was crushed and sieved into ne powder about 45 m. Next, the ne powders with an addition
of 1.75 wt.% Polyvinyl Alcohol (PVA) as the binders, have been pressed at a pressure of 5 tons to form the disk pellets. After
that, all the disk pellets were sintered at various sintering temperature in the electrical furnace with duration of 2 h to form
the glass-ceramics for further characterization.
X-ray diffraction (PANalytical (Philips) XPert Pro PW 3050/60) with Cu K radiation was used to conrm the amorphous
state of the glass samples and to identify the crystalline phase formed in the sintered samples. The x-ray beam diffracted
on the samples through an angle of range of 2 = 20 80 using 0.02 steps. Field Emission Scanning Electron Microscopy
(FESEM, FEI, Nova Nano SEM 30) was employed for the microstructural observation on the top surface and cross-section
area of the glass and glass-ceramic samples. The photoluminescence excitation and emission spectra were measured by (PL,
Perkin Elmer LS 55 Fluorescence) with a 450 W xenon lamp at room temperature at the excitation wavelength of 260 nm,
respectively.

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Fig. 2. FESEM micrograph of 1 wt.% Mn-doped Zn2 SiO4 based glass-ceramic at various sintering temperature (a) 27 C, (b) 600 C, (c) 700 C, (d) 800 C and
(e) 900 C.

3. Result and discussion

3.1. X-Ray diffraction analysis
Fig. 1 compares the XRD patterns of the 1 wt.% Mn-doped Zn2 SiO4 based glass and glass ceramics powder samples
sintered at various sintering temperatures varied from 600 C to 900 C for 2 h. The unsintered glass samples present no
obvious peaks or lines related with any crystalline phase in the pattern which indicate a characteristics of the amorphous
state. In addition, a broad band shown in the pattern centered at 2 = 32 reects commonly the nature of glassy state
[2123]. As the glass samples being sintered at 600 C, the glass samples changed to glass-ceramics and shows crystalline
pattern. This is supported by the formation of -willemite (-Zn2 SiO4 ) observed in the pattern. The formation of -Zn2 SiO4
peaks show that the crystallization process started at temperatures of 600 C. The -Zn2 SiO4 and minor ZnO phases with Joint
Committee on Powder Diffraction Standard (JCPDS) (JCPDS No. 14-0653) and (JCPDS No. 361451) respectively were formed.
All the diffraction peaks are in good agreement with the standard pattern reported by other researcher (JCPDS No. 14-0653),
indicating that the prepared samples is orthorhombic -Zn2 SiO4 with lattice parameter of a = 8.40 , b = 5.10 , c = 32.20
and = 90.00 , = 90.00 , = 90.00 [9,10]. The glass-ceramics samples sintered at 600 C exhibit six major diffraction peaks
at 2 = 21.82 , 25.06 , 31.24 , 36.19 , 60.89 and 65.18 which corresponding to (2 0 2), (0 0 9), (2 1 5), (0 2 3), (0 2 17) and
(3 3 4) planes.
The -Zn2 SiO4 transform to -Zn2 SiO4 (JCPDS No. 371485) after the sintering temperature increased to 700 C and few
ZnO residual phases (JCPDS No. 361451) were detected. Reasoning by the relative intensities of the XRD peaks of these
two -Zn2 SiO4 and -Zn2 SiO4 polymorphs, it can be concluded that the metastable -Zn2 SiO4 crystallized rst at the lower
temperatures and then gradually converted to thermodynamically stable -Zn2 SiO4 as the sintering temperature increased.
It is clear that a good crystallization of zinc silicate can be obtained at about 900 C which is the optimum temperature to
produce zinc silicate based glass ceramics [24].

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(a)

(b) 80

27 C

200

8079

600 C

70
60

Intensity (a.u)

Intensity (a.u)

150

100

50
40
30
20

50

10
0
550

600

650

0
550

Wavelength (nm)

(c)

600

650

Wavelength (nm)

220

700 C
800 C
900 C

200

Intensity (a.u)

180
160
140
120
100
80
60
500

550

Wavelength (nm)

Fig. 3. Emission spectra of 1 wt.% Mn-doped Zn2 SiO4 sintered at different temperatures.
(excitation = 260 nm, emission = (a) 600 nm, (b) 585 nm, (c) 527 nm

The XRD pattern approved that the stable -Zn2 SiO4 can be obtained using melt-quench method at sintering temperature
as low as 700 C. Intensity of diffraction peaks observed in the XRD pattern increase with increasing in sintering temperature,
suggesting increase and improvement in crystallinity [25]. The presence of the ZnO phase indicate that the sample is not
completely crystallized at this temperature. All the -Zn2 SiO4 samples exhibit seven major diffraction peaks at 2 = 22.07 ,
25.54 , 31.53 , 34.00 , 38.82 , 48.93 and 65.63 corresponding to (3 0 0), (2 2 0), (1 1 3), (4 1 0), (2 2 3), (3 3 3) and (7 1
3) planes. At low Mn-dopant concentration, no sign of MnO phase were detected in the spectra. This behaviour could be
attribute to the complete entering of Mn2+ cations into the Zn2 SiO4 host lattice [26].
3.2. FESEM micrograph analysis
In this study, FESEM characterization was performed in order to study the size, shape and also morphology of glass and
glass-ceramic samples. Fig. 2 shows FESEM micrograph of the 1 wt.% Mn-doped Zn2 SiO4 based glass-ceramic at various
sintering temperature at 50 000 of magnication. Clear glassy surface with no growth were observed in the micrograph for
the glass samples (Fig. 2(a)) which in a good agreement with the amorphous pattern shown by XRD analysis. Few changes
in grain size and shape were detected after the sintering process. At low temperature of 600 C and 700 C, (Fig. 2(bc)), the
crystallized particles shows few growth on the surface. The particles were composed of aggregated grains with irregularity
in shape and size. On the other hand, after sintered at 800 C and 900 C (Fig. 2(de)), surface morphology shown that the
samples become more compact with homogenous distribution. It appear that the grains were composed of hexagonal and
rectangular shape like.
From the morphology presented, less grain boundaries were noticed as the temperature increased due to grain growth
[26,27]. The calculated average grain size in the range of 0.5 m to 3.0 m indicate an increasing trend as the sintering
temperature increased up to 800 C due to densication. However, due to uniformity observed for the samples sintered at
900 C, the average grain size decreased. Pulverizing process in the solid-state method were reported to be responsible for
the non-uniform distribution in shape and size [28].
3.3. Photoluminescence
The emission spectra of 1 wt.% Mn-doped Zn2 SiO4 prepared at different sintering temperature were shown in Fig. 3. The
emission intensity of -Zn2 SiO4 exhibited strong green luminescence centered at 527 nm for the samples sintered at 700 C,

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800 C and 900 C [6] while for the sample sintered at 600 C, the yellow emission centered at 585 nm resulted from Zn2 SiO at an excitation of 260 nm [9,29]. However, red emission centered at 600 nm was observed for glass samples [30,31].
These emissions come from the Mn-dopant and correspond to an electronic transition 4 T1 (4 G) 6 A1 (6 S) which is a parity
forbidden emission transition of Mn2+ ions [3234]. This result, coupled with the XRD patterns, revealed that an increase in
crystallinity was responsible for the increase in luminescence [6].
Under UV excitation, an electron from the Mn2+ ground state of 6 A1 is excited to the conduction band of Zn2 SiO4 . The
mechanism can be expressed as Mn2+ + hv Mn3+ + e, where hv is the energy required in the photoexcitation of Mn2+ . The
free electrons in the conduction band can relax to the 4 T1 excited states of Mn2+ through a nonradiative process, and then
radiative transition from the 4 T1 excited state to the ground state 6 A1 occurs which wll results in the green emission of Mn2+
[25]. Signicant increase in emission intensity were revealed as the sintering temperature increased. This result, coupled
with the XRD patterns, revealed that an increase in crystallinity was responsible for the increase in emission intensity [35].
4. Conclusion
In summary, 1 wt.% Mn-doped Zn2 SiO4 based glass and glass-ceramic system have been prepared using melt-quench
method. 1 wt.% Mn-doped Zn2 SiO4 glass-ceramics were obtained after sintering process at 600 C, 700 C, 800 C and 900 C
for 2 h. The structural and luminescencel properties of these glass-ceramics have been studied and discussed. The structural
characterization for examples XRD and FESEM measurements verify the crystalline nature of glass-ceramic and formation
of -Zn2 SiO4 , - Zn2 SiO4 and ZnO phases. The emission wavelength was obtained at 3 different wavelength in the visible
region. The stable -Zn2 SiO4 emits green emission centered at 527 nm while yellow emission emitted by - Zn2 SiO4 at
585 nm. On the other hand, the glass samples shows red emission centered at 600 nm.
Acknowledgements
The authors gratefully acknowledged the nancial support for this study from the Malaysian Ministry of Higher Education (MOHE) and Universiti Putra Malaysia through the Fundamental Research Grant Scheme (FRGS) and Inisiatif Putra
Berkumpulan (IPB) research grant.
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