Physica B 439 (2014) 126–129

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Physica B
journal homepage: www.elsevier.com/locate/physb

Generation of white-light from Dy3 þ doped Sr2SiO4 phosphor

M.A. Tshabalala a, F.B. Dejene b, Shreyas S. Pitale a, H.C. Swart a, O.M. Ntwaeaborwa a,n
a
Department of Physics, University of the Free State, P.O Box 339, Bloemfontein 9300, South Africa
b
Department of Physics, University of the Free State, QwaQwa Campus, Private Bag X13, Phuthaditjhaba 9866, South Africa

art ic l e i nf o a b s t r a c t

Available online 27 November 2013 A single host lattice white light emitting Sr2SiO4:Dy3 þ powder phosphor was synthesized by solid state
Keywords: reaction process using a temperature of 1000 1C. The structure, particle morphology, chemical composi-
Sr2SiO4:Dy3 þ tion and oxidation states, photoluminescence (PL) and decay properties of the phosphor were analyzed
White light using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy
LED and PL spectroscopy, respectively. The objective of this study was to prepare a phosphor that can be used
XPS in white light emitting diodes. The XRD patterns showed a monoclinic structure of Sr2SiO4 with minor
incidental secondary phases from unreacted precursors. An agglomeration of particles with irregular
shapes was observed from the SEM micrographs. The PL emission spectra of the Sr2SiO4:Dy3 þ phosphor
excited at 350 nm consist of blue, yellow and red line emissions at 486 nm, 575 nm and 668 nm
corresponding respectively to the (4F9/2-6H15/2), (4F9/2-6H13/2) and (4F9/2-6H11/2) transitions of Dy3 þ .
The combination of these emissions constituted white light as indicated on the Commission Inter-
nationale de L'Eclairage chromatic coordinate diagram. The decay characteristics show that the phosphor
consists of a single exponential decay process.
& 2013 Elsevier B.V. All rights reserved.

1. Introduction host lattice doped/co-doped with either rare-earths only or a

Current research topics on phosphors are focused on the
generation of white light that can be used in light emitting diodes
(LEDs). White LEDs have several advantages over conventional
fluorescent lamps such as reduced power consumption, compact-
ness, efficient light output, and longer lifetimes [1]. The strategies
used to produce white light in LEDs include combining blue LED
with a yellow phosphor or UV-LED with blue, green and red
phosphors or blue, green and red LEDs. The problems with these
traditional white LEDs is that the yellow YAG:Ce3 þ phosphor has
been reported to show high thermal quenching and poor colour
rendition, and that the efficiency of the blue emission is often
affected by re-absorption by the red or green phosphor in the
three converter system [2,3]. These problems can be overcome by
using a single phosphor that emits simultaneously blue, green and
red light whose combination constitutes white light. Progress has
been made in the preparation and development of such phos-
phors. For example, Huang et al. [4], Kim et al. [5] and Lakshmi-
narasimhan and Varadaraju [1] have generated white light from
Y2O2S:Dy3 þ , Mg2 þ ,Si4 þ Ba3MgSi2O8:Eu2 þ , Mn2 þ , and Sr2SiO4:
Eu2 þ , Ce3 þ phosphors, which were all prepared by the solid state
reaction process. Today, the generation of white light from a single
n
Corresponding author.
E-mail addresses: ntwaeab@ufs.ac.za,
ntwaeab@gmail.com (O.M. Ntwaeaborwa).
combination of rare-earth and alkali earth ions is very common,
and alkali earth silicates such as Ba3MgSi2O8 [5], Sr3MgSi2O8 [6],
Sr2SiO4 [7] and Sr3SiO5 [8] have emerged as preferred matrices for
such phosphors. In present work, strontium silicate (Sr2SiO4) was
doped with trivalent dysprosium ion (Dy3 þ ), using the solid state
reaction process, resulting in a single host phosphor that emits
white light when pumped with 350 nm near UV light. The excita-
tion peaks in the 350–420 nm range implies that the Dy3 þ ions can
be efficiently excited by the popular near-UV (350–420 nm) LEDs.
2. Preparation and characterization techniques
Sr2SiO4:Dy3 þ phosphors were prepared by using high tempera-
ture solid state reaction process. The starting materials used in the
preparation process were SrCO3, SiO2 and Dy2O3, which were
weighed stoichiometrically and mixed thoroughly using a mortar
and pestle. The concentration of Dy3 þ was 6 mol% of Sr2 þ ions
in the Sr2SiO4 lattice. Although different concentrations of Dy3 þ
were evaluated, white photoluminescence was observed from
6 mol% only. The mixture was sintered at 1000 1C for 3 h in air.
The crystal structure, particle morphology, and chemical composi-
tion and electronic states were respectively analyzed by Advanced
D8 Bruker powder X-ray diffractometer (XRD), Shimadzu Superscan
ZU SSX-550 scanning electron microscope (SEM) and Physical
Electronics PHI 5000 Versaprobe X-ray Photoelectron Spectrometer
(XPS). The room temperature photoluminescence excitation and

0921-4526/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.physb.2013.11.022
 M.A. Tshabalala et al. / Physica B 439 (2014) 126–129
emission spectra, and the decay curves were recorded from the Cary
Eclipse fluorescence spectrophotometer using a monochromatized
xenon lamp as the excitation source.
3. Results
3.1. Structure
Fig. 1 presents the X-ray diffraction pattern of Sr2SiO4:Dy3 þ
phosphor. The pattern shows a monoclinic structure of Sr2SiO4
that is consistent with the standard JCPDS powder diffraction data
file. No. 76-1630. In additional, the calculated lattice parameters
(a ¼5.622, b ¼7.171, and c ¼9.1565 Å) were very close to the
Fig. 1. XRD pattern of Sr2SiO4:Dy3 þ phosphors prepared by solid-state reaction
method.
Fig. 2. (a)–(d) XPS deconvoluted scans and fittings results for the selected peaks of O 1s, Si 2p, Sr 3d, and Dy 3d5/2.
127
standard data (a ¼5.663, b¼7.084, c ¼9.767 Å) suggesting that
Sr2SiO4 was successfully crystallized. However, there are addi-
tional secondary phases, marked with asterisks, due to un-reacted
SrCO3 and SiO2 precursors as confirmed from X-ray photoelectron
spectroscopy (XPS) data. The average crystallite size (D) calculated
using the well known Scherrer equation D ¼ 0:9λ=ðβ cos θÞ was
found to be  13 nm.
The chemical composition and electronic states of Sr2SiO4:Dy3þ
were analyzed using XPS. The XPS survey scans confirmed the
presence of all the elements in the Sr2SiO4:Dy3 þ system. Fig. 2
(a and d) shows the fitted high resolution XPS peaks of O 1s, Si 2p,
Sr 3d, and Dy 3d5/2. The peaks at 528.2, 530.5 and 531.3 eV in Fig. 2
(a) are assigned to O peaks in Sr2SiO4:Dy3þ while the 532.3 eV peak is
assigned to O peak in SiO2 (533.070.5 eV) [9]. In Fig. 2(b) the low
intensity Si 2p peak at 103.85 eV is assigned to Si in SiO2 and the peaks
at 100.7 and 102.2 eV are assigned to Si in Sr2SiO4. These peak
positions are consistent with Si 2p XPS peak positions in Y2SiO5
matrix reported by Chambers et al. [10]. The two fitted peaks
in Fig. 2(c) at 135.5 and 133.7 eV are assigned to Sr in Sr2SiO4,
i.e. Sr2SiO4-3d3/2 and Sr2SiO4-3d5/2 from the two Sr2þ sites which
are associated with the Sr bonding in the Sr2SiO4:Dy3þ lattice. The
peaks at 1293.4, 1295.4, 1297.8 and 1304.5 in Fig. 2(d) are assigned
to 3d5/2 state of Dy3 þ while those at 1331.8, 1333.7, 1334.3 and
1335.5 eV are assigned to 3d3/2 of Dy3þ [9]. The background in Fig. 2
(d) is called intrinsic background noise or IBN and it is caused by
inelastic scattered electrons. The IBN increases with the binding
energy because it is by adding all the elastically scattered electrons
from the beginning to the end of the analysis. A summary of the
binding energies, area and compounds related to the fitted XPS peaks
in Fig. 2 (a and d) is presented in Table 1.
3.2. Morphology
Fig. 3(a and b) shows respectively the low and high magnifica-
tion SEM images of Sr2SiO4:Dy3 þ powder phosphor. Shown in
both Fig. 3(a and b) is that the particles did not have regular
128 M.A. Tshabalala et al. / Physica B 439 (2014) 126–129

shapes and that the bigger particles were formed from agglom- photoluminescent data and the interactive CIE software are
eration and adhesion of smaller particles. Our particle morphology x¼ 0.351 and y¼ 0.389, and are very close to those of the standard
is not the same as that reported in the literature for similar white color (0.333, 0.333) in the CIE coordinate system.
phosphor probably due to factors such as different synthesis Fig. 6 shows the afterglow characteristics of the Sr2SiO4:Dy3 þ
techniques, concentrations of reactants, and reaction time among phosphor. The phosphor exhibits a single exponential decay
other things. Due to agglomerated nature of our particles, it was feature with fitting parameters shown in the graph. Note that
not possible to estimate the particles sizes from the SEM images. the decay time (t1) is measured in milliseconds (ms). As it was
reported before [14], Dy3 þ acts as a supplier of traps forming
3.3. Excitation and emission spectrum defects when it replaces Sr in the crystal. The process can be
expressed as 3Sr2 þ ¼2DySr þVSr. Each substitution of two Dy3 þ
Fig. 4 shows the PL excitation and emission spectra of Sr2SiO4: ions would create two positive defects of DySr capturing electrons
Dy3 þ . The excitation peaks at 250–400 nm are assigned to the 4f– and one negative vacancy of VSr. These defects act as trapping
4f transitions of Dy3 þ [11]. The excitation spectrum of Sr2SiO4:
Dy3 þ shows strong absorption at 350 nm due to 6H15/2-6P7/2
transitions, and less intense absorptions at 300 nm, 325 nm,
366 nm and 386 nm due to 6H15/2-4D7/2, 6H15/2-6P3/2 6H15/
6 6 6 3þ
2- P5/2 and H15/2- K17/2 transitions of Dy respectively [12].
3þ
When the Sr2SiO4:Dy powder was excited at 350 nm, simulta-
neous emissions of blue (489 nm), (575 nm) green and red
(668 nm) assigned to the 4F9/2-6H15/2, 4F9/2-6H13/2, and 4F9/
6 3þ
2- H11/2 ions of Dy were observed. Notice that the red emis-
sion is less intense than the blue and green emissions. It is well
known that the 4F9/2-6H13/2 transition is hypersensitive and
therefore, its intensity strongly depends on the host, while the
4
F9/2-6H15/2 transition is less sensitive to the host [13].
Fig. 5 shows the Commission International de l’Eclairage France
(CIE) x–y color coordinates diagram of the Sr2SiO4:Dy3 þ phosphor.
The chromaticity coordinates of this phosphor calculated using the Fig. 4. PL spectra for Sr2SiO4:Dy3 þ under excitation of 350 nm and emission of 575 nm.

Table 1
The XPS peak position, contribution area and chemical compound O 1s, Si 2p, Sr 3d,
and Dy 3d5/2.

Sr2SiO4: Binding energy Area contribution Chemical

Dy3 þ (eV) (%) Compound

O 1s 532.3 10 O in SiO2
528.2 17 O in Sr2SiO4:Dy3 þ
530.5 57
531.3 17

Si 2p 102.2 58 Si in Sr2SiO4:Dy3 þ
103.9 12 Si in SiO2
100.7 30

Sr 3d 135.5 44 Sr in Sr2SiO4:Dy3 þ
133.7 56

Dy 3d 1293.4 (3d5/2) 20 Dy3 þ

1295.4 (3d5/2) 37
1297.8 (3d5/2) 7
1304.9 (3d5/2) 3
1331.8 (3d3/2) 13
1333.7 (3d3/2) 18
1334.3 (3d3/2) 2
1335.5 (3d3/2) 2
Fig. 5. CIE coordinate diagram of as prepared 6% Dy3 þ -doped Sr2SiO4 phosphor.

Fig. 3. SEM images of Sr2SiO4:Dy3 þ phosphor sample and (b) is the enlarged image of (a).
 M.A. Tshabalala et al. / Physica B 439 (2014) 126–129 129

120 confirmed from the calculated CIE coordinates which were found
Equation y = A1*exp(-x/t1) + y0
to be very close to standard white CIE coordinates. Fast single
100 Adj. R-Square 0.99959 exponential decay and stable white light emission suggests that
Value Std. Error
there are good prospects for this phosphor to be used in white
80 B y0 0.72 0.34
Intensity (a.u.)

B A1 228.74 41.38 LEDs in future.

B t1 0.0593 0.012
60

40
Acknowledgments
20
The authors would like to thank the University of the Free State
0 and the South African National Research Foundation for their
financial support. This work is based on the research supported
0 1 2 3 4 5 6 by the South African Research Chairs Initiative of the Department
Time (ms) of Science and Technology and National Research Foundation of
Fig.6. Afterglow characteristics of Sr2SiO4:Dy3 þ phosphor excited at 350 with
South Africa.
Xenon lamp.

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