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A facile and effective strategy to synthesize orthorhombic Sr2Al6O11:Eu2+,Dy3+ with blue-

green persistent luminescence

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2017 IOP Conf. Ser.: Mater. Sci. Eng. 167 012050

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 1st International Conference on New Material and Chemical Industry (NMCI2016) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 167 (2017) 012050 doi:10.1088/1757-899X/167/1/012050

International Conference on Recent Trends in Physics 2016 (ICRTP2016) IOP Publishing

Journal of Physics: Conference Series 755 (2016) 011001 doi:10.1088/1742-6596/755/1/011001

A facile and effective strategy to synthesize orthorhombic

Sr 2 Al 6 O 11 :Eu2+,Dy3+ with blue-green persistent luminescence

Juan Han1, Ziqiu Jiang1, Wenyan Zhang1,4, Lingyun Hao1, Yaru Ni2,3, Chunhua
Lu2,3, and Zhongzi Xu2,3
1
College of Material Engineering, Jinling Institute of technology, Nanjing, China
2
Jiangsu Collaborative Innovation Center for Advanced Inorganic Function
Composites, Nanjing Tech University, Nanjing, PR China
3
State Key Laboratory of Materials-Oriented Chemical Engineering, College of
Materials Science and Engineering, Nanjing Tech University, Nanjing, PR China

E-mail: wiseyanyan@jit.edu.cn

Abstract. Sr 2 Al 6 O 11 :Eu2+,Dy3+ is known as a high efficient material for generating persistent

luminescence. Due to its low structural stability, it is a challenge to prepare such orthorhombic
material in large scale. In this work, a facile and effective strategy was designed for the
preparation of Sr 2 Al 6 O 11 :Eu2+,Dy3+ with high purity by combining the advantages of solid
state reaction and chemical vapor deposition method. The prepared Sr 2 Al 6 O 11 :Eu2+,Dy3+ could
effectively store the UV light energy and emit blue-green luminescence for 240 min by slow
liberation of photo-excited electrons. Its blue-green afterglow was composed of two
luminescent emissions which released from the Eu centers located in different crystal fields.

1. Introduction
Afterglow materials have attracted a great deal of interest since ancient years. Owning to its special
ability to store and release light energy, such material could be applied widely for the rewritable
optical memory media, security signs, traffic signage, dial markers and medical diagnostics[1, 2].
Persistent luminescence of materials depends not only on their crystal structure but on the distribution
and concentration of luminescent centers inside the materials. Consequently, the development of
afterglow material was rather slow until the discovery of SrAl 2 O 4 :Eu2+,Dy2+ in 1996, which made a
significant breakthrough in this field as it extended the afterglow duration from minutes to tens of
hours[3]. From then on, people found it the key to enhance the persistent luminescence is to construct
appropriate trap levels inside the materials to realize effective capturing, storing and slowly releasing
of excited carriers (electron and hole). After that, extensive research was triggered on inventing new
persistent phosphors as well as bringing out reasonable mechanism models of long-lasting
luminescence. Silicates, germinate, gallate and titanate materials were also found to be promising
hosts for storing and releasing photo-generated carriers with high efficiency[1-6]. However, the
aluminates phosphors are still recognized to be the most effective afterglow material at present due to
its high brightness, long phosphorescence time, suitable chemical stability, non-toxicity, and low cost.
Sr 2 Al 6 O 11 :Eu2+,Dy3+ is a “mysterious” species in the family of aluminates afterglow phosphors.
Due to its low structural stability, such material could only be prepared in narrow and strict synthesis
conditions. Smets et al. firstly reported the synthesis of Sr 2 Al 6 O 11 :Eu2+ and suggested that it was a
single phase with similar crystal structure like Sr 1.33 Pb 0.67 Al 6 O 11 , which could yield high efficient

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 1st International Conference on New Material and Chemical Industry (NMCI2016) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 167 (2017) 012050 doi:10.1088/1757-899X/167/1/012050

luminescence [7]. Wang et al. named such material as “so-called Sr 2 Al 6 O 11 :Eu2+” because their work
indicated that the Sr 2 Al 6 O 11 :Eu2+ was not a single-phase crystal but a mixture of SrAl 2 O 4 and
Sr 4 Al 14 O 25 [8]. Furthermore, it is ambiguous that whether Sr 2 Al 6 O 11 is an appropriate matrix for the
generation of persistent luminescence. Takashi et al. studied the optical properties of
Sr 2 Al 6 O 11 :Eu2+,Dy3+ and found that the material could not yield persistent luminescence[9]. Song et al.
also reported that the Sr 2 Al 6 O 11 :Eu2+ didn’t show obvious persistent luminescence whereas the
Sr 2 Al 6 O 11 :Eu2+,Er3+ could emit blue phosphorescence longer than 14 h [10]. Xue et al. investigated
the effects of sintering temperature on the phase formation and luminescent properties of
Sr 2 Al 6 O 11 :Eu2+,Dy3+ [11]. However, as the phosphor they synthesized was a mixture of
SrAl 2 O 4 :Eu2+,Dy3+, Sr 2 Al 6 O 11 :Eu2+,Dy3+ and Sr 4 Al 14 O 25 :Eu2+,Dy3+. Though Sr 2 Al 6 O 11 was main
phase in the mixture, the afterglow luminescence they reported was actually a mingled emission of
those three phosphors [11]. After that, little progress was got about the structure and optical property
of Sr 2 Al 6 O 11 :Eu2+,Dy3+.
To make clear about the optical property of Sr 2 Al 6 O 11 :Eu2+,Dy3+, it is necessary to obtain such
“mysterious” species with high purity and favorable quality. In this work, an effective and moderate
strategy was proposed for the synthesis of such phosphor. Sr 2 Al 6 O 11 :Eu2+,Dy3+ with high purity could
be obtained by that strategy which combined the advantages of solid state reaction and chemical vapor
deposition method. The prepared Sr 2 Al 6 O 11 :Eu2+,Dy3+ exhibited favorable persistent luminescence at
room temperature.

2. Material and Experiments

Al 2 O 3 , Eu 2 O 3 (99.9%), Dy 2 O 3 (99.9%), H 3 BO 3 (99.5%), SrCO 3 (99.5%), urea (99.5%) and active
carbon (99.5%) were purchased from Guoyao Corporation. Reactant ratio for Sr 2 Al 6 O 11 :Eu2+,Dy3+
were 0.01Eu 2 O 3 +0.02Dy 2 O 3 +0.97SrCO 3 +1.5Al 2 O 3 +0.4H 3 BO 3 +1urea (mol%). A blank sample, the
Sr 2 Al 6 O 11 , was prepared by the same reactant ratio of Sr 2 Al 6 O 11 :Eu2+,Dy3+ but without the addition of
Eu 2 O 3 and Dy 2 O 3 . Then the reactants were ground in an agate mortar to mix them together, and
pressed into pellets.
As shown in Figure 1, solid state reaction was carried out in a tubular oven. The tubular hearth is
made up of two regions which were regulated by independent temperature-control system. Active
carbon particles were placed at the first region and heated at 700 oC to produce large amount of
thermal CO gas (2C+O 2 →CO). The pellets were located at the second region and the second region
was then heated at 1000 oC for 2h. Ar gas flew from the first region to the second region continuously
to deliver the CO gas to the pellets.

Figure 1. Scheme of synthesis process.

Material structures were investigated by X-ray diffraction (Thermal ARL X’TRA) and Fourier
transforming infrared spectra (FTIR, Nicolet IS-10, 4000-400 cm-1). Photo-luminescence (PL) and
afterglow spectra were analyzed by fluorescence spectrometer (Edinburghinstruments FS5). Optical
properties were also studied by incident reflection (UV-Vis-NIR spectrometer, Shimadzu, UV
3101PC). Thermal behavior was analyzed by the DSC-TG characterization (NETZSCH STA 409 PC).

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 1st International Conference on New Material and Chemical Industry (NMCI2016) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 167 (2017) 012050 doi:10.1088/1757-899X/167/1/012050

3. Results and discussion

DSC-TG curves indicated the Sr 2 Al 6 O 11 :Eu2+,Dy3+ could be obtained at 1000oC as there were neither
weight loss nor thermal variation above that temperature (Figure 2(a)). XRD pattern shows the
prepared Sr 2 Al 6 O 11 has high purity as all the diffraction peaks matched well with the crystal planes of
orthorhombic Sr 2 Al 6 O 11 (JCPDS#72-7796, Figure 2(b)). The orthorhombic Sr 2 Al 6 O 11 structure was
made up by two kinds of planes: the AlO 4 plane which was connected by corner-shared AlO 4 -
tetrahedra groups, and the AlO 6 plane which was connected by edge-shared AlO 6 -octahedra groups
(Figure 2 (c))[7, 9]. The AlO 4 and AlO 6 planes are cross-linked by AlO 4 -tetrahedra. FTIR spectra
reveal the existence of the two planes, as shown in Figure 2(d). The FTIR bands at 850, 780 and 643
cm-1 corresponds to the stretching vibration of AlO 4 -tetrahedra. The 523, 476 and 430 cm-1 bands are
assigned to the vibration of AlO 6 -octahedra[12].

Figure 2. (a) DSC-TG curves of reactants; (b) XRD patterns of products; (c) Scheme of Sr 2 Al 6 O 11
structure; (d) FTIR spectra of products

In fact, the orthorhombic Sr 2 Al 6 O 11 is fairly unstable as its zigzag AlO 4 planes tends to transform
spontaneously to release its structural stress[9]. That enhanced the difficulty in stabilizing the
Sr 2 Al 6 O 11 structure during the synthesis process. So the Sr 2 Al 6 O 11 structure could only be
synthesized in narrow and strict conditions. Herein, as the CO gas was produced from the oxidation of
carbon, they provided the pellets with not only a reductive atmosphere but high thermal energy to
accelerate the crystallization of Sr 2 Al 6 O 11 phase (Figure 1). Intermediate products, such as CO 2 and
volatile boric acid, have little influence on the crystallization of Sr 2 Al 6 O 11 as they were removed from
the reaction system with the flow of CO gas. Thus the preparation strategy in this work could facilitate
the formation of high purity Sr 2 Al 6 O 11 by taking advantages of solid state reactions and CVD method.
The 909 cm-1 band is assigned to the vibration of residual amorphous boron oxygen compounds,
indicating that the boric acid could help to prevent the structure transformation of orthorhombic
Sr 2 Al 6 O 11 and improve its stability during the reaction.
Under 365 nm excitation, Sr 2 Al 6 O 11 :Eu2+,Dy3+ exhibited a broad emission band in 375-650 nm
(Figure 2(a, b)). The blue-green emission band centered at 492 nm is mainly attributed to the 4f65d-4f7
electron transition of Eu2+ ions. Excitation band of Sr 2 Al 6 O 11 :Eu2+,Dy3+ overlapped with the emission
band at 375-450 nm, indicating the emission light at 375-450 nm could be applied by the
Sr 2 Al 6 O 11 :Eu2+,Dy3+ to excite second emission lights (Figure 2(a)). That was supported by the
reflection spectra, which show that the Sr 2 Al 6 O 11 :Eu2+,Dy3+ could absorb 340-475 nm light whereas

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 1st International Conference on New Material and Chemical Industry (NMCI2016) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 167 (2017) 012050 doi:10.1088/1757-899X/167/1/012050

the Sr 2 Al 6 O 11 without doping have no absorption at that range (Figure 2(c)). Those absorbed light was
captured by the Eu2+ ions to generate its 4f65d-4f7 electron transitions. In addition, the weak absorption
at 797-1655 nm are assigned to the Dy3+ f-f electron transitions and confirms the doping of Dy3+ ions
(Figure 2(c,d)).
The 492 nm emission band is asymmetric and could be de-convoluted into two Gaussian bands at
485 and 521 nm (Figure 2(b)). The splitting of 492 nm band originated from the variation of crystal
fields around the Eu(1) and Eu(2) sites, as the 4f65d-4f7 electron transitions of Eu2+ ions are very
sensitive to coordinate environments. The 492 nm emission of Sr 2 Al 6 O 11 :Eu2+,Dy3+ could still be
detected after 240 min (Figure 2(e)) [7,9,13]. The profile of 492 nm emission did not change with the
decay of emission intensity, indicating the Eu(1) and Eu(2) sites both contribute to the blue-green
persistent luminescence (Figure 2(f, g)).

Figure 3. Excitation and emission spectra of Sr 2 Al 6 O 11 :Eu2+,Dy3+ (λex=365nm, λem=492nm); (b)

Gaussian fitting of 492 nm emission band; (c) UV-vis-NIR spectra of Sr 2 Al 6 O 11 :Eu2+,Dy3+ and
Sr 2 Al 6 O 11 ; (d) Scheme for the electron levels of Dy ions; (e) Persistent luminescence as a function of
time for Sr 2 Al 6 O 11 :Eu2+,Dy3+ (Inset, CIE chromaticity diagram of Sr 2 Al 6 O 11 :Eu2+,Dy3+); (f) Emission
spectrum of Sr 2 Al 6 O 11 :Eu2+,Dy3+ (1 min after excitation ); (g) Emission spectrum of
Sr 2 Al 6 O 11 :Eu2+,Dy3+ (240 min after excitation)

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 1st International Conference on New Material and Chemical Industry (NMCI2016) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 167 (2017) 012050 doi:10.1088/1757-899X/167/1/012050

Modified Clabau theory is recognized to be a reasonable model to explain the afterglow mechanism
of Eu2+,Dy3+ doped aluminates[14-16]. According to that theory, the afterglow emission process of
Sr 2 Al 6 O 11 :Eu2+,Dy3+ could be speculated as follows (Figure 4): (1) the doping of Eu2+ and Dy3+ ions
generated V o and V Sr defects; (2) Under UV irradiation, the electrons excited from Eu2+ 4f7 to 4f65d1
level could move into conductive band (CB), while some electrons were excited from valence band
(VB) to Eu3+ 4f7 level; (3) V o defects trapped the electrons released from CB, while V Sr defects
trapped the holes from VB; (4) The trapped electrons and holes were released slowly from V o and V Sr
to yield the blue-green persistent luminescence.

Figure 4. Proposed afterglow mechanism for Sr 2 Al 6 O 11 :Eu2+,Dy3+

4. Conclusion
In this work, we report the synthesis and optical properties of a distinctive afterglow material
Sr 2 Al 6 O 11 :Eu2+,Dy3+. It was simple and effective to synthesize the orthorhombic Sr 2 Al 6 O 11 :Eu2+,Dy3+
with high purity. Under UV excitation, the special aluminates exhibits broad emissions at 375–650 nm
and the 375-450 nm emission lights could be utilized by the material to excite second emission. The
Eu(1) and Eu(2) sites in Sr 2 Al 6 O 11 lattice both contribute to the blue-green persistent luminescence.

Acknowledgments
This work is supported by Jiangsu Provincial Natural Science Foundation for Youths (No.
BK20130095), Educational Commission of Jiangsu Province (15KJD430014), National Natural
Science Foundation of China (No.51502143), Innovation Foundation for scientific research
(2014-jit-n-06), and Key University Science Research Project of Jiangsu Province
(No.15KJB430022).

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