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School of Nature Resources & Materials Science, Northeastern University at Qinhuangdao, Qinhuangdao, Hebei Province 066004, PR China
School of Chemistry, Monash University, Clayton, Victoria 3800, Australia
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 14 December 2015
Received in revised form
24 March 2016
Accepted 1 April 2016
Available online 5 April 2016
The precursors Sr3Al2(OH)12 can be directly precipitated from solution near room temperature under the
normal pressure. The cubic Sr3Al2O6 with ne grain size can be synthesized from Sr3Al2(OH)12 at the
temperature as low as 600 C. Especially, the rare earth element, such as Eu3 etc., as luminescent center,
has been simultaneously integrated into the lattices of Sr3Al2O6. The luminescent intensities of the
samples annealed at a temperature over 800 C are strong enough for phosphors, and increase with the
annealing temperatures, reach a maximum at 1200 C and then drop down at 1300 C. The grain sizes of
all the samples annealed below 1200 C are smaller than 1 mm and suitable for mixing with other
phosphors in the applications. The photoluminescent spectra of the Sr3Al2O6:Eu3 reveal that the intensities of both emission and excitation peaks increase with the dose of Eu3, and reach maxima at the
dose level about 1.2%, then decrease due to concentration quenching. A new excitation band at 230 nm
has been observed in heavier doped samples due to the complex point defects produced by association.
2016 Elsevier B.V. All rights reserved.
Keywords:
Sr3Al2(OH)12
Sr3Al2O6
Phosphors
Direct synthesis
Fine-grain
1. Introduction
Owing to their unique properties, oxide phosphors have been
recognized as the most promising materials for light emitting devices [1,2]. Among them, rare earth doped strontium aluminates are
particular important from practical point of view [3e10]. With
much abundant species of the aluminates, their compositions can
be much different, for examples, strontium aluminates can have the
formulae as Sr5Al2O8 [3], Sr4Al2O7 [4], Sr3Al2O6 [5e9], Sr12Al14O33
[11], SrAl2O4 [12e36], Sr4Al14O25 [37e40], SrAl4O7 [41], and
SrAl12O19 [42,43] in series, so does barium aluminates also. Among
them, Sr5Al2O8, Sr12Al14O33, and Sr4Al14O25 were not reported in
the early phase diagram, and Sr3Al2O6, SrAl2O4, Sr4Al14O25 are
much more documented as the hosts of phosphors. The rare earth
ions can act as luminescent centres in a certain aluminates host.
Different activate ions can have the different wave-bands emission
lights, such as Eu3 with orange and red lights [3,4], Eu2 with
dominant emission of green or red light [5,24,27,28,31,37], Ce3
with blue green light [6,9,29], Sm3 with orange red light [10], Pr3
* Corresponding author.
E-mail address: jianquanqi@mail.tsinghua.edu.cn (J. Qi).
http://dx.doi.org/10.1016/j.jallcom.2016.04.005
0925-8388/ 2016 Elsevier B.V. All rights reserved.
with yellow orange light [25,29], Mn4 with red light [38], Bi3
with greenish blue to blue light [7], and etc. Their luminescent
properties are associated not only with the ingredients, but also the
processing arts. There are several traditional methods to prepare
aluminates, such as high-temperature solid state reaction [3,6,8],
sol-gel [30,33,34], combustion [31,39], and hydrothermal methods
[44]. So far, high temperature annealing has been required for
synthesizing nal phosphors products. Besides of the highly energy
consumption, another main issue is that the grain size of aluminates may be coarsened due to the rapid grain growth at high
temperature, which may cause colour stain when they are mixed
with other phosphors for white-light emission. It is important to
decrease the synthetic temperature of phosphors powders in order
to depress the point defects in grain bulk to achieve the outstanding
luminescent properties and avoid the grain coarsening to improve
the processing properties for the stepped applications. In this study,
we developed a simple chemical method to prepare a stable hydroxide Sr3Al2(OH)12. We demonstrate that strontium aluminates
phosphors Eu3 doped Sr3Al2O6 phosphors with controlled
composition can been obtained at a low temperature by using
Sr3Al2(OH)12 as the precursor. The photoluminescence of Eu3
doped Sr3Al2O6 phosphors strongly depends on the preparation
conditions and shows great promise for optical devices.
422
Sr Al (OH) pdf:24-1186
1300 C
Intensity/ a.u.
Intensity/ a.u.
SrCO
1200 C
1000 C
800 C
600 C
SrCO pdf:5-0418
RT
10
20
30
40
2Theta/
50
60
70
Sr Al O
10
20
30
40
2Theta/
50
70
SrCO3
SrCO
60
Intensity/ a.u.
Sr Al O H O
Intensity/ a.u.
Sr Al O 2H O
Sr Al O pdf:24-1187
SrCO pdf:05-0418
10
20
30
40
50
60
2Theta/
70
20
30
40
50
2Theta/
60
70
Fig. 1. XRD patterns of (a) as-prepared samples, (b) the samples annealed at different temperature (doping level of Eu3 as1.5%), (c) the samples annealed at 600 C and (d) the
sample annealed at 800 C.both of the pdf-cards are also shown accordingly.
2. Experimental
Direct synthesis from solution method is a processing to direct
crystallization of oxides, hydroxides and some oxysalts through
solution chemical reaction under normal pressure and near room
temperature. The processing of Sr3Al2(OH)12 by the direct synthesis
from solution is similar as that of BaTiO3 [45], BST(Ba1-xSrxTiO3)
[46], BZT (BaZrxTi1-xO3) [47], and etc., as we reported previously. In
this study, Sr(OH)2$8H2O and aluminium resources, such as
aluminium ethoxide or sodium metaaluminate are adopted as raw
materials to synthesis Sr3Al2(OH)12 by direct synthesis from solution method. In a typical synthetic process, 13.288 g Sr(OH)2$8H2O
(BDH Chem. Ltd., UK) was dissolved in a sealed conical beaker
containing 200 ml absolute ethanol (International Laboratory, USA)
and 200 ml DI water as base solution. Then, 5.405 g (C2H5O)3Al
(BDH Chem. Ltd., UK) and a certain content (0, 0.5, 0.8, 1.0, 1.5, 1.8,
2.0, 2.5, 3.0%mol relative to Sr) of EuCl3(BDH Chem. Ltd., UK) were
dissolved in 200 ml absolute ethanol and transferred into a buret as
titrating solution. The conical beaker was linked to a buffer vessel
with a perfusion tube. Another perfusion tube was used to link the
buffer vessel and anther beaker contained with sodium hydroxide
solution to exclude CO2 in air from our synthesis system. After the
base solution was heated to a certain temperature (i.e. 60 C), the
titrating solution was dripped into the base solution in conical
beaker dropwise under vigorous stirring. The white precipitations
were observed in the solution instantaneously. After the completion of the titration and followed by ageing for 3 h, the white
precipitation was obtained and baked at 60 C for 24 h in an oven.
To compare the effect of aluminium resources, the titrating solution
was replaced as sodium metaaluminate water solution such as
2.732 g NaAlO2 (BDH Chem. Ltd., UK) was solved in 200 ml DI water.
423
(1)
(2)
(3)
and
(4)
then
(5)
Fig. 2. SEM images of the samples prepared at different temperature: (a) as prepared, (b) 600 C, (c) 800 C, (d) 1000 C, (e) 1200 C, (f) 1300 C.
424
6000
7000
em=613nm
254nm
intensity/a.u.
intensity/a.u.
5000
4000
3000
2000
1000
5000
300
400
600
intensity/a.u.
2000
1000
300
400
500
600
wavelenth/nm
612nm,
618nm =254nm
ex
5
7
D0- F2
4000
3000
2000
579nm
5
7
D0- F0
0
500
200
3000
0
200
5000
em=593nm
4000
intensity/a.u.
500
wavelenth/nm
593nm
5
7
D0- F1
1000
0
200
6000
550
653nm
685nm
5
7
D0- F3 5 7
D0- F4
600
650
700
wavelenth/nm
ex=394nm
150
100
50
0
500
550
600
650
700
wavelenth/nm
Fig. 3. The photoluminescent spectra of the sample annealed at 1200 C. (a) Excitation spectra monitored at Eu3 emission at 613 nm, (b) Emission spectra by exciting at 254 nm, (c)
Excitation spectra monitored at Eu3 emission at 593 nm, (d) Emission spectra by exciting at 394 nm.
most of carbonate and intermediate hydrated aluminates are disappeared. It is expected that SrCO3 can react with Al(OH)3 to synthesize Sr3Al2O6 at the temperature below 800 C due to their
chemical activity as produced freshly and very ne grain size. The
reaction is expressed as following equation (6)
(6)
425
(7)
or
3Eu2 O3 Al2 O3 /6EuSr 2VAl0 2Al
Al 12OO
00
(8)
00
00
00
(10)
O
EuSr
O/
0
(11)
to
00
O
EuSr VSr
O/
0
e
Fig. 4. (a) The emission spectra of the samples annealed at different temperature by
exciting at 254 nm, inset: the dependence of emission intensity at 613 nm on
annealing temperature. (b) The emission spectra of the Sr3Al2O6:Eu3 samples
annealed at 1200 C with different doping level by exciting at 254 nm, inset: the
dependence of emission intensity at 613 nm. (c) The activation spectra of the
Sr3Al2O6:Eu3 samples annealed at 1200 C with different doping level by monitoring
Eu3 emission at 593 nm, inset: the dependence of emission intensity on the dose of
Eu3.
be synthesized into their lattice cell at this time. The reason of the
emission intensities are weak in this sample is mainly due to the
adsorption of the emissions by so many impure phases, especially
as SrCO3. The luminescent intensities of the samples annealed at a
00
or O
EuSr VAl0 :
O/
0
e
(12)
4. Conclusions
In summary, we have developed a facile and effective approach
for the synthesis of a cubic hydroxide Sr3Al2(OH)12, which can be
directly transformed to cubic Sr3Al2O6 at the temperature as low as
600 C.The method of direct synthesis from solution is simple,
controllable, efcient and pollution free. The cubic Sr3Al2O6 can be
obtained as main phase by annealing at the temperate of 800 C and
426
as single pure phase by that over 800 C. The rare earth element,
such as Eu3 etc., as luminescent center, has been simultaneously
dopped into the lattices. The luminescent intensities of the samples
which anneals at a temperature over 800 C are strong enough for
phosphors, increase with the calcinations temperatures, reach a
maximum at annealing temperature of 1200 C and then drop
down at 1300 C. Therefore, decrease of the synthetic temperature
can either depressing the point defects in grain bulk or avoid the
grain coarsening and achieve the outstanding phosphors properties. The grain sizes of all the samples annealed below 1200 C are
smaller than 1 mm and suitable for mixing with other phosphors in
the applications. Therefore the precursor is very useful for preparation of strontium aluminate phosphors at low temperature. The
photoluminescent spectra of the Sr3Al2O6:Eu3 reveal that the intensities of both emission and excitation peaks increase with the
dose of Eu3, and reach maxima at the dose level about 1.2%, then
decrease due to concentration quenching. When the doping level of
Eu3 is lower than 2%, the cation vacancy cannot inuence on the
charge transfer distinctly, and the CTB shift slightly. In heavier
doped samples, the complex point defects can be produced by association, the transfer energy will increase, and CTB shift towards to
short wavelength. Therefore, a new excitation band at 230 nm can
be observed in heavier doped samples.
Acknowledgements
The authors are grateful the supports of Basic Key Program of
Applied Basic Research of Science and Technology Commission
Foundation of Hebei Province in China (Grant No. 14961108D and
Grant No. 15961005D) and Open Project of State Key Laboratory of
New Ceramic and Fine Processing, Tsinghua University(No.
KF201410).
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