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Materials Letters 58 (2004) 352 – 356

www.elsevier.com/locate/matlet

Combustion synthesis and photoluminescence of SrAl2O4:Eu,Dy

phosphor nanoparticles
Tianyou Peng a,*, Huanping Yang a, Xuli Pu a, Bin Hu a, Zucheng Jiang a, Chunhua Yan b
a
Department of Chemistry, Wuhan University, Wuhan 430072, PR China
b
State Key Laboratory of Rare Earth Materials Chemistry and Application, Peking University, Beijing, PR China
Received 31 March 2003; accepted 5 June 2003

Abstract

Eu2 +,Dy3 + co-doped strontium aluminate (SrAl2O4) phosphor nanoparticles with high brightness and long afterglow were prepared by
glycine – nitrate solution combustion synthesis at 500 jC, followed by heating the resultant combustion ash at 1100 jC in a weak reductive
atmosphere of active carbon. The average particle size of the SrAl2O4:Eu,Dy phosphor nanoparticles ranges from 15 to 45 nm as indicated by
transmission electron microscopy (TEM). The broad-band UV-excited luminescence of the SrAl2O4:Eu,Dy phosphor nanoparticles was
observed at kmax = 513 nm due to transitions from the 4f65d1 to the 4f7 configuration of the Eu2 + ion. The results indicated that the main
peaks in the emission and excitation spectrum of phosphor nanoparticles shifted to the short wavelength compared with the phosphor
obtained by the solid-state reaction synthesis method. The decay speed of the afterglow for phosphor nanoparticles was faster than that
obtained by the solid-state reaction method.
D 2003 Elsevier B.V. All rights reserved.

Keywords: Long-afterglow phosphor; Combustion synthesis; Strontium aluminate; Hole trap; Optical properties

1. Introduction particles. Those processes easily introduce additional defects

The photoluminescence at the blue-green visible region of
Eu 2 + -doped alkaline earth aluminates MAl 2 O 4 :Eu 2 +
(M = Ca, Sr, Ba) phosphors have been studied extensively
[1 –5]. The afterglow lifetime and intensity can be enhanced
by co-doping with some other rare earth ions [4 –6]. Those
phosphors exhibit a rapid initial decay from the Eu2 + ion
followed by a long persistence. This effect has been ascribed
to the thermal activation of holes from traps followed by the
emission of Eu2 + [7– 10]. Compared with sulfide phospho-
rescent phosphors, SrAl2O4:Eu,Dy phosphor possesses safer,
chemically stable, very bright and long-lasting photolumi-
nescence with no radiation [6 – 12], which results in an
unexpectedly large field of applications, such as luminous
paints in highway, airport, buildings and ceramics products,
as well as in textile, the dial plate of glow watch, warning
signs and escape routine, etc. [7,13]. The grain size of
phosphor powders prepared through solid-state reaction
method is in several tens of micrometers. Phosphors of small
particles must be obtained by grinding the larger phosphor
* Corresponding author. Fax: +86-278-764-7617.
E-mail address: typeng@whu.edu.cn (T. Peng).
and greatly reduce luminescence efficiency [14].
With the development of scientific technologies on
materials, several chemical synthesis techniques, such as
co-precipitation [8], sol –gel [15] and combustion synthesis
methods [16], have been applied to prepare SrAl2O4 and/or
its phosphors. All of these methods were conducted in liquid
phases so that each component can be accurately controlled
and uniformly mixed. For sol – gel or co-precipitation tech-
niques, processing routines to prepare the precursor powders
are complicated and the duration is long. The combustion
process to prepare the precursor powders, however, is very
facile and only takes a few minutes, which has been
extensively applied to the preparation of various nano-scale
oxide materials. This synthesis technique makes use of the
heat energy liberated by the redox exothermic reaction at a
relative low igniting temperature between metal nitrates and
urea or other fuels. Furthermore, the process is also safe,
instantaneous and energy saving. Therefore, the combustion
synthesis appears to hold promise for the preparation of
nanosized aluminate phosphors. These phosphor nanopar-
ticles are potential for construction materials in detecting
damage in a bridge or high buildings, as well as in display
and decorative materials in hotels, the plaza and instrument,

0167-577X/$ - see front matter D 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0167-577X(03)00499-3 转载
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T. Peng et al. / Materials Letters 58 (2004) 352–356
etc. To the best of our knowledge, reports on the preparation
of SrAl2O4:Eu,Dy nanoparticles is still rare [8], although
ultrafine SrAl2O4 has been prepared by the combustion of
corresponding metal nitrate – aluminium nitrate –urea mix-
ture synthesis [16]. In view of the special properties
concerning the nano-scale materials, it is interesting to know
the differences in properties between the nanoparticles and
micrometer-scale particles of SrAl2O4:Eu,Dy phosphors. In
this paper, combustion synthesis is applied to prepare the
SrAl2O4:Eu,Dy phosphor nanoparticles. The microstructure
of the as-prepared SrAl2O4:Eu,Dy precursor powders are
investigated by X-ray diffraction (XRD), scanning electron
microscopy(SEM) and transmission electron microscopy
(TEM). The photoluminescent phosphor nanoparticles with
high brightness and long afterglow were obtained by heating
the resultant combustion ash precursor powders at 1100 jC
in a weak reductive atmosphere of active carbon.
2. Experimental
Sr0.97Al2O4:Eu0.01,Dy0.02 phosphor nanoparticles were
prepared by solution combustion synthesis method followed
by heating the precursor combustion ash at 1100 jC in a
reductive atmosphere of active carbon. In a cylindrical
quartz container (80 mm diameter  200 mm height), stoi-
chiometric composition of aluminum nitrate (Al(NO3)3),
strontium nitrate (Sr(NO3)2), dysprosium nitrate (Dy(NO3)3)
and europium nitrate (Eu(NO3)3) were dissolved in a
minimum amount of distilled water together with 1.5 times
excess amount of glycine. The precursor solution was
introduced into a muffle furnace maintained at 500 jC.
Initially, the solution boiled and underwent dehydration,
followed by decomposition with the evolution of large
amounts of gases (oxides of carbon, nitrogen and ammonia).
Then, spontaneous ignition occurred and underwent smoul-
dering combustion with enormous swelling, producing
white foamy and voluminous SrAl2O4:Eu,Dy. The whole
process is over within less than 3 min. The voluminous and
foamy combustion ash can be easily milled to obtain the
precursor powder of SrAl2O4:Eu,Dy. The well-milled pre-
cursor powder is subsequently annealed at 1100 jC for 2 h in
an active carbon atmosphere, producing SrAl2O4:Eu,Dy
phosphor nanoparticles. Sr0.97Al2O4:Eu0.01,Dy0.02 phos-
phors were also synthesized at 1300 jC by the usual
solid-state reaction technique under a weak reductive atmo-
sphere of active carbon for comparing, and boric acid was
added to the mixture as flux [6]. All starting materials were
of the analytical purity.
The morphological studies are carried out on a H-510
scanning electron microscope (SEM) and a H-600 transmis-
sion electron microscope (TEM). Crystal structures of
samples were checked by means of a Rigaku RINT-1400
diffractometer using Cu Ka k = 1.5406 Å. The photolumi-
nescent properties of the obtained phosphor nanoparticles
were measured at room temperature using a Perkin Elmer
http://www.paper.edu.cn
353
LS-5 spectrometer. The excitation (kexc = 350 nm) source
was a xenon lamp. The decay profiles were also recorded
using the same instrument after the samples were sufficient-
ly excited for about 20 min. Prior to the afterglow measure-
ments, samples were exposed to irradiation from an 11-W
conventional tricolor fluorescent lamp.
3. Results and discussion
A typical X-ray diffraction pattern of the resultant
SrAl2O4:Eu,Dy precursor powders are shown in Fig. 1a.
As can be seen, pure monoclinic phase diffraction peaks of
SrAl2O4 are predominant in the XRD patterns, which is
similar with the earlier results [15]. No other product or
starting material was observed, implying that the phase
composition of the precursor powders are all low-tempera-
ture monoclinic phase (a-phase), and the little amount of
doped rare earth ions have almost no effect on the SrAl2O4
phase composition [8]. Fig. 1b shows the diffraction pattern
of phosphor nanoparticles obtained by heating the precursor
powders of SrAl2O4:Eu,Dy at 1100 jC for 2 h. There is no
observable differences between the two diffraction patterns
in Fig. 1a and b, indicating that the pure monoclinic phase
of SrAl2O4 has already formed in the first combustion steps.
In conventional solid-state reactions, the pure SrAl2O4:
Eu,Dy monoclinic phase appears at 1300 jC [6]. Although
no flux is added, SrAl2O4:Eu,Dy phase with high purity can
be obtained at 500 jC through the combustion process to the
starting materials, whereas it is impossible to happen for
solid-state reaction method due to impurities as M3Al2O6 are
formed at lower temperatures. Furthermore, pure single-
phase MAl2O4 (M = Mg, Ca, Sr, Ba and Zn) has already
been prepared by combustion synthesis method [16]. Those
metal aluminates were obtained by the combustion of
corresponding metal nitrate – aluminium nitrate – urea mix-
ture at 500 jC as described above. Furthermore, it has been
also proved that metal aluminates with different structures
such as CaAl2O4, Ca3Al2O6, CaAl12O19 and MgCeAl11O19
can be prepared by just changing the metal nitrate – alumi-
Fig. 1. X-ray diffraction patterns of the SrAl2O4:Eu,Dy: (a) as-prepared, (b)
deoxidized at 1100 jC in active carbon atmosphere.
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354 T. Peng et al. / Materials Letters 58 (2004) 352–356

ninm nitrate – urea ratio in the combustion reaction. The

reason may be attributed to the above 1500 jC of flame
temperature during the combustion synthesis processing
[17]. Moreover, the uniform component in solution phase
is also beneficial for the formation of the pure phase at
relative low temperature. The line broadening feature in Fig.
1 can be seen due to their smaller particle size, indicting that
the phosphor nanocrystallines can be prepared in a far low
temperature (about 500 jC). With the mean crystalline size
of precursor powders and phosphor nanoparticles obtained at
1100 jC deduced according to the Scherrer’s equation
using full-width at the half-maximum (FWHM) data [18],
the calculated crystalline sizes are 12 and 25 nm,
respectively.
The microstructure of the precursor powders and SrAl2-
O4:Eu,Dy phosphor nanoparticles deoxidized at 1100 jC are
studied on their SEM and TEM micrographs (Fig. 2). The
morphology of the precursor powders is unconsolidated,
reflecting the inherent nature of the combustion process
(Fig. 2a). The surfaces of the foams show a lot of cracks,
voids and pores formed by the escaping gases during
combustion reaction. In order to achieve accurate data of
the grain size of SrAl2O4:Eu,Dy precursor powders, its TEM
image is recorded in Fig. 2b. Most of the particles of
SrAl2O4:Eu,Dy precursor powders appear to be irregularly
elliptical with aggregation and an average particle size of
5 – 30 nm (Fig. 2b). The grain size of SrAl2O4:Eu,Dy
phosphor deoxidized at 1100 jC is increased to 15 – 45
nm with some hard agglomeration accompanied with the
formation of necked crystallites, as can be observed from
Fig. 2c. Furthermore, the crystalline size according to
Scherrer’s equation is very closed to the TEM observation,
also implying that the obtained phosphor nanoparticles
have good crystallinity, which is apparently different from
that of SrAl2O4 resulted from solid-state reaction method.
Figs. 3 and 4 show the excitation and emission spectra at
room temperature of SrAl2O4:Eu,Dy phosphor prepared by
solution combustion synthesis and solid-state reaction meth- Fig. 2. SEM and TEM images of SrAl2O4:Eu,Dy. (a) SEM of precursor
ods, respectively. It is observed that the main peaks of powders, (b) TEM of precursor powders, (c) TEM of phosphors deoxidized
excitation spectra of phosphor nanoparticles shift to shorter at 1100 jC in active carbon atmosphere.
wavelength (from 258 to 242 nm, and 323 to 313 nm)
compared with the phosphor resulted from solid-state reac- over, compared with the sample obtained by solid-state
tion method. This may be associated with the quantum size reaction method, the emission maximum peak of phosphor
effect of the phosphor nanoparticles, which increased the nanoparticles shifted to shorter wavelength (from 519 to 513
kinetic energy of the electrons and resulted in a larger band nm). A similar result has also been observed in ultrafine
gap, thus, needing higher energy to excite the luminescent needle-like SrAl2O4:Eu,Dy phosphors reported by Lin et al.
powders [8]. The UV-excited SrAl2O4:Eu,Dy phosphor [8]. The slight blue shift in the emission band may be
nanoparticles at room temperature yielded high bright green attributed to the changes of the crystal field around Eu2 +.
luminescence (kmax = 513 nm) with only one band (Fig. 4). Since the excited 4f65d1 configurations of Eu2 + ion is
The bandwidth was quite large, f 67 nm, but symmetric, extremely sensitive to the change in the lattice environment
indicating only one luminescent centre, which is Eu2 + in contrast to the shielded 4f7 ground configurations due to
luminescence and excitation result from transitions between the shielding function of the electrons in the inner shell, the
the 4f65d1 and 4f7 electron configurations. The resultant 5d electron may couple strongly to the lattice. Hence, the
SrAl2O4:Eu,Dy combustion ash precursor powders has not mixed states of 4f and 5d will be split by the crystal field,
shown this emission spectra, indicating that the active which may lead to the blue shift of its emission peak. The
carbon can effectively deoxidize the Eu3 + to Eu2 +. More- afterglow band (Fig. 4c) had the same position, shape and
中国科技论文在线
T. Peng et al. / Materials Letters 58 (2004) 352–356
Fig. 3. Excitation spectra of SrAl2O4:Eu,Dy phosphors resulting from (a)
solution combustion method, (b) solid state reaction method.
bandwidth as those of the UV-excited spectra, indicating
that the emitting centre is still Eu2 + ion. In the present
system, Eu2 + ions are the luminescent centers, the photo-
excited luminescence is considered to be due the transition
from 5d level to 4f level of Eu2 + and holes in the traps are
responsible for the long afterglow [6]. Therefore, Dy3 +
played an important role and worked as hole traps. The
trap levels lie in between the excited state and the ground
state of Eu2 +. This is because the existence of stable
tetravalent state Dy4 + of this rare earth ion. Moreover,
Dy3 + ion possesses relatively high transfer energies than
any other trivalent rare earth ions. After excitement by the
ultraviolet lights, electrons of Eu2 + ion in the 4f level
transfer to 5d level, and holes were produced from 4f level
to the valence band and Eu2 + ions change to Eu+. Some free
holes created in the valence band of the host were trans-
ported in the conduction band and captured by the Dy3 +
hole traps. Large amounts of Dy3 + is populated, having
captured holes from the valence band, and stay as Dy4 +.
When the excitation source was cut off, some holes captured
by the Dy3 + hole traps were thermally released slowly to
Fig. 4. Emission spectra of SrAl2O4:Eu,Dy phosphors resulting from (a)
solution combustion method, (b) solid state reaction method, (c) afterglow
spectrum of SrAl2O4/Eu,Dy resulting from solution combustion method at
room temperature determined at 2 min after removal of the illumination of
conventional tricolor fluorescent lamp.
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355
valence band, and the released holes travel back of Eu2 +,
finally returning to the ground state of Eu2 + accompanied
with emitting the lights. Furthermore, the hole mobility may
also play an important role and need to be taken into
account. Low rate of hole mobility and electron-hole re-
combination will increase retraping probability and further
slow down the decay process [9].
The decay characteristics of SrAl2O4:Eu,Dy phosphor
indicated that the decay process both of two kinds of
phosphors contained the rapid-decaying process and the
slow-decaying one (Fig. 5). The afterglow of phosphor
nanoparticles, which allowed the time to be visually
recognized ( z 0.32 mcd/m2), lasted for over 16 h after
the excited source was cut off. The initial intensity of
nanometer phosphor (Fig. 5a) is lower than that of the
phosphor powders prepared by the solid-state reaction
method after exciting for 20 min (see also Fig. 4).
Moreover, the phosphor nanoparticles decayed more rap-
idly than that prepared by the solid-state reaction method.
The reason may be that the nanoparticles made the
phosphor crystallize easily and completely during heat-
treatment process as described above, which may lead to
decreasing the amount of defects in the inner phosphor
and fewer crystallographic distortions, as well as shal-
lower trap level than that of phosphor obtained from
solid-state reaction method, so that the relative intensity
of afterglow is lowered and the decay of afterglow is
hastened. In addition, a lot of defects are dispersed on the
surface of phosphors because of the high surface area of
the nanoparticles, and which may result in relatively less
amount of luminescent center Eu2 + in the SrAl2O4 lattice
available for the direct radiation. Therefore, it may result
in the weaker initial intensity of phosphor nanoparticles.
Furthermore, as described above, fast speed of hole
mobility and electron-hole recombination in nanoparticles
with good crystallinity will decrease retraping probability
and further prompt the decay process. Of course, the
Fig. 5. Decay curve of SrAl2O4:Eu,Dy phosphors after exciting for 20 min:
(a) solution combustion method, (b) solid state reaction method (room
temperature 25 jC, excitation time 20 min, source conventional tricolor
luminescent lamp).
中国科技论文在线
356 T. Peng et al. / Materials Letters 58 (2004) 352–356
detailed reasons need to be further investigated, and
relative research is under way.
4. Conclusion
The SrAl2O4:Eu,Dy phosphor nanoparticles can be syn-
thesized by combustion synthesis processing, along with
heating the resultant combustion ash precursor powder at
1100 jC in a weak reductive atmosphere of active carbon.
Analytical results showed that the nanometer phosphors
have pure monoclinic SrAl2O4:Eu,Dy phase, with the aver-
age particles size in the range of 15 – 45 nm. Compared with
the solid-state reaction method, the blue shift of main peaks
of excitation and emission of the nanometer phosphors
occur.
Acknowledgements
Financial support from the State Key Laboratory of Rare
Earth Materials Chemistry and Application of Peking
University and Hubei Province Science and Technology
Commission in China are gratefully acknowledged.
http://www.paper.edu.cn
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