A New Long Phosphorescent Phosphor with High Brightness,

SrAI2O4:Eu2tD/
1. Matsuzawa, Y. Aoki, N. Takeuchi, and Y. Murayama
Nemoto and Company, Limited, Research and Development Center, 4-10-9 Takaido-higashi, Suginami-ku,
Tokyo 168, Japan

ABSTRACT
A green emitting SrAl2O4:Eu2,Dy2 phosphor with very bright and long lasting phosphorescence has been newly
developed. The incorporation of Dy3 ion into the SrAl2O4:Eu2 system as an auxiliary activator dominates the phospho-
rescence, thermoluminescence, and photoconductivity characteristics of the phosphor to a large extent. Evidence is pre-
sented for the mechanism that the phoshorescence is ascribed to the photoconductivity due to holes, and to the trapping
and thermal release of the holes by Dy3 ions in the system. The incorporation of the Dy2 ion forms a highly dense trap-
ping level located at a suitable depth in relation to the thermal release rate at room temperature, thus producing the very
bright and long phosphorescence.

Introduction luminescence of the new phosphor have been examined. In

ZnS:Cu phosphor has been well known as a long phos-
phorescent phosphor and used in a variety of applications
since the beginning of this century. This phosphor shows
green emission peaking at 530 nm which suits the visual
perception of the human eye very well. However, it is not
bright enough for many applications and does not main-
tain its phosphorescence for more than a few hours.
Therefore, in order to sustain phosphorescence, radioiso-
topes, such as tritium (H-3) and promethium (Pm-l47),
have had to be added to luminous paints comprising this
phosphor. Such paints have been used for some applica-
tions like luminous watches and clocks. Because of safety
and environmental considerations, however, there is a
serious demand for the development of a radioactive-free
luminous paint at this time.
Meanwhile, the SrAl2O4:Eu2 phosphor has been known
to be a green phosphor with an emission peak at 520 nm.
Studies on this phosphor were mostly performed in the
1960s and early 1970s mainly for lamp and cathode-ray
tube (CRT) applications.1-3 Palilla et al. 2 have shown that
the phosphor exhibits initial rapid decay followed by long
persistence at very low light level. Abbruscato2 prepared
nonstoichiometric (excess alumina) SrAl2O4:Eu2 phos-
phor samples. These exhibit brighter luminescence com-
pared to the stoichiometric SrAl2O4:Eu2 phosphor under
ultraviolet (UV) and cathode-ray excitation as well as
higher level persistence which lasts for a few seconds. It
was suggested that the persistence of the phosphorescence
is due to the trapping mechanism involving hole conduc-
tion, and the Sr21 vacancy was presumed to be a hole trap
in the phosphor crystalline structure.3
It is known that in certain phosphors which involve a
trapping mechanism, such as phosphorescent phosphors,
thermoluminescent phosphors, and infrared stimulable
phosphors, their optical characteristics are to a large ex-
tent influenced by the incorporation of auxiliary activa-
tors. For example, the incorporation of Co into the ZnS:Cu
system delays the phosphorescence decay,4 and the incor-
poration of Sm2 into the SrS:Eu2 system causes the
increase of the infrared-stimulated luminescence,2 while
the incorporation of Cu and P into LiF:Mg system grves
rise to the intense thermoluminescence.6
In order to develop a luminous paint which uses a very
long phosphorescent phosphor and does not need radioac-
tive substances, we have investigated in the present work,
ways to improve phosphorescence characteristics of the
SrAl2O4:Eu2 phosphor by means of the incorporation of
auxiliary activators, in particular various trivalent rare-
earth ions. As a result, we have succeeded in developing a
new phosphor SrAl2O4:Eu2 ,Dy3 which shows extremely
bright and long phosphorescence. The phosphorescence of
this new phosphor is so bright and long lasting that it can
be perceived almost throughout the entire night. Optical
characteristics including photoconductivity and thermo-
addition, the mechanism of the very long phosphorescence
has been discussed and elucidated.
Experimental
Phosphors were prepared by calcining appropriate mix-
tures of SrCO3, A1203, Eu203, oxide of lanthanide elements
(except Eu and Pm), and B203 as a flux in a mildly reduc-
ing atmosphere at 1300°C for 1 h. The products were
ground and sieved through a 200 mesh screen in order to
obtain a uniform particle-size distribution. The mean
diameters of the phosphor samples prepared were within
the range of 20 to 30 p.m. Phosphors were examined by the
x-ray diffraction analysis and found to have well-crystal-
lized tridymite SrAl2O4 structure. When the phosphors
were prepared in this manner, the introduction of Dy or
Nd ion as an auxiliary activator has been found to give rise
to remarkably intense phosphorescence. The optimum
concentrations of the activators for the phosphors are 1
mole percent (mb) of Eu, and 2 mb of Dy or 1 mb of Nd.
The x-ray examinations also revealed that either DyA1O3
or NdA1O2 was produced as a by-product in the phosphor
samples when the introduced concentrations of auxiliary
activators were higher than 5 mfo. Since the valence state
of Dy (or Nd) in the by-products is trivalent, it is most
likely that in this system, Dy (or Nd) ions are present in the
trivalent state.
For photoconductivity measurements, phosphor sam-
ples were pressed and sintered in a reducing atmosphere
into 1 x 5 x 5 mm shape, and a pair of electrodes was fab-
ricated on the surface using Ag conducting paint. The gap
between the electrodes was 5 mm. Photocurrent by UV
excitation was measured and recorded under 400 V dc
supply.
Results
Figure 1 shows emission and excitation spectra of
SrAl2O4:Eu2Dy3 phosphor. Independently of the exis-
tence or nonexistence of the auxiliary activators, the phos-
phor samples exhibit broad band emission spectra peaking
at 520 nm. It is noted that the emission spectrum is a mir-
ror image of the excitation spectrum. The emission and
excitation are attributed to the 4f-5d transition of Eu2.
Three excited levels may possibly exist, since two shoul-
ders are observed at 270 and 330 nm in addition to the
maximum at 365 nm on the excitation spectrum.
Phosphorescence characteristics, after the removal of
light excitation, have shown that the incorporation of Dy3
or Nd3 as an auxiliary activator leads to a remarkable
increase in the phosphorescence as shown in Fig. 2.
Thermoluminescence (TL) glow curves of the newly pro-
duced phosphors above room temperature are compared to
that of SrAl2O4:Eu2 phosphor as shown in Fig. 3. The
SrAl2O4:Eu2,Dy3 and SrAl2O4:Eu2,Nd3' phosphors are

2670 J. Electrochem. Soc., Vol. 143, No. 5, August 1996 The Electrochemical Society, Inc.

Downloaded on 2019-05-16 to IP 164.67.163.3 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 J. Electrochem. Soc., Vol. 143, No. 8, August 1996 The Electrochemical Society, Inc. 2671

Excitation Emission
100
>.
1-'
In
C m
a,
C

a, 50 (0
C
a)
.4J +1
(5 C
a,
-J
I a,
0
.
>
200 300 400 500 600 700 4-1
(5
Wavelength (nm)
a,
Fig. 1. Emission and excitation spectra of the SrAI2O4:Eu',Dy
phosphor.
0
0 50 100 150 200 250
found to have new large TL distributions with their max- Temperature (°C)
ima at 75 and 60°C, respectively.
Abbruscato3 reported that the SrAl2O4:Eu2 phosphor Fig. 3. Thermoluminescence glow curves measured with the heat-
was photoconductive under UV and x-ray excitation. The ing rate of 2°C/s. The heating started 1 mm after a 10 mm expo-
new SrAl2O4:Eu2,Dy3 phosphor also exhibited the photo- sure to 200 lx of D6, light. A: SrAI2O4:Eu2; B: SrAl2O4:Eu', Dy'; C:

conductivity phenomenon. The excitation spectrum for the SrAl2O4: Euz*,Nd3.

photoconductivity of the phosphor was found to coincide
very closely with that for photoluminescence. As shown in
Fig. 4, the phosphor shows initial rapid decay followed by
the long persistence of photocurrent after the removal of
UV light, which is very similar to the decay characteristics
of the phosphorescence. As shown in the figure, it also
exhibits a thermally stimulated photocurrent when heated
during this persistence. The peak temperature observed
using the heating rate of 6°C/s is about 80°C, which is very
close to the TL glow peak temperature.
Abbruscato3 carried out Hall-effect measurements for
the SrAl2O4:Eu2 phosphor under UV excitation, and iden-
tified the conducting species to be a hole. In order to con-
firm the charged species responsible for the photoconduc-
tivity of the newly produced SrA12O4:Eu2,Dy3 phosphor,
we have conducted the photocurrent measurements under
nonuniform illumination7 using 365 nm UV light. Namely,
1000
C.)
the photocurrent was measured under the illumination of
the half-portion of the sample close to either the negative
or positive electrode, and the photocurrent intensity was
compared. It was found that the photocurrent under illu-
mination in the vicinity of the negative electrode was more
than three times higher than that for the vicinity of the
positive electrode. This clearly indicates that the charged
species is a hole, and the photoconductivity of
SrAl2O4:Eu2,Dy3 is due to the motion of holes in the
valence band. The photoconductivity was found to de-
crease at low temperatures. The temperature dependence
from liquid nitrogen temperature is shown in Fig. 5. The
photocurrent shows a rapid increase from 100 to 200 K
and a subsequent slow increase up to room temperature.
The activation energy for the photoconductivity was esti-
mated from the Arrhenius' equation to be 0.03 eV.
Discussion
The incorporation of Dy3 or Nd3 ions as an auxiliary
activator into the SrAl2O4:Eu2 system causes very intense
and long phosphorescence. The TL glow curves and ther-
mally stimulated photocurrent of the phosphors provide
evidence that the incorporation of these ions form new

100
0
C.)
C 200
(5
C
E .
C
2
100
4-I
10 C
I,
1 41
(5
a, I-
4-I C,
0
4-I
a,
a
0
-C
E
0
0 F-

5 10
0
100 1000 100 200 300 400 500 600
Time (min) Time (s)
Fig. 2. Phosphorescence characteristics measuredat 22°C after Fig. 4. Photocurrent under 365 nm UV excitation, decay charac-
10 mm exposure to 200 lx of D light ( the standard light with the
teristics of photocurrent after the removal of UV light, and ther-
color temperature of 6504 K). A: SrAJ,O4:Eu2, B: SrAl,O4:Eu', mally stimulated photocurrent observed for the SrAl2O4:Eu',D?°
Dy3; C: SrAl,O4:Eu',Nd3; D: commercially used ZnS:Cu,Co. phosphor.

Downloaded on 2019-05-16 to IP 164.67.163.3 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 2672 J. Electrochem. Soc., Vol. 143, No.8, August 1996 The Electrochemical Society, Inc.
200
m shown any remarkable effects on the phosphorescence
C the trapping levels formed by these ions are located at
100 200
Temperature (K)
Fig. 5. Temperature dependence of the photoconductivity under
LW excitation for the SrAI2O4:Eu2,Dy phosphor.
trapping levels within the system. Since the photocurrent
in this system is produced by holes, these ions surely act as
hole traps. The glow peak temperatures of the
SrAl2O4:Eu2,Dy and SrA2O4:Eu2,Nd3 phosphors are
75 and 60°C, respectively, when heated with the heating
rate of 2°C/s (Fig. 3). The trapping level of the
SrAl2O4:Eu2,Dy3 phosphor is located a little deeper than
that of the SrAl2O4:Eu2,Nd3 phosphor, which results in
relatively longer phosphorescence. The depth of hole trap-
ping levels for the SrAl2O4:Eu2,Dy phosphor was exam-
ined by measuring glow peak temperatures using the vari-
able heating rate method proposed by Hoogenstraaten,4
and was found to be 0.65 eV.
In order for phosphorescent phosphors to exhibit long
phosphorescence at room temperature, it is crucial to have
trapping levels located at a suitable depth in relation to
the thermal release rate at room temperature. In particu-
lar, if the depth of trapping levels is too shallow in this
relation, the phosphor would show fast decay which does
not last for long time. Contrarily, if it is too deep, the phos-
phor would no longer show phosphorescence at room tem-
perature. The l)y3 incorporation into the system as an
auxiliary activator is, therefore, thought to create the hole
trapping levels at the optimal depth of 0.65 eV to show the
long phosphorescence at room temperature.
The phosphorescence intensities of the new phosphors
are dependent on the concentrations of the auxiliary acti-
vators. When using 1 m/o of Eu2 concentration, the inten-
sities reached the maxima at about 2 mb of Dy3 and
1 mb of Nd3, respectively. We feel that this is due to the
difference of the solubiity in the system between the two
ions. As the ion radius of Dy3 is a little smaller than that
of Nd3, D? may be more soluble into the system than
Nd3. The Dy3 incorporation with higher concentration
forms a relatively higher number of trapping levels in the
system, resulting in brighter phosphorescence compared to
the Nd3 incorporation. The by-product of DyA1O3 or
NdA1Q3 is produced when the redundant ions are intro-
duced over the soluble limits.
As mentioned already, incorporated D? and Nd3 act
as hole traps. This fact is reasonable, because the tetrava-
lent state of these rare earths, Dy4 and Nd4, is stably
existent as is known in some phosphors like Cs3DyF7:Dy48
or Cs3NdF7:Nd4. The tendency of trivalent rare-earth
ions as to whether they are easily oxidized or reduced is
dominated by the 4f —p 5d transition energy (or the ioniza-
tion energy) and the charge-transfer energy from the host
anion to the rare-earth ion.'° From these points of view
trivalent rare-earth ions are divided into three or four
groups. Ce3, Pr3, and Th3 are known to be easily oxi-
dized. They are characterized by very low 4f —° 5d transi-
tion energies and very high charge-transfer energies. D?
and Nd3 have relatively low 4f — Sd transition energies
Downloaded on 2019-05-16 to IP 164.67.163.3 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
and relatively high charge-transfer energies. Therefore,
they act as hole traps. From the above points, it is natural
to presume that Ce3, Pr, and Th3 ions would also act as
effective hole traps. However, their incorporations into the
SrA12O4:Eu2' system as auxiliary activators have not
characteristics at room temperature. This fact implies that
inappropriate, that is, too deep or too shallow, depths in
relation to the thermal release rate at room temperature.
Among the trivalent rare-earth ions, Dy3 ion can form
highly dense trapping levels with the most suitable depth
in the system to show the brightest and longest phospho-
rescence at room temperature.
The energy level diagram of the SrAl2O4:Eu2, D?
phosphor is proposed as shown in Fig. 6 on the basis of the
above-mentioned experimental results. The bandgap ener-
gy of the SrA12O4 host is estimated to be 6.5 eV from the
low energy edge of the Eu2 excitation spectrum due to the
host lattice absorption.2 The phosphorescence mechanism
is interpreted as follows. Upon the exposure to UV light
(365 nm), the direct excitation of Eu2 due to the 4f —' Sd
transition occurs, but the host is not excited. Results of
photoconductivity measurements clearly indicate that the
hole produced at the 4f ground state level is released ther-
mally to the valence band. In this process Eu2 is assumed
to be converted into Eu't The depth of iXE of the 4f ground
state level of Eu2 is estimated as follows. In the thermal
equilibrium between the Eu2 level and the free hole in the
valence band, the Fermi level for holes is presumably
located in the middle between the Eu2 level and the top of
the valence band. Therefore, the number of free holes
should be proportional to exp (—tE/2kT). The observed
activation energy for the photoconductivity increase from
the liquid nitrogen temperature is 0.03 eV. Then E is
0.06 eV. The released hole migrates through the valence
band and is trapped by a Dy3 ion, which is consequently
assumed to be converted into Dy4. Alter UV excitation
has ceased, the hole is re-excited thermally and liberated
to the valence band. The depth of the trapping level is
0.65 eV. The hole migrates to the excited Eu' and is cap-
tured. Consequently the recombination takes place, giving
rise to the phosphorescence.
An attempt has been made using the CaAl2O4:Eu2 sys-
tem known as a blue emitting phosphor with an emission
peak at 440 nm.2 Various trivalent rare-earth ions were
introduced as auxiliary activators into the system in a sim-
ilar manner, and phosphorescence characteristics were
investigated. As a result, in this case, the incorporation of
Nd3 was found to produce extremely bright and long blue
phosphorescence. The phosphor was also found to have a
large TL distribution with a maximum at 90°C on heating
from room temperature with the heating rate of 2°C/s. It is
quite analogous to the Dy3 introduction into the
SrAl2O4:Eu2 system. Namely, in the CaAl2O4:Eu2 system
Eu — Eut
6.52eV
Fig. 6. Energy level diagram for the SrAI2O4:Eu2,Dy3' phosphor.
 J. Electrochem. Soc., Vol. 143, No.8, August 1996 The Electrochemical Society, Inc.
Nd3 ions form highly dense trapping levels with a depth
suitable for exhibiting the long phosphorescence at room
temperature.
Since the newly produced green phosphor SrAl2O4:Eu2,
Dy3 has extremely bright phosphorescence, it is useful to
compare this phosphor with the ZnS:Cu,Co phosphor
which is presently commercially used for long afterglow
materials. ZnS:Cu,Co is a green phosphor with the emis-
sion peak at 530 nm. As is shown in Fig. 2, both the bright-
ness and decay time of the phosphorescence of the new
phosphor are more than ten times better than those of the
conventional ZnS:Cu,Co phosphor. It is well documented
that the lower limit of the light perception of the dark-
adapted human eye is 0.0032 mcd/m2. The standard
accepted by the escape route markings industry is 100
times higher than this value, i.e., 0.32 mcd/m2. The newly
developed phosphor maintains its phosphorescence inten-
sity above this level for well for over 30 h.
Using a luminous paint prepared by the new phospho-
rescent phosphor, luminous clock dials were fabricated
and compared to conventional luminous dials made by
ZnS:Cu phosphor with radioactive substance 147Pm of
2 MBq. As a result, the new phosphorescent phosphor
paint on the dials was found to maintain a much brighter
luminance level than the radioactive luminous paint even
10 h after 20 mm exposure to 125 lx of white fluorescent
lamp light. This result indicates that the new phosphor
cannot only replace the radioactive luminous paints but
presents a much better performance. In addition to the
superior phosphorescence characteristics, the new phos-
phor further shows excellent light fastness under exposure
to UV light. This will surely broaden the scope of its usage
by making new applications feasible.
Conclusions
A new green long phosphorescent phosphor
SrA12O4:Eu2,Dy3 has been developed. The phosphores-
cence characteristics are interpreted by the mechanism of
Downloaded on 2019-05-16 to IP 164.67.163.3 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
2673
photoconductivity due to holes and by the trapping and
thermal release of holes. It is shown that Dy3 ion intro-
duced as an auxiliary activator acts as the hole trap in the
system and creates the highly dense trapping level located
at a suitable depth in relation to the thermal release rate
at room temperature. Thus, very bright and long lasting
phosphorescence is produced. An analogous phenomenon
has been observed when the Nd3 ion is incorporated into
blue-emitting CaAl2O4:Eu2 system, and long phosphores-
cence is caused.
Acknowledgment
The authors are grateful to Professor Emeritus S.
Shionoya of The University of Tokyo for useful discussions
on the phosphorescence mechanism and to Professor H.
Yamamoto of Tokyo Engineering University for photocon-
ductivity measurements and helpful discussions.
Manuscript submitted Jan. 22, 1996; revised manuscript
received May 22, 1996.
Nemoto and Company Limited, assisted in meeting the
publication costs of this article.
REFERENCES
1. G. Blasse and A. Bril, Philips Res. Reps., 23, 201
(1968).
2. F. C. Palilla, A. K. Levine, and M. R. Tomkus, This
Journal, 115, 642 (1968).
3. V. Abbruscato, ibid., 118, 930 (1971).
4. W. Hoogenstraaten, Philips Res. Reps., 13, 515 (1958).
5. F. Urbach, D. Pearlman, and H. Hemmendinger, J.
Opt. Soc. Am., 36, 372 (1946).
6. T. Nakajima, Y. Murayama, T. Matsuzawa, and A.
Koyano, Nucl. Instrum. Methods, 157, 155 (1978).
7. M. Tabei, and S. Shionoya, J. Lumin., 15, 201 (1977).
8. L. P. Varga, .1. Chem. Phys., 48, 139 (1968).
9. L. P. Varga, ibid., 49, 4674 (1968).
10. C. K. Jergensen, R. Pappalardo, and E. Rittershaus, Z.
Naturforsch., 20a, 54 (1964).