Journal of Luminescence 194 (2018) 446–451

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Journal of Luminescence
journal homepage: www.elsevier.com/locate/jlumin

Synthesis and photoluminescence properties of a novel Sr2Al6O11:Mn4+ red MARK

phosphor prepared with a B2O3 flux
⁎
Takuya Sasaki , Jun Fukushima, Yamato Hayashi, Hirotsugu Takizawa
Department of Applied Chemistry, Graduate School of Engineering, Tohoku University, 6-6-07, Aoba Aramaki, Sendai, Miyagi 980-8579, Japan

A R T I C L E I N F O A B S T R A C T

Keywords: A novel Mn4+-doped aluminate red phosphor Sr2Al6O11:Mn4+ was synthesized by a solid-state reaction, and we
Aluminate investigated its photoluminescence properties. Sr2Al6O11, which has a similar structure to Sr4Al14O25, was
Sr2Al6O11 formed as the main phase after heating alpha-alumina, strontium carbonate, manganese dioxide, and magnesium
Mn4+ phosphor oxide with 2.5% B2O3 at 1000 °C for 12 h or more. The Sr2Al6O11:Mn4+ phosphor exhibited red photo-
Photoluminescence
luminescence with peaks at around 652 and 665 nm, which arise from the spin-forbidden transition of the Mn4+
Boron oxide flux
cation from the 2E to the 4A2 state. The phosphor can be excited by near ultraviolet or blue LED light because it
had a broad excitation band from the near-ultraviolet to the blue light region. The emission intensity was in-
creased by co-doping with Mg2+ cations, which act as charge compensators. The amount of Mg required for the
most effective charge compensation was 10 times the optimum Mn concentration. From these results, we con-
firmed that Sr2Al6O11 could act as the host structure for Mn4+-doped phosphors.

1. Introduction phosphors using near-ultraviolet or blue LED light. Many (oxy)nitride

White light-emitting diodes (LEDs) are becoming more popular and
replacing fluorescent lamps and incandescent bulbs as white light
sources; this is primarily because of their long lifetimes, high effi-
ciencies, and energy saving performance. In addition, they are mercury-
free [1,2]. Commercially available white LEDs comprise a GaN-based
blue LED and a yellow phosphor; typically, this phosphor is cerium-
doped yttrium aluminum garnet (YAG:Ce). The combination of the blue
light emitted by the blue LED and the yellow light emitted by the yellow
phosphor excited by the blue LED produces a pseudo-white light.
However, these LEDs have poor color rendering because of the lack of
red light in their spectra. To improve the color rendering, white LEDs
must contain the three primary colors: red, green, and blue. Some
combinations of various LEDs and phosphors have been designed to
produce high color rendering white LEDs, for example, a blue LED with
red and green phosphors or a near-ultraviolet LED with red, green, and
blue phosphors. Therefore, it is necessary to develop a red phosphor
that is excitable by blue or near-ultraviolet LED for high color rendering
white LEDs.
Tetravalent manganese-activated phosphors have attracted atten-
tion as rare-earth-free, transition metal-activated red phosphors for
white LEDs. To date, many red phosphors, which are excited by the
emission line spectrum (254 nm) of mercury [3–5], for fluorescent
lamps have been reported. However, it can be difficult to excite these
phosphors have an excitation spectrum that matches the emission wa-
velength of near-ultraviolet or blue LED light, for example, CaAl-
SiN3:Eu2+ [6], (Ca,Sr)2Si2N5:Eu2+ [7], and α- or β-SiAlON [8,9].
However, these (oxy)nitride phosphors are synthesized at high tem-
peratures and high nitrogen partial pressures. Furthermore, rare-earth
elements, which are used as the activators in many existing phosphors,
are expensive and unevenly distributed in the Earth's crust. Therefore,
the development of a facile synthetic route to inexpensive phosphors is
required. Mn4+-activated oxide phosphors are expected to be rare-
earth-free red phosphors for high color rendering white LEDs. These
phosphors are excited by the spin-allowed transitions from the 4A2 to
the 2T1 and 2T2 states of Mn4+ and charge transfer transitions from O2-
to Mn4+ in the near ultraviolet to blue region. The phosphors emit red
photoluminescence by the spin-forbidden transition from the 2E to the
4
A2 state of Mn4+. Hence, Mn4+-doped phosphors can be excited by
near ultraviolet or blue LEDs.
In this study, we focused on strontium aluminate (Sr2Al6O11) as a
host material for the Mn4+-activated phosphors. Many aluminates have
been reported as the host materials of Mn4+-doped phosphors, for ex-
ample, CaAl12O19 [10–15], SrAl12O19 [10,15], Sr4Al14O25 [16–21],
Ca2Mg2Al28O46 [22], CaMg2Al16O27 [22], Sr2MgAl22O36 [23,24],
SrMgAl10O17 [25–27], and Ca14Zn6Al10O35 [28–30]. In particular, it
has been reported that the integrated emission intensity of
Sr4Al14O25:Mn4+ is greater than those of α-Al2O3:Mn4+ and

⁎
Corresponding author. Present address: Department of Materials Physics, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya Aichi 464-8603, Japan.
E-mail addresses: tasasaki@aim.che.tohoku.ac.jp, sasaki@mp.pse.nagoya-u.ac.jp (T. Sasaki).

http://dx.doi.org/10.1016/j.jlumin.2017.10.076
Received 12 July 2017; Received in revised form 17 October 2017; Accepted 26 October 2017
Available online 28 October 2017
0022-2313/ <outputStr5>
T. Sasaki et al. Journal of Luminescence 194 (2018) 446–451

Fig. 1. Crystal structures of (a) Sr2Al6O11 and (b) Sr4Al14O25.

SrAl12O19:Mn4+ [16]. In addition, Sr2Al6O11 has a similar structure to
Sr4Al14O25[31]. The crystal structures of Sr2Al6O11 and Sr4Al14O25,
drawn with the program VESTA [32], are shown in Fig. 1. These
compounds consist of a layer of edge-sharing AlO6 octahedra with
corner-sharing tetrahedral AlO4 chains between the AlO6 layers.
Whereas the AlO4 chains of Sr4Al14O25 are linked in a symmetric
fashion, the AlO4 polyhedra of Sr2Al6O11 are linked in zigzag chains. In
the Sr4Al14O25:Mn4+ red phosphor, tetravalent manganese cations,
which are the photoluminescence centers, are located in the octahedral
AlO6 layers. Therefore, we considered that Sr2Al6O11, which has AlO6
layers similar to those of Sr4Al14O25, is a candidate host material for
Mn4+-doped phosphors.
In this paper, we report the synthesis and photoluminescence
properties of a Sr2Al6O11:Mn4+ red phosphor and demonstrate that
Sr2Al6O11 is an excellent candidate as the host structure for Mn4+-
doped phosphors.
radiation). The photoluminescence (PL) excitation and emission spectra
of the specimens were measured at room temperature using a spec-
trofluorometer (JASCO Co., FP-6600) equipped with a Y-44 sharp-cut
filter. The thermal quenching properties were measured by using a
spectrofluorometer (JASCO Co., FP-6500). The quantum efficiency
(QE) was determined using a quantum efficiency measurement system
(Otsuka Electronics Co., Ltd., QE-1000). The particle morphology was
observed by using a field-emission scanning electron microscope (FE-
SEM, Hitachi High-Technologies Co., S4800).
3. Results and discussion
Fig. 2 shows the XRD patterns of Sr2Al6O11:0.1% Mn·Mg, 3zB2O3
synthesized at 1000 °C for 12 h in air, where z represents the molar
ratio of B to Al. The sample with z = 0.0 contained monoclinic SrAl2O4
and Al2O3, but Sr2Al6O11 was not formed without the addition of B2O3.

2. Experimental Sr2Al6O11 Sr4Al14O25 SrAl2O4 Al2O3 SrAl4O7

The Sr2Al6O11:Mn4+ red phosphor was prepared by a solid-state B/Al = 0.10

reaction. The raw materials were powdered SrCO3 (99.9%, Kojundo
Chem. Lab. Co., Ltd.), α-Al2O3 (99.99%, ca. 1 µm, Kojundo Chem. Lab.
Co., Ltd.), MnO2 (99.99%, Kojundo Chem. Lab. Co., Ltd.), B2O3 B/Al = 0.07
(99.995%, Kojundo Chem. Lab. Co., Ltd.), and MgO (99.9%, 0.2 µm,
Wako Pure Chem. Ind. Ltd.). The powders were weighed according to B/Al = 0.05
the formula Sr2(Al1-x-yMnxMgyBz)6O11+9z, where z indicates the ratio of
boron to aluminum. The powders, excluding B2O3, were mixed with
Intensity / a.u.

ethanol using an alumina pestle and mortar. After drying, the powder B/Al = 0.03
mixture was mixed again with the addition of B2O3 to avoid the seg-
regation of B2O3 during drying because B2O3 is soluble in ethanol.
Then, about 0.5 g of the powder mixture was pressed into a 10-mm B/Al = 0.025
diameter pellet at a pressure of 150 MPa. The pellet was placed on a
platinum plate and heated at 1000 °C for 12 h in air using an electric
furnace. For comparison with other host material of SrO-Al2O3 system, B/Al = 0.02
Sr4Al14O25:Mn4+ and SrAl12O19:Mn4+ red phosphors were also pre-
pared by a solid-state reaction. The raw powders for Sr4Al14O25:Mn4+ B/Al = 0.01
and SrAl12O19:Mn4+ were weighed and mixed according to SrCO3:α-
Al2O3:B2O3:MnO2:MgO molar ratio of 2:2.9835:0.15:0.003:0.03 and
SrCO3:α-Al2O3: MnO2:MgO molar ratio of 1:5.967:0.006:0.06, respec- B/Al = 0.00
tively. The pellets were formed by pressing, as described above, and
placed on a platinum plate and heated at 1000 °C and 1600 °C for 12 h 10 20 30 40 50
in air using an electric furnace, respectively. The heated pellets were 2θ / deg.
ground using an alumina mortar and pestle before analysis.
The ground samples were characterized by powder X-ray diffraction Fig. 2. XRD patterns of Sr2Al6O11:0.1% Mn·Mg, 3zB2O3 synthesized at 1000 °C for 12 h in
air.
(XRD) using a powder diffractometer (Rigaku Co., RINT-2200, Cu-Kα

447
T. Sasaki et al. Journal of Luminescence 194 (2018) 446–451

0.025 contained Sr2Al6O11 as the main phase and a trace amount of

Al2O3 as an impurity phase. At z = 0.03, peaks of the Sr4Al14O25 phase
were observed in addition to those of the Sr2Al6O11 and Al2O3 phases.
The XRD patterns of the samples with z = 0.05 and 0.07 exhibited
reflections corresponding to Sr2Al6O11, Sr4Al14O25, and SrAl4O7. On
increasing z above 0.25, the diffraction peak intensities of Sr2Al6O11
and Sr4Al14O25 were decreased and increased, respectively. The XRD
reflections of the Sr4Al14O25 phase alone were observed at z = 0.01.
Although the sample with z = 0.025 contained Al2O3 as the impurity
phase, it contained no SrO-Al2O3 system complex oxide other than
Sr2Al6O11. Therefore, the optimum molar ratio of B to Al for the
synthesis of Sr2Al6O11 is z = 0.025.
Fig. 3 shows the photoluminescence excitation and emission spectra
of Sr2Al6O11:0.1% Mn·Mg, 2.5% B2O3 (z = 0.025) synthesized at
1000 °C for 12 h in air. The sample exhibited red photoluminescence
under near-ultraviolet radiation at 365 nm by UV lamp as shown in the
inset photograph of Fig. 3. Considering the XRD results, it was inferred
Fig. 3. Photoluminescence excitation and emission spectra of Sr2Al6O11:0.1%Mn·Mg, that the red photoluminescence of this sample was due to the Mn4+ in
2.5% B2O3 synthesized at 1000 °C for 12 h in air. The inset photograph is Sr2Al6O11:0.1%
Sr2Al6O11. The excitation spectrum of Sr2Al6O11:0.1% Mn·Mg, 2.5%
Mn·Mg, 2.5% B2O3 under 365 nm UV lamp.
B2O3, monitored at 652 nm, exhibited two broad bands with peaks at
around 300 and 450 nm. The excitation peak at around 300 nm and a
100 shoulder peak at around 330 nm were attributed to the charge transfer
(CT) transition from O2- to Mn4+ and the spin-allowed transition of
Normalized intensity / %

Mn4+ from the 4A2 to the 4T1 state, respectively. The excitation peak at
80 Sr Al O :Mn
around 450 nm derived from the spin-allowed transition of Mn4+ from
Sr Al O :Mn the 4A2 to the 4T2 state coincides with the emissions of blue LEDs. The
60
emission spectrum of Sr2Al6O11:0.1% Mn·Mg, 2.5% B2O3 under 305-nm
excitation contains a narrow band between 610 and 730 nm with peaks
40 SrAl O :Mn
at 652 and 665 nm, which has a full-width at half maximum (FWHM) of
27.6 nm. This band was assigned to the spin-forbidden transition of
20 Mn4+ from the 2E to the 4A2 state.
The XRD results and photoluminescence properties of the sample
0 supported that the host material of this Mn4+-doped phosphor was
200 300 400 500 600 700 800
Sr2Al6O11. If the host structure of this phosphor would be Al2O3, which
Wavelength / nm
was only contained in the sample as impurity phase, the sample should
Fig. 4. Normalized photoluminescence excitation and emission spectra of show red photoluminescence having a peak at about 676 nm [33,34].
Sr2Al6O11:Mn4+, Sr4Al14O25:Mn4+, and SrAl12O19:Mn4+. However, the emission peaks of the sample existed at 652 and 665 nm.
Therefore, it was confirmed that the host material of this phosphor was
The XRD pattern of the sample with z = 0.01 contained reflections Sr2Al6O11. The emission peak of Sr2Al6O11:Mn4+ belongs to the short
corresponding to Sr2Al6O11, SrAl2O4, and Al2O3. At z = 0.02, the peaks wavelength category of the existing Mn4+-doped oxide phosphors [35].
of the monoclinic SrAl4O7 phase were observed in addition to those of The FWHM of Sr2Al6O11:Mn4+ was smaller than that of the existing
the Sr2Al6O11, SrAl2O4, and Al2O3 phases. With increasing z, the dif- Mn4+-doped phosphors, for example, BaMg6Ti6O19:Mn4+ (36 nm)
fraction peak intensities of the Sr2Al6O11 and monoclinic SrAl2O4 [36], Ca2Mg2Al28O46:Mn4+ (39.4 nm), and CaMg2Al16O27:Mn4+
phases increased and decreased, respectively. The sample with z = (35.5 nm) [22].

(a) Sr2Al6O11 :Mn 4+ (b) Sr4Al14 O25 :Mn 4+ (c) SrAl12 O19 :Mn 4+

20 µm 20 µm 20 µm

5 µm 5 µm 5 µm

Fig. 5. SEM images of the fractured surface of (a) Sr2Al6O11:Mn4+, (b) Sr4Al14O25:Mn4+, and (c) SrAl12O19:Mn4+.

448
T. Sasaki et al. Journal of Luminescence 194 (2018) 446–451

Fig. 6. (a) Photoluminescence excitation

(a) (b)
λem = 652 nm λex = ~300 nm and emission spectra of Sr2Al6O11:xMn,
100
2.5%B2O3 synthesized at 1000 °C for 12 h
x = 0.0005 and (b) Mn concentration, x, dependence on
x = 0.001

Relative intensity / %
the relative emission intensity.
x = 0.0015 80
x = 0.002
Intensity / a.u.

x = 0.003
x = 0.004 60
x = 0.005
x = 0.007
x = 0.01 40

20

0
200 300 400 500 600 700 800 0 0.002 0.004 0.006 0.008 0.01
Wavelength / nm Mn concentration, x / -

spectrum of SrAl12O19:Mn4+ was different from that of Sr2Al6O11:Mn4+

Fig. 7. XRD patterns of Sr2Al6O11:0.05% Mn, yMg, 2.5% B2O3 synthesized at 1000 °C for
12 h in air.
Fig. 4 shows the photoluminescence excitation and emission spectra
of the sample, and these of other Mn4+-doped SrO-Al2O3 system
phosphors (Sr4Al14O25:Mn4+ and SrAl12O19:Mn4+). The photo-
luminescence excitation and emission spectrum of Sr2Al6O11:Mn4+ was
different from these of Sr4Al14O25:Mn4+ and SrAl12O19:Mn4+. This
spectral shape indicates that the host material of this phosphor was not
other SrO-Al2O3 system complex oxides but Sr2Al6O11. The excitation
spectrum of Sr4Al14O25:Mn4+, which was a similar structure of
Sr2Al6O11, had two broad bands with peaks at around 340 and 450 nm.
The excitation band of Sr4Al14O25:Mn4+ at around 340 nm consisted of
the CT transition on the shorter wavelength side and the 4A2-4T1
transition on the long wavelength side. Contrary to the excitation band
of Sr2Al6O11:Mn4+, the excitation intensity of the 4A2-4T1 transition
was higher than that of the CT transition in the excitation band of
Sr4Al14O25:Mn4+. The excitation band of Sr4Al14O25:Mn4+ at about
450 nm was ascribable to the 4A2-4T1 transition and existed at the same
wavelength as that of Sr2Al6O11:Mn4+. In contrast, the excitation
and had three broad bands with peaks at around 330, 400 and 470 nm.
These peaks were attributed to the CT, 4A2-4T1, and 4A2-4T2 transitions,
respectively. On the other hand, the emission spectra of
Sr2Al6O11:Mn4+, Sr4Al14O25:Mn4+, and SrAl12O19:Mn4+ was a narrow
band with peaks at 652, 651 and 657 nm, respectively. As mentioned
above, the photoluminescence properties of Sr2Al6O11:Mn4+ differed
from those of Sr4Al14O25:Mn4+ and SrAl12O19:Mn4+.
SEM images of the fractured surface of Sr2Al6O11:Mn4+,
Sr4Al14O25:Mn4+, and SrAl12O19:Mn4+ are shown in Fig. 5. In the (a)
Sr2Al6O11:Mn4+ and (b) Sr4Al14O25:Mn4+, the columnar grains, which
were roughly 1 µm wide and 2–10 µm long, were sintered to form necks
on the addition of B2O3 as a flux. On the other hand, the grains of (c)
SrAl12O19:Mn4+, which has an average diameter size about 2 µm,
showed no significant neck formation. These differences in neck for-
mation are due to the presence or absence of B2O3 as the flux [37].
Fig. 6(a) shows the photoluminescence excitation and emission
spectra of Sr2Al6O11:xMn, 2.5% B2O3 synthesized at 1000 °C for 12 h in
air. Although the excitation and emission peaks of each sample were
almost the same, the excitation and emission intensities differed with
Mn concentration. The relationship between the Mn concentration, x,
and the emission intensity of Sr2Al6O11:xMn, 2.5% B2O3 is shown in
Fig. 6(b). The emission intensity of Sr2Al6O11:Mn4+ increased with
increasing Mn concentration up to x = 0.0005 and decreased drasti-
cally above x = 0.0005 because of concentration quenching. The op-
timal Mn concentration of Sr2Al6O11:Mn4+ (x = 0.0005) was the al-
most the same as that of Sr4Al14O25:Mn4+ [17].
Fig. 7 shows the XRD patterns of Sr2Al6O11:0.05% Mn, yMg, 2.5%
B2O3 synthesized at 1000 °C for 12 h in air. The non-Mg-doped sample,
y = 0.0, contained a trace amount of Al2O3 in addition to Sr2Al6O11.
Although Sr2Al6O11 was the main phase of the sample with each Mg
concentration, impurity phases and the diffraction intensity of them
were increased with increasing Mg concentration. The sample with y =
0.0005 contained trace amounts of SrAl2O4 and Al2O3 in addition to
Sr2Al6O11. Diffraction peaks corresponding to Sr2Al6O11, SrAl2O4,
Al2O3, and SrAl4O7 were observed at y = 0.001–0.01. While the re-
flections arising from SrAl4O7 disappeared, reflections corresponding to
MgAl2O4 appeared at Mg concentrations greater than y = 0.02. As y
increases above 0.02, the diffraction peak intensities corresponding to
SrAl2O4 and MgAl2O4 increased. Therefore, the addition of excess Mg2+
reduces the formation of Sr2Al6O11. Fig. 8(a) shows the photo-
luminescence excitation and emission spectra of Sr2Al6O11:0.05% Mn,
yMg, 2.5% B2O3 synthesized at 1000 °C for 12 h in air. Although the
spectral shape did not change by Mg co-doping, intensity of the ex-
citation and emission spectra varied with the amount of doping Mg2+
because of the effects of charge compensation. The relationship

449
T. Sasaki et al. Journal of Luminescence 194 (2018) 446–451

180 Fig. 8. (a) Photoluminescence excitation

(a) λ = 652 nm y=0 λ = ~300 nm (b) and emission spectra of Sr2Al6O11:0.05%
em
y = 0.0005 ex 160 Mn, yMg, 2.5%B2O3 synthesized at 1000 °C
y = 0.001 for 12 h and (b) Mg concentration, y, de-
y = 0.002 pendence on the relative emission intensity.
140

Relative intensity / %
y = 0.005
y = 0.01
Intensity / a.u.

y = 0.02 120
y = 0.03
y = 0.04 100
y = 0.05
80

60

40

20

0
200 300 400 500 600 700 800 0 0.01 0.02 0.03 0.04 0.05
Wavelength / nm Mg concentration, y / -

Fig. 9. (a) Photoluminescence emission

(a) 25 °C 100 (b) spectra of Sr2Al6O11:0.05% Mn, 0.5% Mg,
λex = 308.5 nm
50 °C Sr2Al6O11 2.5% B2O3 from room temperature to 200 °C
Integrated PL intensity / %

75 °C and (b) the relationship between the tem-

Sr4Al14O25
80 perature and the integral emission intensity
100 °C
for Sr2Al6O11:0.05% Mn, 0.5% Mg, 2.5%
125 °C
Intensity / a.u.

B2O3, and Sr4Al14O25:0.05% Mn, 0.5% Mg,

150 °C 5% B2O3.
175 °C 60
200 °C

40

20

0
500 550 600 650 700 750 800 25 50 75 100 125 150 175 200
Wavelength / nm Temperature / °C

between the Mg concentration, y, and emission intensity of
Sr2Al6O11:0.05% Mn, yMg, 2.5% B2O3 is shown in Fig. 8(b). The
emission intensity increased by 70% with increasing Mg concentration,
up to y = 0.005, while it remained constant above y = 0.005. The
optimum Mg concentration, y = 0.005, was ten times the optimum Mn
concentration, x = 0.0005. In general, when tetravalent manganese
cations occupy the sites of trivalent cations such as Al3+, either some
Mn4+ becomes Mn2+ or lattice defects occur, thereby maintaining
electrical neutrality. The formation of Mn2+ or other defects causes a
decrease in the emission intensity. Therefore, to increase the emission
intensity, charge compensation is necessary. This is achieved by co-
doping the phosphor with Mn4+ and monovalent or divalent cations. It
is expected that the effect of the charge compensation will be most
effective when the co-doped cation is located in a cation site close to
Mn4+. The optimum concentration of Mn as an activator in Sr2Al6O11, x
= 0.0005, corresponds to a trace amount. Therefore, the co-doping of
Mn4+ with Mg2+ requires a higher concentration of the latter than the
former so that Mg2+ cations will neighbor Mn4+ cations in the lattice.
From the reason above, it was inferred that the optimum Mg con-
centration was ten times the optimum Mn concentration. The external
and internal quantum efficiency (QE) of the Sr2Al6O11:0.05% Mn, 0.5%
Mg, 2.5% B2O3 phosphor under ultra-violet irradiation at 365 nm were
8.39% and 44.4%, respectively. Although this value is lower than those
of CaAl12O19:Mn4+ (~63%) and Sr2MgAl22O36:Mn4+ (~80%) [23], it
is higher than those of CaMg2Al16O27:Mn4+ (35.6%) [38] and
Mg2TiO4:Mn4+ (38.3%) [39]. In addition, the absorptance under ultra-
violet irradiation at 365 nm was 19.0%. This absorptance is lower than
that of the rare earth phosphor [8]. Since there is a correlation between
absorptance and QE, an increase in absorption rate contributes to an
increase in QE. In general, the absorption rate is affected by various
factors, for example, the particle size, morphology, and dopant con-
centration. Therefore, the quantum efficiency of the present material
could be improved by optimizing these factors.
To investigate the thermal quenching properties, the photo-
luminescence emission spectra of Sr2Al6O11:0.05% Mn, 0.5% Mg, 2.5%
B2O3 and Sr4Al14O25:0.05% Mn, 0.5% Mg, 5% B2O3, for comparison,
were measured from room temperature to 200 °C. Fig. 9(a) shows the
photoluminescence emission spectra of Sr2Al6O11:0.05% Mn, 0.5% Mg,
2.5% B2O3 from room temperature to 200 °C. The photoluminescence
emission intensity decreased with increasing measurement temperature
because of thermal quenching. The relationship between the tempera-
ture and normalized photoluminescence emission intensity of
Sr2Al6O11:0.05% Mn, 0.5% Mg, 2.5% B2O3 and Sr4Al14O25:0.05% Mn,
0.5% Mg, 5% B2O3 is shown in Fig. 9(b). The emission intensity of
Sr2Al6O11:Mn4+ decreased earlier compared to that of
Sr4Al14O25:Mn4+ until 75 °C. However, the emission intensity of
Sr2Al6O11:Mn4+ was higher than that of Sr4Al14O25:Mn4+ at tempera-
tures greater than 75 °C. The major difference between Sr2Al6O11 and
Sr4Al14O25 is the number of AlO4 polyhedra in the chain of AlO4
polyhedra and their linkages. These structural differences result in
differences in the thermal quenching properties, and it was more dif-
ficult to thermally quench Sr2Al6O11:Mn4+ than for other aluminate

450
T. Sasaki et al.
Mn4+ phosphors, for example, Ca2Mg2Al28O46:Mn4+ [22], CaA-
l4O7:Mn4+ [40], and Lu3Al5O12:Mn4+ [41].
4. Conclusion
A novel strontium aluminate phosphor, Sr2Al6O11:Mn4+, was syn-
thesized by a solid-state reaction. The addition of B2O3 is necessary for
the synthesis of Sr2Al6O11, and the optimum molar ratio, z, of B to Al is
0.025. From XRD pattern of the sample with z = 0.025 and the com-
parison with other phosphors in SrO-Al2O3 system complex oxide, it
was confirmed that Sr2Al6O11 was the host material for Mn4+-doped
red phosphor. This phosphor exhibited red photoluminescence at
around 652 nm due to the 2E → 4A2 spin-forbidden transitions of the
Mn4+ ion induced by excitation with near-ultraviolet or blue light;
thus, this phosphor can be excited by near ultraviolet or blue LEDs. The
optimum concentrations of the Mn activator and Mg charge compen-
sator are x = 0.0005 and y = 0.005, respectively. The internal
quantum efficiency of Sr2Al6O11:0.05% Mn, 0.5% Mg, 2.5% B2O3 was
44.0%. These results suggest that Sr2Al6O11 can be used as the host
structure for Mn4+-doped red phosphors.
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