Ceramics International 42 (2016) 1301113017

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Effect of H3BO3 ux on the morphology and optical properties of

Sr2MgAl22O36:Mn4 red phosphors for agricultural light conversion
lms
Haiming Zhang, Haoran Zhang, Jianle Zhuang, Hanwu Dong, Yue Zhu, Xiyun Ye,
Yingliang Liu n, Bingfu Lei n
Guangdong Provincial Engineering Technology Research Center for Optical Agricultural, College of Materials and Energy, South China Agricultural University,
Guangzhou 510642, China

art ic l e i nf o

a b s t r a c t

Article history:
Received 12 March 2016
Received in revised form
3 May 2016
Accepted 13 May 2016
Available online 16 May 2016

H3BO3 was added during the preparation of Sr2MgAl22O36:Mn4 phosphors by a high-temperature solidstate reaction method. The inuence of H3BO3 ux on the crystal structure, particle morphology and
photoluminescence properties of the Sr2MgAl22O36:Mn4 phosphors was investigated by employing
X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence spectroscopy, respectively. The results indicate that adding H3BO3 ux can improve the luminescence intensity
and morphology, and reduce the synthesis temperature of the Sr2MgAl22O36 phosphor. The formation
temperature of pure-phase Sr2MgAl22O36 was signicantly decreased when H3BO3 ux as introduced.
The excited state lifetime of the Sr2MgAl22O36:1.2 mol% Mn4 phosphor by the addition of 2.0 wt% H3BO3
was  1.02 ms. We demonstrated the potential of these phosphors to enhance sunlight harvesting by
agricultural light conversion lm testing. We propose that lms containing the Sr2MgAl22O36:1.2 mol%
Mn4 phosphor can be applied to increase the production of agricultural plants.
& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords:
Phosphors
Photoluminescence
Flux
Light conversion lm

1. Introduction
In the 21st century, the world is faced with an energy crisis. To
maintain sustainable economic development, it is very important
to improve the efciency of energy consumption. Solar energy is
widely accepted as a free, abundant and endlessly renewable
source of clean energy. Countless efforts have been dedicated to
develop methods to leverage this cheap energy source. The agricultural light conversion lm, as an important factor in plant
production, can signicantly improve the land utilization rate,
production efciency and economic efciency. We know that
plants harness solar energy via photosynthetic processes to produce sugar and other life-essential compounds [1]. Agricultural
crops harvest sunlight primarily through green-pigment chlorophyll antenna complexes. However, these compounds only absorb blue and red light, leaving the other components of the solar
spectrum unused. Converting unused sunlight to blue and red
light is a valuable method to improve the sunlight conversion efciency of the photosynthetic process [2]. The addition of a light
conversion agent to the lms can greatly improve the utilization of
n

Corresponding authors.
E-mail addresses: tliuyl@163.com (Y. Liu), tleibf@scau.edu.cn (B. Lei).

http://dx.doi.org/10.1016/j.ceramint.2016.05.076
0272-8842/& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

sunlight for crops and thus increase agricultural production. Currently, the function of light conversion can be achieved by adding
the sunlight conversion agent to a plastic lm. This type of agricultural light conversion lm requires blue or red phosphors with
a high quantum efciency. A large number of red- and blueemitting phosphors excited by NUV light, such as CaZnOS:Eu2 ,
MZnOS:Mn2 (M Ca, Ba), KBaBP2O8:Eu3 , M2Si5N8:Eu2
(M Ca, Sr and Ba), NaSrBO3:Ce3 , Ba5(BO3)2(B2O5):Sm3 , have
been reported and generally possess excellent chemical and physical stabilities [311]. Among the red-emitting phosphors, the
most used activators are Eu2 and Eu3 , followed by Ce3 and
Sm3 , among others. Noticeably, most of these rare earth ions are
very expensive, and some of their chlorides, citrates, and oxides
are toxic and harmful, which substantially limits their widespread
application. At the same time, a high demand also stimulates the
search for rare-earth ion doping schemes, for instance,
Eu2 -doped oxynitrides and nitrides have to be synthesized under
high-temperature, high-pressure, or reducing conditions. Additionally, for Eu3 - and Sm3 -doped red phosphors, the sharp
absorption peaks in the UV region limit their application in agricultural light conversion lms because of their low energy converting efciency [12]. Consequently, research into environmentfriendly, cost-effective and rare-earth-free phosphors that can be
prepared at relatively low temperatures and in air remains an

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H. Zhang et al. / Ceramics International 42 (2016) 1301113017

important issue. As a transition metal ion, Mn4 has been widely

used as an activator for red phosphors. The typical spin-forbidden
2
Eg-4A2g transition is capable of generating a bright red emission
with a high quantum efciency [13]. Thus, for example, the
Mg-germanate:Mn4 phosphor has been applied as a color correcting phosphor in high-pressure mercury vapor lamps and in
uorescent lamps to provide light for plant growth. On the other
hand, phosphors such as 3.5MgO  0.5MgF2  GeO2:Mn4 and
ZnS:Mn2 , contain no rare-earth ions. However, toxic and harmful
elements, such as arsenic (As) and sulfur (S), in phosphors have a
long-term adverse effect on the environment [14,15]. Recently, a
novel
highly
efcient
red-emitting
Sr2MgAl22O36:Mn4
4
(SMA:Mn ) phosphor has been investigated, and is regarded as a
potential phosphor for UV-based W-LEDs [16]. Based on the d-d
transitions of the manganese ion with a 3d3 electron conguration, Mn4 -doped Sr2MgAl22O36 has been identied as a red
phosphor with a broad absorption band in the visible region and
superior chromaticity in the deep red region. However, to meet the
practical application of current agricultural light conversion lms,
it is necessary to further enhance the luminescent intensity. At the
same time, a conventional SMA:Mn4 phosphor is prepared by
solid-state methods at temperatures above 1400 C, which leads to
large particle sizes and hard particle agglomerates. The luminescent efciency and stability of phosphors can be reduced due to
the irregular shape of particles and crystal damage by subsequent
ball milling. Therefore, it would be worthwhile to synthesize
SAM:Mn4 at a relatively lower temperature. There have been
many research efforts directed towards the development of promising methods and the improvement of the luminescent intensity. To sufciently improve the luminescent intensity and
morphology, while reducing the reaction temperature, uxes are
used to stimulate the diffusion of ions and the formation of a host
lattice at a low temperature [17]. It has become a popular research
topic to investigate the effect of uxes on the properties of luminescent materials.
In this paper, we prepared SMA:Mn4 phosphors by a hightemperature solid-state reaction method using H3BO3 as the ux.
The effects of the H3BO3 ux on the crystal structure, morphology
and photoluminescence properties of SMA:Mn4 phosphors were
investigated. The results suggest that adding H3BO3 ux improves
the morphology and luminescent intensity, and reduces the crystallization temperature. In addition, agricultural light conversion
lms were fabricated by blending SMA:Mn4 phosphor with
polyethylene. We propose that SMA:Mn4 phosphors are suitable
as potential light conversion agents for application in agricultural
functional lms.

2.2. Characterizations
The crystal structure of the SMA:1.2 mol% Mn4 phosphor was
determined by XRD (Philips Model PW1830) with Cu-K radiation
( 1.5406 ) at 36 kV and 30 mA. A scan rate of 0.02/s was applied to record the XRD pattern. The morphology of the
SMA:1.2 mol% Mn4 phosphor was characterized by SEM (ZEISS,
EVO18) operating at an acceleration voltage of 15 kV. The effects of
the reaction temperature and H3BO3 ux concentration on the
photoluminescence intensity of the SMA:1.2 mol% Mn4 phosphor
were investigated using a uorescence spectrophotometer (Hitachi Model F-7000) equipped with a 150 W Xenon lamp as the
excitation source. The decay curve was measured by a Lecroy Wave
Runner 6100 Digital Oscilloscope (1 GHz) using a tunable laser as
the excitation source. The sunlight conversion effect of the lms
was tested on a ber optic spectrometer (AvaSpec-2048TEC-FI,
Avantes, China) with a 150 W Xe lamp as the light source. The
samples were cut into rectangular strips (1  3 cm2). Each measurement consisted of 500 cycles, with each cycle taking 0.2 s. All
of the measurements were performed at room temperature.

3. Results and discussion

3.1. X-ray diffraction analysis
The melting point and other properties of the raw materials
should be taken into consideration with the high-temperature
solid-state reaction method. Initially, the raw materials were
boiled, dehydrated and nally decomposed with the evolution of a
large amount of gases, such as CO2 and H2O. As is known, H3BO3
will lose a molecule of water at approximately 105 C, MnCO3 will
decompose to MnO and CO2 when heated to 150 C, and SrCO3 will
decompose to SrO and CO2 when the calcination temperature is
above 1000 C. Therefore, we chose 1000 C as the minimum calcination temperature to decompose the carbonate and eliminate
water, and the temperature was gradually raised to obtain the
pure phase of the Sr2MgAl22O36 phosphor.
The XRD patterns of the SMA:1.2 mol% Mn4 powders prepared at various temperatures are shown in Fig. 1. The results
indicate that the SMA:1.2 mol% Mn4 prepared from the hightemperature solid-state reaction without ux contains a large
amount of impurities, such as Al2O3(), which could greatly reduce
the phosphor photoluminescence intensity. The phosphors

2. Experimental
2.1. Materials and synthesis
According to the report of Cao et al. [16] a series of SMA red
phosphors with the composition of SMA:1.2 mol% Mn4 were
synthesized by a ux-assisted conventional high-temperature solid-state reaction method. The oxides including SrCO3 (99.99%),
MgO (98%), Al2O3 (99.99%), H3BO3 (98%) and MnCO3 (99.99%) were
used as starting materials. The starting materials were thoroughly
mixed in an agate mortar. The mixed raw materials were then
placed in a crucible and annealed at 800 C for 3 h and subsequently further sintered at 10001600 C for 6 h in air. The calcinations were conducted at a heating rate of 5 C/min up to the
holding temperature. The products were obtained in the form of
rosy powders. The sunlight conversion lms were continuously
prepared by pelleting and bubble lm technology.

Fig. 1. X-ray diffraction (XRD) patterns of the SMA:1.2 mol% Mn4 phosphor annealed at different temperatures for 6 h in air and JCPDS#89-0571.

H. Zhang et al. / Ceramics International 42 (2016) 1301113017

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Fig. 3. Excitation and emission spectra of the SMA:1.2 mol% Mn4 phosphor prepared at 1500 C without ux. The insets: (a) A photograph of the SMA:1.2 mol%
Mn4 phosphor under a 365 nm UV lamp, and (b) CIE chromaticity coordinates of
the SMA:1.2 mol% Mn4 .

Fig. 2. Unit-cell representation of SMA.

synthesized without ux exhibit the pure SMA crystal phase after

sintering at 1500 C. However, a further increase in the ring
temperature again leads to the formation of the Al2O3 phase,
which can be ascribed to the decomposition of the Sr2MgAl22O36
phase. All of the observed diffraction peaks are consistent with the
Joint Committee on Powder Diffraction Standards (JCPDS) no. 890571.
Fig. 2 shows a schematic of the SMA crystal structure, which is
hexagonal with space group P-6m2 (No. 187), and its lattice
parameters
are
a 5.583(1) ,
c22.225(5) ,
cell
volume599.94(30) 3 and Z 1 [18]. The XRD pattern proves
that the Al3 ions can be partly replaced by Mn4 without
changing the crystal structure because Mn4 (r 67 pm) exhibits
an ionic radius similar to that of Al3 (r 68 pm) in the six-oxygen
coordination [19].
Fig. 3 shows the excitation and emission spectra of the SMA:
1.2 mol% Mn4 phosphor prepared at 1500 C without ux. By
monitoring the emission at 659 nm, three broad excitation bands
at 250350 nm, 350450 nm and 450530 nm were observed,
which originated from the 4A2-4T1, 4A2-2T1 and 4A2-4T2 transitions
of the Mn4 ion in the octahedral coordination, respectively
[16,20,21]. Because of the broadband absorption in the range of
250530 nm, the SMA:1.2 mol% Mn4 phosphor perfectly matches
the radiative light of UV, near UV and blue LED chips. The emission
spectrum of the SMA:1.2 mol% Mn4 phosphor shows an intense
red emission in over the broad range of 630730 nm and centering
near 659 nm, which is due to the characteristic 2E4A2 transition of

the Mn4 ion. The broad emission spectrum shows no signicant

change in the shape and peak position compared with reported
results [16]. The insets (a) and (b) show the photograph of the
SMA:1.2 mol% Mn4 phosphor under 365 nm excitation and the
CIE chromaticity coordinates, respectively. A strong red emission
can be observed when the phosphor excited by a 365 nm UV lamp,
and the CIE chromaticity coordinates of the SMA:1.2 mol% Mn4
phosphor are (0.723, 0.277).
To obtain pure SMA at a temperature less than 1500 C, it is
necessary to avoid the formation of intermediate phases. To solve
this problem, H3BO3 ux was used during the heat treatment of
the starting materials. The amount of H3BO3 ux was changed
from 0.5 to 3.0 wt% of the SMA:1.2 mol% Mn4 phosphor. SMA was
obtained as the dominant phase at 1200 C, while un-reacted
Al2O3 also appeared. According to the above XRD patterns of the
samples prepared at various temperatures, SMA can be produced
when the annealed temperature is above 1100 C. Fig. 4 shows the
XRD patterns of the SMA:1.2 mol% Mn4 phosphor prepared with
various amounts of H3BO3. After the samples were prepared at
1200 C without ux, the SMA phase and Al2O3 phase appeared. As

Fig. 4. SMA:1.2 mol% Mn4 phosphor prepared with various amounts of H3BO3
and annealed at 1200 C.

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H. Zhang et al. / Ceramics International 42 (2016) 1301113017

Fig. 5. PL emission spectra of SMA:1.2 mol% Mn4 calcined for 6 h in air as a

function of the ring temperature (ex 320 nm).

Fig. 6. PL emission spectra of the SMA:1.2 mol% Mn4 phosphor prepared with
various amounts of H3BO3 and annealed at 1200 C for 6 h in air (ex 320 nm).
Inset: the integrated emission intensity of the SMA:1.2 mol% Mn4 as a function of
the H3BO3 content.

shown in Fig. 4, a large amount of unreacted Al2O3 was observed

when the added H3BO3 ux was 0.5 wt%. As the amount of H3BO3
ux was gradually increased, the corresponding diffraction peak
intensities associated with Al2O3 gradually decreased. When
1.5 wt% H3BO3 ux was comingled with the starting materials and
calcined at 1200 C, the diffraction peak intensities of Al2O3 disappeared completely. After further increasing the amount of
H3BO3, the Al2O3 impurity phase was observed again in the XRD
pattern, as shown in Fig. 4. The reason may be that part of B3 is
doped into the host lattice of SMA:Mn4 and occupies the sites of
Al3 [22,23]. Single-phased SMA was obtained at 1200 C with
2.0 wt% H3BO3 ux, which is a low temperature compared with
the temperature required that without H3BO3 ux.
3.2. Photoluminescence properties of SMA:Mn4
The emission spectra of SMA:1.2 mol% Mn4 prepared with
various ring temperatures are shown in Fig. 5. SMA:1.2 mol%
Mn4 phosphors red at 1000 C and 1100 C did not exhibit luminescent peaks. An emission peak was observed in the sample
red at 1200 C, indicating that this sample exhibited some
phosphor-induced luminescence. The luminescent efciency was
enhanced with increasing temperatures, peaking at 1500 C.
However, further increasing the temperature reduced the luminescence because of the formation of the Al2O3 impurity, as discussed above. The powder was melted and glasses were observed
above 1600 C. The emission peak of the phosphors red at
1000 C and 1100 C showed two quite obvious bands at 680 nm
and 695 nm, respectively. The uorescence peak located at 680 nm
can be assigned to the emission from the metastable 2E state of
Mn4 in the -Al2O3 crystal [24].
The emission spectra of SMA:1.2 mol% Mn4 prepared with
various amounts of H3BO3 are shown in Fig. 6. The inset shows the
dependence of the integrated emission intensity on the H3BO3
content. With increasing concentrations of H3BO3 ux up to
2.0 wt%, the emission intensity of the SMA:1.2 mol% Mn4 phosphor increases under excitation at 320 nm. The emission intensity
then decreases when the amount of H3BO3 ux exceeds 2.0 wt%.
The ux has a signicant inuence on ion diffusion in the solidstate reaction and induces a more intense red emission. Light
scattering is reduced with larger grains, and defects in the lattice
and on the surface of the phosphor are reduced with higher
crystallinity. The above XRD results reveal that the excessive addition of ux, results in the formation of the Al2O3 impurity phase,

Fig. 7. PL emission spectra of the SMA:1.2 mol% Mn4 phosphor prepared with
2.0 wt% H3BO3 and the SMA:1.2 mol% Mn4 phosphor red at 1500 C.

which reduced the photoluminescence efciency.

Fig. 7 shows the PL emission spectra of the SMA:1.2 mol% Mn4
phosphor prepared with 2.0 wt% H3BO3 at 1200 C and the
SMA:1.2 mol% Mn4 phosphor prepared without ux at 1500 C. It
is seen that the PL emission spectrum of the as-synthesized with
the ux sample (Fig. 7a) is nearly the same as the spectrum of the
sample grown without ux (Fig. 7b). The integrated emission intensity of the as-synthesized without ux sample is approximately
84.8% as strong as that of the sample prepared with ux.
3.3. Morphology of SMA:Mn4
Fig. 8 depicts the SEM images of the SMA:1.2 mol% Mn4
phosphors prepared at various ring temperatures and with
varying amounts of H3BO3, that is, (a) 1100 C, (b) 1300 C,
(c) 1500 C, (d) 0 wt%, (e) 1.0 wt%, and (f) 2.0 wt%. The phosphor
prepared at 1100 C was contained of a large amount of small irregular particles (Fig. 8a). This particle morphology is not desirable
for phosphor because the small particles may not have crystallized
completely. When the calcining temperature reached 1300 C,
uniform and hexagonal particles of a SMA with homogeneous
microstructure were obtained. However, there were also many
awed particles, as shown in Fig. 8b. The sample red at 1500 C
exhibited better morphology with a particle size of approximately
25 mm. As seen in Fig. 8d, the SMA:1.2 mol% Mn4 phosphor

H. Zhang et al. / Ceramics International 42 (2016) 1301113017

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Fig. 8. SEM images of the SMA:1.2 mol% Mn4 prepared at various temperatures: (a) 1100 C, (b) 1300 C, and (c) 1500 C, and with various amounts of H3BO3 at 1200 C:
(d) 0 wt%, (e) 1.0 wt%, (f) 2.0 wt%.

the SMA host material having the proper amount of ux, which
enhances the crystallinity and particle morphology of the resultant
powder. This in turn results in an improvement of the photoluminescence properties.

prepared without ux and annealed at 1200 C showed severe

agglomeration with particle sizes in the range of 1015 mm. After
introducing 1.0 wt% ux, the surface morphologies indicated better grain growth with shape anisotropy and agglomeration, as
shown in Fig. 8e. The ux melt can enhance the slide and rotation
of particles, which promotes particle-particle contact and particle
growth [25,26].
As shown in Figs. 8f and 9, the samples prepared with 2.0 wt%
H3BO3 ux have multidimensional particle morphologies and
narrow particle size distributions (  6 mm). Because ux has a
melting point below that of the solid-state reaction temperature, it
can dissolve one or more reaction components and allow the
materials to enter the reaction zone. The melting point of H3BO3
can be as low as 170 C. During the calcining process, the ux
melts, which can eliminate the direct solid-solid grain boundaries
and induce the particles to form a smooth surface [27,28]. In brief,
by adding H3BO3, the as-prepared particles possess a smooth
surface, as shown in the SEM images. This may also be ascribed to

The luminescent decay curve of the SMA:Mn4 sample monitored at 659 nm is shown in Fig. 10. It is well known that the
luminescent lifetime of the emission centers in homogeneous
media can be described by a single-exponential decay equation: I
(t) exp(  t/), where I(t) is the luminescent intensity at time t,
is the pre-exponential factor, and is the assigned decay time
constant [29]. However, the distribution of emission centers in
phosphors is frequently inhomogeneous on a microscopic scale.
This is especially the case when the phosphors are prepared by the
conventional high-temperature solid-state reaction method owing
to their irregular morphology and particles induced by sintering

Fig. 9. Size distribution of the phosphor prepared with 2.0 wt% H3BO3.

Fig. 10. Decay curve of the SMA:1.2 mol% Mn4 phosphor calcined with 2.0 wt%
H3BO3 at 659 nm.

3.4. Lifetime decay of SMA:Mn4

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H. Zhang et al. / Ceramics International 42 (2016) 1301113017

Fig. 11. Transition spectra of the blank lm and the light conversion lms under
the articial sunlight source.

and aggregation [30]. Consequently, the heterogeneous distribution of emission centers gives rise to complex decay kinetics that
cannot be tted by the afore-mentioned single-exponential decay
equation. Here, the double-exponential decay equation that is
used to describe the decay process of emission is
I(t) 1exp(  t/1) 2exp( t/2), where I(t) represents the
uorescence intensity at time t and the subscripts 1 and 2 denote
the assigned lifetime components [31]. The tting parameters of
the decay curve are summarized in Fig. 10. An inspection of the
results reveals that the decay curve of the sample prepared by the
high-temperature solid-state reaction method can be well described by the double-exponential decay equation, indicating that
the distribution of Mn4 in SMA is in a nearly homogeneous local
environment. As shown in Fig. 10, the luminescent lifetime of the
SMA:1.2 mol% Mn4 sample calcined with the H3BO3 ux is
1.02 ms.
3.5. Properties of SMA:Mn4 doped sunlight conversion lm
To further investigate the potential of SMA:Mn4 for application in sunlight conversion lms. The conversion lms were fabricated by blending the red-emitting SMA:Mn4 phosphor and
polyethylene. Fig. 11 shows the transition spectra of the blank lm
and the sunlight conversion lms under an articial sunlight
source. The SMA:Mn4 phosphor can be excited by UV (310
380 nm), near UV (380420 nm) and visible light (420530 nm),
where sunlight has the strongest intensity. The phosphor possesses a strong emission band at 630730 nm, matching well the
absorption spectrum of chlorophyll complexes. As seen in Fig. 11,
the relative intensity of the transition spectrum for the
SMA:Mn4 -doped lm improves in the range of 600900 nm and
decreases in range of 400530 nm. The relative intensity of the red
light component of the transition spectrum increases with the
SMA:Mn4 phosphor doping concentration. The results demonstrate that the SMA:Mn4 phosphor-doped lm clearly shows
sunlight conversion.

4. Conclusion
The structural and luminescent properties of SMA:1.2 mol%
Mn4 powders were closely correlated with the ring temperatures and amount of ux. SMA:1.2 mol% Mn4 was obtained as the
dominant phase at 12001600 C, while the Al2O3 phase weakly
appeared as a minor phase. The excitation spectra of the
SMA:1.2 mol% Mn4 powders exhibited broad bands, ranging
from approximately 250 to 530 nm. Three emission peaks were

observed in the red region, and the strongest one appeared at

659 nm. The emission intensity was continuously enhanced with
ring the temperatures up to 1500 C. H3BO3 ux was added when
preparing the SMA:1.2 mol% Mn4 phosphors by a solid-state reaction method. The effect of H3BO3 ux on the crystal structure,
photoluminescence properties and morphology of the
SMA:1.2 mol% Mn4 phosphors were studied. The results show
that H3BO3 ux not only enhances the luminescent intensity of
phosphors but also improves the morphology. The maximum
emission intensity of the SMA:1.2 mol% Mn4 phosphor was
achieved with 2.0 wt% H3BO3 ux. The uorescent lifetime of the
optimized SMA:1.2 mol% Mn4 phosphor prepared with 2.0 wt%
H3BO3 is  1.02 ms. A conversion lm was fabricated by blending
the SMA:Mn4 red-emitting phosphor with polyethylene. The
results indicate that the SMA:Mn4 phosphor will be a promising
candidate as a red conversion phosphor in the eld of agricultural
light conversion lms.

Acknowledgments
The present work was supported by the National Natural Science Foundation of China (Grant nos. 21371062 and 51372091), the
Foundation for High-level Talents in Higher Education of Guangdong Province, the Project for Construction of High-level University in Guangdong Province, and the Teamwork Projects funded
by the Guangdong Natural Science Foundation (Grant No.
S2013030012842), the Provincial Science and technology project
of Guangdong Province (Nos. 2016A050502043, 2015B090903074,
508289876075), and the Student Innovative Project (Grant No.
201610564233) for Mr. Yue Zhu.

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