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