Journal of Luminescence 178 (2016) 388–391

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

Full Length Article

Synthesis and luminescence properties of NaAl11O17:Mn2 þ green

phosphor for white LEDs
Renping Cao a,n, Dedong Peng a, Haidong Xu a, Shenhua Jiang b, Zhiyang Luo c,
Hui Ao a, Pan Liu d
a
College of Mathematics and Physics, Jinggangshan University, Ji’an 343009, China
b
College of pharmacology and Life Science, Jiujiang University, Jiujiang 332000, China
c
College of Mechanical Manufacture and Automation, Jinggangshan University, Ji’an 343009, China
d
Scientific Research Office, Jinggangshan University, Ji’an 343009, China

art ic l e i nf o a b s t r a c t

Article history: Novel NaAl11O17:Mn2 þ green phosphor is synthesized by solid-state reaction method in air. The emission
Received 2 March 2016 band peaking at  508 nm is observed owing to the 4T1-6A1(6S) transition of Mn2 þ ion, and the
Received in revised form chromaticity coordinates are (0.0725, 0.6468). The excitation band peaking at  360, 382, 424, 450, and
11 May 2016
490 nm are attributed to 6A1(6S)-4E(4D), 4T2(4D), [4A1(4G), 4E(4G)], 4T2(4G), and 4T1(4G) transitions of
Accepted 13 June 2016
Available online 16 June 2016
Mn2 þ ion, respectively, which indicate that NaAl11O17:Mn2 þ phosphor may be excited by (near) ultra-
violet and blue LED chip. The luminous mechanism is explained by Tanabe–Sugano diagram of Mn2 þ ion.
Keywords: The optimal Mn2 þ doping concentration is  3.5 mol%. The NaAl11O17:3.5%Mn2 þ phosphor shows high
Mn2 þ ion quantum efficiency of  67.84% with excitation 424 nm. The lifetime decreases from 6.72 to 6.0 ms with
Green-emitting
increasing Mn2 þ concentration in the range of 0–4 mol%.
Optical materials
& 2016 Elsevier B.V. All rights reserved.
Optical properties
Phosphors

1. Introduction important raw materials, such as SiAlON:Eu2 þ , BaSi3O4N2:Eu2 þ ,

It is well known that luminescence plays a major technological
role for mankind. Rare earth (RE) and transitional metal (TM) ions
have been regarded as the important luminescence sources [1,2].
In recent years, new luminescent materials doped with RE or TM
ions have been investigated and developed largely owing to their
widely applications in many fields, such as cathode ray tubes, field
emission displays, light-emitting diodes (LEDs), X-ray imaging
scintillators, and plasma display panels [3–5]. At present, white
LEDs have been considered as the most promising light source for
solid state lighting due to their high luminous efficiency, long
lifetime, environmental friendliness, and energy-saving [6]. The
current widely used method to obtain white light can be produced
by a combination of a InGaN blue chip with a yellow-emitting
phosphor (e.g., Y3Al5O12:Ce3 þ ), however, such white light has
some disadvantages due to the deficiency of the red emission, such
as low color-rendering index (CRI) and high correlated color
temperature (CCT) [7]. In order to solve above problems, white
LEDs fabricated by blue chip combing with green and red phos-
phors or ultraviolet (UV) chip combing with green, blue, and red
phosphors are investigated. So, the green phosphor is one of
n mental results indicate that novel NaAl11O17:Mn2 þ phosphor has
Corresponding author. Fax: þ86 796 8124959.
E-mail address: jxcrp@163.com (R. Cao).
and MSi2O2N2:Eu2 þ [8–10]. It is well known that RE is expensive
and synthesis conditions of nitrides/ oxynitrides are harsh.
Therefore, the non-RE Mn2 þ doped phosphors are gaining atten-
tion and have been selected as target materials in the paper.
Mn2 þ ion has a 3d5 electron configuration with electrons
located in an outer orbit [11]. Mn2 þ with sextet (6S) ground state is
a good activator in many minerals and the broad emission band
derived from the 4T1-6A1(6S) transition of Mn2 þ ion can vary
from green to orange/red because of the influence of the host
crystal field [12]. Aluminate is a good host for phosphors due to
high chemical stability. In Mn ion doped aluminates, luminescence
center usually comes from Mn4 þ ion, such as CaAl2O4:Mn4 þ ,
CaAl12O19:Mn4 þ , SrMgAl10O37:Mn4 þ , and SrAl4O7:Mn4 þ etc [13–
16]. However, in the work, the luminescence center of Mn ion-
doped NaAl11O17 phosphor comes from Mn2 þ ion.
In the paper, novel NaAl11O17:Mn2 þ green phosphor is syn-
thesized by solid-state reaction method in air. The crystal struc-
tures, lifetimes, and luminescence properties are investigated. The
influences of Mn2 þ doping concentration to luminescence prop-
erties and lifetime are discussed. The luminous mechanism is
explained by Tanabe–Sugano diagram of Mn2 þ ion. The experi-
an application prospect as green phosphor for White LEDs.

http://dx.doi.org/10.1016/j.jlumin.2016.06.028
0022-2313/& 2016 Elsevier B.V. All rights reserved.
 R. Cao et al. / Journal of Luminescence 178 (2016) 388–391 389

2. Experimental  0.8 Å and Na þ :  0.95 Å). In NaAl11O17:Mn2 þ phosphor, it is

All the raw materials are purchased from the Aladdin Chemical
Reagent Company in Shanghai China, such as Na2CO3 (A.R. 99.5%),
Al2O3 (A.R. 99.5%), and MnCO3 (A.R. 99.5%). A series of NaAl11O17:
xMn2 þ (x ¼0, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, and 4 mol%) phosphors are
synthesized by solid-state reaction method in air. The stoichio-
metric amount of raw materials are ground in an agate mortar
without further purification, then sintered at 600 °C for 5 h, and
subsequently 1350 °C for 6 h in air. Repeated grindings are per-
formed between two sintering processes to improve the homo-
geneity. All products are obtained after natural cooling to room
temperature.
The crystal structures of phosphors are checked by X-Ray
Powder diffraction (XRD) (Philips Model PW1830) with Cu-Kα
radiation at 40 kV and 40 mA at room temperature. The data are
collected in the 2θ range of 10–90°. Luminescence properties and
fluorescence lifetimes of phosphors are investigated by using a
steady-state FLS980 spectrofluorimeter (Edinburgh Instruments,
UK, Edinburgh) with a high spectral resolution (signal to noise
ratio 412,000:1) at room temperature. A 450 W ozone free xenon
lamp is used for steady-state measurements. A microsecond
pulsed xenon flash lamp μF900 with an average power of 60 W is
available to record the emission decay curves for lifetimes.
difficult to keep charge balance in the host lattice due to the dif-
ferent valence state between Mn2 þ and Na þ ion. In order to keep
the charge balance, Mn2 þ ions have to form pairs by trapping an
interstitial O2  ion and partial occupy Na þ ions sites.
XRD patterns of Joint Committee on Powder Diffraction Stan-
dards (JCPDS) card no. 19-1174, blank NaAl11O17, NaAl11O17:xMn2 þ
(x ¼1, 2, 3, 4 mol%) phosphors at room temperature are shown in
Fig. 2(a). These XRD patterns of these samples almost match well
with the standard data of JCPDS card no. 19-1174. The XRD pat-
terns of other NaAl11O17:xMn2 þ (0 rx r4 mol%) phosphors are
not displayed in Fig. 2(a), but those patterns are also in line with
those of JCPDS card no. 19-1174. No other crystalline phases are
formed. These results indicate that the doping of Mn2 þ ion does
not cause any significant influence on the host NaAl11O17 crystal
structure. In the host lattice, Mn2 þ ions occupy the Na þ ions sites
owing to their similar ionic radii (Mn2 þ :  0.8 Å and Na þ :
 0.95 Å). After Mn2 þ ions are doped, the XRD diffraction peaks
shift towards higher angles, which are illustrated more clearly in
Fig. 2(b). It is reason that the ionic radius of Mn2 þ ion is less than
that of Na þ ion. This indicates that a contraction of the lattice cell

3. Results and discussion

The unit cell of NaAl11O17 drawn on the basis of the Inorganic

Crystal Structure Database (ICSD) #15970 is shown in Fig. 1.
NaAl11O17 is described as the hexagonal crystal system with space-
group P63/mmc (194) and the lattice parameters a ¼5.584 Å,
c ¼22.45 Å, V ¼606.23 Å3, and z ¼2 [17]. In the hexagonal cell, four
layers of oxygens are in cubic closest packing, the A1 atoms occupy
both octahedral and tetrahedral holes, these spinel-like blocks are
spaced well apart by A1-O-A1 columns, and in the inter-spinel
spaces the Na þ ions, which are exceptionally mobile, are arranged
among a set of nearly equivalent sites [18]. According to the Fig. 2. (a) XRD patterns of JCPDS card no. 19-1174, blank NaAl11O17, NaAl11O17:
principle of similar ionic radius, Mn2 þ ions will replace the Na þ xMn2 þ (x¼ 1, 2, 3, 4 mol%) phosphors at room temperature. (b) The enlarged figure
ions sites in the host lattice due to their similar ionic radii (Mn2 þ : in the 2θ range of 7.2–8.3°.

Fig. 1. The unit cell of NaAl11O17 drawn on the basis of ICSD #15970.
390 R. Cao et al. / Journal of Luminescence 178 (2016) 388–391
Fig. 3. (a) PLE and PL spectra of NaAl11O17:3.5%Mn2 þ phosphor at room temperature (λex ¼ 424 nm and λem ¼ 508 nm). The inset: The CIE chromaticity diagram, chromaticity
coordinates, and picture under 365 nm UV lamp. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Fig. 4. (a) PL spectra (λex ¼ 424 nm) of NaAl11O17:xMn2 þ (0 r x r4 mol%) phos-
phorsh at room temperature. The inset: The relation between PL intensity and
Mn2 þ concentration.
according to Bragg equation (2dsinθ ¼ λ, where λ and θ are the
wavelength of the X-ray and diffraction angle, respectively.) is
formed owing to the substitution of Mn2 þ ions for Na þ ions in
host lattice.
Photoluminescence excitation (PLE) and Photoluminescence
(PL) spectra of NaAl11O17:3.5%Mn2 þ phosphor at room tempera-
ture (λex ¼424 nm and λem ¼508 nm), the Commission Inter-
nationale Ed I'eclairage (CIE) chromaticity diagram, chromaticity
coordinates, and picture under 365 nm UV lamp are shown in
Fig. 3(a). Mn4 þ ion-doped materials usually show red or deep-red
emission in the range of 610–750 nm [12,13]. Mn3 þ , Mn5 þ , and
Mn6 þ ions-doped materials show near infrared emission within
the range 1000–1250 nm [19,20]. Here, the host NaAl11O17 with
excitation 424 nm does not show emission, so, we infer that the
emission in NaAl11O17:Mn2 þ phosphor comes from Mn2 þ ion.
With excitation 424 nm, the green PL band peaking at  508 nm
with full-width at half-maximum (FWHM) of  35 nm is observed
owing to the 4T1-6A1(6S) transition of Mn2 þ ion [21], and the CIE
chromaticity coordinates are (0.0725, 0.6468). According to the
picture in Fig. 3(b), NaAl11O17:Mn2 þ phosphor can emit green light
under 365 nm UV lamp. The PLE spectrum contains five distinct
band peaking at  360, 382, 424, 450, and 490 nm, which are
attributed to 6A1(6S)-4E(4D), 4T2(4D), [4A1(4G), 4E(4G)], 4T2(4G),
and 4T1(4G) transitions of Mn2 þ ion, respectively [22–24]. These
PLE band peaks indicate that NaAl11O17:Mn2 þ phosphor may be
effectively excited by near UV or blue LED chip.
Fig. 5. Decay curves of NaAl11O17:3.5%Mn2 þ phosphors at room temperature. The
monitoring wavelength is 508 nm with excitation at 424 nm. The red curves are a
fit of the experimental data to a first order exponential decay equation. The inset:
The influence of Mn2 þ concentration to lifetime. (For interpretation of the refer-
ences to color in this figure legend, the reader is referred to the web version of this
article.)
PL spectra of NaAl11O17:xMn2 þ (0 r xr4 mol%) phosphors at
room temperature (λex ¼424 nm) in Fig. 4 show that PL intensity
increases with increasing Mn2 þ concentration in the range of 0–
3.5 mol% owing to the distance between Mn2 þ ions, and decreases
with further increasing Mn2 þ concentration due to concentration
quenching. The critical transfer distance (Rc) can be calculated via
using the formula suggested by Blasse [12]: Rc E2[3V/(4πXcN)]1/3,
where V is the unit cell volume of host lattice, Xc is the critical
concentration, N is the number of sites available for the dopant in
the unit cell. By taking the experimental and analytic values of V,
Xc, and N (606.23, 0.035, and 2), the critical transfer distance of
Mn2 þ ions in NaAl11O17:Mn2 þ phosphor is about 24.58 Å.
According to the mechanisms for nonradiate energy transfer and
the critical distance between Mn2 þ ions, we infer that the
mechanism of energy transfer is the electric multipolar interac-
tions between Mn2 þ ions [7]. So, PL spectra in Fig. 4 indicate that
the optimal Mn2 þ concentration is  3.5 mol%.
Decay curves of NaAl11O17:3.5%Mn2 þ phosphors and the
influence of Mn2 þ concentration to lifetime at room temperature
are shown in Fig. 5. The monitoring wavelength is 508 nm with
excitation 424 nm. The red curves are a fit of the experimental
data to a first order exponential decay equation. These decay
curves may be well fitted by a first-order exponential decay
 R. Cao et al. / Journal of Luminescence 178 (2016) 388–391
Fig. 6. Tanabe-Sugano diagram of Mn2 þ ion. (For interpretation of the references
to color in this figure legend, the reader is referred to the web version of this
article.)
equation [12].


I ðtÞ ¼ I ð0Þ exp t=τ þ A ð1Þ
where, I(t) is the luminescence intensity at time t, I(0) is the initial
luminescence intensity, t is the time, A is the value for different
fitting, and τ is the decay time for the exponential components.
According the inset in Fig. 5, it is known that the lifetime decreases
from 6.72 to 6.0 ms with increasing Mn2 þ concentration in the
range of 0–4 mol%.
The quantum efficiency (QE) is measured directly via using
FLS980 spectrofluorimeter with integrating sphere. The
NaAl11O17:3.5%Mn2 þ phosphor shows high QE of  67.84% with
excitation 424 nm. The QE can be calculated as follows [12]:
Z Z Z 
η ¼ Ldirect = Ewithout  Edirect ð2Þ
where, η is the quantum yield. Ldirect is the complete emission
spectrum of the sample being measured, collected by using the
sphere. Edirect is the emission spectra of the excitation light,
recorded with the sample in place, collected by using the sphere.
Ewithout is the emission spectra of the excitation light, recorded
with the equipment blank sample in place, collected by using the
sphere.
Now we discuss the possible luminous mechanism of Mn2 þ ion
in NaAl11O17:Mn2 þ phosphor by Tanabe-Sugano diagram of Mn2 þ
ion shown in Fig. 6. It is well known that Mn2 þ ion (3d5) with
sextet (6S) ground state is a well activator in many materials and
its broad PL band due to the 4T1-6A1(6S) transition can vary from
green to orange/red because of the influence of the host crystal
field [12]. Usually, Mn2 þ ion in strong crystal field emits green
light, otherwise, orange/red light. In NaAl11O17:Mn2 þ phosphor,
the electrons of Mn2 þ ion absorb energy and are raised from the
ground state 6A1(6S) to the high level excited states (e.g., 4E(4D),
4 R237.
T2(4D), [4A1(4G), 4E(4G)], 4T2(4G), and 4T1(4G)). The excited elec-
trons then relax to the lower level by a nonradiative process, and
finally populate the 4T1(4G) level. When the 4T1(4G) level is
populated, the possible cross relaxation processes from 4T1(4G)
level to 6A1(6S) level may occur, then, the phosphor emits
green light.
391
4. Conclusions
In summary, a series of NaAl11O17:xMn2 þ (0 rxr 4 mol%)
phosphors are synthesized by solid-state reaction method in air.
The crystal structures, lifetimes, and luminescence properties are
investigated. With excitation 424 nm, broad green emission band
peaking at  508 nm owing to 4T1-6A1(6S) transition of Mn2 þ ion
can be observed with the CIE chromaticity coordinates (0.0725,
0.6468). The PLE spectrum monitored at 508 nm contains five
distinct band peaking at  360, 382, 424, 450, and 490 nm, which
are attributed to 6A1(6S)-4E(4D), 4T4T2(4D), [4A1(4G), 4E(4G)],
4
T2(4G), and 4T1(4G) transitions of Mn2 þ ion, respectively. The
NaAl11O17:3.5%Mn2 þ phosphor shows high QE of  67.84% with
excitation 424 nm. The optimal Mn2 þ concentration is  3.5 mol%,
and the lifetime decreases from 6.72 to 6.0 ms with increasing
Mn2 þ concentration in the range of 0–4 mol%. The luminous
mechanism is explained by Tanabe-Sugano diagram of Mn2 þ ion.
The experiment results indicate that novel NaAl11O17:Mn2 þ
phosphor has an application prospect as green phosphor for white
LEDs based on near UV and blue LED chip.
Acknowledgments
This work is financially supported by the National Natural
Science Foundation of China (Nos. 11464021 and 31360371) and
Natural Science Foundation of Jiangxi Province of China (No.
20151BAB202008).
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