Journal of Luminescence 178 (2016) 479486

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

Full Length Article

EPR and optical properties of Eu2 and Mn2 co-doped MgSrAl10O17

bluegreen light emitting powder phosphors
N. Singh a, Vijay Singh a,n, G. Sivaramaiah b, J.L. Rao c, Pramod K. Singh d, M.S. Pathak a,
S.J. Dhoble e, M. Mohapatra f
a

Department of Chemical Engineering, Konkuk University, Seoul 143-701, Korea

Department of Physics, Government College (M), Kadapa 516 004, India
c
Department of Physics, Sri Venkateswara University, Tirupati 517 502, India
d
Materials Research Laboratory, Sharda University, Greater Noida 201 310, India
e
Department of Physics, RTM Nagpur University, Nagpur 440 033, India
f
Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085, India
b

art ic l e i nf o

a b s t r a c t

Article history:
Received 12 November 2015
Received in revised form
4 June 2016
Accepted 6 June 2016
Available online 11 June 2016

Strong bluegreen light emitting MgSrAl10O17:Eu2 ,Mn2 phosphor was synthesized by a lowtemperature initiated, self-propagating and gas producing combustion process in a very short time
( o5 min). Structural characterization of the luminescent material was studied with X-ray diffraction
analysis and energy-dispersive X-ray analysis. The absorption spectrum exhibits bands due to Eu2 and
Mn3 ions. The excitation spectrum shows a peak at 337 nm. Upon excitation at 337 nm, the emission
spectrum exhibits an intense band centered at 462 nm due to transitions from the 4f65d1 to the 4f7
conguration of the Eu2 ions, whereas sharp peak at 513 nm attributed to 4T1-6A1 transition of Mn2
ions. The X-band EPR spectra of MgSrAl10O17:Eu2 ,Mn2 showed the presence of Eu2 and Mn2 ions.
& 2016 Elsevier B.V. All rights reserved.

Keywords:
EPR
Luminescence
Combustion
Eu2
Mn2
MgSrAl10O17
Phosphors

1. Introduction
Rare-earth and transition metal ions doped alkaline earth aluminates phosphors have attracted much attention since they show
excellent physical and optical properties as well as the fact that
they are environment friendly [16]. In recent years, rare-earth
doped alkaline earth aluminates are extensively investigated for
their wide applications in solid-state optical devices [19]. Among
the alkaline earth aluminates MgSrAl10O17 (MSA) is one of the
promising host candidates for lanthanide and transition metal
ions. The MgSrAl10O17 possesses to -alumina structure, which has
hexagonal symmetry. The -alumina structure consists of conduction plane and closely packed spinel like blocks with stacking
alternatively. Hence it is possible to incorporate a large number of
divalent, trivalent and rare-earth ions into the conduction plane
and the spinel block [1012]. The crystal structure and optical
properties of rare-earth and transition ions doped MSA investigated by many researchers. The use of Eu2 doped MSA as a blue
n

Corresponding author. Fax: 82 2 458 3504.

E-mail address: vijayjiin2006@yahoo.com (V. Singh).

http://dx.doi.org/10.1016/j.jlumin.2016.06.015
0022-2313/& 2016 Elsevier B.V. All rights reserved.

light emitting phosphor for plasma display panels was explored by

Xing et al. [13]. Matsui et al. [14] synthesized this sample that
showed two types of emission spectra and decay curves. Kalaignan
et al. [15] have reported the photoluminescence behavior of Eu2 doped MAS prepared by solgel and spray pyrolysis methods.
MSA:Eu, Dy phosphor was prepared by Tang et al. [16] and the
improved blue luminescence emission of MSA:Eu was observed
under UV excitation by co-doping Dy3 ions. Akiyama et al. [17]
investigated deformation luminescence phenomena and the constituent phases of MSA:Eu phosphor. Singh et al. [18] reported that
the luminescence of Mn2 -activated MSA that shows a greenemission due to the 4T1-6A1 transition of Mn2 ions under the
excitation (453 nm). The relation between photoluminescence and
thermoluminescence from Eu2 doped MSA has been investigated
by Tanno et al. [19].
Recently, much attention has been paid to materials showing
white luminescence [2024]. It is known that the emission
intensity of a Mn2 ion singly doped phosphor is quite low under
UV excitation. Therefore, it is necessary to enhance the emission
intensity of Mn2 doped materials by introducing an efcient
sensitizer. For this purpose, Eu2 and Mn2 co-doped phosphors
have been studied extensively for several years [2530]. It has

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N. Singh et al. / Journal of Luminescence 178 (2016) 479486

been well known that the luminescence of Eu2 consists of the

4f65d14f7(8S7/2) broad-band emission and has the properties of
large absorption of UV light and broad emission ranging from
ultraviolet to red light depending on different crystal-lattice
environment. Manganese (Mn) is known to be an efcient luminescent activator in a number of host lattices and the tetrahedrally
coordinated Mn2 usually exhibits a green emission, whereas the
octahedrally coordinated Mn2 exhibits an orange to red emission. In order to achieve white light, co-doping Eu2 and Mn2
into a single host [such as: CaAl2Si2O8, SrZn2(PO4)2, CaMgSi2O6,
Ba3MgSi2O8, SrAl2Si2O8, Ca9Lu(PO4)7, SrBPO5 etc.] has been
reported by the several researchers [3135].
The electron paramagnetic resonance (EPR) and optical studies
are two important and useful techniques which provide information on the nature of electron spins in the systems. Especially, EPR
investigations of Eu2 and Mn2 ions in host lattices are interesting and have received considerable attention because the EPR
parameters of these two ions are very sensitive to the local symmetry. The main advantage of using Eu2 and Mn2 ions as the
spin probe is that its EPR spectrum can easily be recorded at room
temperature and these spectrum provides useful information
about the oxidation state and site occupancy of these ions in the
host structure. As a part of our program on phosphor materials
[3640], in recent years we have shown that, by combustion
synthesis, complex oxides can be synthesized at ignition temperature of 500 C [3642]. A similar method was used to synthesize MgSrAl10O17:Eu2 ,Mn2 phosphors using carbohydrazide
as a reductant and nitrate as an oxidant. The prepared sample was
investigated by X-ray diffraction (XRD) and energy-dispersive
X-ray (EDX) techniques. EPR, absorption UVvis spectrum and
photoluminescence properties of this phosphor have also been
studied. In addition, the site symmetry of Eu2 and Mn2 ions in
MgSrAl10O17 were investigated by EPR measurements at different
temperatures.

2. Experimental
Mg0.90SrAl10O17:Eu0.07,Mn0.03 was prepared by using the combustion method with the raw materials: Aluminum nitrate [Al
(NO3)3  9H2O, 5 g], Magnesium nitrate [Mg(NO3)2  6H2O, 0.30 g],
Strontium nitrate [Sr(NO3)2, 0.28 g], Carbohydrazide (CH6N4O,
2.55 g), Europium nitrate [Eu(NO3)3  5H2O, 0.0399 g,] and Manganese chloride (MnCl2  4H2O, 0.0079 g). The starting materials
were dissolved in a minimum quantity of deionized water in
300 ml capacity porcelain dish. Then the dish was inserted into a
furnace preheated to 500 C. The reaction mixture undergoes
thermal dehydration and ignites at one spot with liberation of
gaseous products. The entire combustion process was completed
in about 5 min. The combustion of carbohydrazide is exothermic
and releases the energy required for the synthesis. The products
obtained by combustion process were uffy masses and these
were crushed into a ne powder. This product was used for further
characterization.
The phase purity of the synthesized powder was analyzed by
XRD using CuK radiation (Bruker D8 Advance) in the 2 range.
The powders were taken onto a carbon adhesive tape for their
electron microscopic evaluation. Their chemical compositions
were analyzed using the EDX attached to the SEM (S-3400, Hitachi,
Japan). The emission and excitation spectra were recorded using a
Hitachi F-4500 uorescence Spectrophotometer. Absorption
spectroscopy was performed at room temperature by diffuse
reectance with a Cary UVvis-NIR absorption Spectrophotometer.
A powdered sample of 100 mg was taken in a quartz tube for the
EPR measurements. The EPR spectra of all the samples were
recorded on a JEOL FE1X ESR Spectrometer, operating in the X-

band frequencies, with a 100 kHz eld modulation to obtain the

rst derivative EPR spectrum.

3. Results and discussion

3.1. X-Ray diffraction studies
The phase purity and crystal structure of the combustion synthesized sample were analyzed using the XRD pattern. The XRD
pattern of the combustion derived phosphor is shown in Fig. 1a.
All the reections of MgSrAl10O17:Eu2 , Mn2 could be indexed to
those of standard MgSrAl10O17 (JCPDS le no.- 26-0879, Fig. 1b).
The position and intensity of the diffraction peaks of phosphor
samples match well with the values from the standard
MgSrAl10O17, indicating that the crystal lattice and the hexagonal
phase of the MgSrAl10O17:Eu2 , Mn2 could be obtained by the
low temperature combustion synthesis even at 500 C furnace
temperature.
3.2. Scanning electron microscopy and EDX studies
The surface morphology and chemical composition of
MgSrAl10O17:Eu2 , Mn2 phosphor was illustrated by scanning
electron microscopy and EDX (Figs. 2 and 3). Fig. 2a, represents
SEM micrograph at low magnication which indicates that the
sample consists of unshaped agglomerated particles with nonuniform shapes. The voids and pores formed by the escaping gases
during combustion can also be seen in Fig. 2a. These entire features are inherent in combustion derived powders. In order to
verify the distribution and composition of the constituent elements, the entire area of the micrograph (Fig. 2a,) was analyzed
with EDX mapping and spectrum. EDX elemental mapping of
MgSrAl10O17:Eu2 , Mn2 powder is presented in Fig. 2b. EDX
elemental mappings conrm the uniform distribution of Mg, Sr, Al
and O which indicates the homogeneous distribution of each
element in the combustion derived phosphor. Fig. 3 shows the
EDX spectrum of MgSrAl10O17:Eu2 , Mn2 phosphor. The EDX
spectrum revealed that the phosphor was composed of Mg, Sr, Al,
O, Eu and Mn elements. The existence of Eu and Mn peaks in the
spectrum indicated that these dopants are present in the

Fig. 1. Powder XRD patterns of (a) MgSrAl10O17:Eu2 , Mn2 phosphor and

(b) MgSrAl10O17 (JCPDF no. 26-0879).

N. Singh et al. / Journal of Luminescence 178 (2016) 479486

481

Fig. 2. (a) SEM image of MgSrAl10O17:Eu2 , Mn2 phosphor and (b) EDX mapping of Sr, Mg, O, Al, Eu and Mn.

MgSrAl10O17 matrix. It is signicant to note that EDX mapping and

spectrum analysis reveal that both dopants are uniformly distributed in the MgSrAl10O17 matrix. In order to achieve an efcient
luminescence, the homogeneous distribution of dopant ions in a
matrix is essential.
3.3. Absorption studies
Fig. 4 indicates the absorption spectrum of MgSrAl10O17:Eu2 ,
Mn2 phosphor observed at room temperature. This spectrum
exhibits an intense band centered at about 264 nm and another
weak band centered at about 285 nm. This spectrum also exhibits
an intense broad band centered at 368 nm and two broad bands

centered at 508 and 696 nm. The bands observed at 264, 285 and
368 nm due to Eu2 ions. These three bands have been attributed
to 4f7(8S7/2)-4f65d1(t2g) transition of Eu2 ions [43,44]. Singh
et al. [45] studied diffuse reection spectrum of BaAl12O19: Eu2 ,
Mn2 phosphor and observed two bands at around 274 and
347 nm. These bands were attributed to 4f7(8S7/2)-4f65d1(t2g)
transition of Eu2 ions. L et al. [43] detected two broad bands in
diffuse reection spectrum in the wavelength region 250400 nm,
due to Eu2 in calcium aluminate silicate chloride phosphors
when doped with Eu2 and Mn2 ions. Xia et al. [46] observed
maximum absorption in diffused reection spectrum at around
360 nm due to Eu2 ions in the co-doped Eu, Mn calcium aluminate silicate chloride phosphor. The broad band at around 508 nm

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N. Singh et al. / Journal of Luminescence 178 (2016) 479486

Fig. 3. EDX spectrum of MgSrAl10O17:Eu2 , Mn2 phosphor.

Mn3 ions. The intensity of the broad band at around 508 nm is

reduced due to intense broad band at around 368 nm which is due
to Eu2 ions. The broad band at around 696 nm is may be due to
the excitation of host lattice. Wang et al. [48] studied white light
emitting CaAl12Si2O8:Eu, Mn phosphors prepared by solgel
method. The diffuse reectance spectrum of this sample exhibits
strong absorption in near UV spectral region. The reectance has
decreased with increasing Mn2 ions content in the sample.
3.4. Photoluminescence studies

Fig. 4. Absorption spectrum of MgSrAl10O17:Eu2 , Mn2 phosphor.

Eu2+

1.6x10

Eu2+
Mn2+

Intensity (a.u.)

1.2x10

8.0x10

(a)
4

4.0x10

(b)

0.0
200 250 300 350

400 450 500 550 600 650

Wavelength (nm)

Fig. 5. Photoluminescence spectra of MgSrAl10O17:Eu2 , Mn2 phosphor:

(a) Excitation spectrum for emission at 462 nm and (b) Emission spectrum for
excitation at 337 nm.

is due to Mn3 ions and assigned to the spin allowed 5Eg-5T2g

transition. During sample preparation, a part of Mn2 ions is
oxidized to Mn3 and a broad band is observed at 508 nm. Singh
et al. [47] observed an intense broad band at around 485 nm due
to Mn3 ions in LaMgAl11O19 phosphor and is attributed to the
spin allowed 5Eg-5T2g transition. In the case of octahedral or
tetrahedral symmetry one broad band will be observed due to

Fig. 5(a) shows the excitation spectrum of MgSrAl10O17:Eu2 ,

Mn2 phosphor. This spectrum was recorded by monitoring the
strongest 462 nm emission peak. Excitation spectrum exhibits an
intense band centered at about 337 nm. The excitation spectrum
also exhibits a stair case like structure in the region 367395 nm.
The Eu2 ions in crystals produce two broad absorption bands due
to transitions from ground to the excited states. The excitation
band at 337 nm has been attributed to 4f7(8S7/2)-4f65d(t2g)
transition of Eu2 ions [49]. The stair case like structure is due to
ligand eld splitting of the Eu2 d-orbital. The lower energy band
normally shows stair case like structure while the higher energy
band is broad and unstructured. The stair case structure in the
lower band is attributed to different J values in the 4f7 [50]. Yang
and Chen [51] studied white light generation and energy transfer
in SrZn2(PO4)2:Eu, Mn phosphor for UV light emitting diodes. The
PLE spectrum of SrZn2(PO4)2:Eu phosphor exhibited an optimal
excitation band centered at 365 nm and this arises due to the 4f5d multiplets of Eu2 excited state. Wang et al. [48] observed an
excitation band centered at 351 nm in the excitation spectrum of
CaAl2Si2O8:Eu, Mn phosphor. Singh et al. [45] observed an intense
band at around 328 nm due to Eu2 ions in the excitation spectrum of BaAl12O19:Eu2 , Mn2 phosphor. Singh et al. [47] also
reported an intense band at around 324 nm due to Eu2 ions in
the excitation spectrum of combustions synthesized LaMgAl11O19:
Eu2 , Mn2 phosphor.
Fig. 5(b) shows the emission spectrum of MgSrAl10O17:Eu2 ,
Mn2 phosphor. This emission spectrum of sample was recorded
under 337 nm excitation. Emission spectrum exhibited two
intense bands centered at about 462 and 513 nm due to Eu2 and
Mn2 ions, respectively. The intense band centered at around
462 nm is attributed to bright blue emission of Eu2 ions and
assigned to the transition 4f65d(t2g)-4f7(8S7/2) [52]. The second
intense band centered at 513 nm is attributed to green emission of
Mn2 ions and assigned to the transition 4T1-6A1 [52]. Wang
et al. [48] observed blue emission band at around 414 nm due to
Eu2 ions and yellow emission band at around 566 nm due to
Mn2 ions. Yang and Chen [51] observed an emission band at
around 416 nm in the emission spectrum of SrZn2(PO4)2:Eu, Mn

N. Singh et al. / Journal of Luminescence 178 (2016) 479486

Stokes shift
6

513 nm

Green emission

Blue emission

462 nm

Energy transfer

337 nm

4f

0
2+

Eu

E(D)

4
T (D)
4
4 2
A1(G), E(G)
4
T (G)
4 2
T1 (G)

-1

Ex10 (cm )

4f 5d

483

A1(S)

2+

Mn

Fig. 6. Energy level diagram of Eu2 :Mn2 .

phosphor. Singh et al. [45] observed two emission bands centered

at around 442 and 511 nm due to Eu2 and Mn2 ions, respectively, in a BaAl12O19: Eu2 , Mn2 phosphor. Singh et al. [47] also
observed two emission bands at 449, 514 nm due to Eu2 and
Mn2 ions in LaMgAl11O19: Eu2 , Mn2 phosphor. Weak eld
conguration is present in the case of tetrahedral symmetry and
strong eld conguration is present in the case of octahedral
symmetry. Two emission centers in the emission spectra indicate
that the energy is transferred between Eu2 and Mn2 ions
[53,54]. The energy transfer between Eu2 and Mn2 in
MgSrAl10O17 phosphor is shown in Fig. 6. The two emission bands
at 462 and 513 nm due to Eu2 and Mn2 in the present phosphor
conrm that the energy is transferred between Eu2 and Mn2
ions. From the method of energy transfer, it can be predicted that
this phosphor can act as a potential single phased white light
emitting phosphor for UVLEDs.

Fig. 7. EPR spectra of MgSrAl10O17:Eu2 , Mn2 phosphor at different temperatures

(300  110 K).

3.5. Electron paramagnetic resonance studies

Fig. 7 shows the EPR spectra of MgSrAl10O17:Eu2 , Mn2 phosphor
observed at room and different low temperatures from 250 to 110 K.
These spectra exhibit the resonance signals with the effective g values
at g1.97 and 4.72 due to Mn2 and Eu2 ions, respectively. The
hyperne structure centered at g1.97 is due to Mn2 ions in tetrahedral symmetry [55]. Mn2 ion has 3d5 electronic conguration. It is
noticed that EPR of this ion shows a signal around g 2.0 in case of
tetrahedral symmetry. This ion further splits into six hyperne lines
due to interaction of the unpaired electron with 55Mn nucleus having
spin value S5/2. For lower symmetries of Mn2 ion, the ne structure transitions between the ligand eld split levels, corresponding to
o5/242o3/24, o3/242o1/24, o1/242o  1/24,
o  1/242o  3/24 and o  3/242o 5/24, can be observed. However due to large anisotropy, only a central signal with its
six hyperne components, corresponding to o1/242o  1/24 is
observed. The remaining transitions are not resolved due to large
anisotropy.
The weak resonance signal at g 4.72 is due to Eu2 ions [56].
The ground state of Eu2 ion is 8S7/2. The EPR spectrum exhibits
number of signals due to Eu2 ions. In the present case, one weak
signal is observed at g 4.72. The shape of EPR spectrum of Eu2
ions depends on the microwave frequency and the ligand eld
strength. Though Eu2 ions have the same electron conguration
4f7 as Gd3 ions, there have been only a few reports on EPR of
Eu2 doped materials [57]. The g values are independent of temperature variation from 300 to 110 K. This indicates that the

Fig. 8. Number of spins and Gibbs free energy of MgSrAl10O17:Eu2 , Mn2 phosphor at different temperatures (300-110 K).

structural environment is constant between the dopant and the

host lattice with the temperature variation.
The number of spins (N) can be computed by comparing the
area under the absorption curve with that of a standard
(CuSO4  5H2O) of known concentration. Weil and Bolton [58] gave
the following formula including the experimental parameters of

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N. Singh et al. / Journal of Luminescence 178 (2016) 479486

Table 1
Shows the g values, number of spins (N), Gibbs free energy (G), magnetic susceptibility (), and hyperne splitting constant (A) for Mn2 ions in MgSrAl10O17:
Eu2 , Mn2 phosphor at RT and 110 K.
T (K)

g value

N (spin/ m3)

G (kJ/mol)

(m3/kg)

A (mT)

300
110

1.97
1.97

8.04  1021
17.68  1021

 52.30
 20.81

1.89  10  3
11.33  10  3

8.4
8.4

potential and measures the stability of this phosphor. It is a temperature dependent quantity. The stability of this phosphor is high
at 110 K as the Gibbs free energy is low at this temperature. The
negative sign indicates that the exothermic reaction takes place
between the Mn2 ions and the phosphor lattice and there is
strong attractive interaction between the Mn2 ions and the
phosphor lattice.
The activation energy can be calculated using the expression

AeEa=RT ;
Fig. 9. Log10N and log10(N/T) versus reciprocal of temperature of MgSrAl10O17:
Eu2 , Mn2 phosphor.

both the sample (x) and the standard (std):

2
Ax scanx 2 Gstd Bm std g std SS 1std Nstd
N
;


2
Astd scanstd 2 Gx Bm x g x S S 1x

where A is the area under the absorption curve, scan is the magnetic eld corresponding to the unit length of the chart, G is the
amplitude, Bm is the modulation amplitude, g is the g factor, S is
the spin of the ions in the ground state. The subscripts x and std
indicate the sample and the standard, respectively. Nstd denotes
number of spins in 100 mg of CuSO4  5H2O standard. The number
of spins for Mn2 ions at g 1.97 in MgSrAl10O17:Eu2 , Mn2
phosphor is found to be 8.04  1021 and 17.68  1021 spin/m3 at
300 and 110 K, respectively. The number of spins increases with
the decrease of temperature from 300 to 230 K and later on
decreases from 230 to 110 K. The spins increase from 300 to 230 K
in accordance with the Boltzmann distribution law (Fig. 8). The
spins decrease from 230 K to 110 K. The decrease in number of
spins with the decrease of temperature is attributed to antiferromagnetic interactions [59] in the sample. The increase in
spins with the decrease of temperature is attributed to paramagnetic interactions. The number of spins not necessarily to
increase from 300 to 110 K as observed from the spectrum. The
number of spins depends on area of the spectrum and experimental parameters. The number of spin calculations was performed with respect to the origin software. The area of Mn2
signal has increased from 300 to 230 K and later it has decreased.
This is the reason why there is non-uniform increase in number of
spins even though the spectrum intensity appears to be increased
from 300 to 110 K.
The Gibbs free energy can be calculated using the equation [59]



G 2:303 RT log 10 kB T= h ;
2
where G is the Gibbs free energy, R is the Universal gas constant
(8.31 J/K/mol), kB is the Boltzmann constant (1.38  10  23 J/K), T is
the absolute temperature, is the rate constant and is equal to the
number of spins per m3, h is the Planck's constant
(6.63  10  34 Js). The Gibbs free energy of the Mn2 ions in
MgSrAl10O17:Eu2 , Mn2 phosphor at g 1.97 has been determined as 52.30 and  20.781 kJ/mol at 300 and 110 K, respectively. This computed value is in good agreement with the value
reported for glasses and minerals [60,61]. The Gibbs free energy
increases with the decrease of temperature (Fig. 8) in accordance
with the Boltzmann distribution law. This energy is a chemical

where is the rate constant and is equal to number of spins/m , A

is the pre-exponential coefcient, R is the universal gas constant, T
is the absolute temperature and Ea is the activation energy. Fig. 9
shows that the data of log10(N) of the Mn2 center at g 1.97 is
tted to the reciprocal of temperature (1/T). The slope of this plot
yields the activation energy Ea at 2.53 meV. This value is consistent with those reported for Mn2 ions in glasses and minerals
[61]. The activation indicates the minimum energy required to
liberate an unpaired electron from the Mn2 center in phosphor.
This energy also indicates molecular force of attraction between
the Mn2 center and the phosphor lattice. The pre-exponential
coefcient (PEC) has been found to be 51.7/s from the intercept of
Y axis of Fig. 9. This PEC indicates the collision frequency between
Mn2 center and phosphor lattice. Using PEC value, the spin
orientation, spin dynamics and spin concentration can be known.
Fig. 9 also shows that the data of log10(N/T) is tted to reciprocal of temperature. The intercept of this plot gives the entropy
S at 1.8 meV. This is comparable with the value reported in the
literature [62]. The positive sign indicates that more disorder is
found in the phosphor. The slope of this plot gives the enthalpy
H at  0.019 eV. This value is consistent with the value reported
in the literature [62]. The negative sign demonstrates that exothermic reaction takes place between the Mn2 ions and the
phosphor lattice. Thus correlation is present between Gibbs free
energy and the enthalpy. The entropy and enthalpy represent the
total heat content in the phosphor and also related to strain at the
domain boundaries and also indicate the exchange interaction.
The magnetic susceptibility can be determined using the
expression [63]
3

Ng2 2 J J 1=3 kB T

where N is the number of spins/m , g 1.97, is the Bohr magneton, J is the total angular momentum quantum number, kB is the
Boltzmann constant and T is the temperature. The magnetic susceptibility of Mn2 ions in MgSrAl10O17:Eu2 , Mn2 phosphor at
room temperature is computed as 1.89  10  3 m3/kg. The magnetic susceptibility increases from room temperature to 140 K and
later on decreases with the decrease of temperature from 140 to
110 K. The calculated magnetic susceptibility value is in good
agreement with the value reported in the literature [64]. The
importance of this method is the susceptibility is calculated for
paramagnetic component excluding the diamagnetic part of the
sample.
The zero-eld splitting parameter D is determined from the
ratio of intensity of allowed hyperne lines corresponding to the
3

N. Singh et al. / Journal of Luminescence 178 (2016) 479486

selection rule m 0 using the equation [65]





2
A2 35 4m2
5:334D2 35:14D 35  4m2
Im p 2 




2


2


2
g H
2 g H
g H



2
208D4 35  4m2

;


4
g H

observed at 300 and 110 K for the Mn2 ions in MgSrAl10O17:Eu2 ,

Mn2 phosphor.

where m is the nuclear spin magnetic quantum number, Im is the

intensity of the mth allowed hyperne (HF) line, A is the hyperne
splitting constant, D is the zero-eld splitting parameter and the
rest of the symbols have their usual meaning. The zero-eld
splitting (zfs) D emanates due to a combined action of the spin
orbit coupling taken as perturbation on the ligand eld (LF) states
[66]. The zfs parameter for this phosphor is found to be 27 mT at
room temperature.
The hyperne splitting constant (hfs) A is predicted using the
expression [67]
Bm B0 Am  35  4 m2 A2 =8 H0

485

where Bm is the magnetic eld representing m2m hyperne line,

B0 is the resonance magnetic eld. The A value is thus found to be
8.4 mT at room temperature. The A value is independent of temperature variation. The magnitude of the hfs constant A provides
a qualitative measure of the ionicity of bonding between the Mn2
ion and its ligands. van Wieringen [68] empirically asserted a
positive correlation between A and the ionicity of the manganeseligand bond. On this assumption, it is found that the bonding
between Mn2 ions and the surroundings in this phosphor is ionic
in character. In tetrahedral Td or octahedral Oh symmetry, Mn2
ion exhibits a sextet hyperne structure centered at g 2.0 [69]. A
value for Oh and Td symmetry is 10 and 8.3 mT [69]. The green
emission peak at 513 nm in emission is supporting Td symmetry. In
the present case, we observed A value as 8.4 mT at 300 K and
110 K. Therefore the site symmetry is tetrahedral since A value is
nearer to 8.3 mT.
The exchange eld Be is calculated using the expression [63]



Be kB = ;
7
where kB is the Boltzmann constant, is the Curie temperature
and is the Bohr magneton. The exchange eld is also known as
internal molecular eld. This is proportional to the magnetization.
The magnitude of the exchange eld may be of the order of 1000 T
[70].
The exchange integral J is computed using the expression [63]



J kB =3 ;
8
where kB is the Boltzmann constant, is the Curie temperature.
The exchange interaction energy is calculated using the
expression [63]
X
E  2J
S i Sj ;
9
where J is the exchange integral Si and Sj are the nearest neighbor
spins. The exchange eld Be is found to be 177 T. The exchange
integral is found to be 3.42 meV. The exchange interaction energy
is found to be  42.75 meV. The negative sign indicates there is
strong attractive interaction between the spins of Mn2 and the
phosphor lattice. The exchange integral J explains the nature and
stability of magnetic state. If the exchange integral is positive, the
magnetic state is stable. If the exchange integral is negative, the
magnetic state is unstable [63]. The exchange integral in the present case is positive and supports for the stability of the magnetic
system. It must be emphasized that the exchange interaction is
fundamentally electrostatic and that the spin enters into the
energy expression as a consequence of the Pauli Exclusion Principle [63]. Table 1 lists the g values, number of spins, Gibbs free
energy, magnetic susceptibility, hyperne splitting constant values

4. Conclusions
The bluegreen phosphor MgSrAl10O17:Eu2 , Mn2 with hexagonal structure was synthesized using a rapid, simple and onestep economical viable combustion method. This method proved
to be advantageous compared with the other preparation techniques. The EDX analysis showed that both dopants are uniformly
distributed in the MgSrAl10O17 phosphor. The absorption spectrum
exhibits bands due to Eu2 , Mn3 and host lattice excitation. The
excitation and emission spectra exhibit bands due to Eu2 and
Mn2 ions, respectively. The excitation band at 337 nm attributed
to the 4f7(8S7/2)-4f65d(t2g) transition of Eu2 ions. The intense
band centered at 462 nm in the emission spectrum is attributed to
bright blue emission of Eu2 ions and assigned to the transition
4f65d(t2g)-4f7(8S7/2). The sharp peak at around 513 nm due to
Mn2 ions is assigned to the transition 4T1-6A1. The EPR spectrum exhibits resonance signals with the effective g values at
g 4.72 and 1.97. The resonance signal with the effective g value at
g 4.72 is attributed to Eu2 ions. The resonance signal with the
effective g value at g 1.97 is attributed to Mn2 ions in tetrahedral symmetry. The Gibbs free energy increases with the
decrease of temperature from 300 to 110 K in accordance with the
usual Boltzmann distribution law.

Acknowledgments
This paper was supported by the KU Research Professor Program of Konkuk University. Dr. Vijay Singh expresses his thanks to
the Prof Seoung Soo Lee, Dean, College of Engineering, Konkuk
University, Seoul for his constant encouragement.

Appendix A. Supporting information

Supplementary data associated with this article can be found in
the online version at http://dx.doi.org/10.1016/j.jlumin.2016.06.015.

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