Materials Chemistry and Physics 246 (2020) 122826

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Effect of Sm3þ doping on optical properties of Mg2P2O7 and

Mg3P2O8 phosphors
Rubby Mahajan, Ram Prakash *
School of Physics, Shri Mata Vaishno Devi University, Katra, 182320, J&K, India

H I G H L I G H T S G R A P H I C A L A B S T R A C T

� Sm3þ doped Mg2P2O7 and Mg3P2O8

phosphors synthesized by solution
combustion route.
� XRD and Raman spectroscopy results
reveal single phase of synthesized
phosphors.
� Luminescent and optical properties for
solid state lighting application.
� Band gap narrowing effect.

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

Keywords: Reddish-orange emitting Sm3þ activated Mg2P2O7 and Mg3P2O8 (or Mg3(PO4)2) phosphors are synthesized via
X-ray diffraction (XRD) solution combustion method. The structural, vibrational and optical properties of phosphors are investigated in
Fourier transform infrared (FTIR) spectroscopy detail. Raman spectroscopy results reveal that Mg2P2O7:Sm3þ (2 mol %) and Mg3P2O8:Sm3þ (1 mol %) phosphors
Raman spectroscopy
show sharp band at 1061 cm 1 and 983 cm 1, respectively. Photoluminescence (PL) results indicate that the
PL
Diffuse reflectance spectra (DRS)
optimum molar concentration of Mg2P2O7:Sm3þ and Mg3P2O8:Sm3þ phosphors are 2 mol % and 1 mol %,
respectively. The average life-time of Mg2P2O7:Sm3þ (2 mol %) and Mg3P2O8:Sm3þ (1 mol %) phosphors are
found to be 2.21 ms and 0.77 ms, respectively. The optical band gap of Mg2P2O7:Sm3þ and Mg3P2O8:Sm3þ
phosphors show band narrowing effect which reveals that density of states (sub bands) are formed near con­
duction band.

1. Introduction pyrophosphate (Mg2P2O7) and Magnesium orthophosphate (Mg3P2O8)

In the last decades, researchers showed extensive attention towards
the pyrophosphate and orthophosphate as host materials. They have
superior properties such as high chemical stability as well as high
thermal stability, sufficient large band gap, easily prepared, low phonon
frequency, and environmental favourable, etc [1,2]. Magnesium
have Thortveitite and Farringtonite structure with monoclinic symme­
try, respectively [1,3].
However, rare earth doped phosphate materials have got great
attention toward the promising application in solid-state lighting, flat
displays devices, solid-state lasers, temperature sensors, and optical
storage, etc [4,5]. In recent year, white light emitting diodes (WLEDs)

* Corresponding author.
E-mail addresses: rpgiuc@gmail.com, ramprakash@smvdu.ac.in (R. Prakash).

https://doi.org/10.1016/j.matchemphys.2020.122826
Received 18 September 2019; Received in revised form 2 January 2020; Accepted 15 February 2020
Available online 18 February 2020
0254-0584/© 2020 Elsevier B.V. All rights reserved.
R. Mahajan and R. Prakash
has been a hotspot for the researchers because of several advantages like
mercury-free, environmental benignness, high colour rendering index as
well as high efficiency, and low energy consumption, etc [5,6]. But the
current WLEDs has low colour rendering index and high correlated
colour tolerance temperature because of the absence of red component.
For that reason, the red phosphor is very necessary for the generation of
warm light luminescence and enhanced luminous efficiency. Many re­
searchers have explored to use the red emitting phosphor to improve the
phosphor converted-WLEDs lighting quality. The trivalent europium
doped material were limited or rarely used for the development of warm
WLEDs due to the excitation spectra of Eu3þ ion were not fitted near
ultra violet (UV) and blue region [7]. The Eu2þ doped Sr2Si5N8 and Eu2þ
doped CaAlSiN3 were commercially available red phosphors. But, these
phosphors have tough synthesis condition i.e., high pressure and high
temperature were needed [8–11]. The narrow band red emitting
SrLiAl3N4:Eu2þ phosphor was also used for warm WLEDs but, it has
spectral overlap problem [12]. The light emitting diodes (LEDs) were
also made from either III-phosphides or III-nitrides. Quantum efficiency
gap of these LEDs was not enough in visible spectrum for the production
of monochromatic as well as high pure colour light around 600 nm [13].
So, it is necessary to investigate new class of phosphors that show high
degree of absorption in near-UV and blue region. Among the rare earth
ions, Sm3þ ion play an important role in luminescent materials. They
give strong orange-red emission while excited with UV or blue region
and the electronic transitions of Sm3þ ion from higher state 4G5/2 to
lower state 6HJ (J ¼ 5/2, 7/2, 9/2, 11/2) [4,5].
In literature, the reports are available in Sm3þ doped host material
such as Ba2P2O7:Sm3þ, Ca3(PO4)2:Sm3þ, γ-Ca3(PO4)2:Sm3þ and
LiNa3P2O7:Sm3þ [5,14–16]. Zhang et al. had studied the optical prop­
erties of Mg3(PO4)2:Eu2þ, Mn2þ and reported it as good candidate for the
UV LEDs chip application [3]. Recently, we have studied the photo­
emission and optical properties of Dy3þ activated Mg2P2O7 phosphor
[17]. The optical properties of rare earth activated phosphate material
can be tuned by changing the concentration of rare earth ion. To the best
of our knowledge, there is no report available on optical and lumines­
cent properties of Sm3þ doped Mg2P2O7 and Mg3P2O8 as a host.
Furthermore, there are number of synthesis route are available in
literature for the synthesis of phosphor material. In this work, solution
combustion route were used to prepare materials (Mg2P2O7: Sm3þ and
Mg3P2O8: Sm3þ) because it has many advantages like low cost, simple,
fast process, and energy saving. Here, the prepared materials were
characterized by X-ray diffraction (XRD), Fourier transform infrared
(FTIR) spectroscopy, Raman spectroscopy, Photoluminescence (PL) and
ultra violet-visible (UV–Vis) spectroscopy for structural, vibrational, and
optical investigation of samples.
2. Experiment
2.1. Sample preparation
Sm3þ doped Mg2P2O7 and Mg3P2O8 phosphors were synthesized via
solution combustion route. Magnesium nitrate hexahydrate Mg
(NO3)2⋅6H2O (99.0%), Ammonium dihydrogen orthophosphate (NH4)
H2PO4 (99.98%), Urea CH4N2O (99.5%), and Samarium oxide Sm2O3
(99.0%) were used as an initial material according to a balanced
chemical reaction as given in equations (1) and (2). A few drops of nitric
acid (HNO3) were added on Sm2O3 to transform into nitrate form.
6ðx 1ÞMgðNO3 Þ2: 6H2 O þ 6ðNH4 ÞH2 PO4 þ 7CH4 N2 O
þ 3xSm2 O3 →3Mg2ð1 xÞ Sm2x P2 O7 þ 7CO2 þ 68H2 O þ 16N2 (1)
3ðx 1ÞMgðNO3 Þ2: 6H2 O þ 2ðNH4 ÞH2 PO4 þ 4CH4 N2 O
3x
þ Sm2 O3 →Mg3ð1 xÞ Sm3x P2 O8 þ 4CO2 þ 32 H2 O þ 8N2 (2)
2 600-500 cm 1 is attributed to the bending mode of O–P–O bond [15]. In
According to stoichiometric ratio, the weighted material was crushed
2
Materials Chemistry and Physics 246 (2020) 122826
into the agate mortar pestle for 30 min with few drops of distilled water.
They form uniform mixture and transferred into the borosilicate beaker.
The homogeneous mixture was fired into the preheated muffle furnace
at temperature 600 C. The reaction was completed in 4 min with the
�
expansion of huge amount of gases and white foamy product was ob­
tained. The foamy product was cooled at room temperature and
smoothly grinded for 1 min and after that the white color powder was
formed. Further, the powder was annealed at temperature 800 C for 2 h
�
to improve the crystallinity of the material. The process of synthesis is
adopted as reported previously [17].
2.2. Sample characterization
Powder XRD pattern of Sm3þ doped Mg2P2O7 and Mg3P2O8 samples
were recorded using Bruker D8 Advance X-ray diffractometer with Cu-
Kα (λ ¼ 1.5406 Å) using as a radiation source and scanning step size
0.02� in the range 10 –90� . FTIR spectra of synthesized phosphors were
�
monitored by the Shimadzu FTIR tracer-100 spectrometer with Dia­
mond (Attenuated total reflection) ATR accessories. The LabRam-
HR800 micro Raman spectrometer combined with an optical micro­
scope, CCD detector were used to obtain the Raman spectrum of the
prepared samples with excitation source as diode laser (473 nm). PL
excitation, emission and life time spectra of phosphors were carried out
using Cary-Eclipse Spectrofluorometer with xenon lamp as an excitation
source. The Shimadzu double beam UV–Vis spectrophotometer Model
2600 was used to record the diffuse reflectance spectra (DRS) and band
gap of the material.
3. Results and discussion
3.1. Structural analysis
3.1.1. X-ray diffraction
Fig. 1 (a) and 1 (b) represents the XRD pattern of Sm3þ (2 mol %)
doped Mg2P2O7 and Sm3þ (1 mol %) doped Mg3P2O8 phosphors. The
XRD pattern of synthesized phosphors is well indexed with standard
JCPDS card no. 75-1055 (Mg2P2O7:Sm3þ) and 33-0876 (Mg3(PO4)2:
Sm3þ). The ionic radii and coordination number (CN) of Mg2þ, P5þ, and
Sm3þ are (0.72 Å, CN ¼ 6), (0.17 Å, CN ¼ 4), and (0.958 Å, CN ¼ 6),
respectively. The ionic radii of Mg is comparable to Sm ion i.e., the Sm3þ
ion successfully occupies the Mg2þ lattice site in the host matrixes
(Mg2P2O7 and Mg3P2O8). This result reveals that no residues of sec­
ondary phases are seen in the XRD graph as well as no peak of rare earth
ion is observed. So, the synthesized materials are formed in a single
phase. Both Sm3þ doped Mg2P2O7 and Mg3P2O8 phosphors are
confirmed to be a monoclinic crystal structure with B21/c and P21/n
(14) space group, respectively. The average crystallite size of Sm3þ
doped Mg2P2O7 and Mg3P2O8 phosphors are obtained for intense peaks
using Debye Scherer formula and found to be ~28 nm and ~41 nm,
respectively [18]. The lattice parameter of Sm3þ doped Mg2P2O7 and
Mg3P2O8 phosphors are calculated using unitcell win software and listed
in Table 1.
3.1.2. Fourier transform infrared (FTIR) spectroscopy
Fig. 2 depicts the FTIR spectrum of Sm3þ (2 mol %) doped Mg2P2O7
and Sm3þ (1 mol %) doped Mg3P2O8 phosphors. The FTIR spectrum is
used to study the functional group and chemical bonding of the samples
in the range 400–1300 cm 1. There are several band observed due to
phosphate group exist in Sm3þ doped Mg2P2O7 and Mg3P2O8 phosphors.
In Mg2P2O7:Sm3þ phosphor, the intense absorption band present in the
region 900-1300 cm 1 is due to the stretching mode of P–O bond of
pyrophosphate group (P2O7) 4 [19]. The peak at 749 cm 1 is attributed
to stretching mode of P–O–P bond [20,21]. The IR band in the region
Mg3P2O8:Sm3þ phosphor, the strong broadband exist in the range of
1182-860 cm 1 due to the antisymmetric stretching mode of P–O bond
R. Mahajan and R. Prakash Materials Chemistry and Physics 246 (2020) 122826

Fig. 1. (a) XRD pattern of Sm3þ (2 mol %) doped Mg2P2O7 and (b) Sm3þ (1 mol %) doped Mg3(PO4)2 phosphors along with standard JCPDS card no. 75-1055 and 33-
0876, respectively.

Table 1
Crystallite size and lattice parameters of Sm3þ (2 mol %) doped Mg2P2O7 and Sm3þ (1 mol %) doped Mg3P2O8 phosphors.
Phosphor Crystallite size (nm) a (Å) Lattice constants b (Å) c (Å) V (Å)3 Angle

Mg2P2O7:Sm3þ 28 13.129 � 0.002 8.313 � 0.003 9.010 � 0.005 948.46 β¼ 105.33�

Standard (75-1055) Mg2P2O7 13.17 8.290 9.053 954.06 β¼ 105.18�
Mg3(PO4)2:Sm3þ 41 7.590 � 0.001 8.250 � 00.1 5.067 � 0.001 316.50 β¼ 93.967�
Standard (33–0876)Mg3(PO4)2 7.599 8.235 5.076 316.90 β¼ 94.062�

of [PO4] 3 group [15]. The peak located at 668 cm 1 is ascribed to
stretching mode of P–O–P bond [20]. The band in the region 650-520
cm 1 can be ascribed to the bending vibration of O–P–O bond [15]. The
FTIR result suggests that only the phosphate group exist in the sample
and no other residue peak of rare-earth ion is seen in the sample.
3.1.3. Raman spectroscopy
The Raman spectrum of Sm3þ (0 and 2 mol %) doped Mg2P2O7 and
Sm3þ (0 and 1 mol %) doped Mg3P2O8 phosphors is shown in Fig. 3. The
Raman spectrum is used to investigate the structural, vibrational as well
as rotational properties of the samples. The Raman spectra of both
samples are divided into subparts according to which type of vibrations
are present. The Raman spectrum in the range of 100–150 cm 1 is
described the external lattice vibrations and in the range of 150–300
cm 1 is ascribed to internal lattice vibrations. The Raman active band in
the region 300-400 cm 1 is associated to metal oxygen stretching vi­
brations. The Raman bands present in the region 400-800 cm 1 and 800-
1300 cm 1 are ascribed to bending modes and stretching modes of

3
R. Mahajan and R. Prakash
Fig. 2. FTIR spectrum of Sm3þ (2 mol %) doped Mg2P2O7 and Sm3þ (1 mol %)
doped Mg3P2O8 phosphors.
Fig. 3. Raman spectrum of Sm3þ (0 and 2 mol %) doped Mg2P2O7 and Sm3þ (0
and 1 mol %) doped Mg3P2O8 phosphors.
phosphate anions [22].
In Mg2P2O7:Sm3þ phosphor, the bands observed at 1189.8, 1137.0,
1115.0, 1085.6, 1061.0, 982, 803.0, 739.4, 576, 552.3, 486, and 459
cm 1 are due to P2O7 4 group. The feeble Raman band in the region 100-
400 cm 1 may be due to lattice vibration and stretching mode of metal
oxygen (Mg–O) bond. The weak Raman bands at 459 and 486 cm 1 can
be ascribed to bending mode of phosphate group [23]. The Raman band
observed at 552.3 and 576 cm 1 are due to the bending mode of (PO4) 3
group [24,25]. The broad Raman band at 739.4 cm 1 can be assigned to
stretching mode of P–O–P bond of P2O7 4 group [26]. The less intense
band at 803 cm 1 is attributed to (-O-P-O-) of symmetric stretching
mode [27]. The feeble Raman band located at 982 cm 1 is due to
4
Materials Chemistry and Physics 246 (2020) 122826
symmetric stretching mode of (PO4)3- group [24]. The intense Raman
band at 1061 cm 1 is attributed to P–O bridge bond with A1g symmetric
stretching modes [28]. Low intense bands observed at 1189.8 and
1085.6 cm 1 are assigned to asymmetric vibration of ν (P–O) bond and
symmetric vibration of ν(P–O) bond, respectively [28]. The Raman peak
at 1137.0 cm 1 can be examined to P–O bond with Ag and Bg symmetry
modes [28]. The band located at 1115.0 cm 1 is due to the P–O asym­
metric stretching mode [22].
In Mg3P2O8:Sm3þ phosphor, the Raman band observed at 421, 470,
501, 576, 620, 637, 654, 803, 983, 1029, 1076, 1115, and 1152.1 cm 1
are due to (PO4) 3 group. The Raman band at 132 cm 1 and 177 cm 1
may be due to lattice vibration and weak or feeble band at 320 cm 1 and
356 cm 1 may be because of stretching vibration of metal oxygen bond
(Mg–O). The band at 576, 803, and 1115 cm 1 are also seen in Mg2P2O7:
Sm3þ phosphor due to bending, symmetric stretching, and antisym­
metric stretching mode of phosphate group. The weak Raman peaks at
421 and 470 cm 1 are assigned to bending mode of (PO4)3- group [23].
The feeble bands in the region 500-670 cm 1 may be attributed to
bending modes of (PO4) 3 group [22]. The sharp intense peak at 983
cm 1 is ascribed to the symmetric stretching vibration of (PO4)3- group
[24]. The peak at 1029 cm 1 and 1076 cm 1 are assigned to asymmetric
stretching mode of (PO4)3- group [23,29]. The lower intensity peak
located at 1152.1 cm 1 is because of antisymmetric mode of (PO4)3-
group [24]. In both Raman spectra of doped and undoped samples show
that there is slight peak shifting because of difference in ionic radii of
Mg2þ ion and Sm3þ ion in the host lattice as well as there is no residue
peak of dopant observed. Hence, the Raman and XRD results reveal that
the synthesized phosphors are in single phase.
4. Optical analysis
4.1. Photoluminescence
Fig. 4 (a) and 4 (b) depicts the PL excitation and emission spectrum
of Sm3þ activated Mg2P2O7 and Mg3P2O8 phosphors in the range of
200–750 nm. In excitation and emission spectrum of both samples show
a little variation in peak position. The difference in peak positions
because of the shift in energy levels of Sm3þ ion is called as Neph­
elauxetic effect i.e., the overlapping of oxygen orbital to 4f orbital of
Sm3þ ion produced by effect of bonding between the Sm3þ ions and the
local environment [30]. In both phosphors, the excitation spectrum is
monitored at 600 � 1 nm emission wavelength of Sm3þ ion. There are
several peaks are observed in the region 200–450 nm of Sm3þ ion in the
host lattice. In the wavelength region 200–300 nm a broad charge
transfer band (CTB) is observed due to charge transfer from O2 2p filled
orbital to empty 4f orbital of Sm3þ ion in the host matrix (Mg2P2O7) and
negligible or little CTB is observed in Mg3P2O8 phosphor [1]. In the
wavelength region 300–450 nm, the various sharp narrow excitation
peaks are also noticed at 315 nm, 341 � 1 nm, 359 nm, 373 � 1 nm, 400
nm, and 436 � 2 nm from ground state 6H5/2 to excited state 2L15/2,
4
H9/2, 4D3/2, 6P7/2, 4K11/2, and 4G9/2 due to 4f-4f transition of Sm3þ ion
in the host lattice, respectively [4]. The CTB is intense as compared to
the 4f-4f peaks because of Laporte forbidden nature of intra 4f-4f tran­
sitions in Sm3þ doped Mg2P2O7 [1].
In both phosphors, an emission spectrum is recorded at 400 nm
excitation wavelength in the region 450–750 nm. The narrow peaks
positioned at 562 � 1 nm (yellowish), 600 � 1 nm (orange), 644 � 2 nm
(orange-red), and 706 � 2 nm (red) is ascribed to electronic transition
from excited state 4G5/2 to ground state 6H5/2, 6H7/2, 6H9/2, and 6H11/2 of
Sm3þ ion, respectively [4,31]. In literature, the emission peaks of Sm3þ
ion reported at 564 nm, 602 nm, 646 nm and contain doublets i.e., does
not have sharp peaks of Sm3þ ion. The peak position of Sm3þ ion in
present work is approximately equal to literature [14].
In all emission transitions of Sm3þ activated Mg2P2O7 and Mg3P2O8
phosphors, the most dominated peak at 600 � 1 nm is corresponds to
transition 4G5/2 → 6H7/2 of Sm3þ ion. The transition 4G5/2 → 6H7/2 (Δ J
R. Mahajan and R. Prakash Materials Chemistry and Physics 246 (2020) 122826

[1].
Fig. 5 (a) and 5 (b) represent the emission spectra of Sm3þ activated
Mg2P2O7 and Mg3P2O8 phosphors in the region 450–750 nm. The
excitation peak at 400 nm is used to record the emission spectra at
different concentration (0.5, 1, 2, 3, and 4 mol %) of Sm3þ ion activated
Mg2P2O7 and Mg3P2O8 phosphors. The peak positions and peak shapes
of the emission spectra are similar with increasing Sm3þ ion concen­
tration in the host lattice but only change on the phosphorescence in­
tensities of the phosphors are observed.

4.2. Energy level diagram

The whole process of excitation and emission of Sm3þ doped samples

are well explained by energy level diagram is represented in Fig. 6.
Under different excitations at 315 nm, 341 � 1 nm, 359 nm, 373 � 1 nm,
400 nm, and 436 � 2 nm the Sm3þ ion goes from the lower energy state
6
H5/2 to the different higher energy states with corresponding transi­
tions 2L15/2, 4H9/2, 4D3/2, 6P7/2, 4K11/2, and 4G9/2, respectively [1,31].
From different excited states, the Sm3þ ion relaxes into metastable state
4
G5/2 by means of non-radiative transitions. From 4G5/2 state, the Sm3þ
ion undergoes to ground state by radiative transition with the emission
of a photon which can be attributed to 562 � 1 nm, 600 � 1 nm, 644 � 2
nm, and 706 � 2 nm having transitions 4G5/2 → 6H5/2, 4G5/2 → 6H7/2,
4
G5/2 → 6H9/2, and 4G5/2 → 6H11/2 of Sm3þ ion, respectively.

Fig. 4. (a) PL excitation and emission spectra of optimum concentration of

Sm3þ (2 mol %) activated Mg2P2O7 and (b) Sm3þ (1 mol %) doped Mg3P2O8
phosphors in the range of 200–750 nm.

¼ � 1) of Sm3þ ion is partially electric dipole (ED) and partially mag­

netic dipole (MD) in quality [1,32,33]. The peak at 562 � 1 nm is
attributed to transition 4G5/2 → 6H5/2 (Δ J ¼ � 0) is a totally MD in
quality. The peak at 644 � 1 nm is ascribed to electronic transition 4G5/2
→ 6H9/2 (Δ J ¼ � 2) is a totally ED in quality. The peak at 706 � 2 nm is
corresponds to 4G5/2 → 6H11/2 (Δ J ¼ � 3) is forbidden in nature. The ED
transition is hypersensitive to the local environment of host lattice.
When both MD and ED transition is present in the spectrum then Sm3þ
ion occupies both symmetric and antisymmetric site in the host matrix Fig. 6. Energy level diagram of Sm3þ ion activated sample.

Fig. 5. (a) PL Emission spectra of Sm3þ activated Mg2P2O7 and (b) Sm3þ activated Mg3P2O8 phosphors at different concentration of Sm3þ ion in the range of
450–750 nm at excitation wavelength of 400 nm. The insets show the expansion of emission spectra in the region 580–630 nm.

5
R. Mahajan and R. Prakash Materials Chemistry and Physics 246 (2020) 122826

4.3. Concentration quenching (Mg3P2O8:Sm3þ). The value of Q is 4.8363 � 5 (Mg2P2O7:Sm3þ) and

4.6872 � 5 (Mg3P2O8:Sm3þ). These results indicate that dipole-dipole
Fig. 7 shows the effect of Sm3þ in the PL intensity (Mg2P2O7 and interaction is capable for concentration quenching for both Sm3þ
Mg3P2O8). In both Sm3þ activated Mg2P2O7 and Mg3P2O8 phosphors, doped Mg2P2O7 and Mg3P2O8 phosphors.
the maximum phosphorescence emission intensity occur at 2 mol % and
1 mol % of Sm3þ ion, respectively. Thereafter increase in the concen­ 4.4. Decay curve
tration of Sm3þ ion in both host matrix there is a decline in phospho­
rescence emission intensity due to concentration quenching effect [34]. Fig. 9 (a) and 9 (b) represents the phosphorescence curve of Sm3þ (2
The non-radiative energy transfer between the activator ions in the host mol %) activated Mg2P2O7 and Sm3þ (1 mol %) activated Mg3P2O8
lattice causes the concentration quenching effect. There are three phosphors are monitored under most prominent excitation wavelength
non-radiative energy transfers between the activator ions via exchange 400 nm with dominant emission wavelength 600 � 1 nm. The lumi­
interaction, re-absorption, and multipolar interaction. Blasse proposed nescence decay curve of both Sm3þ activated Mg2P2O7 and Mg3P2O8
the formula to calculate the critical distance between the activator ions phosphors are fitted with third order exponential decay (Exp Dec 3)
and which type of interaction responsible for concentration quenching equation (5) and second order exponential decay (Exp Dec 2) equation
effect as given in equation (3) [34]. (6), respectively.
� �1
(5)
t t t
3V 3 IðtÞ ¼ ​ I0 þ A1 e τ1
​ þ A2 e τ2
​ þ A3 e τ3
Rc � 2 (3)
4πXc Z
(6)
t t
IðtÞ ¼ ​ I0 þ A1 e τ1
​ þ A2 e τ2

Where Rc is critical distance between dopant and quenching sites, V is

the volume of the unit cell (Mg2P2O7:Sm3þ 946.56 Å3, Mg3P2O8:Sm3þ Where I is luminescence intensity at time t, A1, A2, A3 are constants, and
315.52 Å3), Z no. of cations present in the unit cell (4), Xc is the optimum τ1, τ2, τ3 are decay time. For Mg2P2O7:Sm3þ phosphor the value of
concentration of dopant ion in the host matrix (Mg2P2O7:Sm3þ 2 mol %, constants A1 (5.15286), A2 (1.89503), A3 (2.58166) and exponential
Mg3P2O8:Sm3þ 1 mol %). The value of the critical distance of both Sm3þ components of decay time τ1 (0.02783), τ2 (0.38959), τ3 (2.3546). For
doped Mg2P2O7 and Mg3P2O8 phosphors are obtained to be 28.27 Å and Mg3P2O8:Sm3þ phosphor the value of constants A1 (3.55926), A2
24.70 Å, respectively. The value of the critical distance between the (8.55053) and exponential component of decay time τ1 (0.89133) and τ2
activator ions is greater than 5 Å then multipolar interaction is capable (0.0588). According to these parameters, the average life time of both
of concentration quenching phenomenon. Sm3þ activated Mg2P2O7 and Mg3P2O8 phosphors are calculated from
Dexter gave an equation (4) to find the multipolar interaction equation (7) [36].
throughout the activation ion in the host matrix for capable of concen­
tration quenching [35].
2 3 1
I Q
(4)
=
¼ K41 þ βðXÞ 5
3

Where K and β are constants, X value of dopant ion concentration greater

than or equal to critical concentration, I is the emission intensity, and Q
is multipolar interaction i.e., 3 (exchange interaction), 6 (dipole-dipole),
8 (dipole-quadrupole), 10 (quadrupole-quadrupole). Fig. 8 shows the
plot of log(I/X) versus log(X) for orange-red emission wavelength 600 �
1 nm of both phosphors. According to equation (4) the graph are fitted
by a straight line with slope are 1.6121 (Mg2P2O7:Sm3þ) and 1.5624

Fig. 7. Variation in PL emission intensity with different concentration of Sm3þ Fig. 8. (a) A graph between log(X) and log(I/X) of Sm3þ ion (X � Xc) activated
ion in the host lattice (Mg2P2O7 and Mg3P2O8). Mg2P2O7 and (b) Mg3P2O8 phosphors.

6
R. Mahajan and R. Prakash
Fig. 9. (a) Decay curve of Sm3þ (2 mol %) doped Mg2P2O7 and (b) Sm3þ (1 mol
%) doped Mg3P2O8 phosphors recorded at excitation wavelength of 400 nm.
P (7)
Ai τ2
i
τeff ​ ¼ P
i
Ai τ i
i
Where τeff is the average lifetime, Ai is constant and τi is decay time. The
value of average lifetime of both Sm3þ doped Mg2P2O7 and Mg3P2O8
phosphors are approximately found to be 2.11 and 0.77 ms, respectively.
The Mg3P2O8:Sm3þ phosphor has small average decay time value 0.77
ms, which shows a faster switching response that is required for LED
devices application.
4.5. CIE coordinates, CCT, and color purity
Fig. 10 represents the commission international de l’Eclairage (CIE)
diagram of Sm3þ (2 mol %) doped Mg2P2O7 and Sm3þ (1 mol %) doped
Mg3P2O8 phosphors. To determine the ability of the synthesized phos­
phors for application purpose, we have examined the CIE coordinates
and correlated color temperature (CCT) of the phosphors.
The CIE chromaticity coordinates are calculated using CIE software
to investigate which color tone of the phosphors [37]. The value of CIE
coordinates of Sm3þ (2 mol %) doped Mg2P2O7 and Sm3þ (1 mol %)
doped Mg3P2O8 phosphors are obtained to be (x ¼ 0.60, y ¼ 0.40) and
(x ¼ 0.59, y ¼ 0.40) under excitation 400 nm, respectively. The CIE
coordinates of Sm3þ activator Mg2P2O7 and Mg3P2O8 phosphors falls
under orange-red emission in color gamut.
To calculate the CCT of Sm3þ activated Mg2P2O7 and Mg3P2O8
7
Materials Chemistry and Physics 246 (2020) 122826
Fig. 10. CIE coordinate of Sm3þ (2 mol %) doped Mg2P2O7 (black color tri­
angle) and Sm3þ (1 mol %) doped Mg3P2O8 (green color circle) phosphors.
phosphors using McCamy empirical formula in equation (8) [38].
CCT ¼ 449n3 þ 3525n2 6823n þ 5520:33 (8)
ðx xe Þ
n¼
ðy ye Þ
Where xe ¼ 0.3320 and ye ¼ 0.1858 are the chromaticity epicenters. x
and y are the value of CIE coordinates. The value of CCT of Sm3þ acti­
vator Mg2P2O7 and Mg3P2O8 phosphors are obtained to be 1622.30 K
and 1631.54 K, respectively. Estimation of color purity is important for
narrow band emission. In our case, we obtain a narrow band emission at
600 � 1 nm in the reddish-orange region. So, we calculate the color
purity of reddish-orange emitting phosphors using formula as given in
equation (9) [39].
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ðx xi Þ2 þ ðy yi Þ2
Color ​ purity ​ ¼ ​ qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi � 100 (9)
ðxd xi Þ2 þ ðyd yi Þ2
Where (x, y) are coordinates of the samples, (xi, yi) are coordinates of
the illuminate point, and (xd, yd) are CIE coordinates of dominate
emission wavelength at 600 � 1 nm. Now, (x ¼ 0.60, y ¼ 0.40) CIE
coordinates of Mg2P2O7:Sm3þ, (x ¼ 0.59, y ¼ 0.40) CIE coordinates of
Mg3P2O8:Sm3þ, (xi ¼ 0.3333, yi ¼ 0.3333) and (xd ¼ 0.634, yd ¼ 0.368),
(xd ¼ 0.642, yd ¼ 0.357). The color purity of Sm3þ doped Mg2P2O7 and
Sm3þ doped Mg3P2O8 are obtained to be approximately 90.84% and
85.69%, respectively. In addition to this, the color purity of Sm3þ doped
Mg2P2O7 and Mg3P2O8 samples is high as compared to the Ca3(PO4)2:
Sm3þ, γ-Ca3(PO4)2:Sm3þ phosphor because the CIE coordinates of Sm3þ
doped Mg2P2O7 and Sm3þ doped Mg3P2O8 locates at the edge that shows
the sample has high purity. These PL results suggest that the prepared
samples would have potential application in orange-red emitter devices
and also be used for WLEDs when mixed with other phosphor.
4.6. Diffuse reflectance spectrum
The DRS of both Sm3þ doped Mg2P2O7 and Mg3P2O8 phosphors is
shown in Fig. 11 (a) and 11 (b). The DRS is used to study the optical
properties of the synthesized phosphors. In both phosphors, the strong
R. Mahajan and R. Prakash Materials Chemistry and Physics 246 (2020) 122826

non-homogenous absorption bands are observed in near IR region

914–1400 nm because of Sm3þ ion. The intensity of absorption bands
increases with increase in the concentration of Sm3þ ion (0.5–4 mol %)
in the host lattice. The four bands are observed at 938 � 2 nm (6H5/2 →
6
F11/2), 1076 � 3 nm (6H5/2 → 6F9/2), 1233 � 2 nm (6H5/2 → 6F7/2), and
1376 � 4 nm (6H5/2 → 6F5/2) of Sm3þ ion [31]. The weak absorption
bands are observed in the region 319–500 nm due to 4f-4f spin forbidden
transitions of Sm3þ ion [1,31]. The dominant peak at 400 nm in the
region 319–500 nm having transition 6H5/2 → 4K11/2 is referred to the
synthesized phosphor may be used for orange-red emitting LEDs appli­
cation. The sharp intense absorption edge in the range 198–248 nm
because of host absorbed a specific amount of photon energy.

4.7. Optical band gap

3þ
Fig. 12 (a) and 12 (b) shows the energy band gap of Sm doped
Mg2P2O7 and Mg3P2O8 phosphors are estimated from diffuse reflectance
spectra using Kubelka Munk function as given in equation (10) [40].
� In Mg3P2O8:Sm3þ, it is observed that the optical band gap decreases
½FðRÞhν�2 ¼ A hν Eg (10)
where Eg energy band gap, A is constant, and hν is photon energy.
For the direct band gap the Tauc plot and energy band gap of Sm3þ
doped Mg2P2O7 and Mg3P2O8 phosphors at different concentration of
Sm3þ ion in the host lattice are tabulated in Table 2.
In Mg2P2O7:Sm3þ phosphors, it is observed that the energy band gap
of phosphors increases up to 2 mol % of Sm3þ ion in the host lattice
because of Moss effect [41]. But, further increase in concentration of
Sm3þ there is a decrease in energy band gap may be because of sub levels
Fig. 12. (a) Optical band gap of Mg2P2O7:Sm3þ and (b) Mg3(PO4)2:Sm3þ with
variation in concentration of Sm3þ ion.
of dopant ion formed near conduction band as shown in Fig. 12 (a) [42].
with increases in the concentration of Sm3þ ion in the host matrix
because of band gap narrowing effect [42]. The density of state may be
formed between the valence and conduction band in the host material i.
e., contraction in energy band gap is represented in Fig. 12 (b).
4.8. Refractive index and metallization criterion
Fig. 13 (a) (Mg2P2O7:Sm3þ) and 13 (b) (Mg3P2O8:Sm3þ) represent
the variation in refractive index and metallization criterion concerning
for variation in concentration of Sm3þ ion and energy band gap. These
values are listed in Table 2. Refractive index is obtained from energy
band gap of the material. The synthesized material absorbs light corre­
sponding to its band gap and rest of light it transmits through a material
is called static phenomenon. The formula is used to calculate the
refractive index is given in equation (11) [43].
pffiffiffiffiffi
η2 1 Eg
¼ 1 (11)
η2 þ 2 20

Where Eg is band gap and η is refractive index of the material.

A metallization criterion is theoretical formula to study the insu­
lating nature of the material. Metallization criterion of the prepared
material is calculated on the basis of refractive index and optical band
gap of the material given by Dimitrov and Sakka using equation (12)
[44].
pffiffiffiffiffi
η2 1 Eg
M¼ 1 ¼ (12)
η2 þ 2 20

where M is a metallization criterion. The value of M < 1 for non-metallic

nature and M > 1 for metallic nature of the material.The values of
metallization criterion for both phosphors are found to less than one as
listed in Table 2 , which confirm non-metallic nature of samples.

Table 2
Optical band gap, refractive index, and metallization criterion of Sm3þ activator
Mg2P2O7 and Mg3(PO4)2 phosphors.
S Concentration of Mg2P2O7 Mg3P2O8
no. Sm3þ ion (mole %)
Eg η M Eg η M
(eV) (eV)

1 0.5 5.20 1.970 0.509 4.75 2.038 0.487

2 1 5.33 1.952 0.516 4.73 2.041 0.486
3 2 5.34 1.951 0.517 4.55 2.071 0.477
4 3 5.23 1.966 0.511 4.48 2.083 0.473
Fig. 11. (a) Diffuse reflectance spectra of Sm3þ doped Mg2P2O7 and (b)
5 4 5.20 1.970 0.509 4.40 2.096 0.469
Mg3P2O8 phosphors at concentration (0.5–4 mol %) of Sm3þ ion.

8
R. Mahajan and R. Prakash
Fig. 13. (a) Influence of concentration of Sm3þ ion on band gap, refractive index, and metallization criterion of Mg2P2O7 and (b) Mg3P2O8 phosphors.
5. Conclusions
In summary, we have successfully synthesized the series of Sm3þ
activated Mg2P2O7 and Mg3P2O8 phosphors via solution combustion
route. These synthesized phosphors are characterized by XRD, FTIR,
Raman, PL, and UV–Vis spectroscopy. XRD and Raman results show that
the synthesized phosphors are in a single phase. It found to be a
monoclinic phase with B21/c (Mg2P2O7:Sm3þ) and P21/n (14)
(Mg3P2O8:Sm3þ) space group. The Mg2P2O7:Sm3þ and Mg3P2O8:Sm3þ
phosphors are excited near UV light which emits orange-red emission.
The CIE coordinates of both Sm3þ doped Mg2P2O7 and Mg3P2O8 phos­
phors are obtained to be (x ¼ 0.60, y ¼ 0.40) and (x ¼ 0.59, y ¼ 0.40)
which lies in orange-red region, respectively. The energy band gap of
Sm3þ doped Mg2P2O7 and Mg3P2O8 phosphors are in the range of
(5.20–5.33 eV) and (4.75–4.40 eV), respectively. These results suggest
that the synthesized phosphors may be useful for solid-state lighting
application when excited with UV chip and to obtain white light these
phosphors are mixed with other phosphors.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors humbly acknowledge Director, UGC-DAE CSR, Indore
for providing experimental facilities at Indore Centre. The authors are
thankful to Dr. M. Gupta and Dr. V. G. Sathe for XRD and Raman mea­
surements, respectively.
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