ISSN: 2320-5407 Int. J. Adv. Res.

11(12), 582-598

Journal Homepage: -www.journalijar.com

Article DOI:10.21474/IJAR01/18020
DOI URL: http://dx.doi.org/10.21474/IJAR01/18020

RESEARCH ARTICLE
SYNTHESIS AND STUDY ON THE PROPERTIES OF CaMoO4:Eu3+ CO–DOPEDTb3+ MATERIALS
TO ENHANCED RED PHOTOLUMINESCENCE

Nhuong Chu Manh1, Mai An Pham2 and Huan Pham Van3

1. Faculty of Chemistry, Thai Nguyen University of Education, Thai Nguyen City 250000, Vietnam.
2. Faculty of Physics, Thai Nguyen University of Education, Thai Nguyen City 250000, Vietnam.
3. Faculty of Natural Sciences, Electric, Electric Power University, Hanoi City 100000, Vietnam.
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Manuscript Info Abstract
……………………. ………………………………………………………………
Manuscript History Ca0.99-yTb0.01MoO4:yEu3+nanophosphors
Received: 15 October 2023 weresuccessfullysynthesizedbyhydrothermal method. All the samples
Final Accepted: 18 November 2023 can be excited by 395nm wavelengths for generation of red color
Published: December 2023 emission. Enhancement in 5D0→7F2 (616 nm) emission (f–f transition)
of Eu3+ionis observed when Tb3+ionis co–doped in CaMoO4:Eu3+. This
Key words:-
Ca0.99-yTb0.01MoO4:yEu3+, is due to the efficient energy transfer from Tb3+ to Eu3+ ions.
Nanophosphors, Red, Lifetime Introduction of Tb3+ in the system does not lead to the change of
emission wavelength of Eu3+. However, Tb3+and Eu3+co–doped in the
system induces a shift in Mo-O charge transfer band absorption from
262nm to (413–431 nm). This may be due to the increase in
electronegativity between Mo and O bond in the presence of
Eu3+andTb3+leading to change in crystal field environment of Mo 6+ in
MoO42−. At the optimal concentration of Eu3+, an enhancement in
emission by a factor of ∼5.6 in the respective excitation at 616nm
(5D0→7F2) is observed. The chromaticity coordinates (CIE) of all
Ca0.99-yTb0.01MoO4:yEu3+ nanophosphors are in the red region. The
luminescence lifetime values are0.812 ms to 1.20 ms. The energy
transfer is observed to occur mainly via dipole–dipole interactions.
Copy Right, IJAR, 2023,. All rights reserved.
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Introduction:-
Nowaday, the luminescence of rare earth ions(RE3+)has attractedintensive investigations due to the abundant
emission spectra caused bytheir special 4f electronic configuration. Phosphors are an important part of whitelight
LEDs, which require a long life, high color rendering index (CRI), high luminosity efficiency, color neutrality, poor
thermal stability, and their emission diminishes over time and environmental friendly characteristics. The above
requirements can be improved by RE3+doped luminescent materials due to 4f–4f transition in rare earths [1–5]. Ion
Eu3+ (1.066 Å) and Tb3+ (1.027 Å) co–doped compounds have been paid considerable attention due to the strong red
emission (5D0→7F2transition of Eu3+, 616 nm) and the green emission at 545 nm( 5D4→7F5) and the blue emission at
489 nm (5D4→7F6), which are due to internal 4f–4f electron transitions of Tb3+. The CaMoO4:RE3+material with
scheelite structure has strong 4f–4f transitional absorption and emission due to the effect of polarization of MoO 42-.
As well known, the luminescence properties of RE 3+ doped materials may be strongly influenced by the crystal field
environmentaround the RE ions in the host. Thus, it is important to choose an appropriate host material. CaMoO4
belongs to the scheelitestructure, which is assembled by CaO 8 dodecahedra and MoO4 tetrahedron. In addition,
CaMoO4 has good chemical and heat stability. Therefore, CaMoO4 is considered to be an excellent matrix material
for luminescence [6–11, 13].

Corresponding Author:- Nhuong Chu Manh 582

Address:- Faculty of Chemistry, Thai Nguyen University of Education, Thai Nguyen City
250000, Vietnam.
ISSN: 2320-5407 Int. J. Adv. Res. 11(12), 582-598

Khanna et al [1] synthesized phosphor crystals of calcium molybdate doped with dopant Eu 3+, Dy3+, Tb3+ grown
using flux growth method have been shown to exhibit higher excitation efficiency than the powders synthesized by
solid state reaction process at a temperature around 1100 oC. Using the excitation wavelengths of 465 nm, 454 nm
and 489 nm for CaMoO4:Eu3+, CaMoO4:Dy3+ and CaMoO4:Tb3+, respectively, intense emission lines at 615 nm
(5D0-7F2 transition of Eu3+), 575 nm (4F9/2-6H13/2 of Dy3+) and 550 nm (5D4-7F5 of Tb3+) were observed. The
optimized doping concentrations of 12%, 2% and 5% for Eu 3+, Dy3+ and Tb3+, respectively, provided the highest
luminescence intensity. These phosphors could potentially be used for the fabrication of phosphor-converted light
emitting diodes (pc–LEDs).

Akta Verm et al [2] have successfully developed CaMoO4:RE3+ (RE = Tb, Sm, Tm, Er, Yb) phosphors as a spectral
converter for solar cell application by using hydrothermal method. The XRD pattern contains prominent peaks
located at 28.74o, 47.08o, 58.03o, 76.11o corresponds to (112), (204), (312) and (316)planes, respectively. The
crystallite size was found in the range of 10–60 nm. The calculated values of band gap for CaMoO4:Tb3+/Sm3+/Tm3+
and (1%)Er3+, (2%)Yb3+ dopedand co–doped CaMoO4 phosphors were found 3.88 eV, 3.85 eV, 3.82 e and 3.76 eV,
respectively. The as synthesized CaMoO4:Tb3+, Sm3+, Tm3+ downshifting (DS) phosphors exhibit hypersensitive
green, red and blue emission at 547 nm, 600 nm and 453 nm corresponding to 5D4→7F5, 4G5/2→6H7/2and1D2→3F4
transitions, respectively. The spectrum of CaMoO4:Tb3+ phosphor consists of a prominent peak at 378 nm arises due
to f–f transition of Tb3+ ions from ground state 7F6 to 5D3 level. The spectrum contains various peaks at 488 nm, 547
nm, 585 nm, 620 nm due to 5D4→7F6, 5D4→7F5, 5D4→7F4, 5D4→7F3 transitions, respectively.

Anees A. Ansari et al [3]synthesized CaMoO4:Tb,

CaMoO4:Tb@CaMoO4andCaMoO4:Tb@CaMoO4@SiO2coreeshell nanoparticles have been successfully prepared
by polyol process with urea thermal decomposition. The XRD results indicate that the obtained CaMoO 4:Tb is
sheelite tetragonal structure and well crystallized at 150 oC. The average crystallite size of the synthesized
nanoparticles is calculated using the Scherrer formula for the major (112) reflection plane observed at ~28.8 oabout
21.1, 32.4 and 48.2 nm, respectively. The absorption spectra of CaMoO4:Tb nanoparticles reveals two well resolved
broad absorption bands at 206 nm (6.0 eV) and 234 nm (5.3 eV). The emission spectra recorded at room temperature
in the spectral range of 400–700 nm with excitation at 325 nm (3.82 eV) displayed several well–known emission
bands corresponding to the intra 4f transitions 5D4→7Fn (n = 0–6), which belong to the characteristic transition of
Tb3+ ion. These emission spectra reveal six emission transitions in the visible region which are observed at 488 nm
(2.54 eV; 5D4-7F6), 545 nm (2.27 eV; 5D4-7F5), 586 nm (2.12 eV; 5D4-7F4), 620 nm (2.00 eV; 5D4-7F3), 641–658 nm
(1.90 eV; 5D4-7F2) and 680 nm (1.82 eV; 5D4-7F0), with the hypersensitive 5D4-7F5 transition as the most prominent
one, and hence can provide information about the chemical environment of the Tb 3+ ion. The comparative emission
spectra show that the peak positions of Tb3+ ions are not affected or destroy the structure and luminescence
properties of CaMoO4:Tb3+ phosphor after covered the CaMoO4 and SiO2 nano–layers around the CaMoO4:Tb3+
nanocrystals, could be due to no alteration of symmetry of the core lattice. The highest phosphorescence intensity is
observed for CaMoO4:Tb regardless of CaMoO4 and SiO2 layer coated coreeshell nanoparticles, most probably by
the UV light absorption and scattering of CaMoO4 and amorphous SiO2 that reduces the excitation irradiation
intensity.

Yongqing Zhai et al [4] synthesized a series of Dy3+/Eu3+ co–doped CaMoO4 phosphors by a facile microwave
radiation synthesis method. The the band gap energy (E g) of Ca0.98MoO4:0.02Dy3+ and
Ca0.978MoO4:0.02Dy3+,0.002Eu3+ is estimated to be 3.68 eV and 3.64 eV, respectively. The SEM of two samples,
show the average size of the fine spherical–like grains is about 0.29 and 0.38 μm, respectively. The emission spectra
of phosphors under the excitation of 301 nm, contain a broad band ranging from 400 to 550 nm and a narrow peak
located at 573 nm. The broad band belongs to the emission of internal MoO 42- and the 4F9/2→6H15/2 magnetic dipole
transition of Dy3+ (484 nm). The peak at 573 nm is attributed to the 4F9/2→6H13/2 electric dipole transition of Dy3+.
Besides, for Ca0.978MoO4:0.02Dy3+,0.002Eu3+ phosphor, the characteristic emissions of Eu3+ can be observed, which
are corresponding to the 5D0→7F1 (589 nm), 5D0→7F2 (613 nm) and 5D0→7F3 (652 nm) transitions, respectively.
The chromaticity coordinates (CIE ) of Ca0.98-xMoO4:0.02Dy3+,xEu3+ (x = 0–0.008) phosphors under the excitation
at 254 nm, were measured (0.3139, 0.4895) to (0.6238, 0.3658) and CCT values of (1198–5956 K). The average
decay time of Dy3+ is determined to be 20.33, 19.49, 17.90, 17.57 and 15.87 μs, respectively. The energy transfer
efficiency (ηET)from Dy3+ to Eu3+, is determined to be 4.1%, 11.9%, 13.5% and 21.9%, corresponding to x = 0.002–
0.008 in Ca0.98-xMoO4:0.02Dy3+,xEu3+, respectively. The energy transfer mechanism of Dy3+→Eu3+ is the dipole-
dipole interaction. The samples can emit multiple colors of yellow–green, yellow, orange–reddish and red by
adjusting Eu3+ doping content. Under 301 nm excitation, the increase of Eu 3+ content in CaMoO4:Dy3+,Eu3+ led to

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the enhancement of red emission (613 nm) of Eu 3+ and the decrease of blue and yellow emissions of Dy3+, which
was possibly due to the efficient energy transfer (ET) from level of Dy3+ to 5D0 level of Eu3+ through the phonon–
aided non–radiative relaxation. The phosphors could generate different color light from yellow–green through
yellow and orange–reddish and eventually to red by properly tuning the content of Eu 3+ based on the ET process,
which suggested that they might be potentially applied in the fields of lighting and display.

Shidong Li et al [5] successfully synthesized CaMoO4:5%Tb3+,x%Eu3+(x = 0.3, 0.5, 1.0, 2.0) phosphors by
precipitation method. The room temperature PLE spectrum of the CaMoO 4:5%Tb3+sample monitoring at 545.5 nm
and 486 nm, corresponding to 5D4→7F5 and 5D4→7F6transitions of Tb3+. The CaMoO4:1%Eu3+PLE spectrum are
395 nm and 465 nm for 7F0→5L6 and 7F0→5D2 of Eu3+ as the monitoring wavelength is 616 nm. The PLE spectrum
of CaMoO4:5%Tb3+,0.3%Eu3+, monitoring at 616 nm transition from Eu3+ (5D0→7F2). The excitation peaks are from
Eu3+ or Tb3+ different energy level transitions for Eu3+ at 362 nm (7F0→5D4), 381 nm (7F0→5L7), 395 nm (7F0→5L6),
416 nm (7F0→5D3), 465 nm (7F0→5D2), and at 486 nm (7F6→5D4) for Tb3+. The room temperature
photoluminescence (PL) spectra excited by 270 nm of CaMoO 4:5%Tb3+, CaMoO4:5%Tb3+,0.3%Eu3+, and
CaMoO4:1%Eu3+ phosphors, show the 4f–4f transition of Tb3+ locating at 489 nm (5D4→7F6), 545 nm (5D4→7F5),
587 nm (5D4→7F4), and 621 nm (5D4→7F3), of Eu3+ ion’s 4f–4f transition at 592 nm (5D0→7F1), 616 nm (5D0→7F2),
655 nm (5D0→7F3), and 702 nm (5D0→7F4). The fluorescence intensity ratio (FIR) of Eu 3+ to Tb3+ is dependent on
temperature, and the FIR increases with the increase of temperature. When FIR of Eu 3+ to Tb3+ is used to
characterize the temperature, the sensitivity increases with the increase of Eu 3+ concentration.

Hyun–Woo Lee et al [6] developed a new method for preparing transparent suspensions of CaMoO 4:(1-
x)Eu3+,(x)Tb3+ (x = 0–1) nanophosphors by reacting Ca–oleate (with Eu–oleate and/or Tb–oleate) complexes in
hexane with an aqueous (NH4)6Mo7O24 solution via a solvothermal reaction in a hexane–water bilayer system. The
TEM revealed slightly elongated spherical particles with a mean length and width of 9.5±3.6 and 4.1±1.2 nm,
respectively. The photoluminescence emission spectra of the CaMoO 4:Eu3+ and CaMoO4:Tb3+ nanophosphors
exhibited intense peaks in the red (614 nm) and green (545 nm) regions, respectively. These emissions originated
from the 5D0→7F2 transition of the Eu3+ ion and the 5D4→7F5 transition of the Tb3+ ion in the CaMoO4 host,
respectively. The emission colors in the green–red spectral region could be finely tuned by adjusting the molar
fraction of Tb3+ ions in the CaMoO4:(1-x)Eu3+,(x)Tb3+nanophosphors. The PL emission spectrum of the
CaMoO4:Eu3+ nanophosphor exhibits a series of emission lines in the range of 550–750 nm due to the 5D0→7FJ (j =
1–4) transitions of Eu3+. Thus, the CaMoO4:Eu3+ nanophosphor is a red emitting material, as evident from its
strongest emission peak appearing at 614 nm, which is assigned to the 5D0→7F2 transition of Eu3+. Similarly, the PL
excitation spectrum of the CaMoO4:Tb3+ nanophosphor exhibits a broad CT band at approximately 300 nm, while
the PL emission spectrum of the CaMoO4:Tb3+ nanophosphor exhibits sharp emission peaks at 489, 545, 587, and
621 nm that originate from the 5D4→7Fj (j = 6, 5, 4, 3) transitions of Tb3+, respectively. Thus, the CaMoO4:Tb3+
nanophosphor is a green–emitting material with the most intense emission peak appearing at 545 nm. The
characteristic strong peaks at 614 and 545 nm correspond to the 5D0 → 7F2 transition of Eu3+ and the 5D4→7F5
transition of Tb3+, respectively. With an increase in x value, the emission intensities at 614 and 545 nm
simultaneously decreased and increased, respectively. The ratio of the emission intensity at 545 nm to the sum of the
intensities at 545 and 614 nm increased with increasing x value for the CaMoO4:(1-x)Eu3+,(x)Tb3+ nanophosphors.
Thus, the emission color can be finely tuned from red to green by adjusting the fractions of Tb3+ and Eu3+ activator
ions in the CaMoO4:(1-x)Eu3+,(x)Tb3+nanophosphors. This shows that the emission color of the CaMoO 4:(1-
x)Eu3+,(x)Tb3+ nanophosphor is tunable. With an increase in x value, the chromaticity coordinates changed from
(0.65, 0.34) for the red–emitting CaMoO4:Eu3+ nanophosphor to (0.31, 0.60) for the green–emitting CaMoO4:Tb3+.
The prepared CaMoO4:(1-x)Eu3+,(x)Tb3+ suspensions can be used in transparent displays as light emitting materials
with tunable emission from red to green region.

R. L. Tranquilinet al [7] successfully synthetized CaMoO4:xRE3+ (RE = Eu, Tb, Tm and x = 1, 2, 4 mol%)
compounds by one–pot ultrasonic spray pyrolysis method. The values of E g were within the range of 3.84–3.93 eV.
The PL spectra of the CaMoO4:RE3+ phosphors exhibited characteristics of each doped ion (Eu 3+, Tb3+, Tm3+)
emission. Under the excitation of 350 nm, the 5 D4→7F6(492 nm) and 5D4→7F5(548 nm) transitions, respectively,
which are associated with the emission of Tb3+. This is related to the charge transfer (CT) process from the [TbO 8]
to the [MoO4]2- tetragonal clusters, which corresponds to the 4f→5d transitions. The emission peak at 800 nm is
attributed to Tm3+, which is associated with the 3H4 → 3H6 transition. With respect to Eu3+, 5D0 → 7Fj (j = 1–4)
transitions occurred at the respective wavelengths of 596, 614, 661, and 704 nm. The most intense emission band,
5
D0 → 7F2, of Eu3+ is known to have an electric dipole, and this type of transition is highly sensitive to the changes

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that occur around the Eu3+ cations. The samples with 2 and 4% of RE 3+ released white emission according to the
chromaticity coordinates (0.34, 0.34) and (0.34, 0.33), respectively.

Xiong Jianhui et al [8] synthesized CaMoO4:Tb3+,Eu3+ phosphors by precipitation method. By adjusting the co–
doped concentration of Eu3+ ion in CaMoO4:Tb3+,Eu3+ phosphors, can be easily adjusted the emission color of
phosphors from green to red. The particle size is uniformly distributed about 1 μm. The emission spectra of
CaMoO4:x%Tb3+ (x = 2–8) phosphors and the excitation wavelength is 486 nm. The concentration quenching of
Tb3+ (5D4→7F5) transition green luminescence of CaMoO4 samples which is excited by 486 nm. With the increase of
Tb3+ concentration, the luminescent intensity of 545.5 nm of Tb3+(5D4→7F5) first increases and then decreases. The
best concentration of Tb3+ is 5%. When the Tb3+ concentration is more than 5%, the luminescent intensity
remarkably decreases. This phenomenon is due to the energy transfer between Tb3+ ions leading to the concentration
quenching. The luminescent properties and the energy transfer mechanism from Tb3+ to Eu3+ in the phosphors were
studied. With the increase of Eu3+ concentration, the luminescent colors could be changed from green to red easily
because of different proportions of Tb3+ and Eu3+.The phosphors had potential application in the anti–counterfeiting
technology. With Tb3+ doped in the phosphors, the red luminescence of Eu3+ by near UV excitation was significantly
enhanced. The study also indicated that the energy transfer rate and energy transfer efficiency from Tb 3+ to Eu3+
were increased with the increase of Eu3+ concentration, and the energy transfer type between Tb3+ and Eu3+ was
electric dipole-dipole interaction.

Jiaming Deng et al [9] synthesized Tb3+, Eu3+ single–doped and co–doped Ca2Al2SiO7 (CAS) phosphors by sol–
gelmethod. CAS:Tb3+,Eu3+ phosphors demonstrate tunable luminescence under 238 nm excitation, in which the
luminescence color gradually changes from purple–red to cool white, and then to warm white by continuously
increasing the concentration of Tb3+ ions. The photoluminescence emission spectra for CAS:0.04Tb3+ sample
excited under 238 nm shows the emission bands at 380–460 nm and 480–650nm, which are ascribed to the 5D3→7FJ
(J = 6, 5, 4, 3) and 5D4→7FJ (J = 6, 5, 4, 3) transitions of Tb3+ ions. The excitation spectra for CAS:0.07Eu3+ sample
monitored at 623 nm shows the strongest excitation wavelength at 395 nm. Then the phosphor excites with 395 nm
and the maximum emission wavelength is observed at 623 nm, which isascribing to the 5D-7F2 transition of Eu3+
ions. The emission spectra of CAS:0.04Tb3+ and the excitation spectrum of CAS:0.07Eu3+ is overlapped in the range
of 371–401 nm, indicating that there may exist an ET process of Tb3+→Eu3+ in Ca2Al2SiO7host. Since 350 nm can
only excite Tb3+ but not Eu3+, the excitation wavelength of 350 nm is selected for investigation the energy transfers
from Tb3+ to Eu3+. Under 350 nm excitation, the CAS:0.07Eu3+ exhibits almost no emission peak at 623 nm.
However, the luminescence intensity of Eu3+ at 623 nm enhances gradually with increasing the doped ratio of Tb3+
ions for the CAS:xTb3+,0.07Eu3+ samples. To clearly, the intensity of the emission peaks of Tb3+ at 549 nm and Eu3+
at 623 nm as a function of Tb3+ content. It can be seen that the emission intensity of Tb3+ at 549 nm increases with
the Tb3+ doped content and then decreases due to the concentration quenching near x = 0.11, while the emission
intensity of Eu3+ at 623 nm shows a similar variation trends as Tb3+ ion. Thus, Tb3+→Eu3+ ET occurs in the CAS
matrix, which enhances the red emission of Eu3+ ions. The fluorescence lifetimes determinated are 1.17 ms, 1.25 ms,
1.66 ms, 1.71 ms, 2.26 ms, for x = 0.01, 0.03, 0.07, 0.09, 0.11, respectively. Therefore, the lifetime of Eu3+ gradually
increases with increasing Tb3+ concentration for a fixed Eu3+ concentration, which further indicates the existence of
energy transfer from Tb3+ to Eu3+. The elongation of the fluorescence lifetime of Eu3+ with increasing Tb3+ ions
content further confirms the energy transfer of Tb3+→Eu3+. The thermal behavior of CAS:Tb3+, Eu3+ phosphors
shows enhanced luminescence intensity for 404 nm emission while suppressed luminescence intensity for 616 nm
emissions withraising temperature, implying its potential in optical temperature sensing.

In previous work [10], we successfully synthesized luminescent nanomaterial CaMoO 4:(0-7%)Eu3+ using
hydrothermal method. The materials exist in crystalline formscheelite–type tetragonal structure with I41/a, with an
average diameter according to the Scherrer method of about 26–41 nm. Photoluminescence spectra of CaMoO4:Eu3+
nanophosphors show emission peak at 613–616 nm (5D0→7F2). The Judd–Ofelt parameters Ω2 and Ω4 have been
calculated from the photoluminescence emission spectra of CaMoO 4:5%Eu3+, in temperature range 293 K–693 K.
Judd–Ofelt intensity parameters uniformly decrease with increasing temperature. The Judd–Ofelt parameters
radiative lifetimes and emission cross–sections were calculated. The results indicate that the Eu 3+ doped CaMoO4
nanophosphors are expected to have applications in the field of solid state lighting and other optical instruments.

In this study, we present the material's characteristics and photoluminescence properties of nano CaMoO 4 co–doped
europium (III) and tecbium (III) ions, for the purpose of comparing and showing the effect of 1 mol% Tb3+ ion on
the photoluminescent properties of CaMoO4:(1–10%)Eu (CME) materials [10]. The powder X–Ray diffraction,

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Raman scattering, FE–SEMand TEM, EDS, UV–Vis–Drs, the photoluminescence excition, the photoluminescence
emission and the lifetime spectra of the energy level5D0of europium have been studied. The mechanism, energy
transfer efficiency from Tb3+ to Eu3+ and the influence of concentration of Eu3+ ions for photoluminescence
properties ofCaMoO4 co–doped Eu3+ and Tb3+ nanophosphors have been analyzed.

Experimental
Synthesis nanophosphor
A series of nano-sized Eu3+, Tb3+co–doped CaMoO4phosphors were synthesized by hydrothermal methodformCa0.99-
3+
yTb0.01MoO4:yEu (y = 0.01–0.10), using of some chemicals:Ca(NO3)2.4H2O (> 99%),Na2MoO4.2H2O (> 99.5%),
Eu2O3 (99.99%), Tb2O3 (99.99%), HNO3 (65%)and absolute ethanol (d = 0.790 g.cm–3) were purchased from
Merck. Eu(NO3)3andTb(NO3)3solutions was obtained by dissolving Eu2O3and Tb2O3diluted in HNO3 solution,
heating at 60 °C on a magnetic stirrer for 30 min.

The synthesis of Ca0.99-yTb0.01MoO4:yEu3+nanoluminescents are carried out according to the steps described in the
diagram in Figure 1.

Figure 1:- Fabrication process of Ca0.99-yTb0.01MoO4:yEu3+ (CMTE 1–x) nanophosphors annealed at 600 °C.

Instrumentation
Powder XRD measurement was done on a (D2 Phaser, Bruker, Germany) machine equipped with a CuKα radiation
(λ = 1.54056 Å, 40 kV, 20 mA) in a 2θ scanning mode with a step size of 0.02 o andacquisition speed of 4°/min.
Raman measurement was acquiredusing a (XPLORA PLUS–Horiba) machine equipped with an argon laser(532 nm)
in the range of 100–1000 cm–1. The morphologicalcharacterization was carried out using a JEOL JSM–7600F
fieldemission scanning electron microscopy (FE–SEM) (USA) operating under voltage 5KV.A spectrophotometer
UV–Visible/NIR (Hitachi UH4150) were used to recordthe diffuse reflectance spectra (DRS) at 1 nm intervals and
scan speed of 1200 nm/min from 240 to 2600 nm. The EDS system (Hitachi TM4000Plus) is used for analysis

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elemental mapping. The measurements of photoluminescence excitation (PLE) and photoluminescence (PL)
emission, and lifetime measurements were carried out using NANOLOG spectrophotometer (Horiba, USA)
equipped with a 450 W Xe arc lamp and a dual excitation monochromator wwith divergence gap is 0.2 nm in size.

Results:-
XRD characters
Fig. 2 shows the XRD patterns of Tb3+ (1 mol%) and Eu3+ (1–10 mol%) co–doped CaMoO4(denoted as CMTE 1–x)
nanophosphors. All the X–ray diffraction peakswere observed at angles 2θ = ~ 18.18°, 28.64°, 30.77°,
33.77°,38.45°,46.60°, 48.77°, 53.59°, 57.55° and 59.04° corresponding to planes of the samples at (101), (112),
(004), (200), (211), (204), (220), (116), (312) and(224)respectively. All the observed diffraction peaks are found to
match with the tetragonal phase of CaMoO4:(1–7%)Eu [10]and can be indexed with standard JCPDS card No. 29–
0351[1–9, 11].Table 1 shows that the average particle size (D)was estimated from Scherrer’s equation and was
found to be inthe range 41.54–62.45 nm.

Figure 2:- XRD patternsofnanophosphorsannealed at 600 °C: (a)CMTE 1–x (x = 1–10), (b) Zooming at 2θ ≈ 28.64o.

Table 1:- Scherre’s fomula for estimated crystal size (D) of CMTE 1–x at 2θ ≈ 28.64o.
Nanophosphor CMTE1–1 CMTE1–2 CMTE1–4 CMTE1–6 CMTE1–8 CMTE1–10
FWHM (o) 0.12641 0.18946 0.14401 0.19005 0.15013 0.17844
D (nm) 62.45 41.67 54.82 41.54 52.58 44.24
When Tb/Eu is co–doped into the host lattice, it does not affect the crystal structure of the material and the sharp
diffraction peaks prove that the CMTE sample has high purity and good crystallinity (Fig. 2a). The results showed
that the Eu3+ (1.066 Å) and Tb3+ (1.027 Å) ions replaced the position of the Ca2+ ion (1.040 Å), which has a similar
radius [2], but did not replace the position of the Mo 6+ ion (0.410 Å), because its radius is much smaller. In other
words, Tb3+ and Eu3+ ions easily penetrate the host lattice, creating crystals with few defects and strong
luminescence.

Raman analysis
The micro–Raman spectra of the Ca0.99-yTb0.01MoO4:yEu3+ phosphors in the range of 100 to 1000 cm−1 are presented
in Fig. 3. The disordering of local symmetry can be probed with help of Raman scattering technique. There are 26
different vibration modes in the tetragonal structure CaMoO 4 crystal as obtained by the irreducible representation
and they are described as follows:Γ = 3Ag+ 5Au+ 5Bg+ 3Bu+ 5Eg+ 5Eu, where: 4Au and 4Eu are infrared and (3Ag, 5Bg
and 5Eg) are Raman-active; 3Bu vibrations are silent modes; 1Au mode and 1Eu mode are acoustic vibrations.

Result show that only have 9 vibration modes observed. The small change in polarizability will result in less intense
peaks, the highly intense bands may hide some peaks, or the overlapping of bands may cause some peaks to unseen
in the spectra. In thecase of CaMoO4 nanophosphor, the modes observed at 119, 128.34, 160.29, 220.68, 293.21,
340.19 and 380.70 cm−1 are attributed to O–Mo–O vibrations. The peak at725.41 cm−1is due to MoO4 torsional
modes. The peak found at 819.71 cm−1 isassigned as Mo–O4 torsional mode. The mode at 879.05 cm-1 forms due
toMo–O symmetric stretching vibrations. The substitution of Eu 3+ and Tb3+ions in CaMoO4 give raise to the shifting
of the peaks corresponding to theabove discussed modes and are shown in Table 2. A reasonableshift in the

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wavenumber of all the modes has been observed when Eu 3+, Dy3+ions are substituted at CaMoO4 lattice. The
aliovalent substitution of Eu3+, Tb3+ions for Ca2+ ions gives raise to the formation of oxygen vacancies inorder to
preserve electron neutrality. Also, the entering of smaller Eu3+, Tb3+ions in Ca2+ sites causes the tilting of
MoO4tetrahedralresulting in thedistortion of local crystal structure symmetry. Presence of dopant ionsand oxygen
vacancies in the system influence the band vibrations andhence modify the Raman modes. A further change in these
vibrationalmodes is observed when Eu3+, Tb3+ ions are substituted. This is because thesubstitution of Eu 3+, Tb3+ions
still enhances the oxygen vacancies and local structure distortion. But small shifts alone are foundin the vibrational
modeswhen the concentration of Eu3+, Tb3+ ions in Ca0.99-yTb0.01MoO4:yEu3+ phosphor is altered [6]. The Raman
scatteringvibrational modes of CMTE 1–x materials are in good agreement with CaMoO4:(1–7%)Eu
nanoluminescences, which have been studied and described previously [10].

Figure 3:-Raman spectra of CaMoO4 (CMO) and Ca0.99-yTb0.01MoO4:yEu3+(y = 0.01–0.10) nanophosphorsannealed

at 600 °C.

Table 2:- Assignments of Raman modes of Ca0.99-yTb0.01MoO4:yEu3+ nanophosphors.

CaMoO4(cm−1) CaMoO4:(1– Ca0.99- Type of vibrations
7%)Eu(cm−1)[10] yTb0.01MoO4:yEu ,3+

y = 0.01–0.10 (cm−1)
119 115 128.34 T(Bg), CaMoO4 lattice mode
148 140 160.29 T(Eg), O–Mo–O bending mode
211 205 220.68 (AgEg), O–Mo–O bending mode
290 267 293.21 R(Eg), O–Mo–O bending mode
328 320 340.19 ν2(AgBg), O–Mo–O bending mode
399 390 380.70 ν4(Bg) and ν4(Eg), O–Mo–O bending mode
799 790 819.71 ν3(Eg), Mo–O4 torsional mode
852−884 845−879 879.05 ν3(Bg), Mo–O4 torsional mode and
ν1(Ag), Mo–O symmetric stretching

Morphology, composition and distribution of elements in the CMTE materials.

The FE–SEMand TEM observation (Fig. 4a–4d) shows the fabricated CMTE 1–x (x = 2, 6). The morphologies of
samples with different doping concentrations are similar. The particle sizes are about 15–20 nm and uniformly
distributed.

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Figure 4:- FE-SEM images of nanophosphors: (a)CMTE 1–2; (b) CMTE 1–6 andTEM images of nanophosphors:
(c) CMTE 1–2; (d) CMTE 1–6.

Figure 5:- The EDSof CMTE 1–1: (a) Elementimaging; (b) Mapping imaging; (c) Mapped color of Eu, Tb, Mo, Ca,
O.

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The EDS spectra of Ca0.98Tb0.01MoO4:0.01Eunanophosphor shown in Fig. 5 confirms the presence of the elements
asEu, Tb, Ca, Mo and O in the sample, which has both total weight % and total atomic % are 100 %, demonstrating
the high purity of CMTE materials.The quantitative EDS analysis of the phosphor suggests that the obtained
concentrations of the elements are close to the theoretical stoichiometry (Inset of Fig. 5a). Figure 5b show the X–ray
dot mapping images of Ca0.98Tb0.01MoO4:0.01Eu nanophosphor, results showed uniformly distribution of europium,
tecbium, molybdenum, calcium and oxygen for all host matrix, which suggested that Eu 3+ and Tb3+ co–doped of
CaMoO4 occurred homogenously.

Reflectance spectra and band gap

The diffuse reflectance spectra curve and the Kubelka-Munk energy curve of Ca0.99-yTb0.01MoO4:yEu3+ (y = 0.01;
0.02; 0.04; 0.08) nanophosphors are shown in Fig. 6. The absorption band in the region 200–300 nm is found
because of the collective effect of ligand–metal charge transfer transitions in Mo–O, Eu–Oand Tb–O groups. Small
absorption peaks at 312–360 nmcorrespond to the intra f→f transitions of Eu3+ and Tb3+ ions.

The absorption wavelength shifts of the Ca0.99-yTb0.01MoO4:yEu3+are determined about 408–431 nm, so the
phosphors is absorbed in the visible light region. The Eg of Ca0.99-yTb0.01MoO4:yEu3+is identified using Kubelka–
Munk method and Tauc’s equation as being about 2.8750–3.0417 eV, which is much lower than previous studies [2,
3,4,7]. The reflectancespectra demonstrate the probable excitation of these phosphors by radiations in the visible
light region. Herein, the observed photoluminescence is due to the intra4f electronic transitions within the activator
Eu3+, Tb3+ ions and not due to theband gap absorption of the materials. These transitions occur within theband gap of
the materials.

Figure 6:-Diffuse reflectance spectra and inset Kubelka–Munk versus band gap plotsofCa0.99-yTb0.01MoO4:yEu3+
nanophosphors.

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PLE and PL of the CMTE samples

Figure 7:- PLE spectrum of Ca0.93Tb0.01MoO4:0.06Eu (CMTE 1–6).

The excitation spectrum of the typical Ca0.93Tb0.01MoO4:0.06Eu (Fig. 7) consists of characteristic 4f→4f transition
peaks of Eu3+ and Tb3+ ions. At about 262 nm, which is charge transfer band (CTB), the excitation spectrum of
nano–sized Ca0.93Tb0.01MoO4:0.06Eu phosphor shows a broad band and several relatively weak were appeared
between 350 and 550 nmdue to the charge transfer of the dominant MoO42-group. As shown from Figure 7, the
excitation spectrum is predominantly composed of two main parts: (1) The broad band in the range of 245–350 nm,
which is ascribed to O2-/Eu3+ and O2-/Tb3+ charge transfer states (CTS), and Tb3+/Eu3+ intervalence charge transfer,
due to an electron transfer from 2p an (oxygen) orbital to an empty 4f shell of Eu 3+. (2) A different sharp line was
found between 350 and 550 nm due to the f–f transition of Eu3+ and Tb3+ ions.

High extent of spectral splitting in this band is again endowed by the large crystalline field of the nano–sized CMTE
samples. The observed excitation peaks are mainly due to the transitions from the 7F0 and 7F1 levels to the higher
energy levels of the Eu3+ ion: 7F0→5D4(363 nm); 7F1→5D4(366 nm), 7F0→5G1(377 nm), 7F0→5G2(380 nm), 7F0→5G4
(384 nm), 7F1→5L6(408 nm), 7F0→5D3(417 nm),7F0→5G2(442 nm), 7F0→5G4(448 nm), 7F1→5L6(473 nm),7F0→5D3
(484 nm),7F0→5D1(526 nm), and 7F0 → 5D1(536 nm). The observed relatively weak peaks at 494, and 546 nm are
assigned to electronic transitions of 4F9/2→6H15/2, and 4F9/2→6H13/2, respectively, which are originated from the 4f–4f
transitions of Tb3+. At 395 nm and 465 nm excitations, the intense sharp peaks were observed which consistent to
7
F0⟶5L6 and 7F0 → 5D2transitions, have wavelengths consistent with the characteristic emission from near–UV/UV
LEDs and blue LEDs, so the prepared Ca0.99-yTb0.01MoO4:yEu3+phosphors greatly promises for potential practical
applications of wLED and blue LEDs [2–10].

It is to be understood here that f–f transitions are forbidden and are absent in pure Tb2O3. As a result of orbital
mixing when incorporated in a crystalline host, these transitions appear due to the relaxation of the LaPorte parity
rule. Moreover, symmetry around Tb3+ ions has an important role in dictating its intensity and appearance. Intrinsic
porous characteristics, high surface area, and defects of the nano–sized sample make it more distorted in nature, and
hence, the local symmetry around Tb3+ in the nano–sized CMTE is low. Lower symmetry of Tb3+ in the nano–sized
CMTE relaxes the selection rule, making the appearance of the intra–configurational f–f bands of Tb3+ ion in the
excitation spectrum. On the other hand, in the case of the bulkCMTE sample, because of the reduced surface to
volume ratio and enhanced compactness of the local symmetry around Tb3+, high symmetry around Tb3+ ions makes
the f–f selection rule more stringent and curtails the appearance of intra–configurational f–f bands of Tb3+ ion in the
excitation spectrum of the bulk CMTE nanophosphors[2–10].

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As shown from Figure 8, the room temperature PL emissionspectra of Ca0.99-yTb0.01MoO4:yEu3+ nanophosphors were
measured, in which the excitation wavelength was monitored at 395 nm. The emission spectra were composed of a
series ofsharp emission lines, corresponding to transitions from the excited states 5D0 to the ground state 7Fj (j = 0, 1,
2, 3, 4). At about 596 nm, the emission of orange color was observed which is belongs to the magnetic dipole
5
D0⟶7F1 transition of Eu3+, and the transition hardly varies with the crystal field strength 5D0⟶7F2 transition of
Eu3+, which is very sensitive to the local environment around Eu3+ ions, which belongs to the electric dipole effects
in which the red emissions were observed at 616 nm. In spite of this, it depends on the symmetry of the crystal field.
Two strong peaks which were found at 596 and 616 nm emissions peaks, which are magnetic and electric dipole
transitions of Eu3+ ions respectively, indicate that there are two Ca2+ positions in the Ca0.99-yTb0.01MoO4:yEu3+ lattice.
One position, Ca(I), is inversion symmetry and the other side, Ca(II), is noninversion symmetry. Other two emission
peaks located at 655 and 702 nm are relatively weak, which is corresponding to the 5D0⟶7F3 and 5D0⟶7F4typical
transitions of Eu3+ ions, respectively.

A fairly strong peak at 545 nm(5D4 → 7F5), and emission peaks located at 489 nm, 592 nm, 613 nm, 652 nm, 695 nm
are relatively weak, which is corresponding to the 5D4 → 7Fj( j = 6–1)typical transitions of Tb3+ ions, respectively,
all of which are electric dipole transitions. From this result, it was shown that when doping Eu3+ and Tb3+ ions into
CaMoO4, there was efficient energy transfer from the matrix to the energy levels of Eu 3+and Tb3+ions [4–9, 12–
13].The strong luminescence of the electric dipole transitions show that Eu3+and Tb3+ions have replaced Ca2+ ions.

It can be seen from the figure 8 that there is not much change in the emission spectral features as a function Eu 3+ ion
concentration. However,emission intensity gradually increased when doping 1.0 to 4.0 mol% Eu 3+ and then
gradually decreased when the doping concentration of Eu3+ was greater than 4 mol%. This resulted from energy
transfer from Tb3+ ions to Eu3+ ions, which caused concentration quenching of luminescence intensity.

Figure 8:- Photoluminescence (PL) spectra (λexc =395 nm) ofCa0.99-yTb0.01MoO4:yEu3+ (y = 0.01–
0.10)nanophosphors annealed at 600 oC temperatures in air.

Table 3:- The ratio I616 nm/(I545 nm + I616 nm) of theCMTE 1–xnanophosphors.
Nanophosphor
Intensity (a.u.) CMTE1–1 CMTE1–2 CMTE1–4 CMTE1–6 CMTE1–8 CMTE1–10
I545 nm (a.u.) 21379 2722 5943 872 2238 1257
I616 nm(a.u.) 58479 12474 63486 11383 51511 33575
I616 nm/(I545nm+ I616 nm) 0.7323 0.8209 0.9144 0.9288 0.9584 0.9639

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Table 3 show ratios of the emission intensity at 616 nm (red, 5D0→7F2) to the sum of the intensities at 616 nm and
545 nm (green, 5D4→ 7F5) in the Eu3+ and Tb3+ co–doped CaMoO4nanophosphors.When x value increase, the
emission intensities at 616 nm and 545 nm simultaneously increased and decreased, respectively. The ratio of the
emission intensity at 616 nm to the sum of the intensities at 616 nmand 545 nm increased with increasing the x value
from 1 to 10 mol% in the CaMoO4:0.01Tb3+,xEu3+ nanophosphors.Thus, the red emission ( 5D0→7F2) of Eu3+ ion
was enhanced in the presence of Tb3+sensitizer ion in CaMoO4:1%Tb3+,x%Eu3+ nanophosphors. Showing that there
is effective energy transfer from Tb3+ to Eu3+ ions.

In addition, compared with the nano–size CaMoO4 doped 5% Eu3+, which has intensities ratio I616 nm/(I545 nm + I616 nm)
was 0.9930 ≈ 1.0 [10] and higher than the nanoluminescents CaMoO 4 co–doped Eu3+ and Tb3+, showing that the
CMTE 1–x nanophosphors are colors tunable, the photoluminescent colors could be transferred from green to red
easily with of different ratios of Eu3+ and Tb3+.

The energy transfer mechanismfrom Tb3+to Eu3+

It is well known that energy transfer (ET) of phosphors can be produced by exchange interactions or electrical
multipole interactions mainly between luminescent centers. These interactions depend on the critical distance
RTb  Eu between the Tb3+ and Eu3+ ions. With 5–7 Å as the boundary, exchange interactions play a role when the
critical distance not exceed about 5 Å, while electrical multipole interactions dominate if RTb  Eu is larger than 7 Å
[8].

To have better understanding of concentration quenching mechanism the critical distance ( RTb  Eu ) for the energy
transfer has been calculatedfrom the geometrical factors of the host using the relation given byBlasse, according to
1
 3V  3
formula (1) [4–8]: RTb Eu  2  (1)
 4X c N 

where RTb  Eu is the critical distance between the dopant ion and quenching site, V is the volume of the unit cell,
Xc is thetotal critical concentration of Eu3+ and Tb3+ ions, and N the number of crystallographic sites available for
dopant or the activator ions in the unit cell. For CaMoO 4 host lattice V = 313.013 Å3(a = b = 5.2300 Å, c = 11.4435
Å) [8], N = 4 (four formula units per one unit cell), and X c = 0.02–0.11. Based on the values, the average distances
of the donor–acceptor in the current situation are calculated to be 7.786–13.744 Å, which are larger than the critical
value (5–7 Å). This result suggests that the energy transfer through the exchange interaction is impossible and the
energy transfer from Tb3+ to Eu3+ ions in the CMTE 1–x phosphors is mainly by an electric multipole interaction.

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Figure 9:- (a) Energy level diagram showing energy transfer process from Tb3+ to Eu3+; (b) Energy level scheme for
the emission process in Ca0.99-yTb0.01MoO4:yEu3+nanophosphors.

The proposed path for the energy transfer to occur in co–doped glasses could be 5D4 of Tb3+ to 5D0 state of Eu3+
ions. This is shown in Fig. 9 where an excitation wavelength 395 nm raises Tb3+ ions to a higher energy state
(4f75d1) which can relaxe to the 5D4 state by emitting non–radiative energy which is than absorbed by Eu3+ ions in
the ground state which are excited to higher energy states and then relaxes to 5D0 state. Further they cascade non–
radiatively to intermediate states 5D1 and 5D0 and therefore finally decay radiatively to 7F0 ground state [8–9, 12–13].

CIE and CCT studies

Figure 10 shows the color coordinate diagram (CIE) and correlated color temperature (CCT) of CMTE 1–x (x = 1–
10) materials calcined at 600 oC. The CIE and CCT color coordinate values of the samples are listed in table 4,
demonstrating the luminescence of CMTE materials in the red region from (0.484; 0.428) to (0.606; 0.337) with
CCT values large in the range 1142–2512 K, which values are equivalent to light on a clear day compared to
common color temperature tables. These results are consistent with previous studies [5–6].

Figure 10:- CIE and CCT diagram ofCa0.99-yTb0.01MoO4:yEu3+ nanophosphors.

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Table 4:- CIE and CCT values of Ca0.99-yTb0.01MoO4:yEu3+nanophosphors.

Nanophosphor CIE CCT (K)
xaxis yaxis
CMTE 1–0 0.285 0.554 N/A
CMTE 1–1 0.484 0.428 2512
CMTE1–2 0.528 0.373 1745
CMTE1–4 0.571 0.370 1465
CMTE1–6 0.606 0.337 1142
CMTE1–8 0.522 0.367 1748
CMTE1–10 0.552 0.356 1498

Fluorescencelifetime, energy transfer efficiency and concentration quenching mechanism

The decay profiles of the emission spectra of 1 mol% Tb3+ and y (from 0.01 to 0.06 mol%) Eu3+ co–doped CaMoO4,
are recorded at 395 nm excitation and 616 nm emission wavelength for the energy level 5D0. The decay profiles are
shown in Fig. 12. The decay curves were observed to have biexponential nature and further analyzed to understand
the energy transfer behavior from Tb3+ ion to Eu3+ ion. The average value of lifetime (τ) was calculated as follows
formula (2)and the values are presented in Fig. 11:
A1t12  A2t 22
 (2)
A1t1  A1t2
Where t1 and t2 stands for fast and slow decay times respectively; A1 and A2are constants. The obtained  values are
0.81165–1.19950 ms and the lifetime values were decreased as compared to singly doped 1 mol%Tb 3+(CMT1) such
as (  Tb ) is 2.87241 ms, which supported the previous non radiative energy transfer arguments and suggested that
Tb3+ is acting as sensitizer while Eu3+ is acting as activator in this matrix. The trend of observed decay values is also
due to mix rare earth ion effect since here concentration of both the RE 3+ ions are varied [8].

The energy transfer rate ( Ada (Tb  Eu ) ) from Tb3+to Eu3+is also calculated by the following equation(3) and the
efficiency of energy transfer ( Tb  Eu ) from Tb3+ to Eu3+ are calculated by the equation (4), and the efficiency of
energy transfer ( CMOEu ) from CMO to Eu3+ are calculated by the equation (5). The  Tb and  in the above
relation are the corresponding lifetime decays of Eu3+ ions in single–doped and co–doped Eu3+/Tb3+respectively [8].

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1 1   CMO
Ada (Tb Eu )   (3) Tb Eu  1  (4) CMOEu  1  (5)
  Tb  Tb 
The Ada (Tb  Eu ) , Tb  Eu and CMOEu of CMTE 1–x nanophosphors arepresented in table 5.

Figure 11:- Luminescence Decay curves at 616 nm of the Ca0.99-yTb0.01MoO4:yEu3+ (y = 0.01–0.06)nanophosphors

annealed at 600 oC under the excitation wavelength of 395 nm.

Table 5:- Average lifetime, energy transfer rate, efficiency, and average distance of CMTE 1–x nanophosphors.
Nanophosphor   (%)  (%) A (s-1) R (Å)
Tb  Eu CMO Eu da (Tb  Eu ) Tb  Eu
CMT1 2.87241 (  Tb ) - - - -
CMTE 1–1 1.1995 0.5824 0.8201 485.54 7.7861
CMTE 1–4 0.81376 0.7167 0.7348 880.72 10.5673
CMTE 1–6 0.81165 0.7174 0.7341 883.92 11.8215
CMO 0.21584 - - - -
Table 5 shows, that the lifetime of nanophosphors gradually decreased with increased Eu3+ doped in, this is because
the electrons have more opportunities to move from a higher energy level to a lower energy level and this can cause
the time the electrons spend to stay at the energy level to decrease. The possible energy transfer channels attributed
to the going out of 5D4fluorescence of Tb3+ by Eu3+are shown in Fig. 9a. The energy transfer from Tb3+ionto Eu3+ion
is very efficient because they have large emission spectra overlapping each other.Addition, the increasing of
Eu3+co–doped, both Tb  Eu and Ada (Tb  Eu ) are increased.

The concentration dependent luminescence intensities are fitted to Dexter's energy transfer formula for multipolar
interaction and Reisfeld's approximation by equation (6) below:

log(I/(0.01+y)) = C - (θ/3)*log(0.01+y) (6)

where I is emission intensity, (0.01+y) is the total concentration of Tb3+ and Eu3+, C and θ are fitting constants. As
per the above formalism, the value of the fitting constant θ is in the increasing order for exchange coupling, electric
dipole–dipole, dipole–quadrupole and quadrupole–quadrupole interactions and the values are 3, 6, 8 and 10,
respectively [4, 6–8]. The intensity data is fitted to Equ. (6) and given in Fig. 12. From the slope, the θ value is
∼6.004 which is close to 6 showing that the dominant concentration quenching mechanism of Tb3+ and Eu3+ in
CaMoO4is the non–radiative dipole–dipole interaction [8].

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Figure 12:- log(I/(0.01+y)) vs log(0.01+y) plot of the 5D0 → 7F2 transition intensity (I) of Eu3+ ions in
Ca0.97-yTb0.01MoO4:yEu3+(y = 0.01–0.10) and the line and co–doping concentration (0.01+y) is fit with equation (6).

Conclusions:-
The influence of co–doped Tb3+ ion in enhancing the photoluminescence properties of CaMoO4:Eu3+was studied by
examining characteristics of nanophosphors using modern analysis methods. The Ca0.99-yTb0.01MoO4:yEu3+materials
as well as red nanophosphors, were successfullyprepared viahydrothermaltechnique.

The nanostructure analysis and surface morphology were studiedusingscanning and transmission electron
microscopy spectroscopy techniques. Eu3+ and Tb3+ ions occupied the position of Ca2+ ions, were verified by XRD
pattern, Raman scattering and EDSelemental/mapping studies.The Raman spectra analysis confirmed that the
substitution of rare earth ions altered the local crystal structure symmetry.The photoluminescence (PL) spectra of
Ca0.99-yTb0.01MoO4:yEu3+ nanophosphors show emission peak at 616 nm ( 5D0→7F2) correspondingto the red region
from (0.484; 0.428) to (0.606; 0.337)of CIE. The co–doped of Tb3+ ions brought about 5.6 timesenhancement of
luminescence intensity and the luminescence lifetime value calculated about0.81165–1.19950 ms.The increasing of
Eu3+ co–doped, both the energy transfer rate and the efficiency of energy transfer from Tb 3+ ions to Eu3+ ions is are
increased. This research showed that co–doped CaMoO4:1%Tb3+,x%Eu3+nanophosphorshave a potential for
application as a red–emitting powder for warm white LEDs.

Author Contributions:
N.C.M has contributed to Sample synthesis, Sample processing, Data analysis, Intellectual content design, Result
interpretation and Writing–original draft preparation. Collection of samples, Interpreting resultdata curation,
Software and Conceptualization by H.P.V, M.A.P. Writing–review and editing by N.C.M, H.P.V. All authors have
drafted, read and agreed to the published version of the manuscript.

Supervision:
N.C.M.

Acknowledgments:-
This research is funded by Thai Nguyen University under grant number ĐH2022-TN04-01.

Ethical approval and consent:

Not applicable.

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