Ceramics International 48 (2022) 20940–20947

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Spectroscopic, optical properties and ab-initio calculation of thermally

stable Na2Ca1-xP2O7:xEu3+ phosphors for wLEDs
Mohan Lal Meena a, Sudipta Som b, Rajneesh Chaurasiya b, Shawn D. Lin a, Chung-Hsin Lu a, b, c, *
a
Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei, 10607, Taiwan
b
Department of Chemical Engineering, National Taiwan University, Taipei, 10617, Taiwan
c
Advanced Research Center for Green Materials Science and Technology, Taipei, 10617, Taiwan

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

Keywords: A series of Na2Ca1-xP2O7:xEu3+ phosphors (x = 0.01–0.1) were synthesized via solid-state reaction route. The
Eu3+ phosphor phase purity and crystal structure were confirmed via XRD and Rietveld refinement analysis. Density functional
Light-emitting diodes theory (DFT) calculations and experimental analysis were utilized simultaneously to study the electronic and
Density-functional theory
optical properties. The phosphors emit the typical Eu3+ ions emissions associated with the f-f transitions when
Thermal stability
Photoluminescence
excited at 394 nm. Energy transfer with the nearest neighbor or next nearest neighbor dopants caused the
concentration quenching in present phosphors. To confirm the Eu3+ ion’s local symmetry characteristics, the
optical transition parameters were calculated using the Judd-Ofelt theory. Furthermore, the thermal stability was
explored in depth. The temperature-dependent photoluminescence (PL) emission spectra of the developed
phosphors showed excellent thermal stability (90.63%) at 423 K and the calculated activation energy was 0.26
eV. Moreover, the Na2Ca1-xP2O7:xEu3+ phosphors were mixed with commercial green-blue emitting and coated
over a NUV chip to fabricate the wLED. The findings indicate that Eu3+ activated Na2CaP2O7 phosphors are
potential wLED materials.

1. Introduction phosphors to obtain the red-emitting phosphors, however, such type of

phosphors suffers from environmental issues and broad emission [5,11].
The low efficacy of incandescent lamps leads the researchers to focus Instead, Eu3+ ions are known for narrowband red emission around 612
more on the white light-emitting diodes (WLEDs) owing to durability, nm owing to 5D0-7FJ (J = 1, 2, 3, 4) transitions [12]. Among several
high efficacy, and eco-friendliness [1,2]. In the near future, WLEDs will transitions of europium trivalent ion, 5D0→7F2 transition dominates the
substitute the traditional illumination sources such as incandescent emission intensity in between 610 and 630 nm and is used for modern
lamps [3]. So far, most of the utilized WLEDs are fabricated using YAG: applications such as display devices and lighting [13,14]. One of the
Ce3+ phosphor-coated over blue InGaN chips [4]. However, the scarcity most significant criteria for industrially technological application in
of the red segment restricts the plausibility of low correlated color wLED systems is thermal quenching characteristic [15]. Furthermore, at
temperature (CCT) and high color-rendering index (CRI) in such types of high temperatures, the efficacy of optical materials is limited, and the
WLEDs [5]. Besides, previously reported studies show harmful effects of degradation rate of the LED junction is enhanced [15,16]. Recently,
WLEDs on human health [6]. As an alternative healthy approach, Na2Ca2Nb4O13:Eu3+ phosphor showed 65% thermal stability at 423 K
red-blue-green phosphors mix and are coated over the near-ultraviolet [17]. BiLaWO6:Eu3+ phosphors showed poor thermal stability and
(NUV) chip [6,7]. Notably, ultraviolet sources are proficient to give retained 50% of initial intensity at 374 K [18]. Sun et al. showed the
sufficient excitation energy compared to blue sources without influ­ 60% thermal stability of NaCaTiTaO6:Eu3+ phosphors at 420 K [19].
encing emission properties of WLEDs [8,9]. Furthermore, this method­ Sr3NaSbO6:Eu3+ phosphor showed a low internal quantum yield of
ology provides a broad scope for the selection of the various type of 17.3% [20]. Moreover, the host material structure affects the phosphors
phosphor materials utilized in WLEDs [9]. The incorporation of red emission properties [21]. To improve the performance, the selection of a
segment in the WLEDs can minimize the limitations of the white light suitable host matrix is crucial for efficient phosphors [22]. Among the
[10]. Several studies are reported using Mn4+ and Eu2+ activated various host materials, phosphate-based materials have stable structure,

* Corresponding author. Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei, 10607, Taiwan.
E-mail address: chlu@ntu.edu.tw (C.-H. Lu).

https://doi.org/10.1016/j.ceramint.2022.04.086
Received 11 March 2022; Received in revised form 11 March 2022; Accepted 8 April 2022
Available online 12 April 2022
0272-8842/© 2022 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
M.L. Meena et al. Ceramics International 48 (2022) 20940–20947

low cost [23]. Owing to the charge stabilization properties of phosphate phosphors’ photoluminescence properties. To make phosphor mixtures,
materials provide opportunities in lighting applications [24]. Phos­ the phosphor materials were disseminated in silicon-resin. For the
phates are known as potential host substances due to their fascinating fabrication of wLEDs, the resulting mixtures were covered on a 394 nm
qualities, which include easy synthesis, economic, excellent thermal InGaN NUV chip. CCE spectrophotometer (BRC112E) with integrating
strength and chemical stability in a wide-ranging temperature sphere was used to obtain EL spectrum, thermal stability, and quantum
400–800 ◦ C [25]. Still, phosphate based efficient red emitting phosphor efficiency.
studies are rare. Hence, a series of Na2Ca1-xP2O7:xEu3+ phosphors were The density functional theory (DFT) was employed to compute the
prepared through solid state reaction method. The luminescent and electronic structure of Na2CaP2O7 host material using The Quantum-
structural properties are studied in detail. Along with experimental ESPRESSO package. On the basis of experimental data derived
studies, DFT calculation were performed to obtain the detailed insights through Rietveld refinement, the crystal structure of Na2CaP2O7 was
of density of states. The JO theory was performed to obtained the modelled. The Generalized Gradient Approximation (GGA-PBE) type
structural stringency and stability of Na2Ca1-xP2O7:xEu3+ phosphors. exchange-correlation potentials predicted by Perdew-Burke-Ernzerhof
The emission spectra of prepared materials showed sharp peaks of red (PBE) were employed. To approximate the core electron potential, ul­
emission with high color purity. Changing the concentration of Eu3+ trasoft pseudopotentials were utilized. The wave function cut-off, 520eV
ions in the host materials revealed the concentration quenching effect. considered. The self-consistent field energy cutoff was chosen 1 × 10− 7
To test the thermal stability of prepared Na2Ca1-xP2O7:xEu3+ materials, Ry and 5 × 4 × 3 k-points mess utilized for calculation. Energy cutoff
temperature-dependent emission spectra were obtained. Lastly, a WLED and force cutoff for optimizing the atomic positions of crystal structure
was fabricated via mixing the synthesized Eu3+ doped Na2CaP2O7 are 0.0001 Ry and 0.001 au, respectively [49].
phosphor with commercially available blue and green phosphors. The
obtained outcomes suggest that the synthesized phosphors are suitable 3. Results and discussion
for the lighting application.
The phase purity of Na2Ca1-xP2O7:xEu3+ phosphor materials was
2. Materials and methods determined using XRD patterns. As demonstrated in Fig. 1a, the
observed diffraction peaks were consistent with ICSD #89468 standard
A solid-state reaction was used to produce a sequence of Na2Ca1- data. As the Eu3+ ion concentration increased from x = 0.01 to 0.10, the
3+
xP2O7:xEu . The initial materials Eu2O3 (99.9%), Na2CO3 (99%), recorded peaks did not change much, demonstrating that Eu3+ ion
CaCO3 (99.5%), NH4H2PO4 (99.5%), were processed to a stoichiometric doping had negligible influence on phase purity. Rietveld refinement
ratio in a ball mill for 3 h. The precursors were then calcined in a muffle was executed with PDXL software to corroborate the space group and
furnace at 680 ◦ C for 4 h before being cooled to room temperature. crystal symmetry of Na2Ca1-xP2O7:xEu3+ phosphors, the refinement re­
Finally, more grinding was used to create fine particles. sults and crystal structure are shown in Fig. 1 (b-c), respectively. The
A Rigaku X-ray diffractometer was used to investigate the structural refinement outcomes confirmed that the prepared phosphors had a
characteristics of the produced phosphor. A JEOL JSM7600F field triclinic structure and belonged to the space group P1‾[2]. The obtained
emission scanning electron microscope was utilized to examine the lattice parameters were a = 5.45 Å, b = 7.04 Å, c = 8.93 Å. The calcu­
morphology of the acquired phosphors. X-ray photoelectron spectros­ lated Rp, Rwp, and χ 2 values were found to be 7.35%, 9.66%, and 1.87,
copy (XPS) was utilized to examine the valence state of elements, which correspondingly. Table S1 summarizes various structural characteristics
was performed by XPS, Theta Probe, Thermo Scientific. A Hitachi and atomic coordinate positions. Two types of octahedral forms P2O7
(F4500) fluorescence spectrophotometer was used to investigate the and CaO6 are present in the crystal structure [26]. Six oxygen atoms are

Fig. 1. (a) Na2Ca1-xP2O7:xEu3+ phosphors (x = 0.01–0.1) XRD pattern (b) Rietveld refinement pattern of Na2Ca0.95P2O7:0.05 Eu3+ phosphors carried out via PDXL
software, (c) Illustration of crystal structure of Na2Ca0.95P2O7:0.05 Eu3+ phosphors drawn via VESTA software.

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coordinated with calcium, and seven oxygen atoms are coordinated with phosphors in Fig. 3 b (inset) show that the particles are homogeneous in
Na [27]. The resultant crystal structure is shown in Fig. 1c. Due to size and have strong grain connectivity. The morphology and structural
similar ionic radii, Eu3+ ions are anticipated to be doped in place of Ca2+ analyses results indicated homogeneous distribution of doping elements
sites. In addition to altering the crystallinity and composition of phos­ inside the phosphor materials. However, to check the electronic
phors, dopants also altered ion ligand fields. To check the doping effect behavior of the materials after doping, density functional theory was
and corresponding composition, X-ray photoelectron spectroscopic utilized.
(XPS) analyses of Eu3+ doped Na2CaP2O7 phosphors were measured. The Na2CaP2O7 crystal structure was simulated in accordance with
The XPS spectrum of as-prepared Na2Ca0.95P2O7:0.05Eu3+ phos­ the experimental data acquired from Rietveld refinement and optimized
phors is revealed in Fig. 2 (a) depicting the chemical composition and it. The optimized crystal structure was further used to calculate the
oxidation state of constituting elements. The core levels of sodium 1s, electronic properties. The electronic band structure is shown in Fig. 4a,
Calcium 2p, Phosphorus 3d, Oxygen 1s, and europium 4d can be easily which shows that the valence-band maximum (VBM) and conduction-
perceived. The composition of europium was obtained as 4.81% from band minimum (CBM) are situated at U and Γ, respectively. The indi­
the XPS compositional results. The obtained value was equivalent to the rect band gap of 5.23 eV was observed in the band structure. The direct
theoretically calculated value (5%). The smaller compositional amount and indirect band gaps have an energy difference of less than 26 meV.
of europium ion is attributed to the detection of excess oxygen atoms The band gap derived from band structure is validated by the total
[9]. The detected binding energy peak of ~1072.7 eV in Na 1s XPS density of states (DOS). In addition, the partial DOS was estimated, as
shows +1 oxidation state in prepared phosphors as shown in Fig. 2b shown in Fig. 4b. The O-s, O-p, and P-s orbitals dominate CBM, while the
[28]. Fig. 2c shows the characteristic Ca 2p1/2, 2p3/2 peaks around 348.3 O-p orbital contributes to the VBM at Fermi level. For Na, Ca, P, and O,
and 351.9 eV affirmed the +2 oxidation state of Ca ion [5,28]. The Bader charge analysis yielded 8.11e, 8.37e, 0.09e, and 7.87e, respec­
HR-XPS profile of P-2p confirmed the existence of P–O species at binding tively. The electron-density plot (Fig. 4(c–d)), shows more charge
energy of ~133.7 eV, as depicted in Fig. 2d [29]. The characteristic peak localized at Ca and minimum charge at P because of its charge depletion
for the O 1s was detected at ~532 eV (Fig. 2e). The recorded Eu 4d behavior. The electron density verified the Bader charge analysis as
spectra with the binding energy peak at ~133.6 eV, as shown in Fig. 2f, shown in Table S2. We developed a Na2CaP2O7 supercell (2 × 2 × 2) by
corroborated the europium ion’s 3+ valence state [30,31]. replacing one Ca with a Eu atom and optimizing it without any con­
The composition analyses of each element were further carried out to straints (Fig. S3). The change in the structural parameters take place
check the distribution of each element in the phosphor materials via near to Eu side which confirm the effect of dopant is localized. Electronic
elemental mapping analysis. Fig. 3(a) and (b) show elemental mapping property is analyzed through the total and partial density of state
pictures and EDS spectrum, respectively. Fig. 3a shows that the required (pDOS) and compare it with pristine. The obtained pDOS are shown in
elements Na, Ca, P, O, and Eu contributed consistently to the prepared Fig. S4. The total density states show the additional states in the
phosphor particles throughout. Meanwhile, Fig. 3b depicted that the forbidden region due to the presence of Eu3+. Partial density of states
constituting elements were found in the EDS spectrum without any other gives more information about the additional states in the forbidden re­
impurity element peaks, which is consistent with earlier XPS outcomes, gion. The additional states near to Fermi energy is mainly occurred due
implying that Na2CaP2O7:Eu3+ luminescent materials have great con­ to the Eu-f orbital and states below the conduction band minimum is
sistency and purity. For prepared sample, SEM micrographs were taken mainly arises due to Eu-d orbitals (Fig. 4e). The electron density plot of
at a 1 μm scale. The SEM micrographs of Na2Ca0.95P2O7:0.05 Eu3+ Eu doped Na2CaP2O7 supercell is shown in Fig. 4d, which confirmed the

Fig. 2. (a) Complete XPS profile of Na2Ca0.95P2O7:0.05 Eu3+ phosphor material with HR-XPS spectra of (b) Na, (c) Ca, (d) P, (e) O, and (f) Eu.

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Fig. 3. (a) Elemental mapping and, (b) The inset shows the SEM picture of the produced phosphor and the EDS spectrum of Na2Ca0.95P2O7:0.05Eu3+ materials.

Fig. 4. (a) host material’s electronic band structure (b) total/partial density of states of host materials, electron density of (c) host, (d) Eu3+ ion doped phosphors (e)
Eu3+ ions total and partial density of states in host.

that high charge localized at the Eu site. Moreover, the electron density 394 nm excitation. The phosphors display a number of narrow emission
of Na, Ca, P and O are more similar to pristine Na2CaP2O7. The charge of peaks at ~590 nm, 612 nm, 650 nm, and 696 nm, which correspond to
each atom was calculated using Bader charge analysis (Table S3). Eu, Eu3+ ion transitions 5D0→ 7FJ (J = 1, 2, 3, 4) accordingly. Orange/red
Na, Ca, P, and O have estimated charges of 24.93e, 8.11e, 8.37e, 0.09e, emission peak around 612 nm corresponding to 5D0 →7F2 dominates
and 7.87e, respectively. over other emission peaks. A hypersensitive electric-dipole (ED) tran­
In Fig. 5 (a,b), characteristic PL/PLE spectra of Na2Ca1-xP2O7:xEu3+ sition causes a strong emission peak at 612 nm, which is sensitive to the
phosphors are shown. At 612 nm emission peak, excitation spectrum symmetry of the Eu3+ local crystal field, but the magnetic dipole (MD)
was recorded. The PLE spectrum was divided into two sections: a broad- transition 5D0 →7F1 is unaffected to local environment [5]. Therefore,
band area known as the charge transfer (CT) band and a region with the 5D0→ 7F1 transition will be robust even in centrosymmetric envi­
multiple narrow peaks. The wideband ranging in 250–292 nm could be ronments. The emission peak at 612 nm had a high intensity compared
because of charge transfer from O2− 2p orbital to vacant Eu3+ ions 4f to the 590 nm peak, as seen in Fig. 5b. Since, Eu3+ situated at low
orbital, recognized as the charge transfer from ligand to metal (LMCT) symmetry positions of Na2CaP2O7lattice, and bonding environment was
peak. The width of the LMCT band was 0.71 eV, which was within the diverged from inversion symmetry, and the transitions were partially
range of Eu3+ CT transitions [32]. The other peaks of excitation posi­ allowed. Eu3+ ions site symmetry within host lattice can be investigated
tioned around ~298, 318, 361, 380, 394, 417, 463, and 530 nm relate to by comparing intensity and emission ratio Intensity(ED)/Intensity(MD),
Eu3+ electrons excited from the 7F0 ground-state to 5F1, 5H6, 5D4, 5G2,3, which is recognized as an asymmetric ratio [34]. Calculated values of
5
L6, 5D3, 5D2, and 5D1 transition state in the f orbital (Fig. 5a). Excitation asymmetric ratio are revealed in Table 1. Obtained high asymmetry
peak near 394 nm was the most powerful of observed excitation peaks even after the doping of 10 mol% indicated the dominance of electric
and implying that in the NUV range, it has a strong absorption efficacy. dipole transition, thereby emitting red-light emission. Electron transi­
This indicated that NUV LEDs may successfully pump Na2Ca1-xP2O7: tion diagram is shown in Fig. S1. Luminous properties of Eu3+-doped
xEu3+ phosphors [33]. phosphor are usually determined by the amount of activators doped. For
Fig. 5b shows the PL spectra of Na2Ca1-xP2O7:xEu3+ phosphors using phosphor materials, the concentration quenching phenomena is

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Fig. 5. (a) PL excitation and, (b) emission spectrum of prepared phosphors, (c) Emission intensity of prepared phosphors varies logarithmically with Eu3+ con­
centration, inset shows bar diagram of PL emission intensity, (d) color coordinates of Na2Ca1-xP2O7:xEu3+ phosphors. (For interpretation of the references to color in
this figure legend, the reader is referred to the Web version of this article.)

Table 1
Obtained parameters from Judd Ofelt theory.
Mol (%) Ω2 (pm2) Ω4 (pm2) transition A0-2 (s− 1) A0-4 (s− 1) Aτ (s− 1) Τrad (ms) β Assy. ratio
5 7
1 0.68 0.74 D0 → F1 170.1 5.8 0.26 1.58
5
D0 →7F2 79 41.1 0.52
5
D0 →7F4 0.21
5
2 0.72 0.83 D0 →7F1 178.9 5.4 0.27 1.59
5
D0 →7F2 82.7 46.1 0.46
5
D0 →7F4 0.26
5
3 0.85 0.84 D0 →7F1 194.2 5.2 0.26 1.89
5
D0 →7F2 98.1 46.2 0.50
5
D0 →7F4 0.24
5
4 0.86 0.81 D0 →7F1 195.2 5.1 0.26 1.90
5
D0 →7F2 98.5 46.7 0.51
5
D0 →7F4 0.23
5
5 0.98 0.88 D0 →7F1 211.4 4.7 0.24 2.18
5
D0 →7F2 112.8 48.6 0.53
5
D0 →7F4 0.23
5
7 0.75 0.96 D0 →7F1 85.8 53.4 189.2 5.3 0.26 1.66
5
D0 →7F2 0.45
5
D0 →7F4 0.28
5
10 0.62 1.07 D0 →7F1 70.9 59.3 180.2 5.5 0.28 1.37
5
D0 →7F2 0.39
5
D0 →7F4 0.33

relatively widespread, and its mechanism has to be researched. The concentration-quenching effect. Correlation amongst peak intensity and
main cause of luminescence concentration quenching is non-radiative Eu3+-concentration was explored using the given formula to gain a su­
energy mobility between doped elements influenced via structural perior knowledge about concentration-quenching mechanism [37,38].
characteristics of the lattice of the host materials [35,36]. So as to find ( )
the optimum doping amount of Eu3+ in the prepared phosphor, Eu3+ (1)
s
I∝α1− d Γ 1 + s/
d
amount was varied in range of 1–10 mol% (Fig. 5b). Under NUV light, all
phosphors produced red light, and the emission patterns did not vary ( )[ ( )]d/s
substantially except for the peak intensity as the quantity of Eu3+ α = xΓ 1 − d/s Xo 1 + A/γ (2)
increased. As the amount of doping was raised, the peak intensity rose as
well, peaking at x = 0.05. (Fig. 5c inset). Peak intensity, on the other here I denote intensity, x shows the moles of Eu3+ ion. s is allied to
hand, declined substantially above 5 mol%, which was attributed to dipole-dipole (6), dipole-quadrupole (8), quadrupole-quadrupole (10)

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interactions, whereas γ denotes the donors intrinsic-transition plausi­ 2

bility and d represents size. Coefficients are shown by A, X0. Equation (3) AED ′ =
64π 4 v3 e2 n(n2 + 2) ′ ′2
Ωλ Ψ JU λ Ψ J (8)
can be used to observe the interaction mechanism between Eu3+ ions
J→J
3h(2J + 1) 9
[39]. In the above equation, Here, e symbolizes electronic charge (4.80 ×
( ) [
I s ] 10− 10 esu), J||U||J/ >2 signifies reduced matrix element for J → J′ ED
log = − log(x) + logf (3) transitions, with values of 0.00320 and 0.00230 for J/ = 2, 4, respec­
x 3
tively [47]. Obtained results using JO theory are shown in Table 1.
f denotes a constant that is independent of the amount of europium. The Among various JO parameters, Ω2 has a close relationship with ligand
intensity and concentration curve in Fig. 5c is used to define s value. environment and it generally signifies the low symmetry nearby Eu3+
Obtained slope of the linear-fitting curve was 1.38 using equation (3). ions, whereas Ω4 is unaffected by chemical surrounding, is connected to
The s value was calculated as 4.14 as a result of above equation. This bulk property and stiffness of luminous host lattice. Fig. 6 (a) and (b)
implied that the most prevalent mechanism resulting in the concentra­ depict the deviation of Ω2 and Ω4 as the concentration of Eu3+ increases.
tion quenching behavior of Na2Ca1-xP2O7:xEu3+ phosphors was energy The following calculation can be used to compute the fluorescence
transfer with the nearest neighbor or next nearest neighbor doped ele­ branch ratios at the 5D0 level [48]:
ments [40]. The obtained results revealed 5 mol% Eu3+ ion amount was AJ→J′
optimum amount in Na2Ca1-xP2O7:xEu3+ phosphors. β=∑ (9)
J=1,2,3,4 AJ→J
The emission of Na2Ca1-xP2O7:xEu3+ phosphors is classic red colour
′

and found better than marketable Y2O2S:Eu3+ (0.62, 0.35) red phosphor The obtained results from the JO theory showed that the ED transi­
at optimum concentration 5 mol% Eu3+ (0.623, 0.364) positioned in red tions dominated the emission and results are shown in Table 1. High
section [41], as indicated in International de L’Eclairage (CIE) chro­ electric dipole transition indicates the dominance of red light emission
maticity illustration (Fig. 5d). Using formula below, the color purity of and hence we can observe sharp red light from the present phosphors.
the prepared samples was obtained from recorded emission spectra of The thermal stability of synthesized phosphors should be explored in
the Na2Ca1-xP2O7:xEu3+ materials [42]. order to investigate their promising usages in solid-state lighting, as it
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ can alter the light efficacy and CRI of LED devices [47]. The temperature
(xs − xi )2 + (ys − yi )2 dependent PL spectra of Eu3+ activated Na2CaP2O7 materials with
ColorPurity = √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ × 100% (4) optimized doping amount were obtained under excitation of 394 nm,
(xd − xi )2 + (yd − yi )2
displayed in Fig. 6c. With a temperature increase in between 303 and
The (xs, ys), (xi, yi), (xd, yd) represent CIE coordinates of Na2Ca1- 473 K, position of the emission band remains nearly constant. Even at
3+ high temperatures, the unvarying PL peak position aided in achieving a
xP2O7:xEu material, white-light, major wavelength, respectively.
Color purity for Na2Ca1-xP2O7:xEu3+ phosphors was calculated and steady emission. The thermal quenching, on the other hand, caused PL
found to rise with increasing europium ion concentrations, reaching a intensity to fall steadily. The normalized temperature dependent peak
maximum of 96.3% at 5 mol% Eu3+ concentrations. Fig. S2 shows how intensity is revealed in Fig. 6d. Besides, peak intensity at 423 K, retained
color coordinates and color purity change as the quantity of Eu3+ nearby 90.63% of the initial intensity at ambient condition (Fig. 6d),
changes. indicating that synthesized phosphors showed incredible thermal sta­
The local structure was examined further established via Judd-Ofelt bility. The activation energy need to examined for better understanding
theory to better understand crystal structure among Eu3+-ions in of related thermal quenching effect, it was calculated by the following
Na2CaP2O7 lattice [43,44]. The optical transition behaviors of Eu3+ ions expression [49].
were calculated utilizing the intensity parameters (Ωλ λ = 2, 4, and 6) in (
Io
)
ΔE
Judd-Ofelt theory [45]. Table 1 shows the estimated transition rates for ln − 1 = lnA − (10)
I kT
the existing transitions. The link among radiative transition rate (A)and
intensity was described as follows, according to previous literary works Where I0 denotes intensity at ambient temperature, intensity I is at
[5]: various temperature-dependent, A signifies the constant. The letters k,
∑ ∑ ΔE, and T stand for Boltzmann constant, activation energy, and tem­
I= I 7 FJ = α A7FJ (5)
J=1,2,3,4 J=1,2,3,4
perature, correspondingly. The plot for activation energy calculations is
shown Fig. 6e. The obtained ΔE was calculated as 0.26 eV. The obtained
α is assumed to be constant. Decay time (τ) is inversely proportional value was better than previously reported studies [50,51]. To confirm
to A as given below the application feasibility of the synthesized Na2Ca1-xP2O7:xEu3+
∑ 1 phosphors, the WLED devices were fabricated by combining a NUV chip
A 7 FJ = (6) (394 nm) with a combination of as prepared phosphor as well as com­
τ
mercial green and blue emission phosphors. The EL spectra of a prepared
J=1,2,3,4

Table 1 shows the results, which show that degradation time declines wLED (125 mA) is shown in Fig. 6e. Wide green and blue peaks of
with increase in doping amount and then decreases after 5 mol% Eu3+- marketable phosphor along with typical Eu3+ transitions of
ions, demonstrating presence of concentration-quenching in the current Na2Ca1-xP2O7:xEu3+ phosphor materials can be seen in recorded spec­
host. trum. The produced WLED’s CRI and CCT were determined as described
Alternatively, the radiative transition rate of 5D0 →7F1 (AMD ) for previously [52,53] and found to be 83.0 and 6068 K, respectively. The
J→J′
Eu3+, can be calculated using equation (7) [46]. aforesaid findings suggested that as-synthesized Na2Ca1-xP2O7:xEu3+
phosphor materials can act as an excellent contender for red-emitting
AMD ′ =
64π4 v3 3
n SMD (7) phosphor material in wLED applications.
J→J
3h(2J + 1)
The crystal field of the host lattice surrounding The ions of Eu3+ have 4. Conclusions
no impact on 5D0 → 7F1 transition. The Possibility of ED According to the
J-O hypothesis, spontaneous emission from the original J state to the J′ In summary, the crystal structure and optical characteristics of
state may be described as follows [43,44].: Na2Ca1-xP2O7:xEu3+ phosphors were studied for the first time as single-
phase materials. The refinement outcomes confirmed that the prepared
phosphors had a triclinic structure and belonged to the space group

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Fig. 6. (a) Ω2, (b) Ω4 deviation with Eu3+ concentration, (c) Temperature-dependent PL emission, (d) normalized peak intensity, (e) activation energy plot and, (f)
fabricated wLED.

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