Introduction:

The phosphor converted white light emitting diodes are considered as a promising candidate for

the conventional lighting source such as incandescent bulb and fluorescent lamp owing to their

advantages like high energy conversion efficiency, good color rendering, long duration ability

and eco-friendly nature. [1. Geng W, Zhou X, Ding J, Wang Y. NaBaY(BO3)2:Ce3+, Tb3+: A

novel sharp green‐emitting phosphor used for WLED and FEDs. J Am Ceram Soc.

2018;101:4560–71. 2. Du P, Huang X, Yu JS. Facile synthesis of bifunctional Eu3+ ‐activated

NaBiF4 red‐emitting nanoparticles for simultaneous white light‐emitting diodes and field

emission displays. Chem Eng J. 2017;337:91–100. 3. Zhao M, Liao H, Ning L, Zhang Q, Liu Q,

Xia Z. Next‐generation narrow‐band green‐emitting RbLi(Li3SiO4)2:Eu2+ phosphor for

backlight display application. Adv Mater. 2018;30:1802489.]

Phase conformation and crystal structure study:

The powder XRD pattern of the Sm3+ activated Li 3BaSrLn3(MoO4)8 (Ln = La Gd and Y)

phosphors were depicted in Fig.1. As exhibited in Fig .1, all the XRD peaks are identical with

the Joint Committee for powder diffraction system (JCPDS) card number 77-0830, there is no

impurity was observed. The synthesized phosphors were crystallized in the monoclinic phase

with space group C21/c and the cell parameters are …… Also, the Sm3+ activated phosphors

doesn’t show any changes in the XRD patterns, which confirms that the successful incorporation

of Sm3+ in the Ln3+ sites, because of the similar ionic radii of the Sm3+ and Ln3+ ions. The

lattice parameters of the of the synthesized phosphors were calculated by the linear fitting

method, the parameters of the Sm3+ activated Li3BaSrLn3(MoO4)8 phosphors are decreases with

increasing the concentration (Table ST1).

Fig. 1 Powder XRD pattern of Li3BaSrLn3(MoO4)8:Sm3+ (Ln = La (a), Gd (b) and Y (c))

phosphor.
 Fig.2 Crystal structure of Li3BaSrY3(MoO4)8 phosphor.

SEM

To investigate the morphology of the synthesized phosphor the SEM images were collected by

the scanning electron microscope. Fig.3 illustrates the SEM images of the Sm3+ activated

Li3BaSrLn3(MoO4)8 (Ln = La, Gd and Y) phosphors, which indicate that the phosphor contains

irregular morphology and the particles are aggregated. The average size of the particle ranging

from 2-5 micro meters. The bigger size of the particles were ascribed to Li substance of

Li3BaSrGd3-xSmx(MoO4)8 which expands the crystalline size of the phosphor along with

increases the grain growth by calcinating at the lower temperature. [M. Shang, G. Li, X. Kang,

D. Yang, J. Lin, J. Electrochem. Soc. 2011, 158(5) H565-H571.] The elemental mapping and

EDX analysis of the Sm3+ activated Li3BaSrLn3(MoO4)8 (Ln = La, Gd and Y) phosphors were

presented in Fig.S3-6. The elemental mapping reveals that the presence of all the elements and

also it was distributed homogeneously on the surface of the phosphors. The EDX spectrum

indicates the existence of all the Ba, Sr, La, Gd, Y, Sm, Mo and O elements. It showed that the

most of the ions like Ba, Sr, La, Gd, Y, Sm are occupied at the K shell and the other elements

like ….are employed at the L shell.

Fig.3 SEM image of Sm3+ activated Li3BaSrLn3(MoO4)8 ( Ln = La (a and b), Gd (c and d) and Y

(e and f)) phosphors.

FT-IR spectroscopy:

Fig.3 shows the FT-IR spectrum of the Li 3BaSrLn3(MoO4)8 (Ln =La, Gd and Y) phosphor. The

sharp peak placed at 416.8 and 433.3 cm-1 is ascribed to the stretching vibrations of O-Mo-O of

MoO4 group in the host lattice. Usually, the MoO4 group stretching vibration was observed

below 500 cm-1 region. Besides, the Ln-O stretching frequency could observe in the 400-500

cm-1 region.[ Marikumar Rajendran, Sivakumar Vaidyanathan, Journal of Alloys and

Compounds 789 (2019) 919e931] Therefore the Ln-O stretching vibrations are not visible

because of the possible overlap between the MoO4 groups and Ln-O stretching vibrations. Also

the spectra contains the strong band at 850 cm-1 which is corresponds to the stretching vibrations

of the Mo-O of MoO4 groups. [S. Kasturi, V. Sivakumar, ChemistrySelect 2 (2017) 5143-5156.]

The small peaks were attributed in the 1700 cm-1 region is ascribed to O-H stretching vibration

of the H2O molecule which is observed from the air atmosphere.

PL study:

The photoluminescence excitation spectra of the Sm3+ activated Li3BaSrLn3(MoO4)8 (Ln = La

(a), Gd (b) and Y (c)) phosphors were presented in Fig.4. All the excitation spectra contains

broad band in the region of 220-350 nm which can be attributed to the charge transfer transition

of the O2- -Sm3+ and the electronic transition from the 2p orbital of the oxygen to the 5d orbital
of the MoO4 groups. Also, the spectra consist of several sharp intense peaks in the range of 360-

500 nm which are attributed to the 4f-4f electronic transition of the Sm3+ ions, the sharp peaks

placed at 363, 376, 406, 421 and 465 nm which are attributed to the 6H5/2→4L15/2,

6H5/2→6P7/2, 6H5/2→4F7/2, 6H5/2→4P7/2, 6H5/2→4I11/2 electronic transitions

respectively. Among them the peak at 406 nm (6H5/2→4F7/2) is stronger than the other peaks.

[Xiulan Wu, Jinle Zheng, Qiang Ren, Wenni Bai, Yuhan Ren, Ou Hai, Synthesis and

luminescent properties of a novel orange-red Ba3Y(BO3)3:Sm3+ phosphors for white LEDs,

Polyhedron 164 (2019) 17–22]

Fig.4 PL excitation spectrum of the Li3BaSrLn3(MoO4)8:Sm3+ (Ln = La (a), Gd (b) and Y (c))

phosphor.
The PL emission spectrum of the Sm3+ activated Li 3BaSrLn3(MoO4)8 (Ln = La (a), Gd (b) and Y

(c)) phosphors were presented in Fig.5,which is monitored under the excitation at 406 nm. All

the emission spectra exhibited the sharp orange red emission at 646 nm, also it consist of several

sharp peaks at 563, 599, 645 and 705 nm which are assigned to the 4G5/2→6H5/2,

4G5/2→6H7/2, 4G5/2→6H9/2 and 4G5/2→6H11/2 transitions, respectively. [Kukku Thomas,

Dinu Alexander, S. Sisira, Linju Ann Jacob, P.R. Biju, N.V. Unnikrishnan, M.A. Ittyachen,

Cyriac Joseph, Sm3+ doped tetragonal lanthanum molybdate: A novel host sensitized reddish

orange emitting nanophosphor, Journal of Luminescence 211 (2019) 284–291] The 646 nm

(4G5/2→6H9/2) peak shows the maximum intensity than the other peaks. All these transitions

obeys the selection rule ∆J = ±1. [V.R. Bandi, B.K. Grandhe, M. Jayasimhadri, K. Jang, H.S.

Lee, S.S. Yi, J.H. Jeong, J. Cryst. Growth 326 (2011) 120–123.] The major part of the 4G5/2 →

6H5/2 transition is considered as a magnetic-dipole allowed transition (MD) and the

4G5/2→6H7/2 transition is considered as a partially magnetic dipole (MD) and partially

electric dipole transition (ED), whereas the 4G5/2→6H11/2 transition is completley electric

dipole transition (ED). [Y.I. Jeon, L.K. Bharat, J.S. Yu, J. Lumin. 166 (2015) 93–100. M.

Fhoula, M. Dammak, Journal of Luminescence 210 (2019) 1–6] The intensity ratio between the

646 nm(4 G5/2 → 6 H9/2) and 563 nm (4 G5/2 → 6 H5/2) is called as a R1, which can be used

to measure the departure from the centrosymmetry of sites occupied by Sm3+ ions. Likewise the

intensity ratio between the 599 nm and 563 nm is denoted as R2, which is used to indicate the

polarizability of thr chemical environment around the Sm3+ ion. The R1 and R2 values were

calculated from the PL spectra and the same were tabulated in Table .1. The R1 and R2 values

are greater than 1, these values indicates that the Sm3+ ion occupies the low-symmetry centre in

the host lattice. [C. Tiseanu, B. Cojocaru, D. Avram, V. I. Parvulescu, A. V. Vela-Gonzalez and
M. Sanchez-Dominguez, Isolated centres versus defect associates in Sm3+-doped CeO2: a

spectroscopic investigation, J. Phys. D: Appl. Phys., 2013,46, 275302.] There is no MoO4 group

emission was observed in the Sm3+ activated phosphors, it indicates that the MoO4 completely

transferd the absorbed energy by non-radiative process.

Fig. 5 PL emission spectrum of the Li3BaSrLn3(MoO4)8:Sm3+ (Ln = La (a), Gd (b) and Y (c))

phosphor.

Concentration quenching studies:

Fig.7 exhibited the emission intensity of the Sm3+ activated Li 3BaSrLn3(MoO4)8:Sm3+ (Ln = La

(a), Gd (b), Y (c) and comparison emission intensity of the three host lattice (d)) phosphor with

respect to their Sm3+ doping concentration. The optimal concentration quenching study is

important to evaluate the luminescent nature of the phosphor. The optimum concentration of
Sm3+ ion was found to be 0.1, 0.05 and 0.1for La, Gd and Y host lattice. When increases the

Sm3+ ion concentration the emission intensity also increase till the optimum concentration,

afterwards the emission intensity started decreases with adding the Sm3+ ion in the host lattices.

This phenomena is called as concentration quenching which is mainly arises due to the cross

relaxation process among the Sm3+ ions.

Fig.7 PL emission intensity of 4G5/2→6H9/2 transition of Li3BaSrLn3(MoO4)8:Sm3+ (Ln = La (a),

Gd (b) and Y (c)) phosphor. (e) Overall emission intensity of Sm3+ doped Li 3BaSrLn3(MoO4)8

(Ln = La, Gd and Y) phosphor.

Further the concentration quenching process can be well explained by finding the critical

distance (Rc) between the adjacent Sm3+ ions, which is derived by Blasse. The Rc energy

transfer can be determined by the critical concentration of the activator ion. [P. Chen, D. Yang,

W. Hu, J. Zhang, Y. Wu, Chem. Phys. Lett. 689 (2017) 169.]

Here Rc refers the critical distance, N corresponds to the number of available cationic sites in the

host lattice, V is the volume of the unit cell and Xc relates the critical concentration of the Sm3+

ions. [G. Blasse, Energy transfer in oxidic phosphors, Phys. Lett. A 28 (1968) 444–445.] In this

present study N = …, V = … and Xc = …for La, Gd and Y host lattices respectively. The Rc of

the La, Gd and Y host lattices were found to be ….. Respectively.

The type of energy transfer interaction can be determined by the Dexter theory, the relationship

between the emission intensity and activator ion concentration exhibited by the below equation.

I
=k ¿
x

Where I corresponds to the emission intensity, x refers the activator ion concentration, θ and k is

the coefficients. The θ values 6, 8 and 10 representing the dipole-dipole, dipole – quadrupole and

quadrupole – quadrupole interactions respectively, the θ values were found from the plots of the
log(I/x) vs log(x), which is shown in Fig.8. As shown in Fig.8, the slope values are ... for La, Gd

and Y host lattices. Consequently, the θ values were calculated to be …. For the La, Gd and Y

host lattices, the calculated values are near to 6. It suggested that the dipole – dipole interaction

is the main responsible for the concentration quenching mechanism in the

Li3BaSrLn3(MoO4)8:Sm3+ (Ln = La (a), Gd (b) and Y (c)) phosphor. [Jiyun Xianga, Meihua

Yanga, Yi Chea, Jing Zhua,b,⁎, Yong Maoa, Kai Xionga, Heyun Zhao, Ceramics International

45 (2019) 7018–7024. Luhui Zhou, Peng Du Jae Su Yu, J Am Ceram Soc. 2019;1–12.]
Energy transfer study:

Fig 10 shows the schematic energy transfer diagram of the MoO42- to Sm3+ ions in the

Li3BaSrLn3(MoO4)8 phosphor. Initially, upon the excitation the MoO4 group absorb the energy

and get excited from the 1A1 ground sate to the 1T1 excited state, subsequently transferred the

energy to the 6P7/2 highest excited state of the Sm3+ ion by non-radiatively. Simultaneously the

transferred energy dropped from the 6P7/2 to 4G5/2. As a final point, the emission arises from
 the 4G5/2 to the 6HJ (J = 5/2, 7/2, 9/2 and 11/2). [Yan Chen, Jing Wang, Chunmeng Liu,

Xiaojun Kuang, and Qiang Su, APPLIED PHYSICS LETTERS 98, 081917, 2011]

Conc. of Sm3+ Li3BaSrLa3-x(MoO4)8:Sm3+ Li3BaSrGd3-x(MoO4)8:Sm3+ Li3BaSrY3-x(MoO4)8:Sm3+

R1 R2 R1 R2 R1 R2
0.03 8.4392 2.929 7.3552 2.963 7.4291 3.0003
0 7
0.05 7.8525 2.841 8.0757 3.047 8.0807 3.1081
1 5
0.1 7.7371 2.881 7.7080 3.014 7.9549 3.1357
9 0
0.3 8.5093 3.029 7.2455 3.032 7.5700 3.0735
2 6
0.5 8.1553 3.021 7.4006 3.066 7.4185 3.0483
8 2
Fig.9 Schematic diagram of energy transfer of Li3BaSrLn3(MoO4)8:Sm3+ phosphor.
Decay curve analysis:

Fig.11 depicted the decay curve profile of the Sm3+ activated Li 3BaSrLn3(MoO4)8 (Ln = La (a),

Gd (b) and Y (c)) phosphor series, which is monitored under the excitation at 406 nm and the

emission at 646 nm. Fig.11d shows the lifetime values of the Li3BaSrLn3(MoO4)8:Sm3+

phosphors. All the decay curve of the Sm3+ activated Li3BaSrLn3(MoO4)8 phosphors can be well

fitted by the single exponential function:

When increasing the concentration of the Sm3+ the lifetime values were decreases gradually,

which arises because of the rapid energy transfer between the Sm3+ ions in the host lattices as

the distance between Sm3+ ions decreases. [S. Wang, Q. Sun, B. Devakumar, L. Sun, J. Liang,

X. Huang, RSC Adv. 8 (2018) 30191e30200. J. Liang, L. Sun, G. Annadurai, B. Devakumar, S.

Wang, Q. Sun, J. Qiao, H. Guo, B. Li X. Huang, RSC Adv. 8 (2018) 32111e32118.]

 Fig.10 Decay curve of Sm3+ activated Li3BaSrLn3(MoO4)8 (Ln = La (a), Gd (b) and Y (c))

phosphor. (e) Lifetime values of the all the phosphors.

CIE:

CIE is essential parameter to identify the exact emission color of the synthesized phosphor.

Fig.12 shows the CIE chromaticity coordinates of the Sm3+ activated Li3BaSrLn3(MoO4)8 (Ln =

La (a), Gd (b) and Y (c)) phosphors, which is calculated from the PL emission spectra under the

406 nm excitation. All the synthesized phosphor exhibits the orange red emission with excellent
CIE chromaticity coordinates. The CIE chromaticity coordinates of the synthesized phosphors

are …….for La, Gd and Y host lattice respectively, these values are close to the commercial

Y2O3 red phosphor CIE chromaticity coordinates. These outcomes demonstrate that Sm3+

doped Li3BaSrLn3(MoO4)8 phosphor can be a potential possibility for the orange segment

utilized for WLED application.

In addition the color purity also was calculated to evaluate the luminescent character of the

synthesized phosphors.
Fig.11 CIE images of the Sm3+ activated Li3BaSrLn3(MoO4)8:Sm3+ (Ln = La, Gd and Y) orange-

red phosphors.

In order to assess the commercial application of the synthesized Sm3+ activated

Li3BaSrLn3(MoO4)8 phosphors, the orange LEDs were fabricated for the synthesized phosphors

with the combination of NU-LED chip. Fig.13 shown the electroluminescence spectrum (EL) of

the fabricated orange LEDs. All the LEDs exhibits the orange red emission in the EL spectrum

and the Sm3+ ion emission dominates the NU-LED emission, these results conclude that the

synthesized phosphor could be a potential orange red emitting component in the WLED

fabrication.
Fig. 12 EL spectrum of the fabricated orange red-emitting LED device by the combination of

InGaN LED with Li3BaSrLn3(MoO4)8:Sm3+ (Ln = La, Gd and Y) phosphors.