j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 6 5 8 e6 8 0

Available online at www.sciencedirect.com

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

Original Article

Optical and visible and near-infrared fluorescence

aspects of Er3þ, Tm3þ, and Nd3þ-doped B2O3-rich
glasses for fiber amplifiers and NIR lasers

G. Lakshminarayana a,*, A.N. Meza-Rocha b, O. Soriano-Romero c,

~ o d, A. Lira e, Dong-Eun Lee f,**, Jonghun Yoon g,***,
U. Caldin
Taejoon Park h,****
a
Intelligent Construction Automation Center, Kyungpook National University, 80, Daehak-ro, Buk-gu, Daegu,
41566, Republic of Korea
b
CONACYT-Benemerita Universidad Autonoma de Puebla. Postgrado en Fı́sica Aplicada. Facultad de Ciencias
Fı́sico-Matema ticas, Av. San Claudio y Av. 18 sur, Col. San Manuel Ciudad Universitaria, Puebla, Pue. 72570,
Mexico
c
ticas, Benemerita Universidad Autonoma de
Posgrado en Fı́sica Aplicada, Facultad de Ciencias Fı́sico-Matema
Puebla, Av. San Claudio y Av. 18 Sur, Col. San Manuel Ciudad Universitaria, Puebla, Pue. 72570, Mexico
d
Departamento de Fı́sica, Universidad Autonoma Metropolitana-Iztapalapa, P.O. Box 55-534, Mexico, D.F. 09340,
Mexico
e
Departamento de Fı́sica, Facultad de Ciencias, Universidad Autonoma del Estado de Mexico, C.P. 50000, Toluca,
Mexico
f
School of Architecture, Civil, Environment and Energy, Kyungpook National University, 1370, Sangyeok-dong, Buk-
gu, DaeGu, 702-701, Republic of Korea
g
Department of Mechanical Engineering, BK21 FOUR ERICA-ACE Center, Hanyang University, 55, Hanyangdaehak-
ro, Sangnok-gu, Ansan-si, Gyeonggi-do 15588, Republic of Korea
h
Department of Robotics Engineering, Hanyang University, 55 Hanyangdaehak-ro, Ansan, Gyeonggi-do, 15588,
Republic of Korea

article info abstract

Article history:
Received 27 December 2021
Accepted 23 February 2022
Available online 3 March 2022
Keywords:
B2O3-rich glasses
Trivalent rare-earth ions
For synthesized each 1 mol% Er3þ, Tm3þ, and Nd3þ-doped borate-rich glasses, optical and
luminescence traits including fluorescence decay dynamics were explored. For Er3þ: glass,
at 1.4e1.65 mm range a wide NIR (near-infrared) luminescence band centered at 1.531 mm
(4I13/2 / 4I15/2) and in Tm3þ: glass, at 1.35e1.6 mm span a broad NIR fluorescence band
centered at 1.458 mm (3H4/3F4) are obtained by 980 nm LD (laser diode) pumping
(4I15/2 / 4I11/2) and 808 nm LD excitation (3H6/3H4) separately. Under 808 nm LD pumping
(4I9/2 / 4F5/2þ2H9/2), in Nd3þ: glass, three emission bands peaked at 0.901 mm (4F3/2 / 4I9/2),
1.057 mm (4F3/2 / 4I11/2), and 1.329 mm (4F3/2 / 4I13/2) respectively are observed and in all

* Corresponding author.
** Corresponding author.
*** Corresponding author.
**** Corresponding author.
E-mail addresses: gandham@knu.ac.kr (G. Lakshminarayana), dolee@knu.ac.kr (D.-E. Lee), yooncsmd@gmail.com (J. Yoon), taejoon@
hanyang.ac.kr (T. Park).
https://doi.org/10.1016/j.jmrt.2022.02.115
2238-7854/© 2022 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 6 5 8 e6 8 0 659

C-optical band amplifier such emissions, comparably the one obtained from transition 4F3/2 / 4I11/2 is highly
S-optical band amplifier intense. For acquired main visible and NIR emissions, Dleff (effective bandwidth), by
O-optical band amplifier FüchtbauereLadenburg approach semi (stimulated emission cross-section), gain band-
NIR lasers width, and optical gain are evaluated. 75.73 nm, 113.67 nm, and 57.37 nm are the Dleff
values for Er3þ: 4
I13/2 / 4
I15/2, Tm3þ: 3
H4/3F4, and Nd3þ: 4
F3/2 / 4
I13/2 transitions
accordingly. Using McCumber's theory, the calculated peak semi for Er : I13/2 / 4I15/2 and 3þ 4

Nd3þ: 4F3/2 / 4I9/2 transitions are 1.495  10e20 cm2 and 0.5556  10e20 cm2, respectively.
4
I13/2 / 4I15/2 transition gain cross-section spectra reveals C-band amplification at P (pop-
ulation inversion) ¼ 50% in Er3þ: glass, whereas at P ¼ 30% for 4F3/2 / 4I9/2 transition gain
cross-section is positive for lasing action at ~0.9 mm in Nd3þ: glass. All analyzed NIR
luminescence outcomes reveal that studied glasses could be potential gain media for C-, S-,
and O-bands fiber amplifiers and solid-state lasers.
© 2022 The Author(s). Published by Elsevier B.V. This is an open access article under the CC
BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

[4,5]. Here ~1.06 mm luminescence is highly attractive to

1. Introduction
By Snitzer [1], after the first discovery of lasing action in Nd3þ-
doped SiO2-based glasses in 1961, RE3þ (trivalent rare-earth)
ion-doped inorganic glasses possessing flexible composition,
cost-effectiveness, easy manufacturing method, and large-
volume production than crystals have been gained much
research interest from materials’ scientists for the develop-
ment of high power NIR (near-infrared) solid-state lasers.
Also, owing to low-transmission loss of SiO2 fiber at
1.2e1.7 mm NIR region, for optical communication systems,
SiO2-based EDFAs (Erbium-doped fiber amplifiers) and
TDFAs (Thulium-doped fiber amplifiers) are designed and
commercialized with limited C- (1.530e1.565 mm) and S-
(1.460e1.530 mm) optical bandwidths. But for applications in
tunable NIR lasers and broadband amplifiers to enhance the
channels number as many as possible of WDM (wavelength-
division multiplexing) systems, acquiring wide and flat NIR
fluorescence bands at 1.2e1.7 mm range in RE3þ-doped glasses
is vital that cover all U-band (1.625e1.675 mm), L-band
(1.565e1.625 mm), C-band (1.530e1.565 mm), S-band
(1.460e1.530 mm), E-band (1.360e1.460 mm), and O-band
(1.260e1.360 mm) regions [2]. Usually, to act as a host matrix for
lasing process, at both excitation and luminescence wave-
lengths, glass should be transparent optically, and it must
allow photons absorption and emission by RE3þ ions. Further,
for high power lasers, narrow bandwidth with greater semi
(stimulated emission cross-section) and high absorption co-
efficient is favorable while for fiber amplifiers, wider optical
spectra are desirable [3].
In all RE3þ ions, Nd3þ (trivalent neodymium, 4f3), Er3þ
(trivalent erbium, 4f11), and Tm3þ (trivalent thulium, 4f12) are
widely popular owing to their dense and ladder-like situated
energy states for efficient optical pumping that causes various
NIR and MIR (mid-infrared) lasing emissions when doped into
glasses. Nd3þ: 4G5/2 þ 2G7/2 and 4F5/2 þ 2H9/2 states could be
efficiently populated under Xe lamp (~582 nm) or cheaper 808
LD (laser diode) pumpings for obtaining ~0.9 mm (4F3/2 / 4I9/2),
~1.06 mm (4F3/2 / 4I11/2), ~1.32 mm (4F3/2 / 4I13/2), ~1.85 mm
(4F3/2 / 4I15/2), ~2.5 mm (4I13/2 / 4I9/2), ~4.75 mm (4I15/2 / 4I13/2),
~4.9 mm (4I13/2 / 4I11/2), and ~5.1 mm (4I11/2 / 4I9/2) emissions
fabricate NIR lasers operating at ambient temperature as it
has a minimum threshold four-level lasing scheme [6,7].
~0.9 mm emission is useful for frequency doubling to generate
blue light for displays [8], and ~1.32 mm fluorescence is po-
tential for O-optical band amplification [9]. To acquire a strong
~1.32 mm centered emission, Nd3þ population at the 4F3/2 level
must be high with a quick Nd3þ ions relaxation to 4I13/2 state.
To achieve this by bridging the gap (~2000 cm1) between 4I13/2
and 4I11/2 states with two phonons (MPR (multiphonon relax-
ation)) generally glasses with high phonon energy (e.g., B2O3)
could be advantageous. Further, bio-imaging is also possible
utilizing Nd3þ-doped materials because of emission transition
4
F3/2 / 4I13/2 [10]. Besides, Nd3þ also gives UC (upconversion)
emissions at ~0.44 mm (2P1/2 / 4I9/2), ~0.54 mm (4G7/2 / 4I9/2),
~0.61 mm (4G7/2 / 4I11/2), and ~0.66 mm (4G7/2 / 4I13/2) upon NIR
excitation [11,12].
Likewise, Er3þ and Tm3þ ions could also exhibit NIR and
MIR luminescences upon 980 nm (4I15/2 / 4I11/2) LD and
~1480 nm (4I15/2 / 4I13/2), and ~ .79 mm (3H6/3H4) and ~1.7 mm
(3H6/3F4) excitations accordingly [3]. Er3þ could give emis-
sions at ~0.85 mm (4S3/2 / 4I13/2), ~1.25 mm (4S3/2 / 4I11/2), ~1.53 mm
(4I13/2 / 4I15/2), ~1.7 mm (4S3/2 / 4I9/2), ~2.8 mm (4I11/2 / 4I13/2),
~3.3 mm (4S3/2 / 4F9/2), and ~3.5 mm (4F9/2 / 4I9/2) wavelengths
[13,14] whereas as stated in Ref. [15] Tm3þ could emit at ~0.8 mm
(1G4/3H5/3H4/3H6), ~1.2 mm (1G4/3H4/3H5/3H6), ~1.47 mm
(3H4/3F4), ~1.9 mm (3F4/3H6), ~2.3 mm (3H4 /3H5), and ~3.8 mm
(3H5 /3F4) wavelengths relying on glass low phonon energy.
Here respective Er3þ: 4I13/2 / 4I15/2 and Tm3þ: 3H4/3F4 transi-
tions are utilized in C- and S-optical bands amplification [16,17].
Both Er3þ and Tm3þ also generate UC emissions under
cw (continuous-wave) optical pumping like Er3þ at
~0.66 mm (4F9/2 / 4I15/2), ~0.55 mm (4S3/2 / 4I15/2), ~0.525 mm
(2H11/2 / 4I15/2), ~495 nm (4F7/2 / 4I15/2), ~470 nm (2P3/2
/ 4I11/2), and ~450 nm (4F5/2 / 4I15/2) [14,18] and Tm3þ at
~360 nm (1D2/3H6), ~450 nm (1D2/3F4), and ~480 nm
(1G4/3H6) [19]. Specifically, MIR fiber lasers are highly useful
in industry, medicine, remote sensing, and defense [20].
Further, all Nd3þ, Er3þ, and Tm3þ ions could be utilized in
luminescence thermometry as for example DE (energy gap)
between Nd3þ: 4F5/2 and 4F3/2 states and Er3þ: 2H11/2 and 4S3/2
levels is ~1000 cm1 and ~780 cm1 accordingly [21,22]. For
660 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 6 5 8 e6 8 0

attaining wide IR luminescence bands for fiber lasers and
amplifiers application, recently, Er3þ/Nd3þ [23] and Er3þ/
Tm3þ [24] codoped, and Er3þ/Tm3þ/Nd3þ [25] tri-doped
glasses have been studied and reported in literature.
In all distinct kinds of oxide glasses like tellurites, germa-
nates, phosphates, and silicates, borates, having B2O3 as a
network former, are attractive for RE3þ ions doping owing to
their wide range glass-forming potential, low melting point,
good optical transparency, large mechanical and thermal
stabilities, and sufficient RE ion solubility [26,27]. Generally, in
multicomponent borate glasses, both [BØ3] and [BØ4]e
(Ø ¼ bridging oxygen (BO)) structural units coexist. For
improving chemical stability, and to reduce large phonon
energy (~1400 cm1) of borates for observing RE3þ ions’ lesser
NR (non-radiative) losses and enhanced radiative emissions,
suitable amounts of alkali or alkaline metal fluorides (e.g., NaF
[28], MgF2 [29], CaF2/BaF2 [30]) could be added to B2O3 glass
matrix. As modifiers, when added to a glass network, both BaO
and Li2O could improve the generation of NBOs (nonbridging
oxygens) by disrupting the network. Also, BaO inclusion en-
hances the glass-forming capability and increases glass ther-
mal stability [31] whereas Li2O could lower the glass melting
point, and decreases the glass hygroscopicity [32]. Further,
depending on the incorporated amount (low or high) to a
glass, ZnO plays either a modifier or a network former (ZnO4
units) role and improves transparency, refractive index, and
glass-forming range [33].
In this regard, as an example, by various research groups,
recently different B2O3-based glass systems doped with Nd3þ
[9, 28e30, 34e37], Er3þ [32, 38e40], and Tm3þ [15, 41e44] have
been studied and reported for possible visible/NIR fiber lasers
and NIR optical amplification application.
For RE-doped optical materials, Judd-Ofelt (J-O) theory
[45,46] is commonly utilized as an effective tool to estimate
multiple absorption and fluorescence bands' oscillator
strengths. Here oscillator strength which defines band in-
tensity is a function of the area under the band and fexp.
(experimental oscillator strengths) are routinely attained from
absorption spectra. This theory describes three intensity pa-
rameters i.e., Ul (l ¼ 2, 4, 6), which could be obtained from
related optical transitions by least-square fitting approaches.
Such parameters are sensitive to RE ions' environment and
host matrix and clarify the RE bond covalence, symmetry, and
local structural factors. Further, Ul (l ¼ 2, 4, 6) values could be
employed to predict various radiative features like branching
ratios (bR), transition probabilities (AR), and radiative lifetimes
(trad) of distinct excited-states of RE ions in exploring the
emission qualities of solids (e.g., glasses and crystals) [45‒47].
Though in RE3þ ions f-f transitions are mainly ED (electric
dipole) in character, such ions also generate MD (magnetic
dipole) contributions reacting to magnetic fields’ presence. So
to obtain Ul (l ¼ 2, 4, 6) values, generally the MD part will be
subtracted from the total observed line-strength as MD line-
strengths are not highly affected by the host matrix [3,48,49].
To contemplate RE-doped phosphors or glasses or glass-
ceramics for possible solid-state lighting applications, essen-
tially, determining the CIE (Commission Internationale de
clairage) (x, y) values, and CP (color purity) and CCT (corre-
l'e
lated color temperature) quantities from CIE (x, y) values
utilizing such materials' visible luminescence spectra is
pivotal [50‒52].
Considering above all details, in this work, we investigate
optical and fluorescence features of Er3þ, Tm3þ, and Nd3þ
(1 mol%) -doped B2O3-rich glasses comprising BaO, ZnO, Li2O,
LiF, and NaF constituents primarily for potential applications
in C-, S-, and O-optical bands amplification and NIR lasers. AR,
trad, and bR of upper-levels of Er3þ, Tm3þ, and Nd3þ ions have
been computed using deduced J-O parameters. NIR emissions
were attained under 980 nm or 808 nm LD pumpings. semi max
(peak stimulated emission cross-section), Dleff (effective
bandwidth), and gain cross-section have been computed for
identified NIR emission transitions and discussed. Er3þ: 4I13/2
and Nd3þ: 4F3/2 levels decay times were attained upon 980 nm
LD and 582 nm Xe lamp excitations accordingly and analyzed.
2. Experimental
2.1. Synthesis and measurements
Glasses nominal composition studied in current work is (50ex)
B2O3-10 BaO-10 ZnO-10 Li2O-10 LiF-10 NaF-x Er2O3/x Tm2O3/x
Nd2O3 (x ¼ 0 and 1 mol%) and such samples are coded as H
(x ¼ 0, host glass), A (Er3þ, x ¼ 1), B (Tm3þ, x ¼ 1), and C (Nd3þ,
x ¼ 1) accordingly for convenience. A customary melt-quench
technique was utilized to fabricate these glasses in the air
atmosphere. Chemicals B2O3 (99.98%), BaCO3 (99.98%), ZnO
(99.99%), Li2CO3 (99.99%), anhydrous LiF (99.99%), NaF
(99.99%), Er2O3 (99.9%), Tm2O3 (99.99%), and Nd2O3 (99.9%)
purchased from Sigma-Aldrich have been used for sample
synthesis. Here for Li2O and BaO oxides, we adopted proper
amounts of Li2CO3 and BaCO3 in corresponding gravimetric
factors of 2.473 and 1.287. At first, considering the respective
glass's composition (mol%), for 20 g batch, all relevant com-
pounds have been correctly weighed with a digital balance
and then carefully for 1-h well-mixed and ground evenly by an
Fig. 1 e X-ray diffraction (XRD) profiles of all the prepared
glasses. Inset: photograph of pieces of all prepared
samples polished to 1.5 mm thickness.
Table 1 (a) e The intrinsic characteristics of the different cations present in the studied glasses.
Cations B3þ Ba2þ Zn2þ Liþ Naþ Er3þ Tm3þ Nd3þ
Structural role Glass former Glass modifier Glass modifier Glass modifier Glass modifier Dopant ion Dopant ion Dopant ion
Coordination 3, 4, 6 6, 7, 8, 9, 10, 11, 12 4, 5, 6, 8 4, 6, 8 4, 6, 8 6, 8 6, 8 6, 8, 9
number (CN)
Cation oxidation 3 2 2 1 1 3 3 3
number (Z)

Ionic radius, r (A) 0.01 (C.N. ¼ 3, 3þ 1.35 (C.N. ¼ 6, 2þ 0.60 (C.N. ¼ 4, 2þ 0.59 (C.N. ¼ 4, 1þ 0.99 (C.N. ¼ 4, 1þ 0.890 (C.N. ¼ 6, 3þ 0.880 (C.N. ¼ 6, 3þ 0.983 (C.N. ¼ 6, 3þ
charge); charge); charge); charge); 0.76 charge); charge); 1.004 charge); 0.994 charge); 1.109
0.11 (C.N. ¼ 4, 3þ 1.38 (C.N. ¼ 7, 2þ ¼ 5, 2þ (C.N. ¼ 6, 1þ charge); 1.02 (C.N. ¼ 6, 1þ (C.N. ¼ 8, 3þ (C.N. ¼ 8, 3þ (C.N. ¼ 8, 3þ

j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 6 5 8 e6 8 0
0.68 (C.N.
charge); charge); charge); 0.92 (C.N. ¼ 8, 1þ charge); charge) charge) charge);
0.27 (C.N. ¼ 6, 3þ 1.42 (C.N. ¼ 8, 2þ 0.74 (C.N. ¼ 6, 2þ charge) 1.18 (C.N. ¼ 8, 1þ 1.163 (C.N. ¼ 9, 3þ
charge) charge); charge); charge) charge)
1.47 (C.N. ¼ 9, 2þ 0.90 (C.N. ¼ 8, 2þ
charge); charge)
1.52 (C.N. ¼ 10, 2þ
charge);
1.57 (C.N. ¼ 11, 2þ
charge);
1.61 (C.N. ¼ 12, 2þ
charge)
Field strength, 30,000 for 0.01 1.0974 for 1.35 5.5556 for 0.60 2.8727 for 0.59 1.0203 for 0.99 3.7874 for 0.890 3.8739 for 0.880
F ¼ Z/r2 (
A)2 (C.N. ¼ 3, 3þ charge); (C.N. ¼ 6, 2þ (C.N. ¼ 4, 2þ charge); (C.N. ¼ 4, 1þ charge); (C.N. ¼ 4, 1þ charge); (C.N. ¼ 6, 3þ (C.N. ¼ 6, 3þ
247.9339 for 0.11 charge); 4.3253 for 0.68 1.7313 for 0.76 0.9612 for 1.02 charge); 2.9761 for charge); 3.0363 for 3.1046 for
(C.N. ¼ 4, 3þ charge); 1.0502 for 1.38 (C.N. ¼ 5, 2þ charge); (C.N. ¼ 6, 1þ charge); (C.N. ¼ 6, 1þ charge); 1.004 (C.N. ¼ 8, 3þ 0.994 (C.N. ¼ 8, 3þ 0.983(C.N.¼ 6, 3þ
41.1523 for 0.27 (C.N. ¼ 7, 2þ 3.6523 for 0.74 1.1815 for 0.92 0.7182 for 1.18 charge) charge) charge); 2.4392 for 1.109

(C.N. ¼ 6, 3þ charge) charge); 0.9919 (C.N. ¼ 6, 2þ charge); (C.N. ¼ 8, 1þ charge) (C.N. ¼ 8, 1þ charge) (C.N.¼ 8, 3þ

charge);2.2180 for 1.163

for 2.4691 for 0.90
1.42 (C.N. ¼ 8, 2þ (C.N. ¼ 8, 2þ charge) (C.N.¼ 8, 3þ charge)

charge); 0.9255
for
1.47 (C.N. ¼ 9, 2þ
charge);
0.8657 for 1.52
(C.N. ¼ 10, 2þ
charge);
0.8114 for 1.57
(C.N. ¼ 11, 2þ
charge);
0.7716 for 1.61
(C.N. ¼ 12, 2þ
charge)

661
662 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 6 5 8 e6 8 0

Table 1 (b) e Physical parameters of all the prepared glasses.

Property Sample code
H A B C
Average Molecular Weight (g/mol) 68.0669 71.1962 71.2293 70.7354
Density, r (g/cm3) 2.954 3.046 3.045 2.992
Ion concentration, N3þRE (  10
20
ions/cm3) … 2.5768 2.5748 2.5476

Interionic distance, ri (A) … 15.7394 15.7434 15.7992
Polaron radius, rp (A) … 6.34199 6.34363 6.36613
Field strength, F (cm2  1014) … 7.45882 7.45496 7.40237
Refractive index, nd 1.659 1.663 1.662 1.665
Dielectric constant, ε 2.7523 2.7655 2.7622 2.7722
Optical dielectric constant, 1.7523 1.7655 1.7622 1.7722
dt
p
dp
Molar volume, Vm (cm3/mol) 23.0422 23.3736 23.3922 23.6415
Oxygen packing density, OPD (mol/L) 78.1172 77.0097 76.9486 76.1372
Molar Refractivity, Rm (cm3) 8.4962 8.6595 8.6561 8.7795
Metallization criterion, M 0.6312 0.6295 0.6299 0.6286
Energy gap, Eg (eV) 5.6819 5.6419 5.6519 5.6220
Reflection loss, RL (%) 6.1423 6.1984 6.1844 6.2265
Molar Polarizability, am (cm3  1024) 3.3699 3.4346 3.4333 3.4822
Glass optical basicity, L 0.4918 0.4968 0.4967 0.4981
Linear optical susceptibility, c (1) 0.1395 0.1405 0.1403 0.1411
Third-order non-linear optical 6.4405 6.6368 6.5873 6.7381
susceptibility, c(3) (  1014) esu
Non-linear refractive index, n2 (  1012) 1.4627 1.5037 1.4934 1.5249
esu

agate mortar. Next, obtained glasses' chemical mixtures have
been loaded into high purity Al crucibles and closed with lids
before heating at 950  C in an electric furnace. To make each
molten liquid bubble-free and clear, it was periodically stirred
by a glass rod during melting. 30 min later, for fast solidifica-
tion, such attained refined melts were rapidly cast onto a
stainless steel plate and pressed by another identical one. At
this optimized melting time and temperature, Al2O3 inclusion
from the crucible could be neglected, and glass constituents'
like B2O3, Li2O, LiF, and NaF evaporation and glass melt
corrosion on the crucible might also be insignificant. Then,
promptly as-synthesized bulk samples were annealed at
350  C for 5 h in a muffle furnace to facilitate thermal strain
and stress dissipation caused by the quick quenching process.
At last, all glasses were naturally cooled to ambient temper-
ature by turning off the furnace. For optical traits inspection,
all annealed transparent H, A, B, and C samples have been cut
and surfaces were polished with distinct grades of emery
papers on both sides while for XRD (X-ray diffraction), a minor
section of each sample was ground separately to get smooth
powders.
For all acquired samples, optical path length, density
(±0.001 g/cm3), and refractive index (error: ±0.001) have been
determined employing digital Vernier caliper gauge, via
Archimedes's principle with toluene (99.9%) as a reference
liquid, and Abbe refractometer at 589.3 nm individually. Kinds
of equipment and settings utilized for all samples XRD and
absorption, and H, Er3þ, and Tm3þ: glasses visible fluorescence
and excitation spectra, including Er3þ: 4S3/2 and Tm3þ: 1D2
levels decay times experiments have been the same as we
have given in previous works [15,27] thus those particulars are
not repeated here. NIR fluorescence spectra at wavelength
range 1400e1650 nm for Er3þ: sample and 1350e1600 nm span
for Tm3þ: sample and 830e1500 nm extent for Nd3þ: sample

Table 1 (c) e Glass elements optical basicity properties.

Cation Electronegativity L ¼ (0.75/(Х i  0.25) Oxides Fluorides
[Х i] 1
Basicity Oxide L¼g Basicity Fluoride L ¼ g1
moderating moderating
parameter, g parameter
B3þ 2.04 0.4190 2.4208 B2O3 0.4131
Ba2þ 0.89 1.1719 0.8568 BaO 1.1671
Zn2þ 1.65 0.5357 1.8904 ZnO 0.5290
Liþ 0.98 1.0274 0.9792 Li2O 1.0212 2.2522 LiF 0.4440
Naþ 0.93 1.1029 0.9112 Na2O 1.0975 2.0958 NaF 0.4772
Er3þ 1.24 0.7576 1.3328 Er2O3 0.7503
Tm3þ 1.25 0.75 1.3464 Tm2O3 0.7427
Nd3þ 1.14 0.8427 1.1968 Nd2O3 0.8355
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 6 5 8 e6 8 0 663

Table 2 e Electronegativity (Х i), ionic character factor (Cionic (%)), and covalent character factor (Ccovalent (%)) of A, B, and C
glasses.
Glass compounds Х i of elements ХC ХA DХ Cionic (%) Ccovalent (%)
B 2O 3 B (2.04), O (3.44) 4.08 10.32 6.24 99.99 0
BaO Ba (0.89) 0.89 3.44 2.55 80.32 19.68
ZnO Zn (1.65) 1.65 3.44 1.79 55.12 44.88
Li2O Li (0.98) 1.96 3.44 1.48 42.17 57.83
Er2O3 Er (1.24) 2.48 10.32 7.84 99.99 0
Tm2O3 Tm (1.25) 2.50 10.32 7.82 99.99 0
Nd2O3 Nd (1.14) 2.28 10.32 8.04 99.99 0
LiF F (3.98) 0.98 3.98 3 89.46 10.54
NaF Na (0.93) 0.93 3.98 3.05 90.23 9.77

For all A, B, and C glasses, ionic character factor (Cionic (%)) ¼ 85.72.
For all A, B, and C glasses, covalent character factor (Ccovalent (%)) ¼ 14.27.

were registered by an FLS1000 fluorescence spectrometer Table 1(b) shows different physical properties of all examined
(Edinburgh Instruments, UK) under 980 nm (of 50 mW power) samples calculated by using r and n (refractive index) values.
and 808 nm (of 100 mW power) LD excitations (direct pump- Related formulae utilized to obtain Table 1(b) data could be
ings from Er3þ: 4I15/2 state to 4I11/2 level, Tm3þ: 3H6 level to 3H4 dt
found elsewhere [53]. p dp (optical dielectric constant) value is
state, and Nd3þ: 4I9/2 state to 4F5/2 level) accordingly with the largest for glass C where ε (dielectric constant) is varied
spectral resolution ~ 1 nm. Respective Er3þ: 4I13/2 and Nd3þ: 4F3/ with glass composition. Next, following the expression given
2 levels decay times were recorded utilizing the same instru- in Ref. [54], computed L (optical basicity) values for all H, A, B,
ment by 980 nm pulsed LD and 582 nm (using a 450 W Xe lamp) and C glasses are listed in Table 1(b). Table 1(c) depicts Xi
excitations equipped with a NIR-PMT (InGaAs) detector cooled (Pauling electronegativity), g (optical basicity moderating
by LN2 (liquid nitrogen) and a digital oscilloscope. All the op- parameter), and L values for all cations of H, A, B, and C
tical tests have been performed at ambient temperature. All glasses, including L of all compounds comprised in such
data were analyzed by Origin software. glasses. Here g ¼ 1.36 (Xi  0.26). L value is almost the same for
both A and B samples while it is slightly higher for glass C than
both of them and is relatively lesser for glass H in all samples.
3. Results and discussion Commonly, improving L specifies oxide ions' increasing po-
tential to donate electrons to nearby cations.
3.1. XRD results
Further, cð1Þ (linear optical susceptibility), cð3Þ (third-order
non-linear optical susceptibility), and n2 (non-linear refractive
For all H, A, B, and C glasses, Fig. 1 exhibits XRD profiles at
index) are evaluated for all H, A, B, and C samples following
10  2q  80 (2q) range. Fig. 1 inset shows the photograph of
the expressions [55] as:
pieces of all prepared samples polished to 1.5 mm thickness.
All samples XRD patterns show virtually the same shapes, 1
2 
cð1Þ ¼ n 1 (1)
and as predicted only two broad humps at 2q ¼ 16 e38 and 4p
38 e61 spans are noticed owing to non-crystalline state of
 2 4
studied glasses. Here, nonexistence of any intense and sharp
4 n 1
cð3Þ ¼ 1:7  1010 cð1Þ ¼ 1:7  1010 (2)
peaks related to any samples' compounds within the exam- 4p
ined 2q limit specifies that atoms are in an irregular arrange-
and
ment in long-range and affirms samples' amorphous structure
with short-range ordering. When atoms are disorderly ori- 12p ð3Þ
n2 ¼ c (3)
ented in a solid having no crystalline phases, X-rays upon n
interaction with them scatter randomly in different directions Obtained cð1Þ , cð3Þ , and n2 values are listed in Table 1(b) for
causing wide diffuse bands generally at lower and higher all studied glasses, and here sample C possesses the larger cð3Þ
angles [15]. in all glasses for feasible non-linear optical devices
application.
3.2. Physical traits For a particular host, the degree of Cionic (ionic bonding
character) or Ccovalent (covalent bonding character) could be
Table 1(a) showcases some intrinsic characteristics of Nd3þ, roughly predicted utilizing related formulae [56,57] as:
Tm3þ, Er3þ, Naþ, Liþ, Zn2þ, Ba2þ, and B3þ cations present in
h n oi
studied glasses. Generally, for all cations, r (ionic radius) Cionic ð%Þ ¼ 1  exp  0:25ðDХ Þ2  100 (4)
changes relying on CN (coordination number) that causes
additionally variations in F (Field strength) (http://www.mrl. h i
ucsb.edu/~seshadri/Periodic/ ). As one can see here, CN Ccovalent ð%Þ ¼ exp  0:25ðDХ Þ2  100 (5)
could occur as six for all cations in the examined samples.
664 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 6 5 8 e6 8 0

where DХ ¼ glass electronegativity which can be obtained by
(Х A‒Х C) values i.e., anions and cations electronegativity dif-
ferences that present in such glass.
In this context, for example, if Ccovalent (%) or Cionic (%) value
exceeds 50%, the glass is considered as covalent or ionic fac-
tors accordingly. Table 2 presents Х i (electronegativity) of all
elements, Х C, Х A, DХ, Cionic (%), and Ccovalent (%) values of all A,
B, and C glasses. Here, following Eqs. (4) and (5), for all A, B,
and C glasses, derived respective Ccovalent (%) and Cionic (%)
values are 14.27 and 85.72 (see Table 2). For A, B, and C sam-
ples, it is identified that the Cionic characteristic is more
evident than the covalent one.
3.3. Optical absorption studies
For glass H, Fig. 2(a) presents UV-Vis-NIR absorption spectrum
at 240e1000 nm wavelength range. It is obvious from Fig. 2(a)
that owing to sample H's amorphous state, there exists no
sharp absorption edge at the UV (ultraviolet) region where lcut-
Following Eq. (6), using Fig. 2(a), evaluated Eopt (direct
and indirect) value from Tauc plots at (ahn)2 ¼ 0 and (ahn)1/2 ¼ 0
(see inset plots of Fig. 2(a)) is 3.823 eV and 3.56 eV accordingly.
Here Eopt (direct) > Eopt (indirect) since Eopt (direct) profile fit lies
on the higher energy span. Being non-crystalline, generally,
glasses have transitions non-directly only from CB (conduc-
tion band) edge to VB (valence band) maximal.
Fig. 2(b) shows UV-Vis-NIR absorption spectrum of glass A
at 240e1800 nm spectral span. Thirteen absorption bands
peaked at 256 nm (39,062 cm1), 356 nm (28,089 cm1), 365 nm
(27,397 cm1), 378 nm (26,455 cm1), 407 nm (24,570 cm1),
450 nm (22,222 cm1), 488 nm (20,491 cm1), 521 nm
(19,193 cm1), 543 nm (18,416 cm1), 651 nm (15,360 cm1),
796 nm (12,562 cm1), 974 nm (10,266 cm1), and 1529 nm
(6540 cm1) attributed to transitions originating from Er3þ: 4I15/
2 2 2 4 4 2
2 ground state to related D5/2, K15/2/ G7/2, G9/2, G11/2, G9/2
(4F3/2þ4F5/2), 4F7/2, 2H11/2, 4S3/2, 4F9/2, 4I9/2, 4I11/2, and 4I13/2 upper-
states [32,59,60] are observed from Fig. 2 (b). Of them, 4I15/
4
2 / I13/2 transition only contains both MD and ED contribu-

off (fundamental absorption edge) is ~335 nm. tions. Here both transitions 4I15/2 / 4G11/2 and 4I15/2 / 2H11/2
Next, as described in Ref. [58]: are correlatively highly intense as they comply with DS ¼ 0, |

r DL|2, and |DJ|2 selection rules as HS (hypersensitive) ones
hv  Eopt [15,27]. Primarily, relying on RE3þ ions’ interaction ability with
aðvÞ ¼ B  (6)
hv hosts, HS transitions intensity changes noticeably in a local
where hn ¼ photon energy, r ¼ ½ and 2 respectively for vicinity that eventually influences Ul (l ¼ 2, 4, 6) values.
transitions direct and indirect, B (band-tailing Fig. 2(c) and (d) display absorption spectra of glass B at
parameter) ¼ constant, and Eopt ¼ optical band gap. 240e300 nm and 300e2000 nm spectral ranges accordingly.
From Fig. 2(c), identified three wide bands with high absorp-
Here aðlÞ ¼ 2:303  O:D:=t (7)
tion coefficients centered at 261 nm (38,314 cm1), 274 nm
where t ¼ optical path length (in cm), O.D. ¼ optical density. (36,496 cm1), and 287 nm (34,843 cm1) might be due to

Fig. 2 e (a) UV-Vis-NIR optical absorption spectrum of host glass (Insets: Plots of (ahn)2 vs. (hn) for direct optical band gap and
(ahn)1/2 vs. (hn) for indirect optical band gap). (b) UV-Vis-NIR optical absorption spectrum of 1 mol% Er3þ-doped glass. UV-
Vis-NIR optical absorption spectra of 1 mol% Tm3þ-doped glass at (c) 240e300 nm and (d) 300e2000 nm wavelength ranges.
(e) UV-Vis-NIR optical absorption spectrum of 1 mol% Nd3þ-doped glass. In all Fig. 2(aee), the y-axis scale is shown in the
absorption coefficient (cm¡1) values.
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 6 5 8 e6 8 0 665

electron transfer processes of trace impurities (e.g., Fe3þ ion),

retained even at ppm level in the starting chemicals used for
glass synthesis [15]. However, because of transitions from
Tm3þ: 3H6 ground state to respective 3P2, 3P1, and 3P0þ1I6
higher energy levels such stated three UV absorption bands
could be noticed in particularly UV transparent Tm3þ-doped
crystals [61]. Later, seven absorption bands centered at 358 nm
(27,932 cm1), 464 nm (21,551 cm1), 658 nm (15,197 cm1),
685 nm (14,598 cm1), 791 nm (12,642 cm1), 1211 nm
(8257 cm1), and 1667 nm (5998 cm1) assigned to transitions
arising from Tm3þ: 3H6 to relevant 1D2, 1G4, 3F2, 3F3, 3H4, 3H5,
and 3F4 excited states [15,59] are detected from Fig. 2 (d). Here
transition 3H6 / 3H5 only comprises both MD and ED parts
whereas 3H6 / 3F4 is an HS transition.
At 240e1000 nm wavelength span, Fig. 2(e) illustrates UV-
Vis-NIR absorption spectrum of glass C. Fifteen absorption
bands peaked at 329 nm (30,395 cm1), 350 nm (28,571 cm1),
356 nm (28,089 cm1), 429 nm (23,310 cm1), 459 nm
(21,786 cm1), 474 nm (21,097 cm1), 512 nm (19,531 cm1),
525 nm (19,047 cm1), 582 nm (17,182 cm1), 624 nm
(16,025 cm1), 681 nm (14,684 cm1), 740 nm (13,513 cm1),
746 nm (13,404 cm1), 802 nm (12,468 cm1), and 873 nm
(11,454 cm1) assigned to transitions from Nd3þ: 4I9/2 ground
state to (2L15/2þ4D7/2), (4D5/2þ2I11/2þ4D1/2), 4D3/2 (2P1/2þ2D5/2),
(2D3/2þ2P3/2) (2K15/2þ2G9/2þ4G11/2), 4G9/2, (4G7/2þ2K13/2) (4G5/
2 2 4 4 4 4 2 4
2þ G7/2), H11/2, F9/2, S3/2, F7/2 ( F5/2þ H9/2), and F3/2 excited
states correspondingly [6,59,62] are identified from Fig. 2(e).
Here, in all transitions 4I9/2 / 4G5/2þ2G7/2 centered at 582 nm is
highly intense owing to its HS nature [9] and it has larger
doubly reduced matrix element values and oscillator
strengths in comparison to other transitions.
Further, owing to samples A, B, and C disorder structure,
absorption bands centered at 974 nm (Er3þ: 4I15/2 / 4I11/2),
791 nm (Tm3þ: 3H6/3H4), and 802 nm (Nd3þ: 4I9/2 / 4F5/2 þ 2H9/
2) that are utilized commonly for optical pumpings by 980 nm
LD for Er3þ and 808 nm LD for Tm3þ and Nd3þ are inhomoge-
neously wide. Fig. 3(aec) depict such bands for A, B, and C
glasses at 900e1050 nm, 700e830 nm, and 770e850 nm spec-
tral ranges accordingly. From Fig. 3(aec), determined transi-
tion width (Dla) for Er3þ: 4I15/2 / 4I11/2 is ~25.01 nm, for Tm3þ:
3
H6 / 3H4 is ~28.49 nm, and for Nd3þ: 4I9/2 / 4F5/2 þ 2H9/2 is
~18.54 nm respectively. For example, in comparison, glass C
possesses higher Dla than those of Nd: YVO4 (Dla ¼ 2 nm) and
Nd: YAG (Dla ¼ 1 nm) crystals [63] and SiO2-based [64] glass
(Dla ¼ 15 nm) related values and comparable to that of P2O5-
based [65] glass (Dla ¼ 20 nm) respective value. This implies
that when suitable high power LDs are utilized as excitation
sources for practical applications, there is a minimal necessity
for temperature control of them [34].
For all A, B, and C samples, considering observed transi-
tions from Fig. 2(b), (d), and (e), fexp, U2, U4, and U6 parameters,
fcal (calculated oscillator strength), and drms (root-mean-square
deviation) for fexp and fcal are computed using the J-O model
[45,46] and all such results are provided in Table 3. For J-O
Fig. 3 e (aec) Absorption spectra of (1 mol%) Er3þ, Tm3þ,
parameters evaluation, the values of reduced matrix elements
and Nd3þ-doped glasses at 900e1050 nm, 700e830 nm,  2
of all Er3þ, Tm3þ, and Nd3þ ions (Ut  (t ¼ 2, 4, 6)) were taken
and 770e850 nm spectral ranges. In all Fig. 3(aec), the y-
from Ref. [66] (see Tables S1‒S3 in SM (Supplementary Mate-
axis scale is shown in the absorption coefficient (cm¡1)
rial)). Here, tensor operators' reduced matrix elements are
values.
 666
Table 3 e Absorption band assignments from the ground state, experimental (fexp £ 10¡6 cm2), and calculated (fcal £ 10¡6 cm2) oscillator strengths of all 1.0 mol% Er3þ,

j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 6 5 8 e6 8 0
Tm3þ, and Nd3þ-doped glasses along with J-O parameters. Wavelengths correspond to average transition energies.
Glass Code A B C
Transition l (nm) fexp fcal Transition l (nm) fexp fcal Transition l (nm) fexp fcal
4 4 3 3 4 4
I15/2/ I13/2 1517 5.73 5.72 H 6/ F4 1710 4.98 5.00 I9/2/ F3/2 875 4.75 4.76
5.20 ed
0.53 mda
4 3 4
I11/2 978 2.69 2.72 H5 1194 3.73 3.74 F5/2, 2H9/2 802 17.60 17.64
2.44 ed
1.29 mda
4 3 4
I9/2 804 0.50 0.52 H4 788 6.49 6.42 F7/2, 4S3/2 744 19.48 19.46
4 3 4
F9/2 655 5.78 5.74 F3 686 6.85 6.92 F9/2 681 1.48 1.48
4 3 2
S3/2 522 2.33 2.41 F2 660 1.56 1.56 H11/2 628 0.41 0.41
2 1 4
H11/2 524 23.01 22.82 G4 468 1.70 1.68 G5/2, 2G7/2 582 39.84 39.84
4 1 4
F7/2 488 7.93 7.92 D2 358 5.05 4.83 G7/2, 2K13/2, 4G9/2, 520 12.49 12.48
4 2
F5/2,3/2 449 4.36 4.43 K15/2, 2G9/2, 4G11/2, 2D3/2, 2P3/2 468 2.98 2.98
2 2
G9/2 407 3.18 3.24 P1/2, 2D5/2 429 1.23 1.23
4
G11/2,4G9/2, 376 45.95 46.14 4
D3/2, 4D5/2, 2I11/2, 4D1/2 354 22.59 22.55
2
K15/2
2 2
D5/2 256 0.58 0.59 L15/2, 4D1/2 329 2.29 2.26
6
RMS deviation (  10 ) 0.008 0.006 0.002
20 2
JeO parameters ( 10 cm )
U2 14.417 ± 0.008 6.719 ± 0.004 8.684 ± 0.001
U4 2.051 ± 0.002 3.488 ± 0.007 7.974 ± 0.001
U6 5.521 ± 0.002 3.150 ± 0.002 12.751 ± 0.002
U4/U6 0.625
a
Magnetic dipole (md) oscillator strength was subracted from experimental oscillator strength for J-O analysis.
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 6 5 8 e6 8 0 667

Table 4 e Comparison of JuddeOfelt intensity parameters (Ul £ 10¡20 cm2) and their trend of glass A with different Er3þ
-doped glass systems.
Glass system U2 U4 U6 Trends of Ul Reference
49B2O3e10BaOe10ZnOe10Li2Oe10LiF e10NaFe1Er2O3 (mol%) glass 14.417 2.051 5.521 U2>U6>U4 Present work
70TeO2e9PbF2e10AlF3e10BaF2e1Er2O3 (mol%) glass 6.56 1.84 1.53 U2>U4>U6 [23]
64.9TeO2e15ZnOe10WO3e10Bi2O3-0.1Er2O3 (mol%) glass 4.64 1.31 0.82 U2>U4>U6 [25]
64B2O3e15Na2Oe10PbOe5ZnOe5Li2Oe1Er2O3 (mol%) glass 6.19 5.68 0.13 U2>U4>U6 [32]
49B2O3þ10Bi2O3þ20Li2Oþ20K2Oþ1Er2O3 (wt%) glass 3.196 1.377 2.158 U2>U6>U4 [38]
64H3BO3þ10MgOþ5PbOþ15CaF2þ5ZrO2þ1Er2O3 (wt%) glass 5.56 1.44 2.15 U2>U6>U4 [39]
10Li2Oe10PbOe9Al2O3e70B2O3e1Er2O3 (mol%) glass 4.35 0.26 2.29 U2>U6>U4 [40]
44P2O5þ23PbOþ17K2Oþ9Al2O3þ6Na2Oþ1Er2O3 (mol%) glass 4.79 0.78 1.22 U2>U6>U4 [68]
55SiO2e30Bi2O3e10B2O3e1Er2O3 (mol%) glass 6.40 2.96 1.52 U2>U4>U6 [69]
65GeO2e12Ga2O3e23(BaF2 þ La2O3 þ Li2O)e0.5Er2O3 (mol%) glass 4.74 1.89 0.82 U2>U4>U6 [70]
40GeO2e40B2O3e10ZnOe10BaOe0.5Er2O3 (mol%) glass 6.10 1.70 1.45 U2>U4>U6 [71]
70TeO2e5Na2CO3e15BaCO3-10GaF3þ1ErF3 (mol%) glass 6.95 2.24 2.07 U2>U4>U6 [72]
53ZrF4e20BaF2e4LaF3e3AlF3e20NaFe1ErF3 (mol%) glass 2.70 1.68 1.18 U2>U4>U6 [73]

usually insensitive to host compositions. Applied formulae for
J-O analysis can be found elsewhere [23,25]. As one can see
from Table 3, derived drms quantities are so small (8e2  10‒9
range), indicating the J-O model calculation method's reli-
ability. Here, uncertainties of U2, U4, and U6 values have been
deduced directly from the J-O fit considering the residual
values of calculated and measured intensities. Obtained J-O
parameters show U2>U6>U4, U2>U4>U6, and U6>U2>U4 trend
for samples A, B, and C respectively. Here, different courses of
U2, U4, and U6 could be owing to the existence of Er3þ, Tm3þ,
and Nd3þ ions in different site symmetry in the host matrix.
Usually, U2 is sensitive to the asymmetry in the RE ions'
proximity, and it also indicates the extent of covalence be-
tween surrounding ligand anions and RE ions while U4 and U6
correspond to the host matrix's degree of rigidity and viscosity
[25,27]. For glasses A and B, higher U2 specifies stronger EreO
and TmeO bonds covalency combined with Er3þ and Tm3þ
sites' asymmetry. Generally, EreF or TmeF bond is more ionic
than EreO or TmeO bond as F owns a larger Xi (3.98) than O
(3.44) element. For glass C, greater U6 hints at the higher ri-
gidity of the sample structurally. Specifically, for Nd3þ ion, NIR
fluorescence transition intensities from 4F3/2 level could be
 2
described by U4/U6 ratio as U2  ¼ 0 for this level (see Table S3
in SM), and U2 does not contribute to such intensities [67]. Here
U4/U6 ratio is termed as c (spectroscopic quality factor).
Usually, if c < 1, 4F3/2 / 4I11/2 transition intensity will be higher
than that of 4F3/2 / 4I9/2 transition and strongest intensity of
4
F3/2 / 4I11/2 can be expected when U6 [ U4, hinting at po-
tential lasing action from 4F3/2 / 4I11/2 at ~1.06 mm [67]. For
glass C, calculated c ¼ 0.625, so it might show intense lumi-
nescence for transition 4F3/2 / 4I11/2 as c < 1.
Tables 4e6 present U2, U4, and U6 values and their trend
obtained for A, B, and C glasses against different reported
Er3þ-doped [23, 25, 32, 38e40, 68e73], Tm3þ-doped [15, 25,
41e44, 74e79], and Nd3þ-doped [6, 9, 23, 25, 29, 30, 35e37, 80,
81] glass systems respectively. As can be noticed from Table 4,
U2 and U6 values for sample A are higher than those of all
compared glasses related values, revealing that glass A has
lower symmetry at Er ion sites locality and a larger degree of
covalency between Er ions and nearby ligands than in them, in
addition to relatively higher rigidity in structure. Next, for
glass A, U2, U4, and U6 tendency is similar to 49B2O3þ10Bi2
O3þ20Li2Oþ20K2Oþ1Er2O3 (wt.%) [38], 64H3BO3þ10MgOþ
5PbOþ15CaF2þ 5ZrO2þ1Er2O3 (wt.%) [39], 10Li2Oe10PbOe
9Al2O3e70B2O3e1Er2O3 (mol%) [40], and 44P2O5þ 23PbOþ
17K2Oþ 9Al2O3þ6Na2Oþ1Er2O3 (mol%) [68] glasses respective
values trend. Likewise, glass B U2, U4, and U6 values are larger
than those of all compared glass systems in Table 5, except
49B2O3e10BaOe10ZnOe10LiFe20Na2Oe1.0Tm2O3 glass [15]
related values. Here, for glass B, U2, U4, and U6 course is

Table 5 e Comparison of JuddeOfelt intensity parameters (Ul £ 10¡20 cm2) and their trend of glass B with different Tm3þ
-doped glass systems.
Glass system U2 U4 U6 Trends of Ul Reference
49B2O3e10BaOe10ZnOe10Li2Oe10LiF e10NaFe1Tm2O3 (mol%) glass 6.719 3.488 3.150 U2>U4>U6 Present work
49B2O3e10BaOe10ZnOe10LiFe20Na2Oe1.0Tm2O3 (mol%) glass 9.649 3.789 3.535 U2>U4>U6 [15]
64.2TeO2e15ZnOe10WO3e10Bi2O3-0.8Tm2O3 (mol%) glass 3.54 0.63 1.51 U2>U6>U4 [25]
1.5Tm2O3e45Bi2O3e55B2O3 glass (mol%) glass 3.65 1.32 1.37 U2>U6>U4 [41]
49.5B2O3e10TeO2e10PbOe10ZnOe10Li2Oe10Na2O‒0.5Tm2O3 (mol%) glass 3.69 1.27 2.97 U2>U6>U4 [42]
16.6Li2Oe16.6K2Oe66.4B2O3e0.4Tm2O3 (mol%) glass 4.37 0.05 1.41 U2>U6>U4 [43]
50Bi2O3e35B2O3e10Al2O3e5BaF2e8Tm2O3 (mol%) (BBAT4) glass 3.78 1.46 1.24 U2>U4>U6 [44]
56SiO2e5Al2O3e20CaOe14BaOe5BaF2e1Tm2O3(1Eu2O3) (mol%) glass 3.17 0.56 0.58 U2>U6>U4 [74]
ZBLAN:3% at.Tm3þ (mol%) glass 2.31 1.28 1.17 U2>U4>U6 [75]
58.5P2O5e17K2Oe14.5BaOe9Al2O3e1Tm2O3 (mol%) glass 5.23 1.95 0.72 U2>U4>U6 [76]
36Bi2O3e44GeO2e10Ga2O3e10Na2Oe1Tm2O3 (mol%) glass 5.00 1.13 1.17 U2>U6>U4 [77]
85TeO2e5Nb2O5e5ZnOe5LiFe1Tm2O3 (mol%) glass 4.162 1.872 1.140 U2>U4>U6 [78]
30SiO2e10GeO2e25PbOe25PbF2e10CdF2e1Tm2O3 (mol%) (B4) glass 3.563 1.727 1.437 U2>U4>U6 [79]
668 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 6 5 8 e6 8 0

Table 6 e Comparison of JuddeOfelt intensity parameters (Ul £ 10¡20 cm2), their trend, and spectroscopic quality factor (c)
of glass C with different Nd3þ -doped glass systems.
Glass system U2 U4 U6 Trends of Ul c (U4∕ U6) Reference
49B2O3e10BaOe10ZnOe10Li2Oe10LiF e10NaF-1Nd2O3 (mol%) glass 8.684 7.974 12.751 U6>U2>U4 0.625 Present work
63P2O5e7K2Oe14BaOe10Al2O3e4La2O3-2Nd2O3 (mol%) glass 3.08 4.99 4.36 U4>U6>U2 1.144 [6]
49.5B2O3e10PbOe10BaOe10Al2O3e10ZnOe10Na2O-0.5Nd2O3 (mol%) glass 17.15 1.03 11.20 U2>U6>U4 0.092 [9]
70TeO2e9PbF2e10AlF3e10BaF2e1Nd2O3 (mol%) glass 6.18 3.99 4.10 U2>U6>U4 0.973 [23]
64.97TeO2e15ZnOe10WO3e10Bi2O3-0.03Nd2O3 (mol%) glass 5.58 2.08 3.99 U2>U6>U4 0.521 [25]
49.2B2O3þ20PbOþ15MgF2þ15NaClþ0.8Nd2O3 (mol%) glass 5.37 4.03 3.27 U2>U4>U6 1.232 [29]
10CaF2e15ZnOe4Al2O3e10BaF2e60B2O3-1Nd2O3 (mol%) glass 8.3751 6.4529 3.9807 U2>U4>U6 1.621 [30]
54.5B2O3e10SiO2-25Gd2O3e10CaO-0.5Nd2O3 (mol%) glass 2.14 2.57 1.93 U4>U2>U6 1.331 [35]
LiCaBO3 (25Li2Oþ50CaOþ25B2O3):1Nd2O3 (mol%) glass 3.08 5.17 5.01 U4>U6>U2 1.032 [36]
15Na2Oþ15Li2Oþ19.5CdOþ50B2O3þ0.5Nd2O3 (mol%) glass 3.35 4.99 3.89 U4>U6>U2 1.282 [37]
54SiO2e25Bi2O3e20Li2Oe1Nd2O3 (mol%) glass 3.36 2.82 3.19 U2>U6>U4 0.884 [80]
65GeO2e8Ga2O3e17BaF2e5La2O3e5Li2Oe1Nd2O3 (mol%) glass 3.58 3.41 3.68 U6>U2>U4 0.926 [81]

identical to (mol%) 49B2O3e10BaOe10ZnOe10LiFe20Na2-
Oe1.0Tm2O3 [15], 50Bi2O3e35B2O3e10Al2O3e5BaF2e8Tm2O3
[44], ZBLAN:3% at. Tm3þ [75], 58.5P2O5e17K2Oe14.5BaOe9Al2-
O3e1Tm2O3 [76], 85TeO2e5Nb2O5e5ZnOe5LiFe1Tm2O3 [78],
and 30SiO2e10GeO2e25PbOe25PbF2e10CdF2e1Tm2O3 [79]
glasses corresponding values trend. Following Table 6, it can
be observed that glass C possesses a greater U2 value in all
compared glasses, except for 49.5B2O3e10PbOe10BaOe10Al2-
O3e10ZnOe10Na2O-0.5Nd2O3 glass [9], where U4 and U6 are
relatively higher for sample C than those of all compared glass
systems respective values, reflecting sample C's higher vis-
cosity and rigidity than them. Here, for glass C, U2, U4, and U6
drift is similar to only 65GeO2e8Ga2O3e17BaF2e5La2O3e5Li2-
Oe1Nd2O3 (mol%) glass [81] respective values course. As c is
vital to estimate the stimulated fluorescence in a laser-active
host, for sample C, obtained c is higher than those of (mol%)
49.5B2O3e10PbOe10BaOe10Al2O3e10ZnOe10Na2Oe0.5Nd2O3
[9] and 64.97TeO2e15ZnOe10WO3e10Bi2O3e0.03Nd2O3
[25] glasses related values only in all compared glasses
(see Table 6).
For A, B, and C samples, employing U2, U4, and U6 values
and refractive indices, radiative properties like AR, bR, and
trad of main visible and NIR emission transitions of Er3þ, Tm3þ,
and Nd3þ ions are calculated utilizing related formulae [23,25].
Attained such outcomes for glasses A and B in Table 7, and
for glass C in Table 8 are presented. Here, sample A has better
AR (¼ 231 s1) and bR ¼ 100% for transition 44I13/2 / 4I15/2
suggesting its high potential for C-optical band amplifica-
tion. Also, for transition 4S3/2 / 4I15/2 obtained high AR
(¼ 2035 s1) and bR (¼ 67%) indicates glass A favorability for
effective green lasing action. Likewise, sample B possesses a
larger AR (¼ 3769 s1) and considerable bR (¼ 22%) for transition
1
D2/3F4 specifying its feasibility for blue lasing action, where
such bR value is almost the same as evaluated for glass B (¼
22.92%) [15] for transition 1D2/3F4. Additionally, for 3H4/3F4
transition, glass B has sufficient AR (¼ 79 s1) revealing its finer
ability for S-optical band optical amplification. Comparably,
trad of transition 1D2/3F4 in sample B (¼ 59.29 ms) is identified
to be larger than those of 49B2O3e10BaOe10ZnOe10LiFe
20Na2Oe1Tm2O3 (¼ 47.5 ms) [15] and LiKB4O7: Tm (¼ 53 ms) [43]
glasses respective values. Following Table 8, in glass C, tran-
sition 4F3/2 / 4I11/2 has greater AR (¼ 1428 s1) and bR (¼ 53.1%)
than the remaining two other NIR optical transitions for effi-
cient NIR lasing action, and for 4F3/2 level AT ¼ 2688 s1 and
trad ¼ 372 ms. The larger AT, the quicker decay time ensues.
Here transition 4F3/2 / 4I13/2 is useful for O-optical band
amplification.
Particularly, for Nd3þ ion, using ‘c’ value, for NIR optical
transitions originating from 4F3/2 state branching ratios ðbÞ
could be calculated using expressions [82] as:

 0:3194c þ 0:07671
b 4 F3=2 / 4 I9=2 ¼ (8)
0:4247c þ 0:4567

 0:1053c þ 0:2874
b 4 F3=2 / 4 I11=2 ¼ (9)
0:4247c þ 0:4567

 0:09023
b 4 F3=2 / 4 I13=2 ¼ (10)
0:4247c þ 0:4567

Table 7 e Peak wavelength (lp , nm), radiative transition probability (AR , s¡1), radiative branching ratio (bR ), measured (tmeas ,
ms) and radiative lifetime (trad , ms), effective bandwidth (Dleff , nm), stimulated emission cross-section maximum (sem max , £
10¡21 cm2), gain bandwidth (sem max  Dleff , £ 10
¡26
cm3), optical gain (sem
max  trad , £ 10
¡24
cm2s), and quantum yield (h, %) of
the main NIR and visible emission transitions in A and B glasses.
Sample code/Transition lp AR bR tmeas trad Dleff sem
max sem
max  Dleff sem
max  trad h
A
4
I13/2 / 4I15/2 1531 231 1.00 460 4323.88 75.73 7.984 6.046 34.523 11
4
S3/2 / 4I15/2 548 2035 0.67 9.59 331.54 24.33 3.631 0.883 1.204 3
B
1
D2/3F4 452 3769 0.22 23.28 59.29 18.96 3.966 0.752 0.235 39
3
H4/3F4 1455 79 0.06 … 816.66 113.67 1.484 1.687 1.212 …
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 6 5 8 e6 8 0 669

Table 8 e Peak wavelength (lp , nm), electric dipole line strength (Sed , £ 10¡20 esu2cm2), radiative (AR , s¡1) and total
transition probabilities (AT , s¡1), radiative (bR ) and experimental (bexp ) branching ratios, effective bandwidth (Dleff , nm),
¡21 ¡26
stimulated emission cross-section maximum (sem max , £ 10 cm2), gain bandwidth (sem
max  Dleff , £ 10 cm3), optical gain
¡24 2 8 2
(smax  trad , £ 10
em
cm s), and saturation intensity (IS , £ 10 W/m ) of the NIR emission transitions in glass C under 808 nm
LD excitation. Radiative (trad , ms) and measured (tmeas , ms) lifetimes including quantum yield (h, %) of the 4F3/2 level are also
included.
Transition lp Sed AR bR baR bbR b exp Dleff sem
max sem
max  Dleff sem
max  trad IS
4
F3/2 / 4I9/2 901 2.527 949 0.353 0.386 0.223 0.248 50.73 5.94 3.01 2.21 60.35
4
F3/2 / 4I11/2 1057 6.139 1428 0.531 0.489 0.542 0.632 32.46 26.05 8.45 9.69 11.72
4
F3/2 / 4I13/2 1329 2.659 311 0.116 0.125 0.235 0.120 57.37 7.98 4.58 2.97 30.42
AT ¼ 2688 trad ¼ 371.96 tmeas ¼ 61.61 h ¼ 17
a
Lomheim and De Shazer's method.
b
Kaminskii's method.

Computed b values by Eqs. (8‒10). ðbaR Þ and by method

 0:00231
b 4 F3=2 / 4 I15=2 ¼ (11) described in Ref. [66] ðbbR Þ are listed in Table 8. Here it is obvious
0:4247c þ 0:4567
that baR values are comparable to bR for all three NIR emission
Also, b can be obtained by Kaminskii's method that is well
transitions where for transition 4F3/2 / 4I11/2 bbR and bR values
explained in page 236, eq. 3.13 in Ref. [66] which is similar to
match well.
Ref. [82] method, only with other elements of the matrix.
For all H, A, and B glasses, obtained visible luminescence
spectra under relevant UV light excitations and related CIE
plot (Figs. S1‒S4), derived CP and CCT values (Table S4),
including decay time profiles of Er3þ: 4S3/2 / 4I15/2 transition in
glass A and Tm3 þ: 1D2 / 3F4 transition in glass B with curve fit
upon UV pumpings (Fig. S5), all with related discussions
consisting of Refs. [83‒87] and Eqs. (12‒20) are given in SM for
readers’ reference.

3.4. NIR luminescence analysis

Fig. 4(a) depicts the recorded NIR fluorescence spectrum of

sample A at 1400e1650 nm wavelength range, upon 980 nm LD
pumping wielded at 50 mW output. As predicted, a broad
asymmetric emission band centered at 1531 nm (6531 cm1)
attributed to Er3þ: 4I13/2 / 4I15/2 transition [25] is observed in
glass A. Here acquired NIR luminescence (having both MD
and ED parts) wraps the whole C- þL-optical bands'
(1.53e1.625 mm) span hinting at glass A's possible utilization in
fiber amplifiers. Typically, owing to the ground and excited
states Stark splitting combined with inhomogeneous broad-
ening, the NIR emission band (4I13/2 / 4I15/2) width divides into
different bands [88,89]. Here identified wide NIR fluores-
cence comprises five Gaussian bands peaked at 1493 nm,
1531 nm, 1540 nm, 1557 nm, and 1609 nm. Fig. 4(b) presents
the deconvoluted NIR emission spectrum of sample A at
1400e1650 nm spectral span. Here narrow 1531 nm, 1540 nm,
and 1557 nm bands represent MD, and broad 1493 nm and
1609 nm centered bands reflect ED contributions. This
outcome suggests that Er3þ ions are located in an alike local
environment in glass A and inhomogeneous broadening is not
so crucial compared to Stark splitting as the former one is
prevalent in SiO2-based glasses mostly [16,90]. Commonly,
glass disordered structure provides a widespread of coordi-
nation sites for RE3þ ions.
Under 808 nm LD excitation obtained NIR luminescence
spectrum of glass B at 1350e1600 nm extent is shown in Fig. 5.
Fig. 4 e (a) NIR luminescence spectrum of 1.0 mol% Er3þ-
A wide fluorescence band centered at 1458 nm (6858 cm1)
doped glass upon 980 nm LD excitation. (b) Deconvoluted
assigned to Tm3þ: 3H4/3F4 transition [15] is identified in
NIR emission spectrum of 1.0 mol% Er3þ-doped glass.
670 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 6 5 8 e6 8 0
Fig. 5 e NIR luminescence spectrum of 1.0 mol% Tm3þ-
doped glass upon 808 nm LD excitation.
sample B. Here because of detector sensitivity upper limit, NIR
emission was acquired up to 1.6 mm only, hence 3F4/3H6
(~1.8e2 mm) luminescence transition is not noticed. As one
can observe from Fig. 5, the 3H4/3F4 transition is ranged
from 1355 nm to 1570 nm wavelength covering E þ S- þ C-
optical bands for feasible amplification where larger Dleff is
an essential factor for multichannel propagation in WDM
systems. Since NIR luminescence from the 3H4 state is effi-
cient once it is straightly pumped, it may be reasonable to
expect that at 1 mol% doping enough Tm3þ ions at 3H4 state
can be achieved at lexci. ¼ 808 nm. Moreover, 3H4 / 3F4
transition intensity could be observed higher than the in-
tensity of 3F4 / 3H6 transition owing to lower 3F4 level
depopulation via utilized pumping wavelength's ESA (excited
state absorption) [91].
At 830e1500 nm spectral range, upon 808 nm LD pumping,
the registered NIR emission spectrum of glass C is displayed in
Fig. 6. Three luminescence bands peaked at 901 nm
(11,098 cm1), 1057 nm (9460 cm1), and 1329 nm (7524 cm1)
Fig. 6 e NIR luminescence spectrum of 1.0 mol% Nd3þ-
doped glass upon 808 nm LD excitation.
are observed from Fig. 6 corresponding to transitions
4
F3/2 / 4I9/2, 4F3/2 / 4I11/2, and 4F3/2 / 4I13/2 accordingly [9]. Of
them, the 1057 nm centered band is found to be highly intense
than the other two bands. Owing to possible 4F3/2 state Stark
splitting, the 901 nm peaked band consists of three compo-
nents. Here transition 4F3/2 / 4I13/2 is highly significant in
optical solids which are utilized as 1.057 mm lasers.
Fig. 7(a) exhibits Er3þ: 4I13/2 / 4I15/2 emission transition
decay profile of glass A obtained under 980 nm LD pumping.
Here, as one can see from Fig. 7(a), the 4I13/2 level decay pattern
could be well fit to single-exponential functions (R2 ¼ 0.99976)
using eq. (19) and tmeas value of 4I13/2 metastable state is found
to be 0.46 ms. Commonly, larger tmeas values of 4113/2 state
could give desired high population inversion with engaged
appropriate pump powers for amplification. Comparably, in
glass A, Er3þ: 4I13/2 / 4I15/2 transition tmeas is less than those of
64.9TeO2e15ZnOe10WO3e10Bi2O3e0.1Er2O3 (¼ 3.53 ms) [25],
BLK1.0Er glass (¼ 5.515 ms) [38], 55SiO2e30Bi2O3e10B2O3
e1Er2O3 (¼ 1.57 ms) [69], and 65GeO2e12Ga2O3e23(BaF2 þ La2
O3 þ Li2O)e0.5Er2O3 (¼ 6.98 ms) [70] glasses corresponding
values.
Similarly, Fig. 7(b) depicts the luminescence decay curve of
Nd3þ: 4F3/2 level in glass C upon 582 nm (4I9/2 / 4G5/2þ2G7/2)
excitation at lemi. ¼ 1.057 mm. Obviously, the acquired decay
profile shows double exponential character and is fitted by
applying eq. (17) (R2 ¼ 0.99891) (see Fig. 7(b)). For glass C, the
tmeas value of the 4F3/2 emitting state is found to be 61.61 ms.
Here, higher tmeas is beneficial to realize the lasing process.
In comparison, derived 4F3/2 / 4I11/2 transition tmeas value is
higher than that of CaB4O7: 1 mol% Nd3þ glass (¼ 55 ms) [36],
slightly lower than that of 49B2O3e10PbOe10BaOe10Al2O3-
e10ZnOe10Na2Oe1Nd2O3 glass (¼ 65.5 ms) [9], similar to
BZBNd10 glass (¼ 62 ms) [92], and lower than those of
BSGdCaNd1.0 (¼ 322 ms) [35] and 63P2O5e7K2Oe14BaOe10Al2-
O3e4La2O3e2Nd2O3 (¼ 406.7 ms) [6] glasses respective values.
Often, Nd3þ: 4F3/2 tmeas is smaller in B2O3-based glasses
because of certain structural and vibrational aspects of such
glasses, for example, Refs. [9,36,92].
For glass A, Fig. 8 presents Er3þ ion's partial energy-level
scheme under lexci. ¼ 363 nm and 980 nm LD pumping,
where all noticed visible and NIR fluorescence transitions and
related NR channels indicated. Upon 363 nm pumping,
initially, in sample A, Er3þ ions in 4I15/2 ground state are
directly excited to 4G9/2 level. Then, such ions will non-
radiatively relax to 2G9/2, 2H11/2, and 4S3/2 levels accordingly.
From these states, Er3þ ions quickly depopulate to the 4I15/2
state in a radiative way emitting respective violet (410 nm) and
green (526 nm and 548 nm) lights. As observed 410 nm and
526 nm peaked emissions are so weak than 548 nm one, it
could be reasonable to assume that most of the exciting Er3þ
ions rapidly non-radiatively relax to 4S3/2 state and then to the
ground state radiatively, giving strong green luminescence
(548 nm). Likewise, upon lexci. ¼ 980 nm, Er3þ ions in 4I15/2 state
stimulate at first to 4I11/2 level and then populate on to 4I13/2
metastable state via NR (MPR) process. Finally, Er3þ ions in the
4
I13/2 level will relax radiatively to the 4I15/2 state producing a
NIR emission band centered at 1531 nm in glass A.
Fig. 9 exhibits Tm3þ ion's partial energy-level structure in
glass B upon lexci. ¼ 358 nm and 808 nm LD excitation indi-
cating all observed visible and NIR emission transitions and
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 6 5 8 e6 8 0
associated NR and CR (cross-relaxation) processes of 1D2 and
3
H4 emitting states. Under lexci. ¼ 358 nm, at first, Tm3þ ions in
3
H6 ground level are pumped to 1D2 upper state and then most
of such ions in 1D2 state radiatively relax to 3F4 level, giving
intense 452 nm centered blue light, in addition, a weak 513 nm
green luminescence by reaching to 3H5 level. For transition
1
D2/3F4, (1D2, 3H6)/(3F2, 3H4) and (1D2, 3H6)/(3F3,3F3) are po-
tential CR routes. Remaining Tm3þ ions in 1D2 state will relax
through an NR channel to 1G4 state and then finally radiatively
to 3H6 level, generating a weak blue emission (480 nm). Simi-
larly, under lexci. ¼ 808 nm, initially, Tm3þ ions in 3H6 level are
excited to 3H4 state, and then a sizeable portion of such ions
will relax radiatively to 3F4 level causing a NIR fluorescence
band centered at 1458 nm. Here (3H4þ3H6/3F4þ3F4) CR
channel influences Tm3þ ions' population at 3H4 level.
Upon lexci. ¼ 808 nm and 582 nm pumping, Nd3þ ion's
partial energy-level scheme for glass C illustrating NIR lumi-
nescence transitions combined with NR, MPR, and CR
Fig. 7 e (a) Decay lifetime profile of Er3þ: 4I13/2 / 4I15/2
transition in glass A under 980 nm excitation wavelength.
(b) Luminescence decay curve of Nd3þ: 4F3/2 / 4I11/2
transition in glass C upon 582 nm excitation wavelength.
671
processes are shown in Fig. 10. At lexci. ¼ 808 nm, initially, 4F5/
2
2þ H9/2 states are populated by Nd
3þ
ions GSA (ground state
absorption) while at lexci. ¼ 582 nm, at first, Nd3þ ions are
pumped to 2G7/2 level from 4I9/2 ground state, and then relax to
4
F5/2 level by successive NR processes. Later, by the MPR pro-
cess, 4F3/2 state will be populated. Here, to bridge DE ~000 cm1
existing between 4F5/2 and 4F3/2 levels, one phonon of sample C
(B2O3-rich glass) is sufficient, which leads to a rapid popula-
tion of 4F3/2 emitting level. At last, Nd3þ ions in state 4F3/2
radiatively relax to respective 4I9/2, 4I11/2, and 4I13/2 lower
states, giving NIR emissions peaked at 901 nm, 1057 nm, and
1329 nm. Here (4F3/2þ4I9/2 / 4I15/2þ4I15/2) is a feasible CR
channel for Nd3þ ions for examining the NIR fluorescence.
Next, for all A, B, and C glasses, to explore observed main
visible and NIR emissions qualitatively, by scaling Figs. S2 (b)
and S3 (b) (see SM), and Fig. 4 (a), 5, and 6 semi (stimulated
emission cross-section) is determined applying the Fücht-
bauereLadenburg formula [93] as:
Aij l5 IðlÞ
semi ðlÞ ¼ 2
Z (21)
8pcn
lIðlÞdl
where c, n, Aij (¼ Aed þ Amd), and I(l) denote light speed in
vacuum, refractive index, spontaneous fluorescence proba-
bility, and fluorescence relative intensity at l from i to j state
accordingly.
Figs. S6(a) and S7(a) in SM illustrate derived semi profiles of
glasses A and B for 4S3/2 / 4I15/2 and 1D2/3F4 transitions at
500e590 nm and 425e500 nm ranges, whereas such patterns
for 4I13/2 / 4I15/2 transition at 1400e1650 nm span in glass A,
for 3H4/3F4 transition at 1350e1580 nm range in glass B, and
for 4F3/2 / 4I9/2 transition at 830e980 nm range, 4F3/2 / 4I11/2
transition at 1000e1160 nm span, and 4F3/2 / 4I13/2 transition
at 1270e1440 nm extent in glass C are shown in Figs. 11(a),
Fig. 8 e Partial energy-level diagram of the Er3þ ion in glass
A, depicting the UV and NIR excitations, and visible and
NIR emission transitions, including related NR channels.
672 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 6 5 8 e6 8 0

Fig. 9 e Partial energy-level diagram of the Tm3þ ion in glass B, depicting the UV and NIR excitations, and visible and NIR
emission transitions, including CR channels for 1D2 and 3H4 excited levels.

12(a), and 13(aec) respectively. From all such plots identified
peak semi ðsemi
max Þ quantities are given in Tables 7 and 8.
In this case, Dleff for visible and NIR fluorescence bands is
computed via the expression [15]:
Z 1.057 mm lasers fabrication.
1 For producing desired visible or NIR fiber lasers and NIR
Dleff ¼ IðlÞdl
Imax
where Imax ¼ intensity at band maximum.
Such calculated Dleff values for all A, B, and C samples
are listed in Tables 7 and 8. Later, semi
max  Dleff (peak gain
bandwidth) and semi
max  trad (optical gain) are evaluated and
given in Tables 7 and 8 including bexp for acquired NIR emis-
sion transitions in glass C and h (quantum efficiency) for
related transitions, for example h ¼ 17% for transition
4
F3/2 / 4I11/2 in glass C. bexp values are deduced considering
relative areas under the luminescence bands. Here, bexp
(¼ 63.2%) is high for 4F3/2 / 4I11/2 transition for potential
(22)
optical amplifiers, larger semi for Er3þ: 4S3/2 / 4I15/2, Tm3þ:
1
D2/3F4 or Nd3þ: 4F3/2 / 4I9/2 and 4F3/2 / 4I11/2 transitions,
and Er3þ: 4I13/2 / 4I15/2, Tm3þ: 3H4/3F4, and Nd3þ:
4
F3/2 / 4I1/3/2 transitions is essential. Further, higher Dleff for
NIR emissions is necessary for improving optical communi-
cations systems’ competence. Generally, semi  Dleff and
semi  trad indicate the amplification and laser threshold.

Fig. 10 e Partial energy-level diagram of the Nd3þ ion in glass C, depicting excitation, NIR emissions combined with NR,
MPR, and CR processes.
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 6 5 8 e6 8 0 673

Glass A possesses 75.73 nm Dleff and 6.046  1026 cm3

semi
max  Dleff for 4I13/2 / 4I15/2 transition, suggesting its feasi-
bility for C-band amplification. Likewise, glass B has 113.67 nm
Dleff and 1.687  1026 cm3 semi 3 3
max  Dleff for H4 / F4 transition,
indicating its potential for S-band amplification, whereas
sample C holds 57.37 nm Dleff and 4.58  1026 cm3 semi
max  Dleff
for 4F3/2 / 4I13/2 transition for O-band amplification. As an
example, comparably, Dleff of 4I13/2 / 4I15/2 transition in glass
A is larger than those of all H1eH5 (¼ 51e58 nm range) [69]
and 0.5ErZMB (¼ 72.1 nm) [39] glasses and similar to Glass C (¼
75.2 nm) [40] related values and lower than those of LiBEr4 (¼
98.36 nm) [32] and BLK1.0Er (¼ 81.21 nm) [38] glasses’ respec-
4 4
tive value. Likewise, semi
max  Dleff value of I13/2 / I15/2 in
sample A is higher than those of LiBEr4 (3.017  1026 cm3)
[32], 1Er ZMB (¼ 3.944  1026 cm3) [39], and Glass C
(¼ 1.607  1026 cm3) [40] glasses corresponding values and
lower than that of BLK1.0Er (¼ 6.671  1026 cm3) glass [38]
related value. In comparison, glass B Dleff and semi
max  Dleff

Fig. 12 e (a) Stimulated emission cross-section profile of

Tm3þ: 3H4/3F4 transition in glass B. (b) Predicted
theoretical gain spectra of 3H4/3F4 transition in glass B.

values for 3H4/3F4 transition are lower than that of glass

Fig. 11 e (a) Stimulated emission cross-section profile of
Er3þ: 4I13/2 / 4I15/2 transition in glass A. (b) Predicted
theoretical gain spectra of 4I13/2 / 4I15/2 transition in
glass A.
A related values (¼ 121.228 nm and 2.22  1026 cm3) [15].
Moreover, for Er3þ: 4S3/2 / 4I15/2 transition in glass A
derived Dleff and semi  trad values are 24.33 nm and
1.204  1024 cm2s accordingly. Here, glass A possesses higher
26
Dleff and semi
max  Dleff (¼ 0.883  10 cm3) values than all
3þ
reported Er : LiPbAlB glasses (Dleff ¼ 22e20.3 nm range and
26
semi
max  Dleff ¼ 0.196e0.271  10 cm3 span) [40] respective
values, for its consideration for possible green lasing action.
Also, Tm3þ: 1D2/3F4 transition in glass B has considerable
Dleff, semi
max , and semi  trad values (see Table 7) for such sam-
ple's utilization for blue lasing action. Intrinsically, owing to
10e15% error in J-O computation, estimated radiative factors
like trad could change within calculated error extents [94] in
addition to decay time experimental errors, causing very high
or low h values.
674 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 6 5 8 e6 8 0

Fig. 13 e (aec). Stimulated emission cross-section profiles of Nd3þ: 4F3/2 / 4I9/2, 4F3/2 / 4I11/2, and 4F3/2 / 4I13/2 transitions in
glass C. (d) Predicted theoretical gain spectra of 4F3/2 / 4I11/2 transition in glass C.

Later, in glass C transition 4F3/2 / 4I9/2 possesses Dleff and Additionally, for all identified NIR fluorescence transitions
semi  trad values of 50.73 nm and 2.21  1024 cm2s respec- in glass C from 4F3/2 level, evaluated IS (saturation intensity)
tively with moderate bexp (¼ 24.8%) for feasible NIR lasing ac- values utilizing formula [9] as:
tion at ~0.9 mm (see Table 8). Here, for such transition obtained
21 hc
max (¼ 5.94  10
semi cm2) is found to be higher than those of all IS ¼
 (23)
lp s lp t exp
Nd : BBFB (¼ 1.262e3.849  1021 cm2 range) [95] and
3þ

SBNCNd10 (¼ 3.2  1021 cm2) [96] glasses related values.

are listed in Table 8. Here, transition 4F3/2 / 4I11/2 has the
Likewise, in glass C, for transition 4F3/2 / 4I11/2 derived Dleff
lowest IS (¼ 11.72  108 W/m2) than the other two transitions
and semi  trad values are 32.46 nm and 9.69  1024 cm2s
depicting sample C's potential for lasing action at 1.057 mm
accordingly. Here Dleff is identified to be greater than those of
with a required lower threshold for cw operation. So for any
all Nd3þ: BBFB (¼ 25.7e28 nm range) [95] and all Nd3þ: SBNC (¼
laser host, bigger values of s(lp)  texp are desirable in
30.2e30.71 nm span) [96] glasses corresponding values.
21 achieving minimal IS values, which results in lower laser
max (¼ 26.05  10
Further, calculated semi cm2) for transition
4
thresholds. In our case, attained IS value for transition
F3/2 / 4I11/2 is noticed to be larger than those of 49.2B2O3 4
F3/2 / 4I11/2 is higher than those of 49.5B2O3e10PbOe10BaOe
þ20PbO þ15MgF2 þ15NaClþ0.8Nd2O3 (¼ 2.01  1021 cm2) [29],
10Al2O3e10ZnOe10Na2O-0.5Nd2O3 (¼ 3.67  108 W/m2) [9] and
BSGdCaNd0.5 (¼ 13.9  1021 cm2) [35], LiCaBO3: Nd3þ
65GeO2e8Ga2O3e17BaF2e5La2O3e5Li2Oe1Nd2O3 (¼ 4.14 
(¼ 24.2  1021 cm2) [36], 0.5 mol% Nd3þ: bismuth silicate
108 W/m2) [81] glasses related value.
(¼ 23.3  1021 cm2) [80], and 65GeO2e8Ga2O3e17BaF2e5La2O3-
Next, considering related bR and semi values, with an
e5Li2Oe1Nd2O3 (¼ 20.9  1021 cm2) [81] glasses corresponding
assumption that 4S3/2 and 4I13/2 levels in glass A, 1D2 and 3H4
values and lower than those of 63P2O5e7K2Oe14BaOe
states in glass B, and 4F3/2 level in glass C are populated
10Al2O3e4La2O3-2Nd2O3 (¼ 29.2  1021 cm2) [6] and 49.5B2O3-
by Er3þ, Tm3þ, and Nd3þ ions respectively at 20e100%
e10PbOe10BaOe10Al2O3e10ZnOe10Na2O-0.5Nd2O3 (¼ 62.16 
extent under UV and NIR excitations, for observed major
1021 cm2) [9] glasses related values.
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 6 5 8 e6 8 0 675

visible and NIR emissions theoretical gain is predicted by a

relation [9] as:

Gðl; PÞ ¼ 10 log 10 expðPNbR semi ðlÞÞ (24)

3þ 3þ 3þ
where P ¼ excited Er , Tm , and Nd ions' fractional factor
in considered excited levels, N ¼ total Er3þ, Tm3þ, and Nd3þ ion
concentrations accordingly.
Figs. 11(b), 12(b), and 13(d) display computed theoretical
gain spectra of 4I13/2 / 4I15/2 transition at 1400e1650 nm
range in glass A, 3H4/3F4 transition at 1350e1580 nm span in
glass B, and 4F3/2 / 4I11/2 transition at 1000e1160 nm extent
in glass C accordingly. Figs. S6(b) and S7(b) in SM exhibit
similar spectra obtained for Er3þ: 4S3/2 and Tm3þ: 1D2 states in
glasses A and B respectively at 500e590 nm range and
425e500 nm span. Here, at P ¼ 100% and 60%, glass A has G(l,
P) values of 4.064 and 2.438 dB/cm at 548 nm, and 8.935 and
5.361 dB/cm at 1531 nm, respectively. Similarly, at P ¼ 100%
and 60%, glass B shows G(l, P) values of 0.975 and 0.585 dB/cm
at 452 nm, and 0.099 and 0.06 dB/cm at 1455 nm accordingly.
At P ¼ 100% and 60%, glass C possesses G(l, P) values of 15.305
and 9.183 dB at 1057 nm individually. Comparably, for 3H4
state, in glass B G(l, P) values at P ¼ 100% and 60% are minorly
lower than that of glass A relevant values (¼ 0.142 dB/cm and
0.085 dB/cm) [15].
Supplementarily, sabs (absorption cross-section) of transi-
tion 4I15/2 / 4I13/2 in glass A and 4I9/2 / 4F3/2 transition in glass
C could be calculated from Fig. 2(b) and (e) using equation [6]:
2:303
sabs ðlÞ ¼ O:D:ðlÞ (25)
tN
where O.D. (l) ¼ optical density at wavelength l, N (ions/
cm3) ¼ Er3þ or Nd3þ ions' concentration in glass A or glass C,
t ¼ sample thickness.
Further, sabs and semi could be connected by McCumber's
theory [97] as:
  
 Fig. 14 e (a) Absorption cross-section (4I15/2 / 4I13/2
Zu  Ezl  hcl1
sabs ðlÞ ¼ semi ðlÞ  exp (26) transition) and stimulated emission cross-section (4I13/2 /
Zl KB T 4
I15/2 transition) profiles of glass A (b) Calculated gain cross-
section spectra of 4I13/2 / 4I15/2 transition at different P
where T ¼ temperature, h ¼ Planck's constant, Ezl ¼ energy gap
values for sample A. Here, dotted lines indicate S-, C-, and
between the lowest Stark level of upper (4I13/2 or 4F3/2) and
L-optical bands amplification region.
lower (4I15/2 or 4I9/2) states at T ¼ 300 K, KB ¼ Boltzmann con-
stant, and Zu and Zl ¼ upper and lower manifolds' partition
functions.
From eqs. (25) and (26), evaluated sabs and sM
emi profiles in from Fig. 15(a), at l < ~0.88 mm, sabs is higher than semi, and
glasses A and C at respective 1400e1650 nm and 840e940 nm semi contains a wider bandwidth than that of sabs owing
ranges are shown in Figs. 14(a) and 15(a). Table 9 shows peak to Stokes shift.
sabs (4I15/2 / 4I13/2 and 4I9/2 / 4F3/2) and sM 4 4
emi ( I13/2 / I15/2 and
Moreover, G(l, P) (Gain cross-section) could be determined
4
F3/2 / 4I9/2) values in samples A and C accordingly. from obtained sabs and sM
emi in glasses A and C by using rela-
4 4
Comparably, sM
emi value of transition I13/2 / I15/2 in glass A tion [98,99]:
is larger than those of BLK1.0Er (¼ 1.1072  1020 cm2) [38],
Gðl; PÞ ¼ ½P  semi ðlÞ  ð1  PÞ  sabs ðlÞ (27)
1Er ZMB (¼ 0.457  1020 cm2) [39], all H1eH5
(¼ 0.51e0.723  1020 cm2 range) [69], and 1 mol% Er3þ: Fluo- where P ¼ population inversion (0e1). Here P value indicates
roaluminate (¼ 0.53  1020 cm2) [98] glasses related values the population on the 4I13/2 or 4F3/2 level to the total population
and lesser than that of LiPbAlB1.5Er glass (¼ 2.34  1020 cm2) at the 4I13/2þ4I15/2 levels' or 4F3/2þ4I9/2 levels' ratio.
[40] respective value. Likewise, acquired sM
emi value of
G(l, P) profiles of 4I13/2 / 4I15/2 and 4F3/2 / 4I9/2 transitions
4
F3/2 / 4I9/2 transition in glass C is higher than those of all in glasses A and C at 1400e1650 nm and 840e940 nm spectral
0.5e3 mol% Nd3þ: NaYF4 nanocrystalline glass-ceramics spans are illustrated in Figs. 14(b) and 15(b) accordingly at
(¼ 0.099e0.193  1020 cm2 range) [99] related values re- different P values. In Fig. 14(b), dotted lines represent optical
ported for ~0.89 mm lasers. Interestingly, as can be seen bands S-(1.46e1.53 mm), C-(1.53e1.565 mm), and L-
676 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 6 5 8 e6 8 0

causing heat generation where typical SiO2-based EDFAs

Table 9 e Values of peak absorption cross-section (sabs) of
4 exhibit narrower gain spectra and are utilized only in the C-
I15/2 / 4I13/2 and 4I9/2 / 4F3/2 transitions and emission
cross-section ðsM 4 band span [98], but in our study, for glass A, computed gain
emi Þ (from Mc-Cumber theory) of I13/2
4 4 4
/ I15/2 and F3/2 / I9/2 transitions in glasses A and C. cross-sections cover the L-band region also with flatness.
From Fig. 15(b), one can observe that for 0.9 mm and P ¼ 0.3, G(l,
Sample code sabs (  1020 cm2) emi (  10
sM 20
cm2)
P) is positive and shifts to shorter wavelengths with further P
A 1.336 1.495 increment. Also, the bandwidth pattern becomes smooth at
C 1.082 0.5556 P > 30% in 0.9e0.93 mm spectral span. Here, an FWHM of
~48 nm (0.868e0.916 mm extent) reveals its possible utilization
in tunable lasers. Thus, glass C could be promising for laser
production at ~0.9 mm.
Nevertheless, currently, RE3þ-doped B2O3-based glasses
are impractical for NIR fiber amplifiers and lasers owing to the
high phonon energy (~1400 cm1) of B2O3, as such high
phonon energy causes significant NR transitions in contrast to
radiative relaxations from the RE3þ ions' emitting levels in
those glasses. As a result, specifically, NIR emissions are
highly quenched. For instance, in B2O3-rich glasses, Er3þ: 4I13/2
metastable state decay time is low as in our case, in glass A,
because of high NR transitions possibility from this level,
which occurs by potential Er3þ ions' coupling with BeO bonds
in a large quantity having high phonon energy [100]. But, for
practical applications in EDFAs, for achieving high population
inversion under moderate optical pump power, a longer decay
time of Er3þ: 4I13/2 level is essential [101]. Thus, for a realistic
NIR lasers and fiber amplifiers application, it could be more
conducive to explore Nd3þ, Er3þ, and Tm3þ ions in low phonon
energy possessing hosts like TeO2 (~700 cm1) or fluorides
(~500e600 cm1) or chalcogenides (~350e450 cm1) [102] with
optimized compositions (for better thermal and chemical
stabilities) for attaining longer lifetime, wide bandwidth, and
high quantum efficiency for related NIR luminescence tran-
sitions of such ions.

4. Conclusions

Optical and luminescence attributes of (50ex) B2O3-10 BaO-10

Fig. 15 e (a) Absorption cross-section (4I9/2 / 4F3/2
transition) and stimulated emission cross-section (4F3/2
/ 4I9/2 transition) profiles of glass C (b) Calculated gain
cross-section spectra of 4F3/2 / 4I9/2 transition at different P
values for sample C.
(1.565e1.625 mm) amplification area. From Fig. 14(b) one can
notice that amplification in the C-optical band begins when
P ¼ 50%. Here, the achieved highest value at P ¼ 1 is found to
be 1.495  1020 cm2 for glass A. Taking into account larger
sM
emi , sabs, Dleff, smax  Dleff, and considerable tmeas values of
emi
4
I13/2 / 4I15/2 transition in glass A, this sample could be useful
for wideband amplification with a low pumping threshold.
Usually, in EDFAs, P gets to ~60% with enhanced pump power,
ZnO-10 Li2O-10 LiF-10 NaF-x Er2O3/x Tm2O3/x Nd2O3 (x ¼ 0 (H)
and 1 Er3þ (A)/Tm3þ (B)/Nd3þ (C) (mol%)) glasses have been
analyzed detailedly. For all samples, the Cionic characteristic was
more evident than the covalent one. Absorption spectra of A, B,
and C glasses displayed distinct extended Er3þ, Tm3þ, and Nd3þ
ions bands from UV to NIR region, and Dla for Er3þ: 4I15/2 / 4I11/2,
Tm3þ: 3H6 / 3H4, and Nd3þ: 4I9/2 / 4F5/2 þ 2H9/2 transitions was
~25.01 nm, ~28.49 nm, and ~18.54 nm accordingly.
Utilizing J-O theory, U2>U6>U4, U2>U4>U6, and U6>U2>U4
trends for glasses A, B, and C respectively were obtained. For
glasses A and B, higher U2 specifies stronger EreO and TmeO
bonds covalency combined with Er3þ and Tm3þ sites’ asym-
metry, and for glass C, greater U6 hints at the higher rigidity of
the sample structurally. Relying on U2, U4, and U6 values and
refractive indices, AR, bR, and trad of main visible and NIR
emission transitions of Er3þ, Tm3þ, and Nd3þ ions were eval-
uated in A, B, and C glasses. For sample A, under lexci.-
¼ 363 nm, visible luminescence bands peaked at 0.41 mm,
0.526 mm, and 0.548 mm corresponding to Er3þ transitions 2G9/
4 2 4 4 4
2 / I15/2, H11/2 / I15/2, and S3/2 / I15/2 accordingly were
identified. Next, three bands centered at 0.452 mm, 0.48 mm,
and 0.513 mm corresponding to Tm3þ: 1D2/3F4, 1G4/3H6, and
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 6 5 8 e6 8 0
1
D2/3H5 transitions respectively have been observed from
glass B visible fluorescence spectrum. Upon lexci. ¼ 358 nm,
glass B produced blue emission with CP ¼ 98.1% making it
potentially suitable for application in blue-LEDs. Er3þ: 4S3/2 and
Tm3þ: 1D2 upper-level decay time profiles showed double and
single exponential characters for deducing related tmeas
values under UV light excitation. Glass A possesses better AR
(¼ 231 s1), bR (¼ 100%), and trad (¼ 4.323 ms) for Er3þ: 4I13/
2 /
4
I15/2 transition, and a broad NIR fluorescence band
peaked at 1.531 mm (4I13/2 / 4I15/2) was acquired by 980 nm LD
excitation. Higher sM 20
cm2), sabs (¼
emi (¼ 1.495  10
1.336  1020 cm2), Dleff (¼ 75.73 nm), semi max  Dleff (¼
6.046  1026 cm2), and considerable tmeas (¼ 0.46 ms),
including G(l, P) (¼ 5.361 dB/cm at P ¼ 60%) values of 4I13/
4
2 / I15/2 transition in sample A indicate its potential as an
active medium for C-band amplification and ASE (Amplified-
spontaneous-emission) source. Also, the peak gain cross-
section was 1.495  1020 cm2 at 1.531 mm for glass A and
the derived gain spectra are positive from P ¼ 50% and illus-
trate a flat gain. Likewise, large Dleff (¼ 113. 67 nm) wrapping
21
entire S-band, high sem max (¼ 1.484  10 cm2), sem
max  Dleff (¼
26
1.687  10 cm ), smax  trad (¼ 1.212  1024 cm2s), and G(l,
3 em
P) ¼ 0.06 dB/cm at P ¼ 0.6 for transition Tm3þ: 3H4/3F4 in glass
B suggests its favorability for S-band amplification. Further,
glass C shows significant AR (¼ 311 s1), bexp (¼ 12%), Dleff (¼
57.37 nm), sem 21
cm2), and sem
max (¼ 7.98  10 max  Dleff (¼
26
4.58  10 cm ) values for transition Nd3þ: 4F3/2 / 4I13/2 for its
3
feasible O-band amplification utilization. Additionally, in
glass C, greater AR (¼ 1428 s1), bexp (¼ 63.2%), Dleff (¼
24
32.46 nm), sem max  trad (¼ 9.69  10 cm2s), moderate
threshold (¼ 11.72  10 8 2
W/m ), high sem max (¼
21 2 material fiber for a 1.05 mm laser. Opt Mater Express
26.05  10 cm ) and G(l, P) (¼ 9.183 dB/cm at P ¼ 60%),
including considerable h (¼ 17%) obtained for transition 4F3/
4 [7] Wang Y, Wu J, Zhao Q, Wang W, Zhang J, Yang Z, et al.
2 / I11/2 demonstrate its potential for cw or ultra-short pulse
lasing action at 1.057 mm. Moreover, in glass C transition 4F3/
2 / 4I9/2 possesses AR, Dleff, sM
emi ; and semi  trad values of
949 s1, 50.73 nm, 0.5556  1020 cm2, and 2.21  1024 cm2s
respectively with sabs (¼ 1.082  1020 cm2) and moderate bexp
(¼ 24.8%) for possible tunable lasing action at ~0.9 mm having
the gain cross-section positive at P ¼ 0.3.
CRediT author statement
G. Lakshminarayana: Conceptualization, Methodology, Visu-
alization, Writing e Original Draft, Writing e review & editing,
Supervision A.N. Meza-Rocha: Investigation, Data Curation,
Validation O. Soriano-Romero: Investigation U. Caldin ~ o:
Investigation, Data Curation, Validation A. Lira: Formal anal-
ysis, Data Curation Dong-Eun Lee: Resources, Project
administration, Funding acquisition, Supervision Jonghun
Yoon: Resources, Supervision Taejoon Park: Resources,
Funding acquisition, Supervision.
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.
677
Acknowledgements
This work was supported by the National Research Founda-
tion of Korea (NRF) grant funded by the Korea government
(MSIT) (No. NRF-2018R1A5A1025137).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jmrt.2022.02.115.
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