Journal of Non-Crystalline Solids 575 (2022) 121214

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Journal of Non-Crystalline Solids

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

Physical and spectroscopic characteristics of lithium-aluminium-borate

glass: Effects of varying Nd2O3 doping contents
Osama Bagi Aljewaw a, e, Muhammad Khalis Abdul Karim a, *, Halimah Mohamed Kamari a,
Mohd Hafiz Mohd Zaid a, Ali Aqeel Salim b, Mohammad Hasan Abu Mhareb c, d
a
Department of Physics, Faculty of Science, Universiti Putra Malaysia, Serdang 43400 UPM, Selangor, Malaysia
b
Laser Center, Department of Physics, Faculty of Science, Universiti Teknologi Malaysia, Johor Bahru, Johor, Malaysia
c
Department of Physics, College of Science, Imam Abdulrahman Bin Faisal University, P.O. Box 1982, Dammam 31441, Saudi Arabia
d
Basic and Applied Scientific Research Center, Imam Abdulrahman Bin Faisal University, P.O. Box 1982, Dammam 31441, Saudi Arabia
e
Biotechnology Research Center-National Nanoscience and Nanotechnology Project, P.O. Box 30313, Tajoura, Tripoli, Libya

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

Keywords: The influence of different Nd2O3 doping contents on the physical and optical properties of the glasses was
LAB glasses evaluated. XRD patterns of the as-quenched samples confirmed their glassy nature. Density, ion concentration
Absorption spectra and field strength increases with the addition of Nd2O3 content, respectively. The absorption spectrum of the
Emission spectra
glasses exhibit intense peaks at approximately 580, 744 and 800 nm corresponding to the electronic transitions
Nd2O3
Physical properties
in Nd3+. With increasing Nd2O3 contents, the refractive indices of the glasses were increased from 2.363 to
2.415. FTIR spectra revealed the presence of BO4 and BO3 structural units in the glasses. Emission spectrum of
glasses (at 300 nm excitation) displayed four prominent peaks at 368, 421, 483 and 514 nm due to the electronic
transition in Nd3+from 4I9/2 to 4P3/2, 2P11/2, 2G11/2, 2G9/2, 4G11/2, and 4G9/2, respectively. The proposed glass
system were highly sensitive to the Nd2O3 contents changes.

1. Introduction
In recent years, intensive researches have been performed to deter­
mine the physical, structural and optical characteristics of various rare
earth ions (REIs)-doped borate glasses. Distinct absorption and visible
photoluminescence (PL) emission properties of these glasses emerged
from the 4f-4f and 4f-5d electronic transitions in the REIs [1]. These
glass systems have been used for many potential technological appli­
cations in the field of solid-state laser, optoelectronics, scintillation,
sensors, X-ray imaging, waveguides, display devices, up-conversion la­
sers, amplifier, dosimeters and optical fibers [2,3]. Amongst all the
borate glass system lithium-aluminum-borate (LAB) glasses show many
advantages due to its excellent thermal, mechanical and optical prop­
erties desirable for various applications, especially in optoelectronic and
photonic devices [4] Numerous studies have been conducted to under­
stand the undoped and REIs-doped LAB glass formation mechanism and
network structure symmetries [5–8].
In the borate glasses the alkaline or alkaline oxide as modifiers were
incorporated to increase mechanical stability and decrease their glass
network hygroscopic properties. Lithium oxide (Li2O) has been used as
both glass former and modifier to convert the BO3 functional groups to
BO4 via the creation of non-bridging oxygen (NBO) in the host network
[8,9]. Inclusion of Al2O3 in the Li2O–B2O3 glass system is another
method for improving its chemical stability, enabling the modification
of the glass characteristics required for practical applications [6,10].
The RE oxide Nd2O3 has many unique traits and widely used in pho­
tonic, laser, luminescent and thermo-luminescent applications. The
neodymium ions (Nd3+)-doped glasses due to their strong 4F3/2 → 4I11/2
emission at around 1064 nm were extensively researched as one of the
most efficient materials for fabricating solid-state lasers [11,12].
The structural properties of the as-quenched samples usually evalu­
ated using X-ray diffraction (XRD), Fourier transform infrared (FTIR),
ultraviolet-visible-near-infrared (UV–Vis-NIR) absorption and PL spec­
troscopy. It was found that the structural, optical and physical properties
of the proposed glass system can be customized by carefully adjusting
the Nd2O3 doping contents. Based on the abovementioned facts, this
study focuses on the synthesis of Nd2O3-doped LAB glasses using the
melt-quenching method, that allows a higher chemical homogeneity
both of the precursors and of the final vitreous material. Furthermore,
other primary aim of the study is to evaluate the substitutions of

* Corresponding author.
E-mail address: mkhalis@upm.edu.my (M.K.A. Karim).

https://doi.org/10.1016/j.jnoncrysol.2021.121214
Received 26 July 2021; Received in revised form 11 September 2021; Accepted 5 October 2021
Available online 14 October 2021
0022-3093/© 2021 Elsevier B.V. All rights reserved.
O.B. Aljewaw et al. Journal of Non-Crystalline Solids 575 (2022) 121214

different Nd2O3 doping contents on the structural, physical and optical

Vm = (M / ρ) (2)
properties of the glasses for thermoluminesence dosimetry and laser
application.
where M is the molecular weight and ρ is the density of sample. Mean­
while, the ion concentration (N in ions/cm3) was estimated using:
2. Experimental and theoretical
D × ρ × NA
N= (3)
2.1. Glass preparation M

where D is the dopant contents (in mol%) in the glass and NA is the
xNd2O3–doped glasses with nominal compositions (in mol%) of
Avogadro number. The values of polaron radius (rp in Å), inter-nuclear
23Li2O–7.5Al2O3–(69.5-x) B2O3 (mol%) were produced using the melt-
distance (ri in Å) and field strength (F in cm− 2) of the glasses were
quenching method. The Nd2O3 doping contents in the LAB glasses were
evaluated using:
x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1 mol% and summarized as in Table 1. 20
mg of high purity powder chemical constituents in each batch were 1[ π ]1/3
rp = (4)
homogeneously mixed and placed in alumina crucible. The mixed glass 2 6N
constituents melted inside an electrical furnace (at 1000 ◦ C) for 30 min. [ ]1/3
Afterwards, the molten specimen was rapidly poured in a pre-heated 1
ri = (5)
brass mold before being subjected to thermal treatment in another N
electrical furnace (at 400 ◦ C) for 3 h and annealed at a cooling rate of [ ]
10 ◦ C/min to eliminate the thermal stress that may cause glass cracking. Z
F= 2 (6)
The frozen solid was cut in desired size and polished for further char­ rp
acterization optically. A part of all samples were crushed for structural
measurements. where Z is the molecular mass of the dopant [13]. The value of oxygen
packing density (OPD in g.atom/L) was computed using:
2.2. Glass characterization OPD = n(ρ/M) × 1000 (7)

XRD patterns of the prepared as-quenched sample were recorded where n is the number of oxygen atoms per unit formula, M is the mo­
(PANalytical X’Pert Pro PW3040/60, Philips) using Cu-Kα radiation and lecular weight and ρ is the density of sample [14]. The glass absorption
analyzed by X’Pert High Score software. UV–Vis-NIR absorption spectra coefficient α(v)was evaluated in terms of absorbance (A) and sample
of the glasses in the range from 200 to 2600 nm were obtained using thickness (t) using [15]:
Lambda 35 absorption spectrophotometer (Perkin Elmer). The FTIR
α (ν) = 2.303(A / t) (8)
spectra of glasses in the range of 400 – 4000 cm− 1 were measured
(Perkin Elmer spectrometer), with the equipment accuracy ranged ±10 The optical band gap energy (Eg ) of the glasses was calculated from
cm− 1. The PL spectra of glasses were recorded using a Perkin Elmer (LS the Tauc plot (hν versus (hαν)1/2 ). The relation between α(ν) and Eg for
55) luminescence spectrophotometer. All the characterizations of the amorphous system yields:
glasses were conducted at room temperature. The Judd–Ofelt (J-O) ( )n /
theory has been used to investigate the spectra arising from 4f n − 4f n α(ν) = C hν − Eg (hν) (9)
transitions for rare earth ions (REIs)-doped solids. In addition, the J-O
theory analyze the radiative property of glasses by evaluation of oscil­ where the constant C represents the band tailing parameter and n is the
lator strength (f), J-O parameter (Ωλ) where λ = 2, 4, 6, radiative transition index that takes the value 2, 3, 1/2, 3/2 depending on the
transition possibility (AR), stimulated emission cross section (σ) and direct allowed, direct forbidden, indirect allowed and indirect forbidden
branching ratio (βR). optical transition across the band gap, respectively [16]. For the oxide
glasses, n = 2 and ½ for the direct and indirect allowed transitions,
respectively. The value of Urbach energy (Eu ) a measure of disorder or
2.3. Physical and optical properties width of the band tailing of the localized states in the band gap region)
for the studied glasses was calculated using the Urbach rule (Eu) given by
The glass density was measured using a 4-digit sensitive micro- [17] :
balance (Archimedes principle) by immersing in distilled water. The ( )
following relation was used to calculate the glass density ρ (in g/cm3): α(ν) = Bexp
hv
(10)
( ) Eu
wair
ρsample = × (ρwater ) (1)
wair − wwater where B is constant. The glass refractive indices were evaluated via
Kumar-Singh (nK–S), Moss (nM) as well as Reddy-Sakka (nR–S) equation
wherewair and wwater are the weight of glass sample in air and distilled [14].
water (ρwater = 0.999 g/cm3), respectively. The molar volume (Vm ) in ( )− 0.32234
terms of molar mass (M) of the glass was calculated via : nK− S = 3.3668 Eg (11)

The refractive index can be estimated by other relations such as

Table 1
Compositional variation in mol% of each raw material for all glasses. [ ]14
95
nM = (12)
Glass Samples mol% Eg
Li2O Al2O3 B2O3 Nd2O3 ( )
nR− S = − 0.73ln 0.02741Eg + 0.5511 (13)
LABN-0.0 23 7.5 69.5 0.0
LABN-0.2 23 7.5 69.3 0.2
LABN-0.4 23 7.5 69.1 0.4 where (Eg ) is the band gap energy. The reflection loss (RL), molar
LABN-0.6 23 7.5 68.9 0.6 refractivity (Rm), and molar polarizability (αm) of glasses were calcu­
LABN-0.8 23 7.5 68.7 0.8 lated via:
LABN-1 23 7.5 68.5 1

2
O.B. Aljewaw et al. Journal of Non-Crystalline Solids 575 (2022) 121214

[ ]2
nav − 1
RL = (14)
nav + 1
[ 2 ]
nav − 1
Rm = V m 2
(15)
nav + 2
[ ]
3
αm = Rm (16)
4π N

where nav is the refractive index. The electrostatic dielectric constant (ε)
and optical dielectric constant (εopt ) of the glasses were computed in
terms of mean refractive index via the relations [15] :

ε = n2av (17)

∂t ( ) Fig. 1. XRD diffraction pattern of LAB glass system with different concentra­
εopt = p = (ε − 1) = n2av − 1 (18)
∂p tion of Nd3+ ions.
The dielectric susceptibility (χ a measure of material’s transient or
permanent polarization capacity) of the glasses was obtained using: mass by neodymium of higher atomic mass [22]. The variation in the
molar volume was divided in three regions depending on the Nd2O3
ε− 1 contents. In the first region (Nd2O3 contents from 0.2 to 0.4 mol%) the
χ= (19)
4π decrease of molar volume was due to the generation of more NBO bonds
The metallization(M) norm (defined as the inclination of materials to [23]. In the second region, the molar volume of the glass was decreased
be metal) of the prepared glasses were calculated to check their insu­ from 22.454 to 22.429 cm3 with the increase of Nd2O3 contents from 0.6
lating behavior using the relation [18]: to 0.8 mol%. This observation was ascribed to the capacity of B4+ to
( ) transform into B3+ with the variation of coordination number from 4 to
Rm
M =1− (20) 3, leading to a reduction of the glass molar volume and shortening of
Vm
interatomic separation inside the glass network. This in turn enhanced
The theoretical oscillator strengths (f) of each absorption band ac­ the glass compactness (network structure shrinkage) and lowered the
cording to J-O were determined experimentally from the area under the NBO, thereby enhancing the glass hardness. In the third region (beyond
absorption band and can be expressed in terms of absorption coefficient 1.0 mol% of Nd2O3), the molar volume of the glass was again increased,
(α) at a particular wavelength λ by indicating an expansion of the glass network structure. Present findings
∫ are in good agreement with other report [14] (Fig. 3).
mc2 α(v) The Oxygen packing density (OPD) values were first increased from
fexp = 2 dλ (21)
πe N λ2 86.058 to 86.598 g.atom/L with the rise of Nd2O3 levels from 0.2 to 0.6
mol% and then decreased from 86.387 to 86.304 g.atom/L with the
where α(v) is the absorption coefficient at a given wavelength (λ), m is
corresponding increase of Nd2O3 contents from 0.8 to 1.0 mol%. The
the mass and e is the charge of the electron, c the velocity of the light in
observed variation in the OPD values were due to the reduction of ox­
the vacuum. N is the number density of Nd3+ [19]. In order to quanti­
ygen level in the boron units (conversion from BO4 to BO3) caused by the
tatively estimate the radiative properties of Nd3+ ion in the present
alkali metal oxide (lithium oxide) [10]. The obtained decrease in the
glassy systems, the experimental oscillator strength, fcol, values were
OPD values of the glasses was ascribed to the decrease of molar volume
fitted with the theoretical expression derived by J-O theory.
from 29.616 to 29.429 cm3/mol. The covalent nature of the glass
Three phenomenological J-O parameters Ω2; Ω4 and Ω6; exhibit the
network structure was reduced that in turn enhanced the ionic nature
influence of the host on the radiative transition probabilities, represent
with decreased molar volume, indicating the emergence of loose pack­
the effect of the odd symmetry crystal field terms, interconfigurational
ing of the glass network with the increase of Nd2O3 doping contents.
radial integrals and energy denominators. The spectroscopic quality
Fig. 4 illustrates the Nd2O3 contents dependent variation in the
factor x = Ω
Ω6 is an important predictor for stimulated emmisson a laser
4
polaron radius and field strength of the studied glasses. The values of rp
active medium. A measurement accuracy of the fit given by root-mean- were decreased form 1.588–0.928 Å with the increase of Nd2O3 doping
square deviation (δrms ) following by contents, indicating a shortening between Nd to O distance and thus
[∑(
fcol − fexp
)] improvement of the field strength around Nd3+ ions within the host glass
δrms = (23) network. This observation was attributed to the alteration of Nd3+ and
N− 3
newly formed O linkages due to the conversion of BO3 units into BO4
where N is the number of transitions analyzed [20]. units as reported elsewhere [24].
Fig. 5 and Table 3 summarizes the FTIR spectra of the studied glasses
3. Results and discussion which consisted of various characteristics bands related to various
functional chemical groups present in the LAB glass. The observed bands
Fig.1 displays the XRD patterns of the as-quenched samples. The are assigned as follows:
presence of a broad hump without any sharp diffraction peaks verified
the amorphous nature of the prepared sample [21]. • Bands around 412.77 to 547.78 cm− 1 were due to the loose BO4
Fig. 2 shows the density and molar volume of the LAB glass samples units.
as a function of Nd2O3 contents. Table 2 shows the nominal composi­ • Bands around 692.44 to 698.23 cm− 1 were due to B-O-B bonds (in
tions, glass codes and their physical properties. The glass density was BO3) stretching vibration modes within the borate units [25,26].
increased and molar volume was decreased with the increase of Nd2O3 • Bands around 910.40 to 1028.06 cm− 1 were due to the vibration of
contents. The observed increase in the glass density with the increase of BO4 units (tetrahedral) existed tetra-borate and di-borate units.
Nd2O3 contents was due to the replacement of lithium of lower atomic

3
O.B. Aljewaw et al. Journal of Non-Crystalline Solids 575 (2022) 121214

Fig. 2. Variation of density and molar volume (Vm) with Nd2O3 concentration in LAB glass system.

Table 2
Physical parameters of various Nd3+ -ion doped LAB glass system.
Parameter physical parameters unit Nd2O3-doping (mol%)

0.0 0.2 0.4 0.6 0.8 1

Density(ρ) g.cm− 3 2.144 2.150 2.169 2.199 2.212 2.228

Total molecular weight, M(g) mg 62.903 63.436 63.970 64.504 65.038 65.571
Average molecular weight, (MAV) mg 20.967 15.859 15.992 16.126 16.259 16.392
Molar volume (Vm) (cm3/mol) 29.394 29.505 29.616 29.454 29.429 29.536
Ion concentration (N× 1022) ions/cm3 1.632 3.266 4.927 6.554 8.184
Polaron radius, (A˚) 1.588 1.260 1.099 0.995 0.928
(rp) x10 − 8
Inter-nuclear distance, (A˚) 3.941 3.128 2.727 2.480 2.303
(ri) x 10 − 8
− 2
Field strength, (cm ) 5.716 9.076 11.938 14.560 16.744
(F) × 1017
The oxygen packing density (OPD) (g.atom/l) 86.412 86.085 86.121 86.590 86.387 86.304

Fig. 3. Variation of Molar volume (Vm ) and OPD with different Nd2O3 oncentration in LAB glass system.

• Bands around 1228.66 to 1247.94 cm− 1 were due to the stretching Fig. 6 depicts the absorption spectrum of the prepared Nd3+-doped
vibration modes of B-O bonds (in triangular BO3 units with NBO) LAB glasses recorded in the wavelength range of 300–2000 nm. The
[27]. spectra consisted of ten significant peaks located at 352, 427, 469, 521,
• Bands around 1332.81 to 1365.60 cm− 1 were due to the stretching 580, 676, 744, 800, 847 and 872 nm corresponding to the electronic
vibration modes of trigonal BO3 groups present in the meta-, ortho- transitions from the ground state (4I9/2) of Nd3+ to 4D3/2 + 4D5/2 + 2I11/
4 4 2 4 2 2 2 2 4
and pyro-borate units [28]. 2 + D1/2, D5/2 + P1/2, D11/2+( D, F)3/2 + G9/2 + K15/2, G9/2 +
4
G7/2 + K13/2, G7/2 + G5/2, F9/2, F7/2 + S3/2, F5/2 + H9/2, 2H5/2,
4 4 4 4 4 4 4 2

4
O.B. Aljewaw et al. Journal of Non-Crystalline Solids 575 (2022) 121214

Fig. 8 represents the Urbach plot (ln(α) against hν) of the prepared
glasses, wherein the inverse of the tangent to the linear part of the curve
(extrapolated on energy axis) was used to evaluate the Urbach energy
(Eu ). It is important to note that Eu is a measure of disorder or defects in
glasses or crystals. In the current LAB glass system, Eu values were
decreased from 0.624 to 0.556 eV with the increase of corresponding
Nd2O3 contents from 0.0 to 1.0 mol% as depicted in Table 4. These
values are in the range of 0.046–0.66 eV which correspond to amor­
phous semiconductors [34,35]. The decrease in Urbach energy with the
increase of Nd3+ concentration is ascribed to the generation of less
bonding defects and non-bridging oxygen. The glasses with a smaller
Urbach energy would have lower disorder and more compactness [35,
36].
Fig. 9 shows the Nd2O3 contents dependent variation in the optical
band gap energy of the glasses. The values of Eindir were reduced from
3.026 to 2.807 eV with the rise of Nd2O3 contents from 0 to 1.0 mol%,
respectively, indicating structural alteration in the host glass networks.
Fig. 4. Variation of Polaron radius (rp ) and Field strength (F) with Nd2O3
Inclusion of Nd3+ into the glass network led to an improvement in
Concentration in the LAB glass system.
the electron localization, thus raising the donor center and reducing the
values of Eindir [37]. The values of refractive indices of the glasses were
increased steadily with the addition of Nd2O3 into the glass network
which was mainly because of the generation of more NBO by rupturing
the BO linkages and increase of electronic polarizability. In short, the
optical properties of the present glasses were very sensitive to the
changes of Nd2O3 doping contents in the glasses and tallied with pre­
vious study [27].
Fig. 10 presents the Nd2O3 contents dependent variation in the
Urbach energy of the glasses wherein the values of Eu were decreased
from 0.624 to 0.556 eV with the addition of Nd2O3 in the host glass
matrix (Table 4). This reduction in the Eu values with the increase of
Nd2O3 doping contents was due to the creation of fewer defects and NBO
in the amorphous matrix. Lower Eu values indicated the existence of
lesser disorder or defects of the present LAB glasses. Thus, the glasses
achieved extra compactness of the network (shrinkages of network or

Fig. 5. FTIR spectrum LAB glass doped with different Nd2O3 mol%
concentration.

4
F3/2 excited states. The absorption spectra spotted here concordant
consistent with the mentioned Nd3+ ions spectrum absorption in glass
systems [29,30]. In addition, certain the transitions in Nd3+ (called
hypersensitive transitions) were found to be extremely sensitive to the
local environments of the host glass matrix [31] and they followed the
selection rules of |ΔS| = 0, |ΔL| ≥ 2, |ΔJ| ≤ 2.
The absorption peaks positioned at 580, 744 and 800 nm corre­
sponded to the hypersensitive transitions (more intense than other
peaks) from the ground state (4I9/2) of Nd3+ to 4G7/2 + 4G5/2, 4F7/2 +
4
S3/2 and 4F5/2 + 2H9/2 excited states. Current observations are consis­
tent with the earlier reported findings [32,33]. The UV-edge absorption
data was used to determine the optical band gap energy of the glasses Fig. 6. UV–VIS absorption of LAB glass doped at varying Nd3+ mol percent
through Tauc’s plot as illustrated in Fig. 7. concentrations.

Table 3
Band positions in FTIR spectra of Nd3+ doped LAB glass.
Characteristic band positions (cm− 1) for glasses with varied Nd3+ ions contents (mol%) Observation

Nd 0.0 Nd 0.2 Nd 0.4 Nd 0.6 Nd 0.8 Nd 1.0

412.77–514.99 416.62–487.99 416.62–514.99 418.55–534.38 426.27–547.78 416.62–511.14 Loosing of BO4 units.

692.44 692.44 698.23 692.44 694.37 694.37 Bending vibration of B–O–B linkage.
925.69–1044.51 931.62–1035.77 935.48–1041.56 921.97–1045.42 916.19–1029.99 910.40–1028.06 Band due to B-O bond stretching in BO4 units.
1239.88–1334.74 1247.94–1332.81- 1247.94–1338.60 1246.02–1336.67 1228.66–1344.38 1232.51–1365.60 BO3 stretching vibrations, B-O stretching
vibration in BO3 units.

5
O.B. Aljewaw et al. Journal of Non-Crystalline Solids 575 (2022) 121214

Fig. 7. (a) Tauc plot and (b) Nd2O3 contents dependent variation in the optical band gap energy of the glasses.

Fig. 8. Urbach energy plot of the glasses.

6
O.B. Aljewaw et al. Journal of Non-Crystalline Solids 575 (2022) 121214

Table 4 with the increase of Nd2O3 doping contents. With the increase of
calculating direct, indirect band gap, Urbach energy and cut-off wavelength. dielectric constants of the glasses, the optical transmittance was dropped
Sample Edir (eV) Eindir (eV) Eu (eV) λc (nm) [15].
Fig. 11(b) displays the Nd2O3 contents dependent variation in the
LABN-0.0 3.585 3.026 0.624 409
electronic polarization and susceptibility (χ) of the glasses and sum­
LABN-0.2 3.575 2.970 0.616 417
LABN-0.4 3.543 2.905 0.612 426 marize in Table 5. The values of χ for the LAB glasses were increased
LABN-0.6 3.538 2.858 0.585 433 from 0.364 to 0.384 with the increase of Nd2O3 concentration from 0.0
LABN-0.8 3.515 2.840 0.576 436 to 1.0 mol% percent. The observed nonlinear dependence of χ on the
LABN-1.0 3.510 2.807 0.556 441 electronic polarization and refractive index clearly indicated that the
proposed Nd2O3–doped LAB glasses can offer as excellent nonlinear
more symmetric glass environment and thus high density) [36]. Present optical medium desirable for various photonic devices development
observations are consistent with other literature reports [24,38]. [27].
Fig. 11(a) shows the Nd2O3 contents dependent variation in the Fig. 12 depicts the Nd2O3 contents dependent variation in the
dielectric constants (ε and εopt) of the glasses. The values of both ε and metallization norm of the glasses. The downward trend of the metalli­
εopt were correspondingly increased (Table 5) from 5.583 to 5.832 and zation criterion of the doped LAB glasses was supported by the reduction
4.583–4.832 with the increase of Nd2O3 doping contents from 0 to 1.0 of Eg and increase nav . The declining tendency of the metallization cri­
mol% in host glass matrix. The observed increase in the values of both ε terion is linked to the wider valence and conduction band, leading to the
and εopt indicated an increase in the glass absorbance and extinction optical energy band gap narrowing [32]

Fig. 9. Nd2O3 contents dependent variation in the optical band gap energy of the glasses.

Fig. 10. Nd2O3 contents dependent variation in the Urbach energy of the glasses.

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O.B. Aljewaw et al. Journal of Non-Crystalline Solids 575 (2022) 121214

system were reduced from 0.395 to 0.383, indicating their suitability for
nonlinear optical application. The values of Rm and αm for the proposed
glasses were improved with the increase of Nd2O3 doping contents,
suggesting an enhancement in the NBO due to the rupture of BO bonds
and improvement of the glass refractive indices [7,39].
As tabulated in Table 6, the J-O intensity characteristics for all
created glasses are shown to follow the same Ω4 > Ω6 > Ω2 lines trend.
The J-O intensity parameters usually do not have to be very different
with concentration, but sometimes the intensity parameters might be
rather somewhat different owing to the propensity of clustering of Nd3+
ions [30]. In addition, the asymmetry changes around Nd3+ ions owing
to an increase in the concentration that resulting dissimilarity in in­
tensity parameters. The Ω2 intensity parameter is sensitive for both
asymmetry and covalency in REIs sites. Table 6 shows that Ω2 varies
with varied Nd3+ ion concentrations, showing that there are promoted
symmety of site occupied by the Nd3+ ions, which induce the close
packing of the oxygen atom around the Nd ions in turn affects the Ω2
value.
Furthermore, the values of Ω4 and Ω6 rise with the increase of Nd3+
ione concentration to 0.8 mol%, and the glass LABN-0.8 shows a higher
rigidity than those of the other glasses [19,40]. Another important factor
and linked to the stimulated emission cross-section is the spectroscopic
quality factor (χ), The values of LABN-0.8 glasses with some reported
values are tabulated in Table 6. It is observed that glass LABN-0.8 (0.8
mol% Nd3+) exhibits higher χ value than the other glasses.
Fig. 13 displays the PL emission spectra of the glasses under an
excitation wavelength of 300 nm. From these tow spectrum emission
bands are observed at 421 and 443 nm which are assigned to transitions
2
P3/2 → 4I11/2 and 4D3/2→ 4I13/2 transitions respectively. Among these
the transition have shown bright violet emission. with from addition
from spectrum two emission bands are observed at 462 nm and 483 nm
which are assigned to 2K15/2→ 4I9/2 and 2P3/2→ 4I9/2 transitions
respectively [41],with these the transition have been shown blue
emission, this the transition has been shown green emission which the
Fig. 11. (a) Nd2O3 contents dependent variation in the dielectric constants and Nd3+ was due to dopant ions concentration dependent quenching and
(b) in the electronic polarization and susceptibility of the glasses. energy transfer processes between the Nd3+ ions inside the glass matrix
[42,43].
Overall, the PL emission was significantly depend on the Nd3+ con­
Table 5 tents in the glass and other emissions including visible light range. The
calculating Optical parameters of Nd-ion doped LAB glass system. obtained room temperature UV and visible PL from the proposed glass
Optical Doping (mol% Nd2O3) composition clearly indicated their effectiveness to fabricate light
parameters emitting devices [33]. The results of PL properties are is good agreement
0.0 0.2 0.4 0.6 0.8 1.0
with the previously reported studies [44,45].
Refractive Index, 2.363 2.376 2.392 2.403 2.407 2.415
nav
Dielectric 5.583 5.645 5.721 5.774 5.793 5.832 4. Conclusion
Constant (ε)
Molar Refraction, 17.766 17.927 18.109 18.088 18.1009 18.222 Following melt-quenching route some new types of Nd3+-activated
Rm
LAB glasses were prepared. The obtained samples were characterized to
Reflection Loss, 0.164 0.166 0.168 0.169 0.1705 0.171
RL
determine their structural, physical and optical properties as a function
Molar 7.042 7.106 7.178 7.1705 7.175 7.223 of varying Nd3+ contents. Highly transparent and stable glasses were
Polarizability achieved. FTIR spectra of the glasses showed the existence of BO3 and
αm (x 10− 24) BO4 structural units. The UV–Vis-NIR absorption spectra of the glasses
Optical Dielectric 4.583 4.645 4.721 4.774 4.793 4.832
displayed ten significant peaks in which most intense peaks at 580, 744
(εopt )
and 800 nm corresponded to the hypersensitive transitions in Nd3+. The
Metallization 0.395 0.392 0.388 0.385 0.384 0.383
Criterion (M) emission spectra exhibited five characteristic of UV and visible peaks of
Electronic 2.396 2.407 2.424 2.434 2.438 2.445 Nd3+ at 421, 443,462 and 483 nm. It was shown that by adjusting the
Polarizability Nd2O3 contents in the LAB glasses their overall characteristics can be
αe(x10− 25) tailored. According to spectral results, the Nd3+:LAB glasses have shown
Linear Electric or 0.364 0.369 0.375 0.379 0.381 0.384
Dielectric
bright violet, blue and green emissions and are used as novel optical
Susceptibility luminescent materials. It can be asserted that such glass system may be
(χ ) beneficial for diverse applications such as laser application and radia­
tion dosimetry.

It was acknowledged that glass system with the values of metalli­ CRediT authorship contribution statement
zation criterion in between 0.30 to 0.45 can served as good nonlinear
optical medium. The values of metallization criterion of the current glass Osama Bagi Aljewaw: Methodology, Formal analysis, Writing –

8
O.B. Aljewaw et al. Journal of Non-Crystalline Solids 575 (2022) 121214

Fig. 12. depicts the Nd2O3 contents dependent variation in the metallization norm of the glasses.

Table 6
Experimental (fexp , x 10− 5), calculated (fcal ,x 10− 5) oscillator strength and J-O parameters (Ωt , x10− 20
cm2), spectroscopic quality factor(χ )and r.m.s deviation (δrms ,
x10− 6) of LABN glasses.
Transitions from 4I9/2 → Nd-0.2 mol% Nd-0.4 mol% Nd-0.6 mol% Nd-0.8 mol% Nd-1.0 mol%

fexp fcal fexp fcal fexp fcal fexp fcal fexp fcal
4
F9/2 6.783 5.607 5.041 1.203 5.444 9.926 3.094 6.620 1.163 1.841
2
H11/2 3.330 0.675 2.684 2.963 2.813 2.472 2.629 1.713 1.003 0.480
2
G5/2,2G7/2 1.810 1.925 2.232 7.281 4.216 5.697 9.474 1.657 3.762 4.370
4
K13/2,4G7/2 0.447 1.646 1.178 5.513 9.743 6.167 9.360 0.522 0.476 0.935
2
K15/2 0.331 0.787 3.429 3.315 2.089 2.486 3.812 1.346 1.388 0.349
2
P1/2 0.279 0.303 3.040 4.706 4.592 7.886 3.437 5.487 2.112 0.331
4
D3/2,4D5/2, 4I11/2,4D1/2 1.878 1.963 6.188 7.516 3.532 4.147 3.311 3.433 1.534 1.909
J-O parameters Ω2 = 0.872 Ω2 = 0.108 Ω2 = 0.139 Ω2 = 0.128 Ω2 = 0.133
Ω4 = 1.914 Ω4 = 2.3835 Ω4 = 3. 547 Ω4 = 3.555 Ω4 = 1.548
Ω6 = 1.223 Ω6 = 1.8032 Ω6 = 1.846 Ω6 = 4.9574 Ω6 = 3.541
χ = 1.565 χ = 1.321 χ = 1.921 χ = 0.717 χ = 0.437
δrms = 0.745 δrms = 0.771 δrms = 0.408 δrms = 0.566 δrms = 0.580

Declaration of Competing Interest

The Author(s) declare(s) that there is no conflict of interest.

Acknowledgements

This work was supported by Fundamental Research Grant Scheme

from Ministry of Higher Education of Malaysia and Universiti Putra
Malaysia under grant number FRGS/1/2020/STG07/UPM/02/3. We
also wanted to thank Ministry of Higher Education of Libya for spon­
soring student scholarship.

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