Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 267 (2022) 120569

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Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Enhanced optical and structural features of Ni2+/La3+ hybrid borate

glasses
Sarah M. Kamil a,⇑, Ashraf.A. Abul-Magd b, W. El-Gammal c, H.A. Saudi d
a
National Institute for Standards, Giza, Egypt
b
Basic Science Department, Faculty of Engineering, Sinai University, El-Arish, Egypt
c
Egyptian Nuclear and Radiological Regulatory Authority, Cairo, Egypt
d
Department of Physics, Faculty of Science, Al-Azhar University, (Girls’ Branch), Cairo, Egypt

h i g h l i g h t s g r a p h i c a l a b s t r a c t

FT-IR spectroscopy confirmed the

entry of Ni2+ ions as a network
modifier.
2+

Ligand field effect of Ni has been
studied through NIR optical
transitions.

The nephelauxetic effect confirmed
the covalency nature of the Ni2+ ions.

The linear and nonlinear refractive
indexes were increased by Ni2+
addition.

Current glass is an optically active
material for devices operating in NIR
ranges.

a r t i c l e i n f o a b s t r a c t

Article history: Glasses with the formula [80B2O3–4.0La2O3–(16-x) PbO–xNiO, (x ranged from 0.0 to 4.0 mol%)], were
Received 25 July 2021 produced by the standard quenching method. XRD, SEM and EDAX analysis established the success of
Received in revised form 26 October 2021 the obtained samples preparation. Density measurements and FT-IR analysis confirmed the structural
Accepted 28 October 2021
modifications emerging by the entry of Ni2+ ions as a network modifier, where the structural unit’s ratio
Available online 4 November 2021
of BO3 (BO4) was affirmed to increase (decrease) with a gradual rise of NBO’s number. The semiconduct-
ing behavior of the current glassy samples was verified by the role of the structural modifications in
Keywords:
decreasing the gap energy and increasing both Urbach and mineralization criterion. Ligand field analysis
Borate glass
Heavy metal
applied to the absorption spectra exhibited the covalent nature of the Ni2+ bonds. The behavior of elec-
Transition metal tronic polarizability supported the gradual increases of the linear and non-linear refractive index of the
Ligand field effect samples. These properties qualify the present glasses as an optically active material for the devices oper-
Rare-earth oxide ated in the visible-NIR regions.
FT-IR measurements Ó 2021 Elsevier B.V. All rights reserved.

1. Introduction increased interest due to their promising applications in lumines-

cent materials, photonics and laser technology, radiation protec-
Heavy metal borate glasses are a good host matrix for rare earth tion materials, and optoelectronic devices [1–5]. Among the
(RE) oxides and transition metal oxides (TM). These glasses have heavy metal oxides, lead-borate oxide glass is very transparent
within visible and near-infrared (NIR) regions [6]; when the lead
oxide has been added to the borate glasses, it enhances the resis-
⇑ Corresponding author. tance against corrosion, lowers the melting temperature, and
E-mail address: [email protected] (S.M. Kamil).

https://doi.org/10.1016/j.saa.2021.120569
1386-1425/Ó 2021 Elsevier B.V. All rights reserved.
S.M. Kamil, Ashraf.A. Abul-Magd, W. El-Gammal et al. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 267 (2022) 120569

improves chemical durability. Depending on the Pb+ ions concen- the spectrometer (Shimadzu UV-3101 PC) was used to collect the
tration within the glass matrix, the lead oxide can act as a former optical absorption spectra of the studied samples with a wave-
or a modifier [7–11]. length range from 200 to 2500 nm.
Besides, the borate glasses doped with the transition metal (TM)
ions showed many notable optical properties [12–15], which qual-
3. Results and discussion
ified them for many optical and electro-optical applications oper-
ating within the visible, NIR and ultraviolet regions [12,14–15].
3.1. XRD, SEM and EDAX analysis
In addition, the TM ions have more than one valence state and
are very sensitive to the changes of the bond’s nature around them,
Fig. 1 exhibits the X-ray diffraction patterns of selected samples
which qualifies them to enter as a structural modifier for the host
0.0 and 4.0 mol% NiO, the absence of sharp crystal peaks is evident,
glass [15–16]. Among those glasses, Ni2+ ion-doped borate glass
while broad and wide humps appear at 25⁰ and 45⁰, indicating the
has additional properties such as chemical stability, outstanding
presence of disturbances in the structural formation of the pre-
durability and optical density, making it highly qualified for optical
pared system and confirming the amorphous nature for this
filters, optical fiber amplifiers, smart windows and fuel cells
system.
[11,17–19,23,24]. The Ni2+ ions occupy octahedral/tetrahedral
This amorphous nature can also be confirmed by SEM micro-
positions inside the glassy matrix, where the octahedral positions
graph of the prepared samples as shown in Fig. 2a for a 4.0 mol%
grow larger with increasing additions of the Ni2+ ions [15,22].
NiO sample, where the shape shows a smooth and clear surface
The octahedral positions of the Ni2+ ions have higher crystal stabil-
with the absence of the cluster formations. In addition, through
ity energies and distinct optical absorption bands within both
the analysis of the EDAX elements (see Fig. 2b), it was confirmed
regions visible and NIR as they provide eye-safe laser emission at
that all the prepared elements had entered the glass matrix by
k = 1.56 mm with relatively low threshold energy, so those glasses
the specified proportions.
with higher percentages of nickel are used as amplification media
in communication system and laser technology [21,23].
Moreover, the rare-earth (RE) ions provided further optical and 3.2. FT-IR studies
structural improvements when doped in different types of glass,
which qualified them for use in many optoelectronic systems such Fig. 3 presents the Fourier transform infrared (FT-IR) spectra for
as projectors, LEDs, and optical sensors [24–27]. Among these ions, the present system; to explore and understand the structural
lanthanum oxide (La2O3) is distinguished by its thermal stability, groups of this system, the obtained vibrational spectrum is divided
high optical permittivity, and low band gap energy [28–31]. into four spectral groups, and the assignment of each band within
In order to enhance the optical features of heavy metal borate these groups is studied. The FT-IR vibrational bands of all investi-
glasses based on structural modifications, the TM/RE hybrid lead- gated samples and their assignments are included in Table 1.
borate glassy system was synthesized to combine the thermal sta- The absorbed bands through the first spectral range (400–
bility, optical transparency and optical improvements offered by 600 cm1) are ascribed to the vibration of the metal cations and
La2O3, with the multivalency and distinct optical properties of the specific deformation patterns [32]. Within this range, two weak
NiO through the new glassy system [80B2O3–4.0La2O3–(16-x) bands with variable intensity are observed at  454
PbO–xNiO, (x ranged from 0.0 to 4.0 mol%)]. The presence of La3+ and  542 cm1, the first of them is usually ascribed to the Pb-O
and Ni2+ ions within the heavy metal borate glasses may lead to symmetric expansion vibration bonds in PbO4 and/or the LaO6
possible applications for optoelectronic devices. The current work metallic vibrations [11,33–38]; this band can also be related to
was presented to investigate the changes within the heavy metal the OABAO bending vibrations [39]. The second vibration band
borate network by adding a fixed ratio of La2O3 and a changeable at  542 cm1 is attributed to specific vibrations of the Ni-O and
ratio of NiO. Structural modifications, especially those affecting La-O bonds [40–41]; these bands intensity fluctuated with the
borate (BO3/BO4) structural units, were deduced from the density NiO addition, indicating the impact of Ni+ ions to breaking the
measurement and FT-IR analysis. At the same time, the oxidation Pb-O bonds and occurrence of remarkable modifications within
states and optical features were studied by optical spectroscopy the glassy network structure. The next spectral range in between
within the visible and NIR regions in addition to studying the 600 and 800 cm1 formed of a sharp absorption band
ligand field effect (LFE)of the Ni2+ ions.

2. Experimental procedure

The new glassy system [80B2O3–4.0La2O3– (16-x) PbO –x NiO,

(x ranges from 1.0 to 4.0 mol%)] was synthesized by the conven-
tional melt quenching method. The raw materials are mixed in pre-
Intensity (A. U.)

4.0 mol% NiO

cise molar proportions, grinded within an agate mortar, and heated
to 1150 °C. The mixture is stirred at varying intervals to enforce its
homogeneity. After melting is complete, the resulting mixture is
compressed between stainless steel plates and then annealed at
350 °C.
By using the diffractometer (Shimadzu XRD-6000), the XRD pat- 0.0 mol% NiO
terns of all prepared samples were obtained. Besides, the SEM
micrographs were acquired by scanning electron microscope
(Quanta FEG 250-FEI), where an attached power dispersal unit col-
lected EDAX analysis of the prepared samples. Vibrational spec- 10 20 30 40 50 60 70
troscopy (FT-IR Spectroscopy) was obtained using KBr pellet Bragg angle, 2θ (degree)
technology by a Perkin-Elmer-467 spectrometer. The density of
each sample was determined using the buoyancy principle. Finally, Fig. 1. XRD patterns for the selected samples 0.0 and 4.0 mol% NiO.

2
S.M. Kamil, Ashraf.A. Abul-Magd, W. El-Gammal et al. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 267 (2022) 120569

Fig. 2. For the selected glass sample 4.0 mol% NiO (a) SEM micrograph (b) EDAX analysis.

mol% NiO
to the B-O expansion vibrations of the BO4 units [34,41,43] and
0.0 are also associated with the Pb-O symmetrical bending and
1.0
2.0
stretching vibrations of PbO4 [42].
3.0
682 cm-1
1052cm-1
Finally, in the spectral range 1200–1600 cm1, there are two
4.0 wide and varying intensity peaks at  1248 and  1444 cm1;
the intensity fluctuations of these peaks are correlated to the vari-
Absorbance (a.u.)

887 cm-1 ation in the percentage of non-bridged oxygen resulting from the
542 cm-1
1248 cm-1 entrance of Ni+ ions as a matrix modifier here. Both peaks are also
attributed to the vibrion bonds B-O in Penta-, Ortho-, Pyro-and
Meta-borate groups of BO3 units [34,41]. Additionally, the last
broadband detected at 1630 cm1 is ascribed to the symmetric
819 cm-1 1444 cm-1
H-O-H bending vibrations [39].
1630 cm-1
With the gradual increase in the NiO ratio, most observed bands
454 cm-1 gradually shift to the lower wavenumber, which means that the
bond energy between the anions and cations decreases. The inten-
sity of the BO3 vibration band was increased with the addition of
400 600 800 1000 1200 1400 1600 1800 NiO, indicating the replacements of the tetrahedral units (BO4)
Wavenumber /cm by the triangular units (BO3) with the growth in non-bridged oxy-
gen ratio (NBO’s) indicating the structural modifications arising
Fig. 3. FT-IR spectrum of the prepared samples. from the entrance of Ni+ ions at the expense of Pb+ ions.

Table 1 3.3. Density and molar volume:

The assignments for FT-IR bands of [80 B2O3–4.0 La2O3– (16-x) PbO –x NiO] glassy
system with (x = 0.0, 1.0, 1.0, 2.0, 3.0 and 4.0 mol %).
Several parameters should be measured and/or calculated, such
Wavenumber Assignments as molar volume, density, ion concentrations, and interionic dis-
(cm1)
tance, to understand the prepared glass system’s structural
454 - PbAO symmetric vibration of PbO4. changes. The relationships required to evaluate these parameters
- OABAO bending vibrations.
- Metallic vibrations of LaO6.
are aforesaid in Refs. [44–45].
542 - Ionic vibration of NiAO. Fig. 4 shows the decreasing behavior of samples density with
- Ionic vibration of LaAO. NiO addition; this decrease can be attributed to the substitute of
682 - BAOAB angle bending vibrations of BO3 units. the higher molecular weight (223.2 g/mol) and the higher density
- PbAO bonds vibrations of PbO3 and/or PbO4 units.
(9.53 g/cm3) of PbO with a lower molecular weight (74.7 g/mol)
819–887 - PbAO symmetrical stretching and bending vibrations
of PbO4. and lower density (6.67 g/cm3) of NiO. The empirical density of
- BAO expansion vibrations of BO4 units. the prepared samples differed from those measured experimen-
1248–1444 - BAO stretching vibrations of BO3 units. tally (see Table 2), which indicates the amorphous nature of the
1630 - HAOAH bending vibrations. current glassy system [46].
In contrast to decreasing behavior of the density, Fig. 4 exhibits
the gradual increase in the prepared samples’ molar volume, which
at  682 cm1, commonly ascribed to BAOAB bending oscillations can be attributed to the decreases in the inter-particle bonding
in symmetric BO3 triangles [4,34]. This band can also attribute to energy, which were illustrated by the FT-IR measurements.
PbAO bonds vibrations of PbO3 and/or PbO4 units [42]. Likewise, Besides, the presence of a large elongation within a glassy network
the wide spectrum range of 800–1200 cm1 contains three vibrat- can also supports a decrease of the samples density and an increase
ing bands at  819,  887 and  1052 cm1, which are attributed of its molar volume; this extension or elongation can be inferred
3
S.M. Kamil, Ashraf.A. Abul-Magd, W. El-Gammal et al. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 267 (2022) 120569

3.00
mol% NiO
38.0 0.0
2.95
1.0
3 3 2.0
2.90 A 2g (F) T 1g (P)
37.5 3.0
4.0
2.85

Absorbance (a.u.)
37.0

Vm (cm3/mole)
ρ (g/cm3)

2.80
36.5
2.75

2.70 36.0

2.65
35.5
ρ 3
A 2g (F) 3
T 1g (F)
3 3
2.60 Vm A 2g (F) T 2g (F)
35.0
2.55
0 1 2 3 4
400 600 800 1000 1200 1400 1600
NiO (mol% )
λ (nm)
Fig. 4. The opposite behavior between the density and the molar volume.
Fig. 5. Optical absorption spectrum for the current glassy system. The inset shows
the sample’s distinctive yellowish color.
from progressive increase of the average boron-boron separation
hdBB i, where [9]:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
3 Vm
hdBB i ¼ ð1Þ
2NA ð1  X B Þ

where N A is Avogadro’s number, The current values of hdBB i

decreased to  0.445 nm with NiO content, indicating large com-
pressibility within the glass network; this result corresponds to
the behavior of both molar volume and density [15].

3.4. Optical properties

The optical spectra of the current glassy system within the

wavelength range from 300 to 1800 nm are shown in Fig. 5. These
spectra were studied by analyzing the optical absorption edges in
the UV region to determine the optical bandgap energy and the
related parameters. The characteristic absorption bands within vis-
ible and NIR ranges, which are basically the characteristic spectra
of the nickel ion, were also studied and analyzed.
In order to accurately study the current absorption peaks, a
detailed deconvolution process of the resulting optical spectra Fig. 6. The deconvoluted optical spectrum of 4.0 mol % NiO and its relationship to
was carried out, as shown in Fig. 6, as an example of a 4.0 mol% the electronic transitions of octahedral Ni2+ ions.
NiO sample. It is noticeable that in the UV region, the optical
absorption edge shifted with the systematic addition of NiO con-
tent towards the side of the longer wavelength (red-shift), which 3.4.1. Ni2+ ligand field effect
indicates the successive decrease of the optical band gap energy, The ligand environment surrounding the nickel ion influences
as will be shown later. As for the visible range, two overlapping its effect, as the shifting of the optical absorption edge and the
peaks appeared at  425 and  480 nm, while three peaks acquired color depend on the sites occupied by the nickel ion. In
appeared in the NIR region at  797, 1050 and  1300 nm. To the current glass, as shown inset Fig. 5, the nickel-free samples lost
explain these optical absorption peaks, it is necessary to investi- color, while the samples began to show a pale-yellow color that
gate the Ni2+ ligand field effect. In addition, the color of the sam- turns to dark orange when grafted with different percentages of
ples, as shown in Fig. 5, has a close relationship with those NiO. This noticeable change in the sample’s color is related to the
optical peaks, as will be shown later.

Table 2
Physical parameters of [80 B2O3–4.0 La2O3– (16-x) PbO –x NiO] glassy system with (x = 0.0, 1.0, 1.0, 2.0, 3.0 and 4.0 mol %).

Parameters NiO (mol %)

0.0 1.0 2.0 3.0 4.0
Molecular weight (Mw ) (g/mol) ± 0.010 104 103 101 100 98.4
Empirical density ðqemp Þ (g/cm3) 3.83 3.79 3.77 3.74 3.71
Molar volume (V m ) (cm3/mol) ± 0.030 35.0 35.6 36.5 37.5 38.1
Density ðqÞ (g/cm3) ± 0.020 2.97 2.89 2.77 2.67 2.58
Ni+ ions concentration (ni ) (1020 ion/cm3) 0.00 1.69 3.30 6.43 9.47
Boron-Boron separation (hdBB i) (nm) 0.459 0.457 0.456 0.451 0.445

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S.M. Kamil, Ashraf.A. Abul-Magd, W. El-Gammal et al. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 267 (2022) 120569

absorption bands in the visible range and their gradual shifting

with NiO addition. 945 755
Ni2+ ions have a 3d8 electronic configuration. In the octahedral
938
sites, the 3F state is divided into 3A2g (F), 3T2g (F), and 3T1g (F), while
the 3P state turns into 3T1g (P). Thus, there are three allowed spins 931 750
for the expected electron transitions from 3A2g (F) to 3T2g (F), 3T1g
(F), and 3T1g (P), which are here categorized as v 1 , v 2 and v 3 , 924

Dq (eV)
B (eV)
respectively [30]. These three electronic transitions appear with 745
917
the current optical spectra within the range between 300 and
1800 nm, where the first transition v 1 : 3A2g (F) ? 3T2g (F) appears 910
at  1360 nm. The second transition v 2 : 3A2g (F) ? 3T1g (F) is 740

located within the NIR region at  795 nm. Finally, the transition 903
B
band v 3 : 3A2g (F) ? 3T1g (P) appears within the visible region
896 Dq 735
at  422 nm. Additionally, the observed bands at 480 and
1030 nm are assigned to a spin forbidden octahedral transition
3 1.0 1.5 2.0 2.5 3.0 3.5 4.0
A2g?1T2g [47–51].
NiO (mol%)
Fig. 6 relates the electronic transitions with an Orgel energy dia-
gram level. Usually, the ligand field parameters are evaluated Fig. 7. The opposite behavior of Racah and crystal field parameters.
through those transitions, as those parameters are determined
according to the appearance of the transitions available in the opti-
behavior of the Dq =B ratio (see Table 3) indicates the direction of
cal spectrum under study; when the transition v 2 and v 3 appears,
the interaction towards the strong crystal field sites [55].
these parameters are evaluated through the equations mentioned
in reference [15], while when the transitions v 1 ; v 2 and v 3 appears,
  3.4.2. Absorption edge analysis
it is evaluated ligand field strength parameter Dq and the two
Several important optical parameters can be inferred by analyz-
Racah parameters ðBandC Þ through the following relationships
ing the optical absorption edges; these edges are usually used to
[40–41]:  
determine the optical bandgap energy EOpt values through the
v1 relationship between the incident photon energy ðhv Þ and the
Dq ¼ ð2Þ
10 absorption coefficient aðv Þ where [56]:
 2
ðv 3 þ v 2  3v 1 Þ Q hm  Eopt
B¼ ð3Þ aðmÞ ¼ ð5Þ
15 hm
where Q is a constant, the values of EOpt for the current glassy sys-
C ¼ 4:709B  0:5 ð4Þ
tem are obtained by lengthening the linear parts of the curve of the
pffiffiffiffiffiffiffiffiffi
The obtained values of these parameters are listed in Table 3; there relationship between ahv and the photon energy ðhv Þ as shown in
is an opposite behavior between the Dq parameter and the Racah Fig. 8.
parameters (see Fig. 7), where the crystal field parameters increase The obtained values of EOpt were recorded in Table 4. The inset
with NiO addition, indicating a growing delocalization of the elec- of Fig. 8 shows its decreasing behavior with NiO addition. Increas-
tron at Ni2+ ions [52]. Besides, the Racah parameters (B and C) ing the ratio of NBO’s with NiO addition, as inferred from the FT-IR
decrease, reflecting the decreasing field strength of electro- analysis, led to an increase in disorder within the glass matrix,
repulsion within the d-shell, which results in a more covalent char- shifting the valence band to higher energies, and then the optical
acter of the chemical bonds around the Ni2+ ions [20,43,53]. bandgap energy decreased [44].
It is possible to infer the bonding nature around the Ni2+ ions The present of short-range arrangement in the glassy network
through the nephelauxetic effect [54], which can be expressed leads to the emergence of some extended local states in the band
through the ratio between the values of Racah parameter of the gap, which the is so-called Urbach tail [57]. The width of this tail
prepared glass and its free value of the Ni2+ ion, i.e., can be obtained using the Urbach energy ðEu Þ, which can be calcu-
b ¼ BGlass =Bfree , where Bfree ¼ 1080cm1 for the Ni2+ ion. The calcu- lated from the relationship [15,58]:
lated values of b gradually decrease with NiO addition (see Table 3),
a ¼ a0 ehv =Eu ð6Þ
which indicates a high covalent bond formation between Ni2+ ions
and the surrounding bonds [20,43,53]. Additionally, the relation- where a0 is a constant, the current values of Eu are determined from
ship between the crystal field and Racah parameters (Dq =BÞ can the inverted slope of linear parts of the relationship curve between
give light about the interaction strength, in which the increasing ðln aÞ and ðhv Þ as shown in Fig. 9 [56].

Table 3
Ligand field parameters of [80 B2O3–4.0 La2O3– (16-x) PbO –x NiO] glassy system with (x = 0.0, 1.0, 1.0, 2.0, 3.0 and 4.0 mol %).

Parameters NiO (mol %)

1.0 2.0 3.0 4.0
k1 : (3A2g(F)?3T2g(F)) (nm) 1360 1350 1331 1322
k2 : (3A2g(F)?3T1g(F)) (nm) 795 797 799 799
k4 : (3A2g(F)?3T1g(P)) (nm) 422 420 421 424
Crystal field strength (Dq), (cm1) 735 740 751 756
Racah parameter (B) (cm1) 947 942 915 893
Racah parameter (C) (cm1) 4463 4437 4310 4209
Ratio (Dq=B) 0.78 0.79 0.82 0.85
Nephelauxetic ratio (b) 0.88 0.87 0.85 0.83

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S.M. Kamil, Ashraf.A. Abul-Magd, W. El-Gammal et al. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 267 (2022) 120569

mol% NiO
120
0.0
1.0
2.0
100 3.0
4.0
(αhv)0.5 (ev)0.5

80

60

3.2

40
EOpt.(ev) 3.1

3.0
20
2.9
0 1 2 3 4
NiO (mol%)
0
3.0 3.5 4.0 4.5
hv (ev)
pffiffiffiffiffiffiffiffiffi
Fig. 8. ahv vs. ðhv Þ, the inset shows the variation of EOpt: as a function of NiO ratio.
Fig. 9. ðln aÞ as a function of ðhv Þ for all investigated samples, the inset shows the
variation of Eu as a function of NiO ratio.

The obtained values of Eu are listed in Table 4, ranging between

0 ¼ 0:9v þ 3:5
a2
0.124 and 0.139 eV, where it could indicates the semiconductor ð9Þ
nature of the current glasses [56]. On the other hand, the structural
stability of prepared glass can be inferred from the Eu values, The calculated values of Kth and a were increased with NiO addi-
2
0
where an increase of Eu value indicates a decrease in structural sta- tion as tabulated in Table 4. This increase reflects polarization
bility [44]. enhancement and a lowered strength of the single bond of NiO,
For more information about the semiconductor nature of the which means a limitation of the ion to attract electrons from the
current glasses, the metallization criterion ðMÞ can be calculated associated atoms [28–30]. Furthermore, the increase of Kth and a2
0

where EOpt ¼ 20M 2 [14]. The calculated values of the metallization evidence an increase in NBO’s ratio [27,29–30].
parameter are listed in Table 4 and range from 0.280 to 0.265 eV0.5
indicating the narrow band gap between the valence and conduc- 3.4.3. Linear and non-linear refractive index
tion bands and the presence of the semiconductor nature of the The resulting structural modifications by NiO addition which
current glassy system [4,34]. led to more formation of NBO’s ratio with decreased the band
One of the major reasons for crystal field distortion surrounding gap energy can also lead to an increase in the linear refractive
the TM ions is electronegativity [54]. Using the obtained values of index, which can be inferred by calculating the value of this index
the optical band gap energy of the current glassy system, the elec- from the well-known Dimitrov and Sakka relationship [3,59],
tronegativity coefficient may be computed [44]: which can be simplified as:
!1=2
v ¼ 0:269EOpt ð7Þ 13:4
n¼ pffiffiffiffiffiffiffiffi  2 ð10Þ
The calculated values of the electronegativity coefficient gradually EOpt
decrease by NiO adding, which means that the distortion of the
The calculated values of the linear refractive index ðnÞ were
crystal field around Ni2+ ions is reduced. Using the resulting values
recorded in Table 4, which actually witnessed a significant increase.
of electronegativity, the optical basicity ðKth Þ can be obtained by:
Additionally, the linear refractive index ðnÞ can be used to calculate
Kth ¼ 0:5v þ 1:7 ð8Þ the third-order of nonlinear optical susceptibility by the relation-
ship [60–62]:
The acid-base features of oxide glass can be inferred from its optical
basicity [34]. Additionally, the mean electronic polarization (a2  2 4
0 ) is n 1
v3 ¼ 1:7  1010 ð11Þ
determined by the calculated values of the optical basicity by: 4p

Table 4
Optical parameters of [80 B2O3–4.0 La2O3– (16-x) PbO –x NiO] glassy system with (x = 0.0, 1.0, 1.0, 2.0, 3.0 and 4.0 mol %).

Parameters NiO (mol %)

0.0 1.0 2.0 3.0 4.0
Optical band gap energy ðEOpt Þ (eV) 3.18 3.11 3.07 3.03 2.98
Urbach energy ðEu Þ (eV) 0.25 0.29 0.32 0.34 0.37
Metallization criterion (M) (eV)0.5 0.399 0.394 0.392 0.389 0.386
The electronegativity ðvÞ 0.86 0.84 0.83 0.81 0.80
Optical basicity ðKth Þ 1.272 1.282 1.287 1.293 1.299
Mean electronic polarization ða20 Þ
2.73 2.75 2.76 2.77 2.78
Linear refractive index (n) 2.35 2.37 2.38 2.39 2.40
 
Nonlinear optical susceptibility v3 (10-12 esu) 2.83 3.05 3.18 3.34 3.51
Nonlinear refractive index ðn2 Þ (10-11 esu) 4.55 4.86 5.05 5.27 5.51

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S.M. Kamil, Ashraf.A. Abul-Magd, W. El-Gammal et al. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 267 (2022) 120569

The v3 values of the current glass system are tabulated in Table 4, [6] Z. Shen, Y. Zhao, Z. Tian, W. Huang, J. Wu, H. Lin, Effect of doping La2O3 on the
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cial interests or personal relationships that could have appeared cobalt doped erbium–zinc borate glasses, Opt. Quantum Electron. 51 (9)
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