Materials Today: Proceedings 92 (2023) 817–822

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Physical and spectroscopic properties of PbO –ZnF2 – B2O3 glasses doped

with CuO
N. Narasimha Rao a,⇑, P. Naresh b, P. Raghava Rao a, B.J.R.S.N. Swamy a, A. Chitti Babu c
a
Department of Physics, Krishna University Dr.MRAR College of PG Studies, Nuzvid 521201, India
b
Department of Physics, VR Siddharth Engineering College, Vijayawada 520007, India
c
Department of Physics, Krishna University, Machilipatnam 521003, India

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

Article history: The glass samples with the chemical composition of PbO
ZnF2
B2O3: CuO has been prepared by melt
Available online 3 May 2023 quenching technique. All the prepared glass samples exhibits amorphous nature, were confirmed by the
X-ray diffraction studies. The density of the glass samples were measured by using Archimedes’ principle.


Keywords: With help of measured densities various physical properties such as average molecular weight (M Þ, molar
B2O3 glasses volume, Interatomic distance(ri), dopant ion concentrations (Ni) were calculated by using standard for-
Optical Absorption mulas. Optical Absorption spectra studies reveals that the glass samples contains Cu ions exhibits a broad
Infrared Spectra
absorption band at about 780 nm due to 2B1g ? 2B2g transition.The spectra of Infrared transmission show
Cu2+ ions
prominent bands at wave numbers around 1200 to 1400 cm
1, which are caused by the trigonal BO3
units, at 1000 and 1200 cm-1which are caused by vibrations of BO4 structural units, and at about
700 cm
1 which are caused by B-O-B linkages.
Copyright Ó 2023 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the 2nd International Con-
ference on Multifunctional Materials.

1. Introduction strongly affect the spectroscopic and physical characteristics of

B2O3 glasses are distinguished from other types of glasses by
their transparency, low melting temperature, poor chemical resis-
tance, suitable structural balance, and higher electric resistivity [1–
3]. PbO is a heavy metal oxide with interesting properties such as
low field strength, wide energy gap, high refractive index and high
polarizability. When PbO have been added to the B2O3 it acts as a
good stabilizer [4] and improves the chemical durability, increase
the glass transition temperature. By adding the ZnF2 to PbO
B2O3
glasses, it is expected to improve the chemical durability by lower
the viscosity and widening the glass transition temperature to a
considerable extent [5]. In view of these considerations, the glasses
containing PbO
ZnF2
B2O3 are thought to be the superlative
components to utilize in phosphors, lasers, solar electricity con-
verters, and several other digital devices. Furthermore, we can
anticipate structural alternations and neighborhood variations
across the dopant transition metallic ions while those glasses are
blended with modifying ions. These modifications might also
the metallic ions.
Among the many transition metallic ions, copper ions are most
prevalent fascinating network probes for glass because they con-
tain the electrical, optical, and magnetic characteristics of glasses
built into them. The conditions in which copper ions exist in differ-
ent glass systems are subject to enormous ranges of analysis [6–8].
The association between the copper particles position and the
glasses electric characteristics is quite attractive. Cu2+ ions are very
strong magnet ions; therefore it moves really swiftly that ions will
form link with B2O3 groupings. Although there is a wide range of
research available on CuO glasses [9–12], there may still be many
opportunities to examine how CuO has affected the spectral and
physical properties of those glasses and how they are correlated.
The motto of present work are i) prepare the fresh batch of CuO-
doped PbO
ZnF2
B2O3 glasses by melt-quenching method ii)
confirms the amorphous nature by XRD patterns iii) acquire their
physical and spectroscopic characteristics and correlate the physi-
cal, optical and structural properties.

⇑ Corresponding author.
E-mail address: nnrphy@gmail.com (N. Narasimha Rao).

https://doi.org/10.1016/j.matpr.2023.04.382
2214-7853/Copyright Ó 2023 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the 2nd International Conference on Multifunctional Materials.
N. Narasimha Rao, P. Naresh, P. Raghava Rao et al. Materials Today: Proceedings 92 (2023) 817–822

2. Experimental NA M ðMol%Þq
21 
Ni ¼
10 ions=cm2 ð2Þ
M
The PbO
ZnF2
B2O3: CuO glass samples were prepared using
traditional melt quenching method [13–15](Fig. 1). Table 1 pro-  1=3
1
vides the information of chemical formula their codes used for ri ¼ ðAo Þ ð3Þ
Ni
the prepared glass samples.
XRD patterns were recorded by using Philips: PW 1830 X-ray  1=3
1 p
diffraction spectrometer. The details of the instruments used for rp ¼ ð4Þ
record the Optical absorption spectra and Fourier transform Infra- 2 6Ni
red spectra are same as one of our previous work [16].

ðX PbO Z PbO þ X ZnF 2 Z ZnF 2 þ X B2 O3 Z B2 O3 þ X CuO Z CuO Þ
M¼ ð5Þ
100
3. Results and discussion
Where, X PbO , X ZnF 2 , X B2 O3 &X CuO are the mol% of the constituent
3.1. XRD compounds and Z PbO , Z ZnF 2 , Z B2 O3 &Z CuO are the molecularweights
of the constituent compound.
Fig. 2 depicts the XRD patterns of PbO
ZnF2
B2O3: CuO

M
glasses. These patterns exhibit no sharp peaks which suggest that Vm ¼ ð6Þ
there is no crystalline nature of the samples. Further, XRD pattern q
of all samples shows a broad hump at about 2h  20°
30°, which " #
confirms the short
range atomic periodicity exist in prepared q
O:P:D ¼ n
1000 ð7Þ
samples. M
Where, n is the total number of Oxygen atoms in the
3.2. Physical parameters
composition.
From the data presented in Table 2, accomplishes that, inter
The density of the samples are calculated by applying Eq. (1)
ionic distance, polaron radius decreases whereas Dopant ion con-
with help of measured weight of the glass sample in air and appar-
centration and Oxygen Packing Density increases with increasing
ent weight of the glass sample in the O
xylene fluid as a buoyant
concentration of CuO.
liquid.

W air
gm  3.3. Optical absorption

q¼  qXylene
W air
W xylene cm3
Where W air and W xylene are the weight of glass samples in air
and O-Xylene respectively, and qXylene is the density of O-Xylene.
The density of glass decreases from 3.616 g/cm3 to 3.583 g/cm3
and also molar volume decreases from 25.369 to 25.195 cc/mol, by
gradually replacement of CuO by the PbO content. This is expected
due to replacement of lighter molar mass substance CuO
(79.5 g/mol) by the heavier molar mass substance PbO
(223.2 g/mol). Physical characteristic quantities such as the Cu
ion concentration (Ni), Inter ionic distance (Ri), Polaron radius
(Rp), Molar Volume (Vm) and oxygen packing density (OPD) are
derived on the basis of measured density (q) and average molecu-


lar weight value (M ), by applying standard Eqs. (2), (3), (4), (5), (6)
and (7),and same are presented in Table 2 [17].
ð1Þ
The spectra of optical absorption (Fig. 3) suggest that, an
absorption edge slightly shifted to the higher wavelength side with
increase in concentration of CuO. The spectra of each glass sample
(except G0), shows broad absorption peak at around 700–780 nm.
This absorption peak is attributed may be due to the transition of
Cu2+ ion from 2B1g to 2B2g energy level [18]. Further it is observed
that, the full width and half maxima of these absorption bands are
increases with the increase in the content of CuO, as well as the
peak position of these bands are slightly shifted towards red-end.
The data of absorption edges and band positions are collected
and shown in Table 3.
Fig. 4 represents the Tauc plots, the optical band gap (Eo) values
are derived by extrapolating ða
hxÞ
1=2
v shx curves [5] by applying
equation (8).

Fig. 1. Flow char of various step involved in preparation of glass samples.

818
N. Narasimha Rao, P. Naresh, P. Raghava Rao et al. Materials Today: Proceedings 92 (2023) 817–822

Table 1
Composition of glass samples (all in mol %).

Sample code PbO ZnF2 B2O3 CuO

G0 10.0 20 70 —
G2 9.8 20 70 0.2
G4 9.6 20 70 0.4
G6 9.4 20 70 0.6
G8 9.2 20 70 0.8
G10 9.0 20 70 1.0

Fig. 2. X-Ray diffraction pattern of PbO-ZnF2-B2O3: CuO Glasses.

Table 2
Physical parameters of PbO
ZnF2
B2O3: CuO glasses.

Sample Density Avg.Mol Weight (M) Molar Volume Interionic distance (ri) (Å) Polaronradius Dopant ion concentration OPD
(g/c.c) (cc/mol) (rp) (Å) (Ni)(1021 ions/cm2)
G0 3.616 91.734 25.369 ... ... ... 86.72
G2 3.609 91.447 25.334 5.946 3.803 4.754 86.75
G4 3.603 91.159 25.300 4.717 3.017 9.522 86.80
G6 3.596 90.872 25.265 4.119 2.634 14.303 86.82
G8 3.590 90.585 25.230 3.741 2.392 19.097 86.87
G10 3.583 90.298 25.195 3.470 2.220 23.905 86.90

ðahxÞ
1=2
¼ Cðhx
E0 Þ ð8Þ n ¼
0:73 ln ð0:102  vÞ þ 0:551 ð11Þ

The obtained optical band gap of the glass samples are pre- The obtained refractive index values for all the glass samples
sented in Table 3. From these values, it is revealed that, with are also scheduled in Table 3. The refractive index values are also
increasing concentration of CuO, the optical band gaps are slightly increases with increasing the concentration of CuO.
decreases from 2.53 to 2.30 eV. Molar refraction (Rm) and Metallization criterion (M) are calcu-
By using obtained Optical band gaps, the Optical electronegativ- lated by using relations (12) and (13) with help of refractive index
ity of the glass samples calculated by applying Duffy’s [19,20] rela- (n) and molar volume (Vm). These are also shows increasing trend
tion (9). with increasing the concentration of CuO.
 2 
v ¼ 0:2688  Eo ð9Þ n
1
Rm ¼  Vm ð12Þ
The values of optical negativity of samples are slightly
n þ2
2

decreases as the concentration of CuO increases (scheduled in  

Table 3). Rm
M¼ 1
ð13Þ
The Refractive index of the glass samples are calculated by Vm
applying the equation (10 & 11) from the electro negativity values Copper element is one of the well-known elements to the man
[21] from long back. Copper in pure form is soft, malleable and in red-
 2  rffiffiffiffiffiffi
n
1 Eo dish brown colour. In compound, copper exist in two states Cu+
¼1
ð10Þ and Cu2+. The ionic radius of Cu2+ is 73 pm whereas Cu + is
n2 þ 2 20
77 pm. Cu+ ([Ar] 3d10) has no unpaired electron in its outermost
819
N. Narasimha Rao, P. Naresh, P. Raghava Rao et al. Materials Today: Proceedings 92 (2023) 817–822

Fig. 3. Optical absorption spectra of PbO-ZnF2-B2O3: CuO Glasses.

Table 3
Data on optical absorption spectra of PbO
ZnF2
B2O3: CuO glasses.
2
Sample Cut- off wavelength B1g band gap Optical Electronegativity Refractive Index molar refraction Metallization criterion
(nm) ?2B2g(nm) (eV) (v) (n) (Rm) (M)
G0 325 ... 2.53 0.6752 2.504 16.167 0.3627
G2 364 723 2.44 0.6512 2.531 16.293 0.3570
G4 376 728 2.41 0.6432 2.540 16.318 0.3550
G6 390 740 2.35 0.6272 2.558 16.397 0.3511
G8 408 758 2.32 0.6192 2.567 16.422 0.3492
G10 421 778 2.30 0.6138 2.574 16.435 0.3479

Fig. 4. Tauc plots of PbO-ZnF2-B2O3:CuO Glasses.

orbit, exhibits diamagnetism, whereas Cu2+ ([Ar] 3d9) has one assumed to form an octahedral structure coordinated by six oxy-
unpaired electron which is responsible for the paramagnetic nat- gen atoms. That’s why, in the tetragonal distorted octahedral envi-
ure.Cu2+ (d9)’s free ion term is 2D. In the current study, Cu2+ is ronment, the ground state is 2B1, the 2Eg level separates into 2A1

820
N. Narasimha Rao, P. Naresh, P. Raghava Rao et al.
Fig. 6. Infrared spectra of PbO-ZnF2-B2O3: CuO glasses.
and 2B1, and the 2T2g level splits into 2E and 2B2. The schematic rep-
resentation of energy level diagram of d-orbital of tetragonal dis-
torted octahedral elongation is shown in Fig. 5. Fingerprints of
absorption spectra showed a wide absorption at a wavelength of
about 780 nm. The band can therefore be attributed to the 2B1g
to 2B2g transition [22,23].
3.4. Infrared spectral studies
The spectra of IR transmission are shown in Fig. 6. These spectra
reveal prominent bands at wave numbers ranging from 1200 and
1400 cm
1, which are caused by BO3 units, at 1000 and
1200 cm
1, which are caused by BO4 structural units, and at about
700 cm
1, which are caused by B-O-B linkages, respectively.
When PbO is added to a B2O3 glass network, facilitates forma-
tion of non-bridging oxygen’s and the conversion of BO3 structural
units to tetrahedral BO4 structural units. These glasses all of them
also contain a band at 540 cm
1 that is connected to the PbO4
units. As the rise in CuO content, it is shown that the band’s caused
by the BO3 structural components grows at the expense of the
band caused by the BO4 structural units. These data unequivocally
demonstrate that a rise in CuO content causes an incremental rise
-4Dq - Ds + 4Dt
2
T2g
- 4Dq +2Ds - Dt
d9 (2D)
6Dq - 2Ds - 6Dt
2
Eg
6Dq+2Ds - Dt
FREE ION TETRAGONAL OCTAHEDRAL
FIELD (C4V) FIELD (Oh)
Fig. 5. Schematic representation of Cu2+ energy levels in octahedral field [22].
Materials Today: Proceedings 92 (2023) 817–822
in the degree of depolymerisation of the glass network. These find-
ings suggest that Cu2+ ions that occupy modifier sites in the net-
work of glass are gradually rising. As copper oxide concentration
raises, Pb2+ ions become more polarised inside the glass network,
which helps to produce modified Pb2+, modified B-O rings and
associated chains. The intensity of BO4 units is shown to shift in
the metacentre advancing higher wave number with a rise in
CuO concentration, but that of BO3 units is seen to grow for a
change in the band location closer to decrease wave number .BO3
and BO4are the structural components of Borate.
With the increment of CuO, the molar volume of samples
diminishes due to the enhance production of NBOs containing
borate triangles [24,25], which might be expect the decrease in
the density of these samples. For a conventional glasses, refractive
indices increases with increase in production of NBOs due to addi-
tion of modifier oxide [26]. The increase in refractive indices with
content of CuO in the present studied samples confirms enhance
the production of NBOs, which also supports the increase the Oxy-
gen packing density. These results are found in line with the
reported outcomes earlier [27].The outcome of this rise in disorder,
the optical band gap narrows and the edge of absorption shifts to
the higher wavelength side.
4. Summary and conclusions
2
E
Accordingly, when optical absorption of PbO
ZnF2
B2O3
glasses with varying amounts of CuO were analysed, it was discov-
ered these copper ions were primarily in the Cu2+ state, occupied
2
B2 irregular octahedral sites, and stimulated bonding issues. Accord-
2 ing to the spectral data of IR, these glasses contain copper ions in
A1
octahedral locations that lead to non-bridging oxygen’s. While
BO3 unit intensity is seen to go up with a movement in band place-
ment toward reduced wave number, BO4 unit intensity it is seen to
fall with a shift in metacenter heading higher wave number as CuO
rises, which reduces the stiffness of the network of glasses. These
results are correlated with physical properties of the glass samples.
2
B1
Data availability
Data will be made available on request.
821
N. Narasimha Rao, P. Naresh, P. Raghava Rao et al.
Declaration of Competing Interest
The authors declare the following financial interests/personal
relationships which may be considered as potential competing
interests: N. Narasimha Rao reports financial support was provided
by Krishna University. P. Naresh reports a relationship with VR Sid-
dharth Engineering College and P. Raghava rao, B. J.R.S.N. Swamy, A.
Chitti Babu reports a relationship with Krishna University that
includes: non-financial support.
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