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ISSN No. 2321-2705 | DOI: 10.51244/IJRSI |Volume XII Issue X October 2025
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Properties of Vanadium (VO
2+
) doped K
2
O - CdO - B
2
O
3
- SiO
2
(KCdBSi) Glasses
G. Keerti Marita
1
, B. Lakshmi
1,
M. Bala Krishna
1
, Sandhya Cole
2
1
University College of Engineering, Adikavi Nannaya University, Rajahmundry, India-533 296, India
2
Department of Physics, Acharya Nagarjuna University, Nagarjuna Nagar, Guntur-522 510, India
DOI: https://dx.doi.org/10.51244/IJRSI.2025.1210000175
Received: 10 October 2025; Accepted: 20 October 2025; Published: 14 November 2025
ABSTRACT
Glasses of the 20K
2
O - 5CdO - 60B
2
O
3
-15SiO
2
and (20-x) K
2
O - 5CdO - 60B
2
O
3
- 15SiO
2
- xV
2
O
5
(where x =
0.1 to 0.5 mol %) KCBSi systems are prepared by melt quenching technique. Optical and structural properties
of undoped glass, and glasses doped with VO
2+
ions are examined. Their structural properties are determined
with XRD, Fourier Transform Infrared (FTIR) and Electron Spin Resonance spectra (ESR) and Optical
absorption spectra. The ESR spectra of all the glass samples exhibit resonance signals characteristic of VO
2+
ions. The values of spin-Hamiltonian parameters indicated that the VO
2+
ion in KCdBSi glasses are present in
octahedral sites with tetrahedral compression and belong to C
4v
symmetry. Spin-Hamiltonian parameters ‘g’
and ‘A’ are calculated from their Ultra Violet edges. IR spectra of these glasses are analysed in order of each
component to the local structure. The physical parameters are also evaluated.
Keywords: Borosilicate glass, Vanadium, Optical Properties, XRD, FTIR, ESR, and spin-Hamiltonian.
INTRODUCTION
In recent years there has been a considerable interest in the study of glasses doped with transition metal ions
because of their technological applications. Borosilicate glasses constitute a subject of wide spread interest in
number of fields from the earth science to glass industry in particular for special glasses i.e., Pyrex. The early
research is of great importance because it is the first attempt to study symmetrically the relationships between
the composition of glass and its physical and chemical properties [1]. Borosilicate glasses are widely used in
optical glasses, heat resistant glasses and electronic glass industry for its excellent properties
[2]. The structural
role of CdO and K
2
O is unique since they occupy both modifying and glass forming positions. They are glass
modifiers and enter the glass network, by breaking up the B-O-B bonds and introduce co-ordinate defects
along with non-bridging oxygen’s (NBO). On the other hand, potassium Borosilicate glasses have been widely
used in the ceramic industry for the fabrication of glaze glass coatings intended for the application on faience
porcelain and other types of ceramics
[3]. Semiconducting transition metal oxide such as V
2
O
5
based glasses
have gained much interest in solid state chemistry and materials science with regard to their possible
applications as memory and switching devices [4].
Vanadium belongs to the unfilled 3d elements and
possesses many valence states. The V
2+
, V
3+
, V
4+
and V
5+
states are the most well-known valence sates of
vanadium in oxide glasses. Vanadium containing oxide glasses are known to be semiconductors and the
transport mechanism involves the exchange of electrons between vanadium (IV) and vanadium (V) centers
[5].
V
4+
-- O -- V
5+
⇔ V
5+
-- O -- V
4+
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Vanadate glasses are identified as n-type semiconductors for low V
4+
/ V
5+
ratio [6]. It is also known that V
5+
in
low ratios enter the amorphous structure as an impurity whereas V
5+
in high ratios are present in the structure
as glass formers [7]. Some authors studied the effect of single [8] and multiple [9] (TM) transition metal ions
as dopant in alkali and alkaline earth oxide glasses [10]. Binary and ternary V
2
O
5
glasses can exhibit a
semiconducting behavior which arises from an unpaired 3d
1
electron hopping between the transition metal
(TM) ions when the TM ions exist in two or more valence states, i.e., an electron hopping from a V
4
site to a
V
5
[11]. Glasses doped with TM ions came into prominence because of their notable spectroscopic properties
and their suitability for electronic, fiber optic communications, luminescent solar energy concentrators (LSCs)
[12].
In the present study, the absorption and transmission of 20K
2
O - 5CdO - 60B
2
O
3
-15SiO
2
and (20-x) K
2
O -
5CdO - 60B
2
O
3
- 15SiO
2
– xV
2
O
5
(where x=0.1to 0.5mol %) glasses (KCBSi systems) are of particular interest
because these are transparent from the ultra violet to middle infrared region and the addition of V
2
O
5
the
transition metal ion permits the possibility of glass to exhibit semiconducting behavior. Defects of the surfaces
and their structural properties are determined by XRD, ESR, FT-IR
Experimental:
Glass samples are prepared in the composition 20K
2
O
- 5CdO
- 60B
2
O
3
- 15SiO
2
for pure sample and (20-x)
K
2
O - 5CdO - 60B
2
O
3
- 15SiO
2
- xV
2
O
5
for vanadium doped samples where x = 0.1 to 0.5mol% V
2
O
5
. The
composition of glass samples are given in Table 1. Using digital balance of sensitivity ±0.0001gms,
appropriate amount of chemicals in powder form are weighed and grounded into fine powder and mixed
thoroughly. The samples are melted in silica crucibles in an electrical furnace at temperature range of 1100˚C-
1200˚C for 12 minutes. The melted samples are poured on a clean polished brass plate and carefully pressed
with another brass plate to get uniform thickness of the glass. The glasses obtained are transparent and are light
greenish in colour. The obtained glasses are polished finely to obtain optical measurements.
X-ray diffraction pattern of glass samples are recorded using Copper target on Philips PW (1710)
Diffractometer at room temperature. ESR readings are made at room temp on JEOL-JM FE3 with 100 KHz
field modulation EPR spectrometer.
The density of glass samples is determined by using Archimedes’s principle with Xylene as an inert buoyant
liquid.
RESULTS
Physical parameters:
Based on the density (d) and calculated average molecular weight (M), various physical parameters such as the
vanadium ion concentration (N
i
), mean vanadium ion separation (r
i
) and the polaron radius (r
p
) are evaluated
using conventional formulae [13] and presented in Table 2.
The density of glass is undoubtedly one of the most important properties in industrial glass production and is
important for calculating various physical parameters such as the vanadium ion concentration (N
i
), mean
vanadium ion separation (r
i
) and the polaron radius (r
p
) using conventional formulae [13]. Refractive indices
for all the glass samples are also found using Abbe’s Refractometer. The values are tabulated in Table 2 along
with average molecular weight (M). There is a small variation in the density of the glass samples from V
O
to
V
5
samples and error in the density measurements is estimated to be ± 0.0001. The Inter ionic distance and the
polaron radius are observed to be decreasing and the optical basicity remains almost equal for all the samples.
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XRD:
The X-Ray diffraction pattern of the (20-x) K
2
O - 5CdO - 60B
2
O
3
- 15SiO
2
– xV
2
O
5
(where x = 0, 0.1 to
0.5mol %) glasses reveals no sharp peaks which confirms the presence of amorphous nature in the present
glassy matrix shown in Fig. 1 and Fig 2.
The X-ray diffraction is a useful method to detect readily the presence of crystals in a glassy matrix if their
dimensions are greater than typically 100nm.The X-ray diffraction pattern of an amorphous material is
distinctly different from that of crystalline material. The XRD patterns of the present glass system reveal no
sharp peaks which is the characteristic of the amorphous materials. Fig.1, Fig.2 shows the typical X-ray
diffraction patterns for the KCBSi glass system.
ESR Study:
The ESR spectra recorded at room temperature for (20-x) K
2
O - 5CdO - 60B
2
O
3
- 15SiO
2
– xV
2
O
5
(where x=0,
0.1 to 0.5mol %) glasses under investigation are shown in Fig 7. Spectra are observed to be complex made up
of resolved hyperfine components raised from 3d
1
electron of VO
2+
ion in association with
5I
V ( I=7/2 ). As the
concentration of V
2
O
5
is increased up to 0.5mol% an increasing degree of resolution and the intensity of signal
have been observed. Further at low V
2
O
5
content, the ESR spectra observed to be asymmetrical. The values of
g
║
and g
┴
(obtained from these spectra) along with the other pertinent data are furnished in Table 5.
No ESR signal is observed in undoped glasses confirming that the starting material used in the present work is
free from transition metal impurities or other paramagnetic centers (defects). The ESR spectra of all the
investigated samples from V
1
to V
5
exhibit resonance signals and are shown in Fig. 7. Because of the low
content of V
2
O
5
(i.e., x=0.1mol %) these spectra shows a well-resolved hyperfine structure (hfs) typical for
vanadyl ions in a C
4v
symmetry. The 16- line feature with eight parallel and eight perpendicular lines is typical
of the unpaired (3d
1
) electron of VO
+
ion in association with
5I
V ( I=7/2 ) is an axially symmetric crystal field
[23]. The analysis of well resolved hyperfine structure of the ESR spectra was made using an axial spin-
Hamiltonian.
H = g
║
β B
z
S
z
+ g
┴
β (B
x
S
x
+ B
y
S
y
) + A
║
S
z
I
z
+ A
┴
(S
x
I
x
+ S
y
I
y
) (7)
where β-Bohr magneton. g
║
and g
┴
are the parallel and perpendicular principle components of g tensor. B
x
, B
y
,
B
z
– components of the magnetic field. S
x,
S
y ,
S
z,
I
x,
I
y,
I
z
– components of the electron and nucleus spin
operator. A
║
and A
┴
are principal components of the hyperfine coupling tensor. The values of the magnetic
field for the hyperfine peaks from the parallel and perpendicular absorption [24] bands are given by
B
║
(m
l
) = B
║
(0) - A
║
(m
l
) - (63/4 –m
l
2
) A
┴
2
/ 2 B
║
(0) (8)
B
┴
(m
l
) = B
┴
(0) - A
┴
(m
l
) - (63/4 – m
l
2
) (A
║
2
-A
┴
2
) / 4B
┴
(0) (9)
where m
l
is the magnetic quantum number of the vanadium nucleus, which takes the values ±7/2, ±5/2, ±3/2,
, ±1/2.
B
║
(0) = hν / g
║
β and B
┴
(0) = hν / g
┴
β
where the symbols have their usual meaning and ν is the microwave frequency. EPR parameters in studied
glasses are given in Table 4. The values obtained are in good agreement with the other reports given in
literature [23, 25-27]. The data shows that g
║ <
g
┴ <
g
e
and
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A
║ >
A
┴,
the relation that corresponds to vanadyl ions in KCBSi glasses exist as VO
2+
ions in octahedral
coordination with a tetragonal compression and have a C
4v
symmetry. The vanadyl oxygen is attached axially
above the V
4+
site along the Z-axis (V=0 bond) while the sixth oxygen forming the O-VO
4
-O unit lies axially
below the V
4+
site in opposition with “yl” Oxygen. The predominant axial distortion of the VO
2+
octahedral
oxygen complex along V=O direction may be the reason for nearly equal g and A values for all the glass
samples [25]. Fermi contact interaction term (K) and dipolar hyperfine coupling parameter (P) are evaluated
using the expressions developed by Kivelson and Lee [28].
A
║
= -P [(K-4/7) - ∆ g
║
- 3/7 - ∆g
┴
] (10)
A
┴
= -P [(K-2/7) – 11 / 14 ∆g
┴
] (11)
where ∆g
║
= g
║
- g
e
, ∆g
┴
= g
┴
- g
e
and g
e
= 2.0023 is the g factor of the free electrons [29]. The values of (∆g
║ / ∆g
┴
)
which measure the tetrogonality of the V
4+
site are also calculated and are presented in Table 4. A
decrease in (∆g
║ /
∆g
┴
) shows that the octahedral symmetry around V
4+
ions is improved [30]. When the
concentration of V
2
O
5
is increased beyond 0.5mol%, suppression in the hyperfine structure has been observed.
Such suppression may be due to various interactions of electronic spins with their surroundings. In
electronically conducting vanadate glasses, one such interaction occurs via a so-called super exchange of an
electron, i.e, hopping of a mobile electron along a V
4+
--O--V
5+
bond. Thus the analysis of ESR with optical
absorption makes an impression that there is an increasing possibility of electronic conduction in the glasses
containing V
2
O
5
beyond 0.5mol%. From data V
1
sample value of A
║
and P is very high compared to other
samples.
FT-IR Studies:
The Fourier transform infrared (FT-IR) spectra of (20-x) K
2
O - 5CdO - 60B
2
O
3
- 15SiO
2
– xV
2
O
5
(where x = 0,
0.1 to 0.5 mol %) glasses recorded at room temperature have exhibited prominent bands in the region
4004000cm
-1
are shown in Fig 8, these bands are identified due to the characteristic vibrational bands of Boron
Oxygen-Boron, combined stretching vibrations of Silicate-Oxygen-Silicate and B-O-B , B-O stretching
vibrations of BO
4
/V = 0, stretching vibrations of B-O bands in BO
3
units, vibrations of BO
4
structural units
and due to the bending vibrations of B-O-B linkages respectively. stretching vibrations of B-O attached to
large segments of borate network. Close examination of IR spectra reveals that the vibrational intensity
increases gradually as x takes the values as 0.1 to 0.5 mol% of vanadium. A summary of (20-x) K
2
O - 5CdO -
60B
2
O
3
- 15SiO
2
– xV
2
O
5
(where x = 0, 0.1 to 0.5 mol %) glasses doped with different concentrations of V
2
O
5
is presented in Table 6.
FT-IR Studies:
The FT-IR study provides structural information when a thorough analysis of the data is carried out. Fourier
Transformation infrared spectroscopy (FT-IR) absorption spectra of (20-x) K
2
O - 5CdO - 60B
2
O
3
- 15SiO
2
-
xV
2
O
5
for Vanadium doped samples where x =0, 0.1 to 0.5% V
2
O
5
( KCBSi ) glass systems are recorded at
room temperature and the spectra are presented in Fig.8.
The infrared spectra of these glasses show absorption peaks. The peaks are sharp, medium and broad in nature.
The broad bands are exhibited in the oxide spectra are most probably due to the combination of high
degeneracy of vibration states, thermal broadening of the lattice dispersion band and mechanical scattering
from powder sample. The IR spectra of these glasses consist of broad and sharp bands in different regions
(400-4000cm
-1
) are shown in Fig.8 and are tabulated in Table 5. These bands are strongly influenced by
increasing substitution of vanadium. The position of the bands is shifted with the variation of transition metal
ion composition [31]. The vibrational spectra can readily used to identify the presence of defect groups or
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radiation-induced defects, within a glass. Infrared spectroscopy has also been used to identify low
concentration impurities such as water, hydroxyl ions etc in a glass [32].
The FT-IR spectrum of the glass system contains nine major bands presenting the wave number range of 715
cm
-1
, 835 cm
-1
, 922 cm
-1
, 1005 cm
-1
, 1097 cm
-1
, 1092 cm
-1
, 1242 cm
-1
, 1352 cm
-1
, 1471 cm
-1
. These bands are
characteristic vibrational bands of Boron-Oxygen-Boron, combined stretching vibrations of Silicate-Oxygen
Silicate and B-O-B , B-O stretching vibrations of BO
4
/V = 0, stretching vibrations of B-O bands in BO
3
units,
from pyro-orthoborate groups, B-O stretching vibrations attached to large segments of borate network,
stretching vibrations of B-O attached to large segments of borate network. Close examination of IR spectra
reveals that the vibrational intensity increases gradually as x takes the values as 0.1 to 0.5 mol% of vanadium.
At x = 0, in the absence of vanadium asymmetric vibrations Si-O-Si is observed. Thus the analysis of IR
spectra also supports the view point that as the concentration of V
2
O
5
is raised up to 0.5mol%, there is a
growing degree of disorder in the glass network. Hence there is a possibility for the formation of single Boron
– Oxygen – Vanadium frame work to the present glass system.
DISCUSSION
CONCLUSION
1. XRD confirms that all glass samples are amorphous in nature. The physical parameter, density shows a
small increase in its value by the introduction of V
2
O
5
into a KCBSi glasses.
2. The optical absorption study indicates the presence of vanadium predominantly in VO
2+
state which takes
modifier positions, if V
2
O
5
is present in lower Concentrations (up to 0.5mol %).
3. The ESR and Optical absorption spectra of V
2
O
5
doped in KCBSi glasses have been successfully
interpreted as the presence of six coordinate tetravalent vanadium existing as a vanadyl complex with a
tetragonally compressed octahedral site.
4. The optical band gap energies slightly decrease with the addition of vanadium content; It’s due to non-
bridging oxygens.
5. The spin-Hamiltonian parameters g and A are found to be independent of V
2
O
5
content. The
increase in
∆g
║ /
∆g
┴
value indicates the improved octahedral symmetry around VO
2+
ion.
6. The Infrared (IR) spectra of glasses in the present system reveals sharp and diffuse absorption peaks.
ACKNOWLEDGEMENTS
One of the authors Dr. Sandhya Cole (Letter No.39-498/2010(SR)) is thankful to UGC-MRP, New Delhi, for
providing financial assistance.
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INTERNATIONAL JOURNAL OF RESEARCH AND SCIENTIFIC INNOVATION (IJRSI)
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11. E. E. Assem, I. Elmehasseb, J Mater Sci. 46 (2011) 2071–2076.
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19. N. F. Mott, E. A. Davis, Electronic Processes in Non-Crystalline Materials, 2
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21. J. Tauc, Amorphous and Liquid Semiconductor, Plenum, New York, 1974. [20] V. P. Seth, S. Guptha, A.
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FIGURES
Fig 1: XRD pattern of pure sample of KCBSi glass system.
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Fig 2: XRD pattern of 0.1mol% VO
2+
ion doped sample of KCBSi glass system.
Wavelength(nm)
Fig 3: Optical absorption band spectrum of VO
2+
ion doped KCBSi glass system.
400
600
800
0.2
0.4
0.6
V
5
V
4
V
3
V
2
V
1
Optic
al
absor
ption(
abs.u
nits)
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Fig 4: Direct bands of VO
2+
ion doped KCBSi glass system.
Fig 5: Indirect bands of VO
2+
ion doped KCBSi glass system.
Fig 6: Urbach plots of VO
2+
ion doped KCBSi glass system.
3
0
V
1
V
2
V
3
V
4
V
5
Ln
(
)
hv(eV)
3.0
3.5
V
5
V
4
V
3
V
2
V
1
(
hv)
/
2
1
hv(eV)
2.4
2.8
3.2
0
1
2
V
1
v
5
v
4
v
3
v
2
(
hV)
2
h
(eV)
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TABLES
Glass
K
2
O mol%
CdO mol%
B2O3 mol%
SiO2
mol%
V2O5 mol%
V
O
20
5
60
15
-
V
1
19.9
5
60
15
0.1
V
2
19.8
5
60
15
0.2
V
3
19.7
5
60
15
0.3
V
4
19.6
5
60
15
0.4
V
5
19.5
5
60
15
0.5
Table1: Glass compositions of VO
2+
ion doped KCBSi glass system.
Glass
sample
Density
d
gm/cm3
(±0.004)
Avg.mol
Wt.(M)
Transition metal
ion conc. N
i
(10
19
ions/cm
3
)
±0.005
Inter ionic
distance r
i
(A˚)
±0.005
Polaron
radius r
p
(A˚)
±0.005
Optical
basicity
Vo
V1
V2
V3
V4
V5
2.4788
2.5571
2.5006
2.5244
2.5637
2.5551
80.17
80.44
80.26
80.304
80.35
80.3 9
-
1.91
3.75
5.68
7.68
9.57
-
37.38
29.86
26.01
23.51
21.86
-
15.06
12.034
10.48
9.47
8.81
0.4325
0.4328
0.4327
0.4325
0.4326
0.4326
Table 2:
Data of the Physical parameters of VO
2+
ion doped KCBSi glass system.
Glass sample
Cut off wave length
(mm)
2B
2g
→2B
1g
(nm)
2B2g→2Eg
(nm)
V1 V2
V3
V4
V5
321 330
342
348
349
456 431
450
430
458
627 605
607
604
633
INTERNATIONAL JOURNAL OF RESEARCH AND SCIENTIFIC INNOVATION (IJRSI)
ISSN No. 2321-2705 | DOI: 10.51244/IJRSI |Volume XII Issue X October 2025
Page 2000
www.rsisinternational.org
Table 3: Summary of the data on optical absorption spectra of VO
2+
ion doped KCBSi glass system.
Glass sample
Direct (Eopt) eV
Indirect (Eopt)
eV
Urbach Energy
( E) eV
V1
V2
V3
V4
V5
3.328
3.320
3.155
2.904
2.455
3.864
3.640
3.558
3.508
3.472
0.266
0.273
0.280
0.284
0.289
Table 4: Summary of data on direct, indirect, Urbach energy of VO
2+
ion doped KCBSi glass
system.
Glass
sample
g
║
g
┴
A║
10-4cm-1
A┴
10-4cm-1
∆g ║ /∆g┴
k
P
pure
V
1
V
2
V
3
V
4
V
5
-
1.948
1.972
1.964
1.991
1.931
-
1.992
1.999
1.976
1.997
1.969
-
241.9
197.2
172.0
182.0
175.9
-
72.6
58.2
66
72
52.9
-
5.71
11.1
0.3
0.67
2.02
-
0.637
0.633
0.83
0.85
0.66
-
-168
-154
-123
-129
-152
Table 5: Summary of the spin Hamiltonian parameters, molecular orbital coefficients of VO
2+
ion doped
KCBSi glass system.
V0
V1
V2
V3
V4
V5
Assignment
1471
1352
1242
1097
1005
922
1479
1350
1242
1003
833
922
1471
1354
1244
1099
1003
929
1469
1352
1242
1099
920
920
1469
1352
1244
1003
827
927
1479
1352
1240
1003
922
831
B—O stretched vibrations
attached to large to large
segments of borate network.
B-O stretched vibrations attached
to large segments of borate
network. Stretching vibrations of
B(III)-O-B(IV) units
INTERNATIONAL JOURNAL OF RESEARCH AND SCIENTIFIC INNOVATION (IJRSI)
ISSN No. 2321-2705 | DOI: 10.51244/IJRSI |Volume XII Issue X October 2025
Page 2001
www.rsisinternational.org
835
715
457
833
715
493
835
713
484
833
713
489
827
715
489
715
455
Stretching vibrations B-O Bands
in BO
3
units from
pyroorthoborate groups.
B-O stretching vibrations of BO
4
units/V= 0
Combined stretching vibrations
of Si-O-Si and B-O-B V-O-V
units bending B-O stretching
vibrations Asymmetric
vibrtations.
Si-O-Si
Table 6: Summary of the FT-IR study of VO
2+
ion doped KCBSi glass systems.
Glass
sample
g
║
g
┴
A║
10-4cm-1
A┴
10-4cm-1
∆g ║ /∆g┴
k
P
pure
V
1
V
2
V
3
V
4
V
5
-
1.948
1.972
1.964
1.991
1.931
-
1.992
1.999
1.976
1.997
1.969
-
241.9
197.2
172.0
182.0 175.9
-
72.6
58.2
66
72
52.9
-
5.71
11.1
0.3
0.67
2.02
-
0.637
0.633
0.83
0.85
0.66
-
-168
-154
-123
-129 -152
