Characterization of Mn2+ Ion Doped KCdBSi (K2O - CdO - B2O3 - SiO2) Glasses On The Basis of Optical and Physical Properties
Characterization of Mn2+ Ion Doped KCdBSi (K2O - CdO - B2O3 - SiO2) Glasses On The Basis of Optical and Physical Properties
Characterization of Mn2+ Ion Doped KCdBSi (K2O - CdO - B2O3 - SiO2) Glasses On The Basis of Optical and Physical Properties
=
A =
(1)
where n is the total number of cations present, Z
i
is the
oxidation number of the i
th
cation, r
i
is the ratio of number of
i
th
cations to the number of oxides present and
i
is the
basicity moderating parameter where n is the total number of
cations present, Z
i
is the oxidation number of the i
th
cation, r
i
is the ratio of number of i
th
cations to the number of oxides
present and
i
is the basicity moderating parameter of the i
th
cation. of the i
th
cation.
i
can be calculated from the
following equation.
( ) 1.36 0.26
i i
x =
(2)
where x
i
is the Pauling electronegativity of the cation. The
optical basicity can be used to classify the covalent/ionic
character of the glasses since an increasing
th
indicates
decreasing covalence. The theoretical values of optical
basicity (
th
) were calculated for all the glass samples and
are presented in Table 2.
3.3 Optical Absorption Studies
The UV- visible absorption spectra of manganese doped
KCdBSi glass samples in the wavelength region 350-900 nm
is shown in Fig.1. Its observed that, two bands are formed at
720 and 450 nm. The bands observed at 720 and 450 nm are
assigned to the transitions
6
A
1g
(S)
4
T
1g
(G) and
6
A
1g
(S)
4
T
2g
(G). The analysis shows that manganese ions exist
mainly in Mn
2+
state, occupy tetrahedral positions and
increase the insulating strength of the glass if MnO
2
is
present in smaller concentrations. It shows a strong broad
band centered at around 450 nm [3], [4, [5], and another
weak band at 720nm. In general the optical spectra have
been analysed in the framework of crystal field theory [6],
[7]. The excited quartet states
4
G,
4
P,
4
D and
4
F of Mn
2+
ions
in the octahedral crystal field are situated above the ground
6
S state and the trigonal crystal field splits the four levels
into ten sublevels. Hence, all the transitions from the ground
sextet
6
S to the excited levels are spin-forbidden, the
intensity of optical absorption lines of Mn
2+
are weak and in
addition, the Mn
2+
ion had a 3d
5
configuration. The broad
absorption band with the maximum at around 450 nm is
assigned to spin-allowed
5
E
g
5
T
2g
transition of Mn
3+
(3d
4
,
5
D
0
) ions in the octahedral sites of host glass. Furthermore,
this band was asymmetric, indicating that the octahedral
ligand field had suffered a tetrahedral deformation by the
J ahn-Teller effect. The most common manganese ions found
in oxide glass are Mn
2+
.
The most important information resulting from the analysis
of optical spectra is the increase of absorption band intensity
depends on the host glass basicity (Table 2). This concludes
that the structural factor plays an important role in the
formation of valence and coordination state of manganese
ions in host glass system.
Table 2: Physical parameters of Mn
2+
ion in KCdBSi glass
system
Density 2.478 2.584 2.587 2.57 2.58 2.548
Manganese ion
concentratio(N
i
)
(10
19
ions/cm
3
) (0.015)
- 1.88 3.88 5.51 7.47 9.71
Interionic distance (r
i
) A
0
(0.005)
- 37.6 29.58 26.27 23.74 21.76
Polaron radius A
0
(0.005) - 15.15 11.92 10.58 9.56 8.77
Optical basicity - 0.432 0.432 0.432 0.432 0.432
Avg.mol Wt.(M) 80.17 80.12 80.07 80.01 79.97 79.96
Figure 1: Optical absorption bands ofMn
2+
ion doped
KCBSi glass system.
3.4. Optical band gap (E
g
) and Urbach energy (E)
The study of optical absorption and particularly the
absorption edge is a useful method for the investigation of
optically induced transitions and electronic band structure in
both crystalline and non-crystalline materials. The principle
of this technique is that a photon with energy greater than the
band gap energy will be absorbed [8]. It is calculated by
extrapolating the linear region of the graph towards X-axis.
The optical band gap of all the glass samples were obtained
from their ultraviolet absorption edges by plotting(h)
2
,
(h)