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Optical characterization of Mn2+: Li2O-K2O-CdO-B2O3 glass system: Absorption edge,

optical band gap, optical polarizability and optical basicity

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2009 IOP Conf. Ser.: Mater. Sci. Eng. 2 012040

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International Seminar on Science and Technology of Glass Materials (ISSTGM-2009) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 2 (2009) 012040 doi:10.1088/1757-899X/2/1/012040

Optical characterization of Mn2+: Li2O-K2O-CdO-B2O3 glass

system: Absorption edge, optical band gap, optical
polarizability and optical basicity

G. Padmaja and P. Kistaiah

Department of Physics, University College of Science, Osmania University,
Hyderabad 500 007

E-mail: pkistaiah@yahoo.com

Abstract: Mixed alkali borate glasses (30-x)Li2O-xK2O-10CdO-59B2O3 (0 x 30) implanted

with 1mol% manganese ions (LKCBM) were prepared from the melts. These glasses were
characterized using X-ray diffraction (XRD), differential scanning calorimetry (DSC) and
density measurements. Optical absorption studies were carried out as a function of alkali
content to look for ‘Mixed Alkali Effect’ (MAE) on the spectral properties of these glasses.
The optical absorption spectra of LKCBM exhibit a broad band around 21000 cm-1 which has
been assigned to the transition 6A1g(S) 4T1g(G). From the study of ultraviolet absorption
edge, the optical band gap energies and Urbach energies were evaluated. The average
electronic polarizability of the oxide ion ( O2-), Optical basicity ( ) and Yamasita-Kurosawas’s
interaction parameter (A) were also evaluated for all the glasses. In the present investigation
many of the physical parameters like glass transition temperature, density, optical band gap and
optical basicity vary non-linearly with alkali concentration (x) indicating MAE.

1. Introduction
Mixed alkali borate glasses are particularly interesting model systems as they exhibit a variety of
structural changes with alkali content. Many physical properties of oxide glasses show non-linear
behavior exhibiting a minimum or maximum, as a function of alkali content, if one alkali ion is
gradually replaced by another alkali ion, keeping the total alkali content constant. This behavior is
called the ‘Mixed Alkali Effect’ (MAE) and is observed for properties associated with alkali ion
movement such as electrical conductivity, dielectric relaxation and internal friction [1]. The mixed
alkali effect is one of the classic anomalies of glass science [2, 3] and has been the subject of study
over the years [4, 5]. The study of optical absorption of transition metal (TM) ion doped glasses is an
attractive area of research both from the fundamental and technological view point [6-10]. The TM
ions can be used to probe the structure and properties of glasses, since their outer d-electron orbital
functions have rather broad radial distributions and their response to surrounding cations is very


c 2009 IOP Publishing Ltd 1
International Seminar on Science and Technology of Glass Materials (ISSTGM-2009) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 2 (2009) 012040 doi:10.1088/1757-899X/2/1/012040

sensitive [11-13]. It is well known that the optical gap of amorphous glassy materials strongly depends
on their composition. The present investigation is intended to have a clear understanding over the
influence of manganese ion doping on the optical properties and structure of LKCBM glasses.

2. Experimental
Mixed Alkali borate glasses having a general formula (30 – x) Li2O – x K2O – 10CdO – 59B2O3 doped
with 1 mol% manganese were prepared through standard melt - quench technique. XRD, DSC, density
and molar volume measurements were done to characterize the sample. The optical absorption spectra
of the glass samples were recorded at room temperature using Shimadzu 3100 UV - VIS - NIR
spectrometer in the wavelength range of 200 - 800 nm.

3. Results and Discussion

3.1. XRD, DSC, density and molar volume

The X- ray diffraction pattern of an amorphous material is distinctly different from that of crystalline
material and consists of a few broad diffuse haloes rather than sharp rings. XRD patterns of all these
samples depict a diffused peak confirming the amorphous phase (vitreous state) of the glasses.
Differential scanning calorimetry (DSC) is used to characterize the glasses and to determine glass
transition temperature (Tg). The DSC patterns of all the samples are shown in figure.1a. Figure 1b
shows the composition dependence of glass transition temperature and figure.1c shows the
composition dependence of density and molar volume. Glass transition temperature and Density
values vary nonlinearly with the alkali concentration depicting the mixed alkali effect.

495 C
-3
a b
2.9
-4
480 28
Density ( g-cm-3)

2.8
Vm (g/mole)
Heat flow (mW)

-5
Tg (0C)

-6 465 2.7
24
-7
2.6
x=0LKCBM 450
x=10LKCBM
-8 x=15LKCBM

(909
x=20LKCBM
x=30LKCBM
2.5 20
-9
400 425 450 475 500 525 435 0 5 10 15 20 25 30
0 5 10 15 20 25 30 Concentration, x ( mol%)
Temperature (K )
Concentration, x (mol%)

(a) (b) (c)

Figure 1. (a) DSC patterns of LKCBM glasses (b) compositional dependence of Tg and (c)
concentration dependence of density and molar volume of LKCBM glasses

3.2. Optical absorption studies

Figure 2a shows the optical absorption spectra of all the samples of LKCBM glasses in the wavelength
region of 200 – 800 nm. The optical spectra depict one single Gaussian peak around 21,000 cm-1 and
the position of this peak suggests that Mn ion in this glass network is in the form of Mn+2 in a distorted
octahedral site. The absorption edge moves to lower wavelengths with the increase of x values. In the
present case, the band observed around ~ 21,000 cm-1 can be assigned to the transition 6A1g(S) – 4T1g
(G). The band position measured for different mixed alkali LKCBM glasses corresponding to 6A1g(S)
– 4T1g (G) transition is presented in Table 1. From the table, it is observed that the band position shifts

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International Seminar on Science and Technology of Glass Materials (ISSTGM-2009) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 2 (2009) 012040 doi:10.1088/1757-899X/2/1/012040

clearly to higher energy side up to x = 15 reaching a maximum and there after shifts to lower energy
side showing the MAE. Similar variations were observed in some mixed alkali borate glasses [14].

6 LKCBM
LKCBM 8
Optical absorbance (arb. units)

0 LKCBM
10 LKCBM
Optical absorbance (arb. units)

15 LKCBM
4 x=30
30 LKCBM
20 LKCBM
4 x=30
102

)
-1
2

(cm
x=20 x=20

x=15

α
x=15

0 x=10 0
x=10
x=0
400 500 600 700 800 x=0

Wave length (nm) 325 350 375 400

3.2 3.4 3.6 3.8
Wave length (nm)
hν (eV)
(a) (b) (c)

Figure. 2 Optical absorption with wavelength, (b) absorption edge plots with wavelength and (c) α vs
hν plots of LKCBM glass specimens
It can be seen from figure. 2b that the optical absorption edge is not sharply defined unlike in the
case of crystalline semiconductors [15]. It is also seen clearly from the figure that the position of the
fundamental absorption edge shifts to longer wavelengths as the content of K2O increases in the glass.
The absorption co-efficient, ( ), near the edge of each curve ( UV region) shown in figure. 2c was
determined from the relation,
1 I A
α (ν ) = log 0 = 2.303 (1)
d I d
where d is the thickness of each sample, A is the absorbance, and I0 and I are the intensities of the
incident and transmitted beams, respectively. Using the random-phase approximation, Tauc et.al [16]
defined an optical band gap (Egopt) for indirect transitions of many amorphous semiconductors [15],
B ( hν − E g ) 2
opt

α (ν ) = (2)
hν
where B is a constant, Egopt is the optical band gap and h is the photon energy of the incident
radiation. The values of optical band gap energies were obtained by extrapolation of the linear region
of the plots ( h )1/2 vs h to ( h )1/2 = 0. Thus obtained values are given in table 1. The non-linear
variation of Egopt with concentration (x) is an indication of the presence of MAE in these glasses.
It is well known that the shape of the fundamental absorption edge in the exponential region can
yield information on the disorder effects [17]. With the energy for the incident photon less than the
band gap, the increase in absorption co-efficient is followed with an exponential decay of density of
localized states into the gap [18] and the absorption edge is known as the Urbach edge. The can be
estimated using the Urbach equation given by [19, 20].
hν
α (ν ) = α 0 exp (3)
∆E
where 0 is a constant, E is the width of the band tail of localized electron states in the normally
forbidden band gap and is the frequency of radiation. The linear region of plot between ln( ) and
h was fitted to a straight line and the reciprocal of the slope gives values. The values of thus
determined are presented in table.1. The non-linear variation of with composition in the glass
system is an indication of the presence of MAE in these systems.

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International Seminar on Science and Technology of Glass Materials (ISSTGM-2009) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 2 (2009) 012040 doi:10.1088/1757-899X/2/1/012040

According to Dimistrov and Sakka [21], the polarizability of a simple oxide of the type ApOq is
given by,
Eg
α i (N O )
Vm −1 (4)
α O (E g ) =
2− 1− − 2−
2.52 20

2-
where Vm is the molar volume, i denotes the molar cation polarizability and NO denotes the
number of oxide ions in the chemical formula. The values of cation polarizabilities are taken from
[21] and are treated as constants equal to the free ion values assuming that even though a large size, a
cation is likely to be particularly polarized because the cationic charge will tend to hold on to the
cationic electrons [22]. The calculated values of α O-2 (Eg) are given in Table.1. According to Duffy
[23, 24] an intrinsic relation exists between electronic polarizability of the oxide ions α O-2 and optical
basicity of the oxide medium , as given by,
1
Λ ( E g ) = 1.67 1 − (5)
α O 2−

The values of (Eg) estimated for the above glasses are given in Table.1. On the other hand, the
theoretical optical basicity ( th) for the present glasses can be calculated using the following equation
[25],
Λ th = X An Bm Λ An Bm (6)
where X An Bm is the mol% and Λ An Bm is the optical basicity of the respective individual oxide with
chemical formula AnBm. The values of are taken from [26]. The following expression is used for
the calculation of the interaction parameter A for a metal / non-metal oxygen ionic pair;
[α f − − α O 2 − ]
A= (7)
2[α f + + α f − ][α f + + α O 2 − ]
where α f+ and α f- are the electronic polarizabilities of the positive and negative oxide ions in free-
state, while α O2- is the polarizability in the crystalline state under consideration. The obtained values
of A are given in table 1.

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International Seminar on Science and Technology of Glass Materials (ISSTGM-2009) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 2 (2009) 012040 doi:10.1088/1757-899X/2/1/012040

Table 1. Optical absorption edge, peak position, optical band gap, Urbach energy, optical basicity
(theoretical and experimental), oxide polarizability and interaction parameter values of LKCBM
glasses

Sample Code Absor Wavele Wave Band ∆E Optic Optic Oxide Intera
ption ngth ( number gap (eV) al al polariza ction
edge nm ) (cm1) Eopt(ind)( basici basici bility param
(nm) 6A1g(S) – eV) ty( t ty( ( ( O2-) eter
4T1g (G) h) Eg)) (A3)

Mn –Series

0LKCBM 376 478 20,920 3.12 0.862 0.511 0.648 1.635 0.036

10LKCBM 373 472 21,186 3.28 0.892 0.516 0.752 1.820 0.028

15LKCBM 372 465 21,505 3.07 0.598 0.518 0.819 1.962 0.025

20LKCBM 371 490 20,408 3.42 0.414 0.520 0.838 2.008 0.025

30LKCBM 370 473 21,141 3.19 1.086 0.524 0.882 2.121 0.023

4. Conclusions
Multi-component glass system with composition, (30-x) Li2O-xK2O-10CdO-59B2O3 (0 x 30) doped
with 1mol% of MnO2 was prepared through melt quench technique and confirmed the glass transition
and amorphous nature through XRD, DSC measurements. Optical absorption studies were done to
understand the absorption edge and related physical parameters. Evaluated optical parameters show
nonlinear variation with the alkali concentration (x) manifesting the mixed alkali effect in this system.
This is a significant results pertaining to the multi-component glass system and first of its kind in this
area. Although large number of theories is proposed to explain MAE in transport properties of several
glass systems, there is no single theory to account the MAE observed in their optical properties.

Acknowledgements

Ms G Padmaja thanks UGC for financial assistance through merit fellowship and the authors thank
UGC DAE CSR, Indore center for providing experimental facilities.

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International Seminar on Science and Technology of Glass Materials (ISSTGM-2009) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 2 (2009) 012040 doi:10.1088/1757-899X/2/1/012040

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