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Received: 7 March 2002 / Received in final form: 26 May 2002 / Accepted: 7 June 2002
Published online: 12 September 2002 –
c EDP Sciences
Abstract. Binary tellurite glass systems of the forms TeO2 (100 − x)-xAn Om where An Om = La2 O3 or
V2 O5 and x = 5 to 20 for La2 O3 and 10 to 50 for V2 O5 were prepared. UV-spectra of these glasses were
recorded in the range of 200–700 nm at room temperature. The optical energy gaps Eoptical and Etail
have been calculated from the optical absorption edge. UV cut-off and IR cut-off have been measured.
Calculations of the oxide ion average polarizability (α2−
0 ) and optical basicity (Λ) have been done.
(a)
(b)
are most likely related to the structural rearrangement of Urbach rule [5] has been applied.
the glass and the relative concentrations of the various
αω = α0 exp(~ω/Et ) (2)
fundamental units. The absorption edge of each glass de-
pends on the type of network modifier. The absorption where (~ω) is the photon energy, α0 is a constant, ~ is
coefficient, α(ω), can be determined near the absorption Planck’s constant, ω is the angular frequency and Et is
edge using the formula: the Urbach energy which is interpreted as the width of the
tails of the localized states in the band gap associated with
the amorphous nature of the material. When the density
1 I0
αω = ln (1) of states is proportional to some power of energy (α~ω)1/2
d I
and the relation between absorption coefficient and pho-
ton energy gap is considered [6,7], this relation can be
where d is the thickness of the sample, I, I0 are the inten- re-written as follows:
sities of the incident and transmitted beams respectively.
For many oxide glasses and other amorphous materials (α~ω)1/2 = A(~ω − Eopt ) (3)
R. El-Mallawany et al.: UV-IR spectra of new tellurite glasses 167
TeO2 -La2 O3
95-5 335.5 3.51 5.38 0.1006
1/2
92.5-7.5 333 3.52 4.9 0.0987
90-10 331 3.54 4.825 0.0932
87.5-12.5 329 3.55 4.815 0.927
85-15 327 3.578 4.71 0.0916
82.5-17.5 325 3.59 4.785 0.0871
80-20 321 3.61 4.797 0.0826
TeO2 -V2 O5
90-10 413 2.67 3.039 0.2085
80-20 409 2.7 3.07 0.2089
75-25 400 2.76 2.87 0.245
(a)
70-30 392.5 2.79 2.84 0.2489
65-35 388 2.87 3.03 0.2214
60-40 385 2.93 3.22 0.2192
55-45 381 2.97 3.21 0.1801
50-50 377 2.03 3.38 0.1619
(a)
(b)
Fig. 3. (a) Variation of ln(α) with hw for lanthanum tellurite glasses. (b) Variation of ln(α) with (hw) for vanadate tellurite
glasses.
oxygen [8]. The doping with transition metal oxides de- photon energy ~ω as shown by equation (2). Figure 3(a, b)
crease the Eopt of (TeO2 ) which was 3.79 eV to the values shows the variation of ln(α) against ~ω for the present bi-
mentioned before and can be attributed to the increase nary glassy systems. The values of Eta in equation (2) are
of the non-bridging oxygen atoms. So, doping with La2 O3 calculated from the slopes of the linear regions of those
gave a lower concentration of non-bridging oxygen atoms curves. The values of Eta for each glasses system are given
than V2 O5 . The estimated value of Eopt for La2 O3 tel- in Table 1. It is clear that the values of Eta decrease from
lurite glasses are close to the reported values in [9]. For (0.1006 to 0.0826 eV) due to the modification of tellurite
many amorphous materials, Urbach [5] assumed that the glasses by (5 to 20 mol.% La2 O3 ) and from (0.2085 to
absorption coefficient α(ω) was an exponential function of 0.1619 eV) due to the modification of tellurite glasses by
R. El-Mallawany et al.: UV-IR spectra of new tellurite glasses 169
(10 to 50 mol.% V2 O5 ). These values are in the range of cies in the following manner are:
amorphous semiconductors between 0.046 and 0.66 (eV) s
νeq (TeO2 ) = 780 cm−1 , νax
ax
(TeO2 ) = 675 cm−1 ,
were reported by Davis and Mott [6]. It is clear from these
ax
values that the widths of the band tails of the localized νeq (TeO2 ) = 714 cm−1 , s
νax (TeO2 ) = 635 cm−1 .
states are found to depend upon the kind of the modifier. Also, for the binary vanadium tellurite glasses the major
Now in the present study, we calculate the electronic absorption bands of glasses at different composition are
polarizability and optical basicity values by using average summarized in Table 3. The region below 300 cm−1 for
electronegativity (χ2av ) for binary oxide glass V2 O5 -TeO2 all samples did not show any sensitivity, possibly due to
by using equations (4–6) and the results are listed in Ta- excessive noise and hence this region has been excluded
ble 2. from the discussion. The data exhibited a water band
at 3 400 cm−1 . The infrared spectra consist of a major
Xxf + Yxs
χ2av = (4) band in the 650–670 cm−1 , a shoulder at 770–790 cm−1 ,
X +Y a band at 980–1 000 cm−1 , a band at 600–580 cm−1 and a
α2−
0 = 3.319 − 0.3422χ2av (5) band at 480–500 cm−1 . The absorption band at 980 cm−1 ,
Λ = 0.04375 + 0.3097χ2av . (6) attributed to V=O stretching, shifted to 1000 cm−1 with
increase V2 O5 content. This data are closed with those
Both calculated values of electronic polarizability and op- in reference [16]. The band around 480–500 cm−1 is due
tical basicity values are collected in Table 2. Values elec- to Te-O-V stretching. Absorption at 650–670 cm−1 and
tronic polarizability and optical basicity of the present shoulder at 770–790 cm−1 both attributed to TeO3 trig-
V2 O5 -TeO2 are close to values of the electronic polar- onal pyramid was also observed. On the other hand, ab-
izability and optical basicity of V2 O5 -GeO2 [10]. While sorption at 600 cm−1 is due to the stretching vibration of
values electronic polarizability and optical basicity of the Te-Oax bond in the deformed TeO4 units. From these re-
present La2 O3 -TeO2 are higher than values of the elec- sults, we conclude that: infrared spectra of vanadate tellu-
tronic polarizability of La2 O3 -B2 O3 [10]. The optical ba- rite glasses indicate the transformation of the basic struc-
sicity of V2 O5 -TeO2 show large oxide ion polarizability tural unit of TeO4 to TeO3 with the addition of modifier.
between 2–3 Å−3 . Table 4 summarizes the IR absorption band position
for pure oxides TeO2 , V2 O5 and La2 O3 . By using the bond
length of Te-O, La-O and V-O of each molecule as in ref-
erence [17], we can calculate the theoretical wave number
3.2 IR of tellurite glass that present in these glasses. Table 5 summarizes the cal-
culated reduced mass of the cation-anion stretching force
constant by using the next equation
The room temperature IR spectra in the region 200–
4 000 cm−1 of tellurite glasses containing (5 to 20 mol.% (mR mO )
µ= (7)
La2 O3 ) are shown in Figure 4 and for binary vanadium tel- (mR + mO )
lurite glasses are shown in Figure 5. The major absorption
where µ is the reduced mass of the molecule R-O and mR ,
bands of glasses at different composition are summarized
mO are the atomic weight in kg of cation R and anion O
in Table 3. For the binary lanthanide tellurite glasses, the
respectively.
region below 300 cm−1 for all samples did not show any
sensitivity, possibly due to excessive noise and hence this f = 17/r3 (mdÅ−1 ) (8)
region has been excluded from the discussion. No water where f is the bending or stretching force constant and r
bond or –OH stretching modes are observed in the IR bond length of the cation-anion.
s
spectra of the crystalline TeO2 . But the binary samples ex-
hibited a water band at 3 400 cm−1 and an –OH stretching 1 1 f
at 2 920 cm−1 . The main absorption bands are at frequen- ν̃ = =
λ 2πc µ
(9)
cies around 610–670 cm−1 , a shoulder at 580–630 cm−1 ,
a small bands at 560–610 cm−1 and a shoulder at 750– where ν̃ is a wave number in cm−1 , c is the speed of light,
780 cm−1 posses deformed TeO4 groups as mentioned by f is the force constant of the bond, and µ is the reduced
one of the authors [11] and also by Dimitriev [12]. A new mass of the molecule R-O.
shoulder at 580–630 cm−1 was attributed to La-O stretch- Substituting by the reduced mass of different cations
ing vibration as measured by Bahgat [13]. A small band is in equation (9), values of the theoretical wave number can
observed in the spectra at 560–610 cm−1 , which may be be obtained as collected in Table 5. According to equa-
attributed to Te-O bond vibrations, where the oxygen an- tion (9), the calculated wave number from Table 5 is in
ions are considered non-bridging (NBO) as measured by harmony with the values of the experimental values as in
Shaisha [14]. Table 4. Also, from equation (9) it si clear that the wave
By analogy with the crystalline tellurites [15,16] it may number is inversely proportional to the value of reduced
be accepted that with the introduction of other oxides in mass. So quantitatively it is clear that, because La has a
tellurite glasses, part of the TeO4 groups are transformed higher mass than vanadium, the binary lanthanum tellu-
into TeO3 . Tellurites containing TeO4 groups have four rite glass have a lower IR wave number than vanadium
s ax ax s
band νeq , νeq , νax and νax modes. The stretching frequen- tellurite glasses.
170 The European Physical Journal Applied Physics
Table 2. Average electronegativity (χ2av ), optical basicity Λ(χ2av ), oxide ion polarizability (α2−
0 )(χ2av ) values of binary oxide
glass V2 O5 -TeO2 and La2 O3 -TeO2 .
Table 3. The experimental IR absorption band position for binary lanthanum tellurite and vanadium tellurite glasses.
Table 5. The theoretical IR band position of the tellurium, lanthanum and vanadium oxides.
to 2.324 × 10−24 cm−3 ) with increasing La2 O3 content 4. R. El-Mallawany, A. Abdel-Kader, M. El-Hawary, N.
from (5 to 20 mol.%); El-Khoshkhany, to be published in Eur. Phys. J. AP
• while (Λ) is decreased from (0.971 to 0.96) with in- 5. F. Urbach, Phys. Rev. 92, 1324 (1953)
creasing V2 O5 content from (10 to 50 mol.%) and from 6. E. Davis, N. Mott, Philos. Mag. 22, 903 (1970)
(0.977 to 0.945) with increasing La2 O3 content from 7. N.F. Mott, E.A. Davis, Electronic Processes in Non-
(10 to 50 mol.%). crystalline Materials (Oxford Univ. Press, 1971)
8. S. Neov, I. Gerassimova, K. Krezhov, B. Sidzhimov, V.
The IR spectra the ordinary band for pure TeO2 at Kozhukharov, Phys. Stat. Sol. A 47, 743 (1987)
640 cm−1 shifts from (610 to 670 cm−1 ) with increasing 9. K. Al-Ani, C.A. Hogarth, R. El-Mallawany, J. Mater. Sci.
La2 O3 content from (5 to 20 mol.%) and from (650 to 20, 667 (1985)
670 cm−1 ) with increasing V2 O5 content from (10 to 10. R.R. Reddy, Y.N. Ahammed, P.A. Azeem, K.R. Gopal,
50 mol.%). The previous qualitative description will be T.V.R. Rao, J. Non-Cryst. Solids 286, 169 (2001)
analyzed quantitatively according to each stretching force 11. R. El-Mallawany, Infrared Phys. 29, 281 (1989)
constant of bond F , and reduced mass of the cation-anion. 12. Y. Dimitriev, V. Dimitrov, M. Arnaudov, J. Mater. Sci.
A strong correlation between the obtained experimental 18, 1353 (1983)
values of wave number and calculated wave number has 13. A.A. Bahgat, E.E. Shaisha, A.I. Sabry, J. Mater. Sci. 22,
been found. 1323 (1987)
14. E.E. Shaisha, A.A. Bahgat, A.I. Sabry, N.A. Eissa, Phys.
Chem. Glasses 26, 91 (1985)
15. M. Arnaudov, V. Dimitrov, Y. Dimitriev, L. Markova,
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