Accepted Manuscript

Optical and spectroscopic investigation on Calcium Borotellurite glass system

E.C. Paz, T.A. Lodi, B.R.A. Gomes, G.H.A. Melo, F. Pedrochi, A. Steimacher

PII: S1293-2558(16)30037-1
DOI: 10.1016/j.solidstatesciences.2016.02.014
Reference: SSSCIE 5292

To appear in: Solid State Sciences

Received Date: 14 November 2015

Revised Date: 24 February 2016
Accepted Date: 29 February 2016

Please cite this article as: E.C. Paz, T.A. Lodi, B.R.A Gomes, G.H.A. Melo, F. Pedrochi, A. Steimacher,
Optical and spectroscopic investigation on Calcium Borotellurite glass system, Solid State Sciences
(2016), doi: 10.1016/j.solidstatesciences.2016.02.014.

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 ACCEPTED MANUSCRIPT

TeO2
0 Glass 2.5
100 CBT20

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CBT25
20 CBT30
80 2.0
CBT35

(Aehv)1/2 (cm-1 eV)1/2

RI
CBT40
CBT50

2
F
Ca 40
60

Te
1.5

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O+

O2
Ca

60
40
1.0

U
80

AN
20
0.5
100
0

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CaO+CaF2 0 20 40 60 80 100 2.8 2.9 3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4.0
B2O3
B2O3 hv (eV)

D
TE
C EP
AC
 Optical and spectroscopic investigation on
ACCEPTED MANUSCRIPT
Calcium Borotellurite glass system

E. C. Paza,b, T. A. Lodia, Gomes, B. R. Aa, G. H. A. Meloa,c, F. Pedrochia, A. Steimachera,*

a b c
CCSST – UFMA, Imperatriz, MA, Brazil. IFMA, Açailândia, MA, Brazil. IFMA, Imperatriz, MA, Brazil.
*Corresponding author e-mail: steimacher@hotmail.com

HIGHLIGHTS

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• Optical and spectroscopy properties of glasses on Calcium Borotellurite system were studied
• The results suggest that TeO2 addition increases NBO in the structure of CaBTe glass.
•

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TeO2 addition shifts the absorption edge to longer wavelengths and reduce optical band gap
• The density and the refractive index increases with TeO2 content

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• The optical basicity and the electronic polarizability increase with TeO2 content

ABSTRACT
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In this work, the glass formation in Calcium Borotellurite (CBTx) system and their optical properties

were studied. Six glass samples were prepared by melt-quenching technique and the samples obtained
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are transparent, lightly yellowish, without any visible crystallites. The results showed that TeO2 addition
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increases the density, the electronic polarizability and, consequently, the refractive index. The increase
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of electronic polarizability and optical basicity suggest that TeO2 addition increases the non-bridging

oxygen (NBO) concentration. The increase of TeO2 shifts the band edge to longer wavelength owing to
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increase in non-bridging oxygen ions, resulting in a linear decrease of optical energy gap. The addition

of TeO2 increases the temperature coefficient of the optical path length (dS/dT) in room temperature,
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which are comparable to phosphate and lower than Low Silica Calcium Alumino Silicate (LSCAS)
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glasses. The values of dS/dT present an increase as a function of temperature for all the samples

measured. The results suggest that CBTx is a good candidate for rare-earth doping and several optical

applications.

Keywords:

Borotellurite glasses; Optical energy gap; Non-bridging oxygens; Optical basicity; IR

1. Introduction ACCEPTED MANUSCRIPT

Optical and spectroscopic properties of tellurite, borate and borotellurite glasses have been

widely investigated for their scientific interest and practical applications [1–5]. Borate glasses are

known for having high thermal stability, high chemical durability, good solubility of rare-earth ion and

also for their ease of synthesis [4,6,7]. Tellurite glasses have lower phonon energy if compared to

phosphates and silicates glasses, large infrared transparency, good thermal and mechanical stability,

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good chemical durability, low melting temperature, high refractive index, high dielectric constant and

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suitability as host matrix to dopant action [2–5,7–12]. These features make tellurite glasses promising

candidates for photonic applications, such as fiber in optical communication, window materials and up-

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conversion laser. The addition of tellurium oxide to another glass former, such as B2O3, can lead to the

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production of interesting structural units that affect the physical properties of the glass network [13,14].
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The presence of TeO2 in alkali borate glasses decreases their hygroscopic nature, reduces their phonon

energy, increases their refraction index and their IR transmission [14–16]; that makes borotellurite
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glasses candidates for several optical and photonic applications. In order to improve those qualities,

calcium oxide and calcium fluoride were used as glass modifiers due to their excellent contributions to
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the glassy formation. Calcium oxide can form promising luminescent host matrix, in which Ca2+ cation
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can be replaced by rare earth ions [17]. Furthermore, CaO addition increases the glass resistance to

humidity [18] as well as the thermal stability of the glass, as could be observed when other alkaline
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earth was added to tellurite glasses [19]. Besides that, the addition of fluorine compounds, such as CaF2,
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decreases the phonon energy of pure oxide glasses and can improve emission and lifetime of rare earth
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doped glasses [20,21].

In this work, we present a study of glass-forming ability of Calcium Borotellurite (CBTx)

system, with different concentrations of TeO2. Besides that, we present an investigation of the optical

and spectroscopy properties in order to study the effect of glass former TeO2 on CBTx glasses. We

expect that the glass studied in the CBTx system can be used for optical fiber draw, optical amplifiers or

other photonic devices.

2. Experimental procedure
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2.1 Sample Preparation

The synthesis of Calcium BoroTellurite glasses with composition 10CaF2-(30-0.4x)CaO-(60-

0.6x)B2O3-xTeO2 (x=20, 25, 30, 35, 40 and 50 wt%), referred as CBTx, was carried out by melt

quenching conventional technique. The starting materials, chemical reagents of analytical grade (purity

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98-100 %), were melted at ~950° C in platinum crucibles, under air atmosphere. The melt was poured

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into a preheated stainless steel mold at ~500°C and annealed for 4 h to release its inner stress.

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2.2. Characterization

The refractive index was measured at room temperature using the Brewster’s angle method,

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using 2mW He–Ne(632.8nm) laser.[22]

The optical absorption spectra for all the glass samples was recorded using Schimadzu
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Spectrophotometer UV/VIS /NIR/UV-3600 in the wavelength region 180–3300nm.

To determine the thermal coefficient of the optical path length change (dS/dT = 1/L(ds/dT)), an
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optical interferometric technique was used. The experimental setup and the theory for this method is
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described in details in Ref.[23]. The dS/dT value measured with this technique is given by (dS/dT) =

n
 + (dn/dT), where n is the refractive index,
 is the linear thermal expansion coefficient, and
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(dn/dT) is the thermal coefficient of the refractive index [23].

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3. Results and discussion
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Fig. 1 shows the batch of the samples prepared in this study. The samples obtained, with TeO2

varying from 20 to 50 wt%, present good optical quality under visual inspection, without any visible

crystallites or devitrification. The pale yellow color of the samples increases lightly with TeO2 content.

The concentration of TeO2 up to 50 wt% was verified without any effect in the glass formation

field. All the samples prepared in that system has no crystalline phase, as confirmed by XRD (not

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shown). The phase diagram (wt%) of the obtained glass samples are presented in Fig. 2.

Fig. 3 presents the refractive index n and the volumetric density as a function of TeO2 content,

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which increases linearly with TeO2 increase.

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The density of the CBTx glass samples increases from 2.97 g cm-3 to 3.58 g cm-3, which

corresponds to an increase of ~21%. That increase occurs mainly due to the substitution of boron and

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calcium oxide by tellurium oxide, which has a higher molecular weight than B2O3 and CaO, resulting in
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a higher net weight of the glass structure [15,24]. The values of refractive index increase from 1.62 to

1.71, for CBT20 and CBT50, respectively. High values of refractive index are desirable for fiber optic
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design and waveguide applications. The increase of refractive index with TeO2 content is mainly related
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to the increase of volumetric density [25] and the electronic polarizability [26]. The electronic
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polarizability of the oxide ion (αO2-) is one of the most important properties which govern the non-

linearity optical (NLO) response of the material [27].

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The average electronic polarizability (αm), which relates molar refraction (Rm) to refractive

index and molar volume of a glass, was calculated using the The Lorentz–Lorenz equation [28]:
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3R  (1)
α =
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4πN

Theoretical optical basicity (OB) for the glass system under study was calculated by using

basicities assigned to the individual oxides on the basis of the following equation proposed by Duffy and

Ingram [29,30]

Λ  = X Λ + X Λ  + X Λ  … X Λ  (2)
where,  ,  ,  …  ) are the equivalent fractions of different oxides, i.e. the proportion of the oxide
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atom that contribute to the glass system and  ,  ,  …  are optical basicity values assigned to the

constituent oxides, as found in Ref. [31].

The average electronic polarizability and optical basicity for the glass system under study are

presented in Fig. 4.

The concept of optical basicity was defined by Duffy et al. and it is related to the ability of

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oxygen to donate negative charges [29]. The total basicity of a glass containing both bridging and non-

bridging oxigens (NBO) depends on the relative proportion of these two types of linkages. The increase

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of this value (as observed in Fig. 4) with the addition of TeO2 means that the structure is more

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depolymerized, i.e. the number of NBO ions in the network increased. Optical basicity also depends on

the glass constitution (formers and modifiers) and the electronegativity of the cations in the glass

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network. The evaluation of this OB values also can be useful to study changes in coordination number,
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as observed in tellurite glasses by Moraes[32]. OB is inversely proportional to the electronegativity

between bonded atoms in the oxide[30]. It is known that valence and conduction bands essentially
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originate from O2− orbitals and cations. Thus, the promotion of an electron from valence band to
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conduction band by the interaction with an absorbed photon is analogous to electron transfer between
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ions. Consequently, the difference in the electronegativity of the O2− ions and cations of the glass is

related to the band gap of the matrix. As follows, if the OB increases, a decrease in the band gap Eopt
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values is expected. Because of these reasons, the optical basicity is an important parameter to study

physical aspects, such as refractivity, network coordination number changes, chemical durability, UV
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transparency, etc. According to Duffy[33], the increase of optical basicity causes an increase in the
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oxygen polarizability, which is interpreted in terms of the less controlled electron charge clouds being

unable to oscillate at higher ultraviolet frequencies, degrading ultraviolet transmission. The increase in

the polarizability of oxygen ions, as observed in Fig. 4, is also an indication that the concentration of

NBOs increases.

Fig. 5 shows the optical absorption spectra of the samples as functions of TeO2 content. Fig.

5(a) presents the absorption spectra for the CBT20 sample. The transmittance window from 350 to 2200

nm makes the CBTx glasses suitable for several rare earth doping. Erbium doped glasses, for instance,
have attracted attention due to the infrared emission at 1530 nm through the 4I13/2→ 4I15/2 transition,
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which exhibits extensive applications in telecommunications as doped fiber amplifier [34]. The

absorption band around 2400 nm is assigned to OH groups in the glass structure in several oxide glasses

[35][36]. The fundamental absorption edge of the absorption spectra changes with the increase in TeO2

content due to the structural rearrangement in the glass structure. The absence of sharp absorption edge

is characteristic of the glassy state of the samples. We note that the UV optical absorption shifts toward

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higher wavelengths with TeO2 content, as predicted by optical basicity and electronic polarizability

results. Variations of glass basicity are also related to the electronegativity of oxygen and the optical

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band gap (Eopt). The increase of glass basicity results in a decrease of Eopt, reducing the UV

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transmission. According to Stevels [37], the shift of band edge to higher wavelengths occur due to an

increase of non-bridging oxygens (NBO), which increase with TeO2 content. The increase of NBO

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induces a higher depolymerization of CBTx glasses network, leading to a decrease in optical energy
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gap.

The band gap energy values for all the samples were estimated by the following equation, which
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does not consider the nature of the band gap[38,39]:

 ℎ ! ∝ ℎ − $%& !'
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(3)
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in which  is the optical absorption coefficient, presented in Fig. 5, ℎ is the photon energy, and Eopt is

the band gap energy. The parameter m depends on the band gap characteristic as m= ½ for direct
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allowed transition, m= 3/2 for direct forbidden transition, m=2 for indirect allowed transition, and m=3

for indirect forbidden transition. For CBTx glasses the best plots were obtained for m=2. Tauc’s plot of
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(
 ℎ !  as a function of photon energy (ℎ ) for the indirect allowed transitions of the CBTx samples
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are shown in Fig. 6 (left). This indicates that indirect allowed transition is responsible for shifting the

absorption edge to longer wavelength, as observed in the spectra of Fig. 5. The energy band gap values

of the samples were obtained by extrapolating the fittings of Fig. 6 (left), with  ℎ !/ = 0. The band

gap values, obtained by extrapolation, as functions of TeO2 content are shown in Fig. 6 (right).

From Fig. 6 (right) one can see that when TeO2 content increases, the band gap energy values

decrease linearly, varying from 3.62 to 3.18 eV, for CBT20 and CBT50, respectively. These values are

comparable to other borotellurite glass systems [38][40].

 The decrease of band gap values with the increase in TeO2 content occurs mainly due to the
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formation of greater number of NBOs, which take place in the glass network. NBOs are more easily

excited than the bridging oxygen (BO), which changes the absorption characteristics [33,37,38].

The temperature coefficient of the optical path length (dS/dT) is one of the most important

thermo-optical parameters in the design of optical systems, such as lasers, optical fiber for

telecommunications and also in the development of optical glasses. dS/dT carries information about the

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thermal expansion coefficient (cte), electronic polarization and refractive index changes, which are

dependent on temperature. Particularly, in solid state laser using rods as active medium, this parameter

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is of importance, since it describes the distortion of the laser beam induced by a temperature change in

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the medium.

The temperature coefficient of optical path length is obtained from Eq. (4)

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,- ,0 1 ,4 (4)
+ / = + / + 0
 = + /
,. ,. 23 ,.
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in which c6 = 1(L 9dL(dT< is the linear thermal expansion coefficient, m are multiples of wavelength,
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which correspond to the difference between the two optical path lengths (∆>! of the beams reflected in

the sample surfaces and the dS(dT = 1(L 9ds(dT<, which s is the optical path > = 03 = 1(2 4 [23].
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The dm/dT was calculated by numerical differentiation of the data followed by smoothing. The results

for the CBT20, CBT35 and CBT50 are shown in Fig. 7.

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The dS/dT at room temperature for the studied samples is shown in Table 1. It is possible to

verify that the TeO2 addition increases the dS/dT. The addition of TeO2 in borotellurite glasses increases
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the refractive index, the electronic polarizability and the thermal expansion coefficient[25], which are
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directly related with the dS/dT. The dS/dT values of the glasses studied are comparable with phosphate

(~12. 10-6 K-1) and lower than Low Silica Calcium Alumino Silicate glasses (~19. 10-6 K-1) [23]. In Fig.

7 dS/dT increases with the temperature for all the samples studied. This information is very important in

optical systems design such as solid state laser, where the local active medium temperature can reach a

temperature of the order of 150ºC [41,42], increasing therefore the magnitude of dS/dT, and

consequently resulting in a large distortion of the laser beam.

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4. Conclusion

The glass forming ability and optical properties of the CBTx system were investigated for the

first time in this work and the phase diagram was presented. The glass samples obtained are transparent,

lightly yellowish, with no visible crystallites. The density of CBTx glasses increases due the substitution

of B2O3 and CaO (lower molecular weight) by TeO2 (higher molecular weight). Refractive index

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increases mainly due to the increase of density and electronic polarizability. The increase of electronic

polarizability and optical basicity suggest that TeO2 addition increases the NBO concentration. The

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optical basicity values are found to be in range 0.648–0.709 for the CBTx glass system. The increase of

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TeO2 shifts the band edge to longer wavelength owing to increase in non-bridging oxygen ions, resulting

in decrease of optical energy gap. The values of optical energy gap decrease linearly from 3.62 to 3.18

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eV, with TeO2 addition up to 50 wt%. The results of dS/dT present an increase as a function of
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temperature for all measured samples. The addition of TeO2 also increases dS/dT values in room

temperature. The values obtained are comparable with phosphate and lower than LSCAS glasses. The
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results suggest that CBTx are good candidates for rare-earth doping for several optical applications,
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such as fiber in optical communication, optical amplifiers, window materials and up-conversion laser.
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We expect that the results in this work will be useful for understanding the influence of TeO2 on the

optical properties of CBTx glasses.

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Acknowledgments:
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We are thankful to the Brazilian agencies CNPq, CAPES, FINEP, and FAPEMA for financial support of
this study.
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Figure Captions
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Fig.1 - CBTx glasses with different concentrations of TeO2.

Fig. 2 - Phase diagram of the CBTx system (900ºC)

Fig. 3 – Refractive index and density versus TeO2 content

Fig. 4 – Optical basicity (left) and Eletronic polarizability (right) as a function of TeO2 content

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Fig. 5 –Absorption coefficient of CBTx glasses

Fig. 6 - Left: Tauc’s plot of  ℎ !/ vs photon energy for the indirect allowed transitions of CBTx

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glasses. Right: Estimated band gap values as functions of TeO2 content.

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Fig. 7 – dS/dT as a function of temperature of CBTx glasses

Table Captions
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Table 1 - Sample names and composition (wt and mol%), volumetric density (ρ), refractive index (n),

electronic polarizability (αm), theoretical optical basicity (Λth) and band gap (Eopt) of CBTx glasses.
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Table 1

Composition
Physical properties
CaF2 CaO B2O3 TeO2

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Sample wt% mol% wt% mol% wt% %mol wt% mol% ρ n αm (Å3) Ʌth Eopt (eV) dS/dT
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(.10-6 K-1)

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name (g cm ) (± 0.01) (± 0.03) (± 0.01)
(±0.03) (±0.5)

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@300K
CBT20 10.0 9.6 22.0 29.4 48.0 51.6 20.0 9.4 2.97 1.62 3.51 0.648 3.62 12.6

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CBT25 10.0 9.9 20.0 27.7 45.0 50.2 25.0 12.2 3.04 1.64 3.65 0.656 3.55 -

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CBT30 10.0 10.3 18.0 25.9 42 48.6 30.0 15.2 3.14 1.65 3.71 0.664 3.47 -
CBT35 10.0 10.7 16 23.9 39 47.0 35.0 18.4 3.23 1.66 3.80 0.673 3.4 14.0

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CBT40 10.0 11.2 14.0 21.8 36 45.1 40.0 21.9 3.32 1.68 3.94 0.683 3.33 -

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CBT50 10.0 12.2 10.0 17.0 30.0 41.0 50.0 29.8 3.58 1.71 4.11 0.709 3.18 16.5

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Fig.1 – Double column

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TeO2
0 Glass
100

20
80

2
F
40

Ca
60

Te
O+

O2
Ca
60

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40

80
20

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100
0
CaO+CaF2 0 20 40 60 80 100 B2O3

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B2O3

Fig. 2 – Single column

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1.74 3.9
Refractive Index
3.8
1.72 Density
3.7

1.70 3.6
Refractive index n

Density (g cm-3)
3.5
1.68
3.4

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1.66 3.3

3.2
1.64

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3.1
1.62 3.0

2.9

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1.60
2.8
20 25 30 35 40 45 50
TeO2 content (wt%)

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Figure 3 – Single column
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4.2
0.72
CBTx glasses CBTx glasses
0.71 Linear fit 4.1 Linear fit

0.70

Electronic polarizability (Å3)

4.0
0.69
Optical basicity

3.9
0.68
3.8
0.67

0.66 3.7

0.65 3.6

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0.64
3.5
0.63
20 25 30 35 40 45 50 20 25 30 35 40 45 50
TeO2 (wt%) TeO2 (wt%)

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Fig. 4 – Double column

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2.0 CBT20 (a)

1.5

Absorption coefficient Αe (cm-1)

1.0

0.5

0.0
300 600 900 1200 1500 1800 2100 2400 2700
1.2
CBT20 (b)

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1.0 CBT25
CBT30
0.8 CBT35
CBT40
0.6

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CBT50
0.4
0.2
350 400 450 500

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Wavelength (nm)

Fig. 5 –Single column

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2.5
CBT20 3.7
CBT25
CBT30

Optical Energy gap, Eopt (eV)

2.0 3.6
CBT35
1/2

CBT40
(cm eV)

3.5
CBT50
-1

1.5
3.4
1/2
(Aehv)

3.3
1.0

3.2

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0.5
3.1

2.8 2.9 3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4.0 20 25 30 35 40 45 50
hv (eV) TeO2 content (wt%)

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Fig. 6 – Double column

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30

Data2_CBT20
Data3_CBT35
25 Data1_CBT50
Linear Fit
dS/dT (.10 K )
-1

20
-6

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15

10

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300 320 340 360 380 400 420 440 460
Temperature (K)

Fig. 7 – Single column

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