Crystallization and optical properties of alumino-silicate and alumino-borosilicate glasses containing indium tin oxide

Journal Pre-proof Crystallization and Optical Properties of Alumino-silicate and Alumino-borosilicate glasses containing Indium Tin oxide Amir Ashjari, Bijan Eftekhari Yekta, Hamid Reza Rezaie

PII:

S0955-2219(19)30780-0

DOI:

https://doi.org/10.1016/j.jeurceramsoc.2019.11.035

Reference:

JECS 12860

To appear in:

Journal of the European Ceramic Society

Received Date:

10 August 2019

Revised Date:

5 November 2019

Accepted Date:

11 November 2019

Please cite this article as: Ashjari A, Yekta BE, Rezaie HR, Crystallization and Optical Properties of Alumino-silicate and Alumino-borosilicate glasses containing Indium Tin oxide, Journal of the European Ceramic Society (2019), doi: https://doi.org/10.1016/j.jeurceramsoc.2019.11.035

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Crystallization and Optical Properties of Alumino-silicate and Aluminoborosilicate glasses containing Indium Tin oxide

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Amir Ashjari, Bijan Eftekhari Yekta*, Hamid Reza Rezaie

School of Metallurgy and Materials Engineering, Iran University of Science and Technology, P.O.

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Box 1684613114, Tehran, Iran

*Corresponding

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author: Tel.: +982173228873; fax: +982177240480 Email address: [email protected] (Bijan Eftekhari Yekta)

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Abstract

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Transparent alumino-borosilicate based glass-ceramics containing indium tin oxide (ITO) nano-crystals were synthesized through melt casting method. The results showed that the SiO2 − B2 O3 − Al2 O3 − Na2 O glass system were crystallized more intensively than the other, due to a more extensive liquid-liquid phase separation. Thermal behavior and crystallinity of the specimens were investigated by conducting DTA and XRD analysis, respectively. FE-SEM images were used for microstructural evaluation of the specimens. Optical properties of the samples were studied by UV-Vis and Near-IR spectroscopy. Furthermore, FTIR was utilized to identify various bonds in the specimens. The crystallized glasses of the alumino-borosilicate system showed transmittance up to 50% in the visible wavelength, whereas they showed a significant absorption in the UV and near infrared wavelength ranges (> 95%). According to the measurement, the mean crystallite size of the precipitated ITO in the optimum sample of the alumino-borosilicate system was less than 20 nm, which was obtained by heat treatment at 650℃ for 10 h. Keywords: glass-ceramic; Indium Tin oxide; IR absorbing; nanocrystal

1. Introduction Indium oxide and tin-doped indium oxide (ITO) are transparent n-type semiconductors that are widely used in low-e windows, displays, optical filters, and transparent electrodes due to their excellent conductivity and optical properties[1]. If Sn4+ ions dope in the cubic indium oxide structure, an n-type semiconductor

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called ITO, with a direct band gap energy of approximately 4eV, will be formed[2]. ITO is often used as the coating of optical waveguide chips[3], functional glasses[4],

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sensors[5,6], and solar cells[7]. At the moment, In2 O3 or tin-doped In2 O3 are predominantly used as a coating material for transparent electron conductors[8].

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Furthermore, glass ceramics containing In2 O3 are utilized for their non-linearity

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optical properties[9]. However, among these implementations, the transparent electrodes in OLED devices and the infrared reflective coatings are the most

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common applications[10-13].

There are many deposition techniques for ITO films such as direct current

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(DC) or radio frequency (RF) sputtering, reactive evaporation, sol-gel process, and chemical vapor deposition[14-18]. Recently, reports have been made on the fabrication of glass-based composites with ITO nano-particles dispersion to obtain high optical transmittance and high electrical conductivity[18,19]. One of the most

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important optical properties of ITO is its high transmission at visible wavelength range as well as very strong absorption or reflection at near-infrared (NIR)[16]. In addition, glasses containing semiconductive crystallites show interesting

optical properties as semiconductor lasers[20], optical limiters[21] and saturable absorbers[22]. In recent years, high third-order optical non-linearity has also been achieved by utilizing these materials [10,23]. Over the past few years, crystallization

of semiconducting phases have been broadly reported for various bulk glasses containing zinc and cadmium chalcogenides[24,25], TiO2 , SnO2 , and In2 O3 [9,2628]. Among these semiconductor materials, indium oxide bearing glass-ceramics are more feasible due to its higher dissolution in silicate-based glasses[9]. The crystallization behavior of In2 O3 in the soda-lime-aluminosilicate glasses has been studied by Loser et al.[9]. The samples were prepared by melting method

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and they studied the linear and non-linear optical properties of these glass-ceramics. Furthermore, Garkova et al.[28] have studied preparation of In2 O3 and tin-doped

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In2 O3 using glass crystallization method in the system Na2 O/B2 O3 /Al2 O3 /In2 O3 /

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(SnO2 ). Zhong et al. [29] have studied the influence of In2 O3 nano-crystals in sodium borosilicate glass prepared by the sol-gel method. However, it should be

containing ITO crystalline phase.

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mentioned that there are no significant reports in the literature on the glass-ceramics

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The aim of the present work was to synthesize glass-ceramic samples that are transparent in the visible wavelength range, at the same time are completely

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reflective or absorbent in the NUV and NIR wavelength ranges, through precipitation of ITO nanocrystals in melt-derived glasses and subsequent heat treatment.

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2. Experimental Procedures

2.1.

Materials and methods

The materials used in this study were reagent grade ones, including high purity acid-leached 𝑆𝑖𝑂2 , Al2 O3 (MERCK 101077), H3 BO3 (MERCK 100156), Na2 CO3

(MERCK 106392), CaCO3 (MERCK 102067), In2 O3 (MERCK 112201), and SnO2 (MERCK 107818). The chemical composition of the B2 O3 –free and the 𝐵2 𝑂3 containing glasses, i.e. S1, S2, B1 and B2 in terms of molar ratio are given in Table. 1. The thoroughly mixed batches were melted in platinum crucible at 1600℃ for 1 h in an electric furnace. It is important to mention that the crucibles were covered by alumina plates in order to prevent the boron evaporation. In addition, high heating

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rate for melting process (15°C/min) was applied. The molten glasses were shaped into a cylindrical stainless steel mold preheated at 500°C. After that, the glasses were

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annealed at 600 ℃ for 30 min and cooled naturally in the kiln to room temperature.

diameter of 12 mm and 1.2 mm thickness.

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Subsequently, the synthesized cylindrical samples were cut into disks with a

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Differential thermal analysis (DTG-60AH Shimadzu) was used to determine the crystallization temperatures of the glasses. Glassy frits with particle size between

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0.4-0.5 mm and a heating rate of 10 °C/min were used in each DTA run. This relatively coarse particle size was chosen to guaranty DTA results that were closer

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to bulk glass behavior. The reference material in these experiments was α − Al2 O3 powder. The two series of glass samples were heat treated according to the DTA results to achieve the desired crystallization by using a heating rate of 10℃/min and a 10 h soaking of time, in the temperatures of 750-800℃ and 650-730℃,

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respectively. The heat-treatment of glasses was carried out in an electric kiln. The heat-treatment programs are summarized in the Table. 2. The crystalline phases, which were precipitated during heat-treatment, were

identified by X-ray diffraction (XRD, Dron-8) with Cu Kα radiation (λ = 0 ∙ 154 nm) at a scanning speed of 5 degrees per minute in the 2θ angular range of 10° to 80°. Field-emission scanning electron microscope (FE-SEM - TESCAN) with an

acceleration voltage of 20 keV was used for microstructural investigations. The samples were ground and polished, respectively, up to 1 μm diamond paste and were etched in a 2 vol% HF solution for 45 s. Fourier transform infrared spectroscopy (FTIR-8400S Shimadzu) was used to identify the bonding groups and their concentrations in the glass and glass-ceramic samples. The optical properties of samples were investigated by near infrared

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spectroscopy (NIRQuest512-2.5 Ocean Optic) and UV-Vis spectroscopy (Analytik jena Specord 250 spectrophotometer). The sample thickness was 1.2 mm in the

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optical experiments.

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Crystallization of the glass samples

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3.1.

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3. Results and Discussions

3.1.1. Differential Thermal Analysis (DTA)

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DTA thermographs of the glasses S1, S2 and B2 are presented in Fig. 1. Based upon information given in Fig. 1(a), there is no crystallization peak for S1, indicating its weak crystallization ability. However, sample S2 shows a broad hill-like exothermic peak between 770 and 800 ℃ which can be related to its surface

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crystallization. In glass B2 (Fig. 1(b)) the crystallization peak is sharper and it’s happened at a lower temperature than S2. This can be caused by decreasing of the glass viscosity and/or liquid-liquid phase separation as a result of the substitution of boron oxide for calcium one. It is known that phase separation in the glass can facilitate its crystallization. This issue will be further discussed in the following sections by using FE-SEM images of samples.

3.1.2. X- ray Diffraction (XRD) patterns X-ray diffraction patterns of the glass series S and glass B2 prior to heattreatment process are given in Fig. 2. It can be seen that there is no crystalline phase in these samples.

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treatment in the temperature range of 750-800 ℃ (Fig. 3).

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In addition, there is no noticeable peak in the XRD patterns of S1 after heat-

On the contrary, after the heat-treatment of the glass S2 for 10 h above 760℃ peaks related to indium tin oxide were gradually appeared in the XRD pattern (Fig.

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4). It means that increasing of Al2 O3 amount in the glass had a positive effect on the

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crystallization ability[9]. However, the crystallized glasses lost their transparency and S2-800 turned into a gray opaque specimen, as a result of the precipitation of

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large crystallites[30].

It is known that the solubility of In2 O3 can be decreased in the presence of

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B2 O3 in the glass composition[9]. Therefore, the B2 O3 bearing glass can be crystallized with less indium oxide at a lower heat-treatment temperature. Accordingly, the glasses B1 and B2 were prepared via substitutions of 10 mol.% CaO for B2 O3 . In2 O3 was also reduced from 5 mol% to 4 mol% in glass B1. This

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glass became opaque just after casting the melt in the mold because of insolubility of In2 O3 in the glass matrix and precipitation of alpha quartz (Fig. 5). However, the glass showed complete transparency with the reduction of In2 O3 to 3 mol% in glass B2. Based upon the resulted shown in Fig. 6, it can be seen that the glass has been crystallized clearly in all of the heat-treatment temperatures.

As it was mentioned earlier, this may be due to a liquid-liquid phase separation encouraged by B2 O3 . This issue will be further discussed in section 3.1.3. Furthermore, the sample B2-650 retained its transparency after the heat-treatment, which is believed to be caused by occurrence of a nucleation and growth mechanism of phase separation that leads to smaller droplet size limiting the crystallite sizes. It should be noted that in all of the XRD patterns of the heat treated glass B2, there

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was also two peaks at 2θ equal to 20 ∙ 55° and 27 ∙ 025° which were attributed to

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alpha quartz.

The other peaks belong to tin-doped In2 O3 crystals (JCPDS no.06-0416). The

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Scherrer equation (Eq. 1) was used to calculate the crystallite size of ITO crystals

Gλ

(1)

Bcosθ

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d=

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embedded in the glassy matrix for the samples S2 and B2.

Where d is the mean crystallite size, G is a constant equal to 0.899 for cubic systems, λ is the wavelength of Cukα -radiation (0.154 nm), B is the full width of the

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peak at its half maximum (FWHM) and θ is the Bragg diffraction angle. The mean calculated crystallite size which was derived from 3 calculations for each sample are given in Table. 3. Comparing the crystallite sizes of S2 with B2 shows the smaller mean crystallite size for the B2 sample, probably due to its lower heat-treatment

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temperature as well as its relict microstructure originated from its above-mentioned liquid phase separation. Furthermore, Crystallite sizes of the sample B2 heat treated at different temperatures, which were calculated by the Scherrer equation, is depicted on Fig. 7. The crystallite size growth with the increment in the heattreatment temperature is readily observable.

The B2 sample heated at 650 °C showed more transparency and therefore was selected for further studies. In order to evaluate the amounts of Sn4+ ions incorporated in the cubic In2O3 structure, the crystal lattice parameters were calculated at different temperature using the Bragg equation (Eqs. 2 and 3) at different temperatures. The most intense crystallographic plane of cubic indium oxide, i.e, (222) was considered. It is

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necessary to mention that before these calculations, data were analyzed by the Fullprof Rietveld-type program and Rietveld refinement were applied on the XRD

λ = 2 Dsinθ

(2)

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data (Fig. 8).

1 D2

=

(h2 +k2 +l2 ) a2

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planes and θ is the Bragg angle.

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Where λ is the wavelength of Cukα -radiation (0.154 nm), D is the distance of (222)

(3)

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Where a, h k l, and D, are the lattice parameters, miller indices of the plane (222), and the distance of (222) planes, respectively. Fig. 9 shows that the lattice parameter of the In2 𝑂3 structure in the sample B2 is increased from 10.1175 Å with increasing of heating temperature to 10.125 Å,

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indicating substitution of larger Sn4+ for In3+ in In2 𝑂3 structure[2]. 3.1.3. Field emission scanning electron microscopy (FE-SEM) Analysis

FE-SEM micrograph of samples S2 and B2 before the heat-treatment are presented in Fig. 10. It can be seen that while there is no sign of phase separation in S2 (Fig. 10(a)), its occurrence to some extent was observed in the B2 sample (Fig.

10(b)). It is known that phase separation plays a very decisive role on controlling the crystallization process and the microstructure of the resulting glass ceramics. Actually, the boundaries of the phase-separated regions can act as appropriate heterogeneous locations for the fast nucleation of ITO crystals. A fine-scale glassin-glass phase separation has been reported in the borosilicate-based glasses previously[31]. It seems that the lack of such event in the sample S2 has led to

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precipitation of large crystallite size and thus its opacification after heat-treatment (Fig. 11(a)). On the other hand, the microstructure of the heat-treated B2 at 650 °C

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has followed from its phase separated glass (Fig. 11(b)), named “relict microstructure”.

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Fig. 12(a,b) and show the back scattered images of smaple B2-650, and B2680 prepared at a higher magnification. The light regions are the nano-sized ITO

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crystales distributed uniformly through out the sample. Furthermore, in Fig. 12(c,d)

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the crystal growth and the increase in the crystalline phase with increasing of heattreatment temperature to 700 and 730 °C are clearly illustrated. The size of light regions have been increased so that some crystallites are bigger than 100 nm. This

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large crystallite size makes the specimen opaque.

3.2.

Optical Properties

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3.2.1. UV-Vis spectroscopy

UV-Vis total transmission spectra of samples B2 and B2-650 are presented

in Fig. 13. According to the spectra, the maximum optical transmittance of the samples B2 and B2-650 in the visible range are 80 and 48%, respectively. Based upon this experiment, the crystalized sample has retained its transparency only at visible wavelengths and loses it gradually on the both sides of this range reaching to

approximately zero at 400 and 1100 nm. It is obvious that this behavior, i.e. acceptable transparency at visible wavelength range and approximately zero transmission at UV and near infrared wavelength ranges, is unique and is related to precipitated ITO phase. It is important to mention that such an optical spectra for the sample B2-650 is very different from those of ITO films[32,33] and the glass ceramics containing indium oxide nanocrystals[9,29]. The images of the B2 and B2-

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650 samples are presented in Fig. 13 and transparency of the samples is clearly observed. The yellowish gray color of the sample B2-650 is because of low

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transmission at the blue visible range.

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3.2.2. Near-Infrared spectroscopy

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More details for this optical behavior will be given in the following section.

The near infrared transmittances of glass B2 and its glass-ceramic B2-650 are

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presented in Fig. 14. While glass B2 shows a noticeable transmission (> 50%) at near-infrared wavelength range, i.e. 900-2500 nm, sample B2-650 shows a negligible transmission (approximately zero) at this wavelength interval. It can be

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seen that transmission of the glass B2 is decreased at longer wavelengths. The presence of some undetectable ITO crystalline phase as well as collective vibrational absorption in this wavelength region are probably responsible for the absorption in glass B2. This very low transmission at near infrared wavelength range in the sample

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B2-650 is due to ITO nanocrystals precipitation. It should be mentioned that near infrared spectra are in good correspondence to UV-Vis one. This optical behavior of B2-650 makes it suitable for a variety of practical applications such as optical filters, smart windows for energy saving in buildings and vehicles, solar cells, etc.

3.2.3. FTIR spectroscopy

FTIR spectra of two series samples S2 and B2 are illustrated in Fig. 15. In the sample S2, there is a broad and intensive absorption band at wavenumber 1005 cm−1 that is due to the Si − O − Si antisymmetric stretching vibrations bonds[34]. The absorption bands that located on wavenumbers 698 cm−1 and 465 cm−1 could be attributed to the stretching vibration of O − Si − O bonds and bending vibration of Si − O − Si or Si − O − Al, respectively[34]. The peak depicted at wavenumber 407

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cm−1 is related to In − O bending[35].

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It can be seen that there are two excessive absorption bonds in the spectra of sample B2 (Fig. 15(b)) compared to the sample S2, which are located at

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wavenumbers 1450 cm−1 and 768 cm−1 . They could be arisen from [BO3 ] and [BO4 ] antisymmetric stretching vibration bonds and B − O symmetric stretching

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vibration bonds[35-37]. Moreover, small bonds at the range 2600-3800 cm−1 are

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related to hydroxyl groups and hydrogen bonds in the glass. The latter can be originated from boric acid in the batch and water absorption during the

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sampling[38].

4. Conclusion

Transparent glass-ceramics containing ITO nano-sized crystals, which can be

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used in the fields of low-e windows, saving energy and optical filters; were prepared in the SiO2 − B2 O3 − Al2 O3 − Na2 O glass system. Based on the results obtained in this work, the lower solubility of boron containing glasses made those more susceptible for preparing of transparent glass-ceramics. Furthermore, DTA and XRD results showed that the alumino-silicate glasses which contained less than 8 mol% Al2 O3 did not show appropriate crystallization behavior; however, increasing of the

Al2 O3 to 10 mol% improved this deficiency. The best heat-treatment condition for the optimum glass composition, i.e. the alumino-borosilcate, was 650℃ for 10h, which resulted to uniformly precipitated crystals smaller than 20 nm. The resulted glass-ceramic sample showed optimum optical properties, i.e. acceptable transparency at the visible wavelength range as well as a high absorption and

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reflection (> 95%) at the UV and near infrared wavelength ranges.

[3]

[4]

re

Jo

[5]

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[2]

P. Chen, Z. Chen, S. Hou, X. Shen, Y. Chu, Y. Yang, L. Yang, J. Li, N. Dai, In-situ growth of highly monodisperse ITO nanoparticles regulated by mesoporous silica glasses, Mater. Des. 151 (2018) 53–59. https://doi.org/10.1016/j.matdes.2018.04.036 N. Nadaud, N. Lequeux, M. Nanot, J. Jovenstitut, and T. Roisnel, Structural Studies of TinDoped Indium Oxide (ITO) and In4Sn3O12, J. Solid State Chem. 135 (1998) 140–148. https://doi.org/10.1006/jssc.1997.7613 J. P. Bearinger, J. Voros, and J. A. Hubbell, Electrochemical optical waveguide lightmode spectroscopy ( EC-OWLS ): A Pilot Study Using Evanescent-Field Optical Sensing Under Voltage Control to Monitor Polycationic Polymer Adsorption Onto Indium Tin Oxide ( ITO ) -Coated Waveguide Chips, Biotechnol. Bioeng. 82 (2003) 465–473. https://doi.org/10.1002/bit.10591 C. G. Granqvist and A. Hultaker, Transparent and conducting ITO films : new developments and applications, Thin Solid Films, 411 (2002) 1–5. https://doi.org/10.1016/S0040-6090(02)00163-3 X. Lu, L. Zhang, H. Zhao, K. Yan, Y. Cao, and L. Meng, Synthesis , Characterization and Gas Sensing Properties of In(OH)3 and In2O3 Nanorods through Carbon Spheres Template Method, J. Mater. Sci. Technol. 28 (2012) 396–400. https://doi.org/10.1016/S10050302(12)60074-7 J. Zhang, K. H. Au, and Z. Q. Zhu, Sol – gel preparation of poly ( ethylene glycol ) doped indium tin oxide thin films for sensing applications, Opt. Mater. (Amst). 26 (2004) 47–55. https://doi.org/10.1016/j.optmat.2004.01.018 I. Y. Y. Bu, A simple annealing process to obtain highly transparent and conductive indium doped tin oxide for dye-sensitized solar cells, Ceram. Int. 40 (2014) 3445–3451. https://doi.org/10.1016/j.ceramint.2013.09.086 R. Bel, H. Tahar, T. Ban, and Y. Ohya, Tin doped indium oxide thin films : Electrical properties Tin doped indium oxide thin films : Electrical properties, J. Appl. Phys. 83 (1998) 2631-2645. https://doi.org/10.1063/1.367025

ur na

[1]

[6]

[7]

[8]

-p

Refrences:

[14]

[15]

[16]

[17]

[18]

[19]

of

Jo

[20]

ro

[13]

-p

[12]

re

[11]

lP

[10]

C. Löser and C. Rüssel, The crystallization of indium containing semiconductive phases from a soda-lime-aluminosilicate glass, J. Non. Cryst. Solids. 282 (2001) 228–235. https://doi.org/10.1016/S0022-3093(01)00351-9 C. J. Lee, H. K. Lin, S. Y. Sun, and J. C. Huang, Applied Surface Science Characteristic difference between ITO/ZrCu and ITO/Ag bi-layer films as transparent electrodes deposited on PET substrate, Appl. Surf. Sci. 257 (2010) 239–243. https://doi.org/10.1016/j.apsusc.2010.06.074 D. Alonso-álvarez, L. Ferre, A. Mellor, D. J. Paul, and N. J. Ekins-daukes, ITO and AZO films for low emissivity coatings in hybrid photovoltaic- thermal applications, Sol. Energy. 155 (2017) 82–92. https://doi.org/10.1016/j.solener.2017.06.033 H. Liu, V. Avrutin, N. Izyumskaya, Ü. Özgür, and H. Morkoç, Transparent conducting oxides for electrode applications in light emitting and absorbing devices, Superlattices Microstruct. 48 (2010) 458–484. https://doi.org/10.1016/j.spmi.2010.08.011 A. Yabuki, K. Okumura, and I. W. Fathona, Transparent conductive coatings of hotpressed ITO nanoparticles on a plastic substrate,Chem. Eng. J. 252 (2014) 275–280. https://doi.org/10.1016/j.cej.2014.05.024 C. David, B. P. Tinkham, P. Prunici, and A. Panckow, Highly conductive and transparent ITO films deposited at low temperatures by pulsed DC magnetron sputtering from ceramic and metallic rotary targets, Surf. Coat. Technol. 314 (2016) 113–117. https://doi.org/10.1016/j.surfcoat.2016.09.022 Ö. Kesmez, E. Akarsu, H. E. Çamurlu, E. Yavuz, M. Akarsu, and E. Arpaç, Preparation and Characterization of Multilayer Anti-Reflective Coatings via Sol-Gel Process, Ceram. Int. 44 (2017) 3183–3188. https://doi.org/10.1016/j.ceramint.2017.11.088 W. Zhang, G. Zhu, and L. Zhi, Structural, electrical and optical properties of indium tin oxide thin films prepared by RF sputtering using different density ceramic targets, Vacuum. 86 (2012) 1045–1047. https://doi.org/10.1016/j.vacuum.2011.11.008 Y. Ren, X. Zhou, Q. Wang, and G. Zhao, Novel preparation of ITO nanocrystalline films with plasmon electrochromic properties by the sol-gel method using benzoylacetone as a chemical modifier, Ceram. Int. 44 (2018) 3394–3399. https://doi.org/10.1016/j.ceramint.2017.11.130 T. J. Rudzik and R. A. Gerhardt, comparison of hot pressing and spark plasma sintering in the densification behavior of Indium Tin oxide-borosilicate glass composites, J. Am. Ceram. Soc. 12 (2017) 3218–3221. https://doi.org/10.1111/jace.15254 T. L. Pruyn and R. A. Gerhardt, Percolation in borosilicate glass matrix composites containing antimony-doped tin oxide segregated networks. Part i: Fabrication of segregated networks, J. Am. Ceram. Soc. 96 (2013) 3544–3551. https://doi.org/10.1111/jace.12534 H. Giessen, U. Woggon, and B. Fluegel, Femtosecond optical gain in strongly confined quantum dots, Opt. Lett. 21 (1996) 1043–5. http://doi.org/10.1364/OL.21.001043 Y. Takahashi, S. Okada, R. Bel, and H. Tahar, Dip-coating of ITO films, J. Non. Cryst. Solids. 218 (1997) 129–134. https://doi.org/10.1016/S0022-3093(97)00199-3 N. Sarukura, Y. Ishida, T. Yanagawa, and H. Nakano, All solid-state cw passively modelocked Ti:sapphire laser using a colored glass filter, Appl. Phys. Lett. 57 (1990) 229– 230. https://doi.org/10.1063/1.103724 C. P. Singh, K. S. Bindra, and S. M. Oak, Nonlinear optical studies in semiconductor-doped glasses under femtosecond pulse excitation, 75 (2010) 1169–1173. https://doi.org/10.1007/s12043-010-0202-9

ur na

[9]

[21] [22]

[23]

[29]

[30] [31] [32]

[33]

[34]

[35]

of

Jo

[36]

ro

[28]

-p

[27]

re

[26]

lP

[25]

S. R. Luki, M. D. Vu, G. R. Š, and D. D. Š, Study of glass transition process in quasi-binary As2S3 – CdS chalcogenides, J. Non. Cryst. Solids. 377 (2013) 21–25. https://doi.org/10.1016/j.jnoncrysol.2013.01.020 N. Tohge, M. Asuka, and T. Minami, Sol-gel preparation and optical properties of silica glasses containing Cd and Zn chalcogenide microcrystals, J. Non. Cryst. Solids. 148 (1992) 652–656. https://doi.org/10.1016/S0022-3093(05)80693-3 S. H. Risbud, L. Liu, J. F. Shackelford, S. H. Risbud, L. Liu, and J. F. Shackelford, Synthesis and luminescence of silicon remnants formed by truncated glassmelt particle reaction Synthesis and luminescence reaction of silicon remnants formed by truncated, Appl. Phys. Lett. 63 (1993) 1648–1650. https://doi.org/10.1063/1.110724 R. Hayashi, M. Yamamoro, K. Tsunetomo, K. Kohno, Y. Osaka, and H. Nasu, Preparation and Properties of Ge Microcrystals Embedded in SiO2 Glass Films, Jpn. J. Appl. Phys. 29 (1990) 756–759. http://iopscience.iop.org/1347-4065/29/4R/756 R. Garkova, G. Völksch, and C. Rüssel, In2O3 and tin-doped In2O3 nanocrystals prepared by glass crystallization, J. Non. Cryst. Solids, 352 (2006) 5265–5270. https://doi.org/10.1016/j.jnoncrysol.2006.09.001 J. Zhong and W. Xiang, Influence of In2O3 nanocrystals incorporation on sodium borosilicate glass and their nonlinear optical properties, Mater. Lett. 193 (2017) 22–25. https://doi.org/10.1016/j.matlet.2017.01.062 G. H. Beall and L. R. Pinckney, Nanophase glass- ceramics, J. Am. Ceram. Soc. 82 (1999) 5–16. https://doi.org/10.1111/j.1151-2916.1999.tb01716.x V. Marghussian, Nano-Glass Ceramics: Processing, Properties and Applications, Elsevier, 2015. F. Mei, T. Yuan, R. Li, K. Qin, L. Zhou, and W. Wang, Micro-structure of ITO ceramics sintered at di ff erent temperatures and its e ff ect on the properties of deposited ITO films, J. Eur. Ceram. Soc. 38 (2017) 521–533. https://doi.org/10.1016/j.jeurceramsoc.2017.09.008 A. Soleimani-Gorgani, E. Bakhshandeh, and F. Najafi, Effect of dispersant agents on morphology and optical-electrical properties of nano indium tin oxide ink-jet ink, J. Eur. Ceram. Soc. 34 (2014) 2959–2966. https://doi.org/10.1016/j.jeurceramsoc.2014.04.030 J. Wan, J. Cheng, and P. Lu, The coordination state of B and Al of borosilicate glass by IR spectra, J. Wuhan Univ. Technol. Mater. Sci. Ed. 23 (2008) 419–421. https://doi.org/10.1007/s11595-007-3419-9 V. Senthilkumar, K. Senthil, and P. Vickraman, Microstructural, electrical and optical properties of indium tin oxide (ITO) nanoparticles synthesized by co-precipitation method, Mater. Res. Bull. 47 (2012) 1051–1056. https://doi.org/10.1016/j.materresbull.2011.12.040 E. A. Saad, F. H. Elbatal, A. M. Fayad, and F. A. Moustafa, Infrared Absorption Spectra of Some Na-Borosilicate Glasses Containing AgBr and Cu2O ( Photochromic Glasses ) in Addition to One of Transition Metal Oxide, Silicon. 3 (2011) 85–95. https://doi.org/10.1007/s12633-011-9081-z S. Y. Marzouk, R. Seoudi, D. A. Said, and M. S. Mabrouk, Linear and non-linear optics and FTIR characteristics of borosilicate glasses doped with gadolinium ions, Opt. Mater. (Amst). 35 (2013) 2077–2084. https://doi.org/10.1016/j.optmat.2013.05.023 R. Garkova, I. Gugov, and C. Rüssel, Precipitation of In2O3 nano-crystallites from glasses in the system Na2O/B2O3/Al2O3/In2O3, J. Non. Cryst. Solids. 320 (2003) 291–298. https://doi.org/10.1016/S0022-3093(03)00080-2

ur na

[24]

[37]

[38]

of

ro

-p

re

lP

ur na

Jo

Figure Caption: Fig.1. DTA curves of samples: a) S1 and S2 by heating rate of 10℃/min, b) B2 with heating rate of 10 and 20 ℃/min (black and red line, respectively).

(a) S2

of

Voltage(a.u.)

S1

0

200

400

600

800

1000

1200

ur na

lP

re

Temperature(℃)

B2-10

-p

ro

𝑇𝑐𝑟 ≈ 800 ℃

(b)

Jo

Voltage(a.u.)

B2-20

0

200

400

𝑇𝑐𝑟 ≈ 700 ℃

600

800

1000

Temperature(℃)

Fig.2. XRD patterns of the glass samples S1, S2 and B2 before heat treatment.

+

Cubic ITO * Quartz +

*

Intensity(a.u.)

S1-800

S1-775

of

S1-750

0

10

20

30

40

50

60

70

80

-p

2𝑇ℎ𝑒𝑡𝑎(°)

ro

S1

re

Fig.3. XRD patterns of the samples S1-750, S1-775 and S1-800.

lP ur na

Jo

Intensity(a.u.)

B2

0

10

20

30

40

S2

S1

50

60

70

2𝑇ℎ𝑒𝑡𝑎(°)

Fig.4. XRD patterns of the samples S2-750, S2-760 and S2-800.

80

Cubic ITO * Quartz +

*

*

+

*

*

Intensity(a.u.)

S2-800 S2-760

0

10

20

30

40

50

60

ro

S2

70

80

lP

re

-p

2𝑇ℎ𝑒𝑡𝑎(°)

Fig.5. XRD pattern of the glass B1 before heat treatment.

600

Cubic In2O3/ITO * +

*

300

200

Jo

Intensity(a.u.)

400

Quartz

ur na

500

100

*

+

* *

+

0

0

10

20

30

40

50

60

2𝑇ℎ𝑒𝑡𝑎(°)

2𝜃°

70

of

S2-750

80

Fig.6. XRD patterns of the samples B2-650, B2-680, B2-700 and B2-730.

*

*

+

* *

B2-730

Intensity(a.u.)

+

B2-700

ro

B2-680

of

Cubic ITO * Quartz +

0

10

20

30

40

50

60

70

80

re

2𝑇ℎ𝑒𝑡𝑎(°)

-p

B2-650

lP

Fig.7. Crystallite sizes calculated from XRD-line broadening using the Sherrer equation for the sample B2 heat treated at different temperatures

ur na

30

20

15

Jo

Crystallite size (nm)

25

10

5

0 640

660

680

700

Temperature of heat treatment (℃)

720

740

-p

Fig.9. Lattice parameter of B2 with heat treatment temperatures.

re

10.126

lP

10.124

10.122

10.120

ur na

Lattice parameter (Angstrom)

10.128

10.118

ro

of

Fig.8. Rietveld refinement for the XRD pattern of the sample B2-650.

650

670

690

710

730

Temperature of heat treatment (℃)

Jo

Fig.10. FE-SEM images of samples a) S2 and b) B2 before heat treatment.

ro

of Jo

ur na

lP

re

-p

Fig.11. FE-SEM images of samples a) S2-760 and b) B2-650.

Fig.12. Back scattered FE-SEM imaged of samples a) B2-650, b)B2-680, c)B2-700 and d) B2-730.

of ro -p re lP

Jo

ur na

Fig.13. UV-Vis spectra of sample B2 before and after heat treatment at 650℃ for 10 h.

100 90

B2 70 60 50 40

B2-650

30

of

Total transmission (%)

80

20

0 300

400

500

600

700

800

900

Wavelength (nm)

1100

lP

re

Fig.14. Near-infrared spectra of samples B2 and B2-650.

1000

-p

200

ro

10

100 90

ur na

B2

70 60 50 40 30

Jo

Total transmission (%)

80

20 10

B2-650

0

1000

1200

1400

1600

1800

2000

2200

2400

wavelength (nm)

Fig.15. FTIR Spectra of samples a) S2, S2-750 and S2-775 and b) B2, B2-650, B2-680 and B2-700.

100 90

(a)

70 60

698

S2 S2-775 S2-750

50 40 30

of

465

Transmission(%)

80

20 1005 0 0

500

1000

1500

2000

2500

3000

3500

ro

407

10

4000

re

-p

wavenumber (cm-1)

4500

lP

100

2600-3800

(b)

698

1450

465

60

768

ur na

Transmission(%)

80

B2 B2-650 B2-680 B2-700

40

407

1005

Jo

20

0

0

500

1000

1500

2000

2500

3000

wavenumber (cm-1)

3500

4000

4500

5000

Table 1 chemical composition of the samples (molar ratio)

𝐒𝐢𝐎𝟐

Sample

𝐀𝐥𝟐 𝐎𝟑

𝐁 𝟐 𝐎𝟑

𝐍𝐚𝟐 𝐎

𝐂𝐚𝐎

𝐈𝐧𝟐 𝐎𝟑

𝐒𝐧𝐎𝟐

name 58

10

-

16

10

5

1

S2

56

12

-

16

10

5

1

B1

56.71

12.15

10.13

16.21

-

4

0.8

B2

57.43

12.31

10.25

16.41

-

3

0.6

ro

of

S1

Sample

-p

Table 2 heat treatment programs and the corresponding sample codes.

Temperature of heat

S1-750

750 800

lP

S1-800

re

treatment (℃)

750

S2-760

760

S2-775

775

S2-800

800

B2-650

650

B2-680

680

B2-700

700

B2-730

730

Jo

ur na

S2-750

Table3. Crystallite size of different samples calculated by the scherrer

S2-760

B2-650

B2-680

B2-700

B2-730

Crystallite size (nm)

21

5

12

15

17

Jo

ur na

lP

re

-p

ro

of

Sample name