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Effect of Different Dip-Coating Techniques on TiO2 Thin Film Properties

Article  in  Key Engineering Materials · December 2016

DOI: 10.4028/www.scientific.net/KEM.721.128

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Effect of Different Dip-Coating Techniques on TiO2 Thin Film Properties
Kaspars Malnieks1,a*, Gundars Mezinskis1,b, Ilona Pavlovska1,c
1
Institute of Silicate Materials, Riga Technical University, Latvia
a
k-malnieks@inbox.lv, bgundarsm@ktf.rtu.lv, cpilona@ktf.rtu.lv

Keywords: Sol-gel, TiO2, Thin films, Nanorod array, Photocatalysis.

Abstract. TiO2 three-layer sol-gel films have been deposited on soda-lime silicate glass slides and
dried in two different ways to study the effect of drying on thin film structure. The structural
properties, surface topography and photocatalytic activity of the films were studied by X-ray
diffraction, atomic force microscopy, and by analysing photocatalytic degradation of methyl orange,
respectively. The titanium oxide sol-gel layers on glass slides dried at 20 °C before the deposition
of next layers after final calcination at 500 °C resulted in a nanorod array film with good
photocatalytic activity.

Introduction
Ever since 1972 when Fujishima and Honda discovered the photo-catalytic function of
titania [1], there has been increasing interest in titanium dioxide (TiO2) films. TiO2 films find a
variety of applications such as dye sensitized solar cells [2], photo electrodes [3], photocatalysts
[4,5], gas sensors [6], and biomaterials [7] due to titania high activity, photochemical inertness,
non-toxicity, good acid resistance, and low cost.
Many physical and chemical approaches have been used for the preparation of crystalline
TiO2 thin films such as chemical vapour deposition [8], sputtering [9], electron-beam evaporation
[10], and sol-gel [11,12]. The sol-gel technique has emerged as one of the most promising
techniques for growing crystalline TiO2 thin films [13]. TiO2 properties are strongly dependent on
the film’s microstructure, which should be strictly controlled to obtain the required properties. The
sol-gel method is one of the promising methods of controlling the thin film microstructure by
changing the solution composition and deposition conditions [14].
In order to obtain thin films of sol-gel, a variety of methods are used, such as dip-coating,
spin coating, and plasma spray process [15]. Depending on the method used, one can obtain thin
films with different surface structures that affect the thin film properties. The most popular method
is dip-coating, which makes it possible to obtain thin films with a wide range of thicknesses from a
few nanometres up to several micrometres [16]. The viscosity of coating solution and the speed of
withdrawal from the coating solution must be controlled during the preparation of thin films.
Planning the pre-treatment and heat treatment of thin films is also of great importance, as
these processes significantly affect the film properties such as the crystal size, density, and optical
properties [17].
The purpose of the present study is to show the difference between two different dip-coating
obtained films drying techniques before the thermal treatment of films which significantly affect the
coating morphology, optical properties, and photocatalytic activity.

Experimental
The chemicals used for sol preparation were titanium (IV) isopropoxide (TTIP) (Sigma-
Aldrich) as a precursor of TiO2, 2-propanol (Sigma-Aldrich) as a solvent, glacial acetic acid
(CH3COOH) as a chelating agent, and distilled water (H2O). The preparation order was as follows:
First, TTIP was dissolved in 2-propanol and stirred for 1 h, then acetic acid was added and stirred
for 1 h, and after that H2O was added. Then the solution was stirred for 30 min. The molar ratio of
TTIP, 2-propanol, acetic acid, and H2O was 1:10:4:0.5. The deposition process was performed in a
clean room at ambient environmental parameters of 20 °C and relative humidity of 25%.
 The films were grown by two different dip-coating methods on a soda-lime silicate glass
slides. According to the first method (1 × 1 × 1), the substrate was dipped and withdrawn at a speed
of 220 mm/min from sol, then dried at ambient temperature (20 °C) for 5 min, and then immersed
and withdrawn again from sol at the same speed; this cycle was repeated until three layers of
coating were obtained. Then the coating was dried at 200 °C in a furnace for 5 min, and then
calcined in the furnace at 500 °C for 1 h. The second method (3×) differs in that the drying was not
carried out at 20 oC. After each layer deposition sol-gel layers were dried at 200 °C for 5 min,
cooled to ambient temperature, and then the next layer was deposited. Finally 3 sequentially
deposited and dryed layers were calcined at 500 °C for 1 h. The film morphology, surface structure,
and composition were investigated by X-Ray diffraction (Rigaku Ultima+) and atomic force
microscopy (Veeco SPM II). Particle size and roughness were measured from AFM images using
Image Processing v. 2.1 software. Film deposition was carried out by dip-coating (KN 4002 KSV
NIMA Dip Coater Single Vessel System Small), photocatalytic properties were investigated using a
125-W UV lamp and UV/Vis photospectrometer (Thermo Scientific Genesys 10S Vis).
The photocatalytic activities of films were evaluated by analysing photocatalytic
degradation of methyl orange (MO) in aqueous solution. The initial concentration of MO in the
reaction vessel was fixed at 10 mg/l. Before irradiation, samples were stirred for 30 min in the dark
to reach absorption–desorption equilibrium. A 125-W UV lamp was used as the light source.
During irradiation, samples were withdrawn at regular time intervals and the absorbance spectra
were measured in the range of 350 to 550 nm

Results
Figure 1 shows the XRD patterns obtained from TiO2 coating produced by different coating
methods, 1 × 1 × 1 and 3×, as described in the experimental section. It can be seen from Fig. 1 that
the TiO2 coating annealed at 500 °C shows the crystalline phase of anatase with the main peak at
25.3°. The only difference between the XRD patterns is that for the 3× coating this main peak
FWHM is narrower (0.3) than 1x1x1 (0.36), which could be explained by the larger particle or
crystalline size which leads to agglomerates in the coating.

Fig. 1. XRD data from 1 × 1 × 1 and 3× samples

Figure 2 shows the coatings surface morphology. The particle size and average roughness
of coatings are listed in Table 1. From Figure 2 and Table 1, we can see clearly that the structure of
film obtained according to the 1 × 1 × 1 method is formed by nanorod arrays with an average
particle size of 94 nm (the height of nanorods - about 180 nm) and average surface roughness of
5.34 nm.
 a) b) c)

Fig. 2. AFM images of coating with 1 × 1 × 1 method a) 20 µm, b) 5 µm and c) 1 µm

Figure 3 shows the surface morphology of coating obtained by the 3× method. It can be seen
that the film structure obtained with method 3× is different from that obtained with the 1 × 1 × 1
method. In the sample obtained with 3× method we can see agglomerates with an average size of
495 nm. The average surface roughness was 22.88 nm. The formation of agglomerates and such
structures can be explained by the particle nucleation mechanism after the drying of each coating
layer. Each dip-coating cycle according to the 3× method presumably allowed more nucleation
events randomly distributed over the surface of the amorphous regions of the film. After a nucleus
has formed, the next dip-coating cycle contributed further to the mass of nuclei, resulting in the
growth of crystallite agglomerates [18].

a) b) c)

Fig. 3. AFM images of coating obtained with method 3× a) 20 µm, b) 5 µm and c) 1 µm

 Table 1. Properties of TiO2 sol-gel coating
Average Particle Coating thickness
Sample
roughness (nm) size (nm) (nm)
1×1×1 5.3±0.2 94±2 286±5
3× 22.8±0.2 495±2 412±5
The data of photocatalytic activity confirmed that the 1 × 1 × 1 method allowed obtaining
smaller anatase nanoparticles than in the case of the 3× method. As can be seen from Figure 4 that
greater degradation of MO was achieved by the sample obtained with the 1 × 1 × 1 coating method
which was able to degrade 87% of the substance (MO) in 6 hours, while the sample obtained with
the 3× coating method was able to degrade only 54% of the MO. This could be explained by the
fact that the samples obtained with the 1 × 1 × 1 method had a smaller particle size (94 nm), while
the particle size of the sample obtained with the 3× method reached 495 nm. From literature data it
is well known that particle size has a direct effect on photocatalytic activity [19, 20].

Fig. 4. Photocatalytic activity of samples obtained by the 1 × 1 × 1 and 3× methods

Conclusion
TiO2 three-layer sol-gel films were deposited on soda-lime silicate glass slides and dried in
two different ways.
It can be concluded that depositing multilayer sol-gel titania dip-coatings each of layer
before final calcination should be dried at least close to 20-50 oC. Higher drying temperatures could
lead to more intensive nucleation and to the growth of anatase crystallites.
Metil orange degradation after testing during 6 h of sol-gel three layer coatings obtained by
drying the each of deposited layer at 20 oC, was more than by 30% higher than that for coatings
dried at 200 oC.

Acknowledgments
Authors wish to acknowledge the financial support of European Regional Development Fund "The
development of hydrophilic and superhydrophobic nanoparticles containing coatings for steel
borosilicate enamel by the use of sol-gel and laser technologies" (Project No
2014/0049/2DP/2.1.1.1.0/14/APIA/VIAA/104).
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