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TIO2 THICK AND THIN FILMS DEPOSITION: DIFFERENT METHODS ORIGINATE DIFFERENT RESULTS ?

ngela Semitela(1), Daniela Gomes(1)and Diogo Almeida(1) (1) Master in Materials and Biomedical Devices Department of Ceramics and Materials Engineering, University of Aveiro ABSTRACT TiO2 thick and thin films were produced by three different techniques, electrophoretic deposition, sol-gel and RF magnetron sputtering, in order to compare them. TiO2 is of great interest in materials science owing to its excellent properties. This compound exists, predominantly, in two crystalline polymorphs: anatase and rutile; and according to the deposition conditions of each technique, rutile or anatase phase could appear in the film structure. In EPD, in a green stage, anatase phase was present in the film, but when this was sintered, rutile phase appeared. Before sintering, films thickness increased with the deposition time and applied voltage, although not indefinitely. In sol-gel, the only phase present was anatase. The crystallinity increased with the number of layers and annealing temperature. In RF magnetron sputtering, rutile was the phase present. As the deposition time and annealing temperature increased, the films crystallinity was improved. So, different methods originate different results. Keywords: TiO2, anatase, rutile, thick and thin films, EPD, sol-gel, RF magnetron sputtering, thickness

INTRODUCTION TiO2 is one of the most studied compounds in materials science due to its outstanding properties such as the stability of its chemical structure, high refractive index and dielectric constant, its antimicrobial activity, its biocompatibility and durability and also its transparent to visible light (1-7). This compound has been used to photocatalytic systems and solar cells, sensors, corrosion resistant coatings, paint pigments, selfcleaning activity, sunscreen lotions, and some medical applications such as dental implants and drug delivery systems (8-13). TiO2 exists in three different crystalline polymorphs: anatase, rutile and brookite (Table 1). Only the first two play a significant role in industrial applications, because of to its rareness and difficult preparation (14). At standard pressure (1 bar) and normal temperatures, the rutile phase is thermodynamically more stable than anatase and brookite phases, so that they can be easily converted into rutile at high temperatures (15, 16). However anatase becomes the stable phase, when particle size decreases to sufficiently low values, nearly 14nm, due to the increase of the rutile total free energy (16). TiO2 films can be prepared using a variety of methods. The choice of this methodology will determine the thickness of the film. So there are thin films, whose thickness is below 1 m, and thick films with the thickness above 1 m. In this Advanced Preparation Methods 2011/2012

experiment, only were used three of them: electrophoretic deposition (EPD), sol-gel process and RF sputtering. Electrophoretic deposition (EPD) is a colloidal processing technique that uses the electrophoresis process for the movement of charged particles suspended in a slurry under an electric field, to deposit them in an ordered manner on a substrate to develop thick films (17). This technique has a short formation time, needs simple apparatus, controls the degree of stoichiometry, has little restriction of the shape of substrate and no requirement for binder burnout as the green coating contains few or no organics (18).However when large particles are used, they tend to settle due to gravity (18). Solgel is a solution based process using a metal oxide precursor, a solvent and a stabilizer. This process is generally used to the deposition of thin films. It offers several advantages: it allows a better control of the chemical composition and microstructure of the film, it has a low temperature processing, large areas can be coated easily with this process, and finally it requires significantly less equipment and is less expensive. Although this may generate amorphous or low crystallinity materials that requires a subsequent annealing for crystallization or further crystallization and the annealing process may lead to hard aggregation (19, 20). Sputtering is the deposition of particles whose origin is from a surface (target) being sputtered, forming thin films. According to the 1

target material characteristics, the sputtering can be DC sputtering (direct current), RF sputtering (radio frequency) and magnetron sputtering (magnetic) (21, 22). Magnetron sputtering is presently the most widely commercially practiced sputtering method. The chief reason for its success is the high deposition rates achieved (23). Generally, high flows of the reactive gases such as oxygen and argon are required for formation of TiO2 films. The deposition rate of the film, however, drops abruptly when compounds are formed on the target surface at high flows of the reactive gases (2). In contrast to the fractionation of alloy melts during evaporation, with subsequent loss of deposit stoichiometry, sputtering allows for the deposition of films having the same composition as the target source (23). Films prepared by reactive magnetron sputtering always present some structural and morphological heterogeneities, such as porosity and surface roughness (22). The aim of this work is the comparison between TiO2 thin and thick films obtained from three different techniques, previously referred.
Table 1 Crystal structure data of TiO2 (24)

According to the XRD results, thick films obtained by EPD presented, in a green stage, a substantial amount of anatase, and after sintering all the anatase was converted in rutile (Figure 2).
Table 2 - Thickness measurements (m)

Sample 1 2 3 4 5

1st 38 71 69 15 46

2nd 41 59 58 22 48

3rd 37 68 75 22 50

Average 38,(6) 66,0 67,(3) 19,(6) 48,0

Rutile
Crystal structure Lattice constants () Tetragonal a=4,5936 c=2,9587

Anatase
Tetragonal a=3,784 c=9,515

Brookite
Orthorhombic a=9,184 b=5,447 c=5,145

RESULTS AND DISCUSSION Generally, the deposited phase is determined by similarity of the lattice parameters between the substrates and the crystal structures, however, in this case, the chosen phase is preferentially influenced by several factors such as annealing temperature, deposition time and others. In literature there was no reference to EPD in TiO2 films, so these results cannot be compared.
80 70 Thickness ( m) 60 50 40 30 20 10 0 0 100 200 300 400 500 Voltage (V)

Analysing SEM micrographs (top view) of EPD films in platinum substrates, it could be said that, in a green and sintered stages (with 200V during 2 minutes), the surface was rough and in sintered stage, some cracks appeared, that can be seen in Figure 3. The presence of these cracks is due to the different thermal expansion coefficients of the film and the substrate and the release of tensile stress (18). In cross-section, there was a huge differentiation in the particle sizes in the two stages, being the sintered ones bigger (Figure 4). The thickness of the sintered films (approximately 318,(3)m) was much higher than that of green ones (nearly 146m). This last value was obtained using coarse particles in the suspension, so the thickness of the resulting film was much higher than the ones in Table 2. Films thickness increased with the deposition time and applied voltage, as seen in Table 2 and Figure 1, however this thickness will not enhance indefinitely and it will stabilize (18). When deposition time was elevated, at the same stress, the thickness increased abruptly; in Figure 1(b) there were only two points, so it was not possible to determine clearly the influence of the deposition time, but in literature a non-linear increase and even a decrease were referred (18).
60

a)
Voltage
Thickness ( m)

b)
50 40 30 20 10 0 0 1 2 Deposition Time (min) 3 4 Deposition Time

Figure 1 Thickness variation with applied voltage [2 minutes] (a) and deposition time [200V] (b).

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2 1,8 1,6 1,4 Intensity (arbitrary units) 1,2 1 0,8 0,6 0,4 0,2 0 10

Green Sintered Anatase Rutile


R(110)

R(211) A(101) R(101)

A(200)

20

30

40

50

60

70

80

Figure 2 XRD spectra of rutile and anatase TiO2 grown on Pt substrates by EPD when films are in a green or sintered stage.

Figure 3 - SEM micrographs of the surface of TiO2 film in platinum substrate (on the left image in a green stage, and on the right image in a sintered stage [200V and 2 minutes]).

Figure 4 - SEM micrographs of the cross-section of TiO2 film in platinum substrate (on the left image in a green stage, and on the right image in a sintered stage [200V and 2 minutes]).

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According to the XRD results, TiO2 films produced by sol-gel technique presented only anatase phase. In literature, when acetic acid was used as a stabilizer the rutile peaks only appear between 1000 and 1200C (25); but in this case, the temperature range was only 500 to 700C, because substrates could not support high temperatures (platinised silicon); Alumina substrates were the only ones that could handle higher temperatures (15), but they were not used. The amount of this phase was small, as seen in Figure 8. The increase of the peaks intensity and decrease of peak width in Figure 8 showed that the annealing leads to an improvement of the crystalline quality due to the increase of crystallite size of the films by the rising of annealing temperature (26-28). Observing Figure 9, could be concluded that with more layers, the crystalline structure was improved and the influence of the substrate in films growth was reduced, when the substrate was platinised silicon. This situation was more evident with five layers. In previous studies, using glass substrates, the effect of the number of layers was the opposite, as the number of layers was reduced, the intensity of peaks increased (29). The different precursors used originated different amorphous-anatase phase transformation temperature. While, with titanium isopropoxide, the anatase phase appeared with annealing at 500C and four layers, when titanium butoxide was used, the anatase only emerged with annealing at 700C and five layers. In ref. (27), were used two methods, one of them with
400 350 Thickness (nm) 300 250 S/Pt (700C) Linear (S/Pt (700C))

titanium butoxide and the other titanium isopropoxide, and they concluded that the second one had broader temperature range, although the stabilizer and solvent choices were a little different. When the substrate was glass, TiO2 films had substantial anatase phase in direction (101); this have been reported by some researches (29-32). Analysing SEM micrographs (top view) of sol-gel films in platinised silicon substrates, it could be said that all films presented a relatively smooth surface with a small amount of impurities. In the cross-section of the film, the interface between the platinum surface and the TiO2 film was not visible, even in the EDS images, because the amount of TiO2 was very small (Figure 7). In alumina substrates, the surface (Figure 6) and cross-section of the film present a lot of roughness, because of the substrate influence, and the interface between the substrate and the film was not visible in the SEM micrographs, but in EDS images, it was possible to see a small amount of Ti. In glass substrates, the surface of the film appears cracked, when the magnification of the sample was smaller; in other hand, when the magnification was higher, the film appears smooth. The interface between the substrate and the film was not visible in the SEM micrographs, and there were not any EDS images for this substrate, so it was not possible find some Ti. The thickness of the obtained films, measured in the micrographs, increased with the number of layers (Figure 5).
450

a)
Thickness ( m)

400 350 300 250 200 150 100 50 0

4 Layers Linear (4 Layers)

b)

200
150 100 0 2

y = 74,174x

y = -1,1982x + 980,4

400

500

600

700

800

Number of layers

Annealing temperature (C)

Figure 5 Thickness variation in platinised silicon substrates with number of layers [annealed at 700C] (a) and annealing temperature [4 layers] (b).

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Figure 6 SEM micrographs of the surface of TiO2 film in alumina substrate, annealed at 700C (4 layers).

Figure 7 SEM micrographs of the cross-section of TiO2 film in platinised silicon substrate, annealed at 700C (in the left image with 3 layers, and in the right image with 5 layers).

Figure 8 - XRD spectra of anatase TiO2 grown on Si coated with Pt substrates by sol-gel technique (titanium isopropoxide), with different annealing temperatures (500C, 600C and 700C) (Anatase peaks for each temperature are in the same scale (0,05)).

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Figure 9 - XRD spectra of anatase TiO2 grown on Si coated with Pt substrates by sol-gel technique (titanium butoxide), with different number of layers (3, 4 and 5 layers) (Anatase peaks for each temperature are in the same scale (0,05)).

In all substrates, using RF magnetron sputtering, only rutile peaks appeared. This might be due to the low working pressure in the chamber (0.35Pa) and the high substrate to target distance. According to previous studies, with a total pressure of 0,27Pa, rutile TiO2 films were acquired, while anatase TiO2 films were obtained at a pressure of 2,7Pa (33); to originate rutile TiO2 films the substrate to target distance should be 40mm or bigger (34). The annealing temperature increased the intensity of the rutile peaks, and in this way improved the crystallinity (35); this situation can be seen for glass substrate (35), in Figure 12. As the deposition time increased, the crystallinity of the TiO 2 films improved and the influence of the substrate is decreased because the intensity of the substrate
450 400 350 Thickness (nm) 300 250 Thickness (nm) y = 39,097x + 65,247

peaks was inferior; in Figure 11, the alumina case is presented. In literature this phenomenon was also confirmed (36). As it is evident in the cross-section of the SEM images (Figure 13), with RF sputtering the interface film-substrate was not well visible. In the top view, TiO2 films in alumina substrate presented a rough surface, in glass substrate appeared some impurities (Figure 14), but the surface was relatively smooth and in platinised silicon substrate the surface also was smooth. The thickness of the TiO 2 films increased with the deposition time (36), but decreased with the annealing temperature. There was a value (with 5 hours of deposition) that did not agree with the tendency line in Figure 10 (a), but it is probable that this value is wrong.
450 400 350 300 250 200 150 Si/Pt (8h) Linear (Si/Pt (8h)) y = -0,685x + 813,93

a)

b)

200
150 100 50 0 0 2 4 6 8 10 Deposition time (h) 600 Linear (600)

100
50 0

500

600

700
Temperature ( C)

800

900

Figure 10 - Thickness variation with deposition time [annealed at 600C] (a) and annealing temperature [8 hours of deposition] (b).

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4 3,5

d)
3 Intensity (arbitrary unit)

2,5
2

600C

c)

700C 800C Rutile Anatase

1,5 1 0,5

b)

a)
0 10 20 30 40
2

50

60

70

80

a) b) c) d) Figure 11 - XRD spectra of rutile TiO2 grown on alumina substrates by RF sputtering, with different annealing temperatures (600C, 700C and 800C) (Rutile peaks for each temperature are in the same scale (0,15)).
2,5 R(110) R(110) 1,5 R(110)

2 Intensity (arbitrary units)

3h 5h 8h Glass Rutile

0,5

0 10 20 30 2 40 50 60

Figure 12 - XRD spectra of rutile TiO2 grown on glass substrates by RF sputtering, with different deposition time (3 hours, 5 hours and 8 hours).

Figure 13 SEM micrographs of the cross-section of TiO2 film in platinised silicon substrate, annealed at 600C varying the deposition time ( 3, 5 and 8 hours, on the left, middle and right, respectively). Note: the magnifications are different (20kx , 10kx, 5kx, on the left, middle and right, respectively).

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annealing temperature increased, the films crystallinity was improved. SEM micrographs shown, in glass and platinised silicon substrates, a smooth surface was found, but in alumina substrates the roughness, characteristic of alumina, was also present in the film. In future work, other characterization techniques should be applied to do a better comparison of methods.
Figure 14 SEM micrographs of the surface of TiO2 film in glass substrate, annealed at 600C, with 5 hours of deposition time. MATERIALS AND METHODS There were used four substrates: platinum, platinised silicon, alumina and borosilicate glass. Each of them was a specific lattice parameter that influences the film deposition: Platinum (cubic structure) and platinised silicon (the platinum coating determine the deposition); o a=3,9231. Alumina (trigonal structure); o a=4,7587. o c=12,9929. Silicon (cubic structure); o a=5,43053. Three different techniques were employed to deposit the film on top of the referred substrates: electrophoretic deposition, sol-gel and RF magnetron sputtering. In the electrophoretic deposition (EPD) process, a dc electrical field was placed in a suspension, in order to promote the motion of charged particle to a substrate and create a film. The suspension had 100mL of acetone, 2mL of triethanolamine (pH=7,8) and 0,05g of titanium dioxide. Platinum was the material of the substrates; in this case it was not used platinum on top of the silicon because this has minor annealing temperature. The dimensions of substrates were 1cm by 1cm. The substrates were cleaned with acetone and placed in an ultrasonic.

As expected, EPD process produced thick films, while with sol-gel and RF magnetron sputtering methods thin films were obtained; but TiO2 phases in these last two techniques were different: in sol-gel, anatase was the only phase present, whereas only rutile was found with RF magnetron sputtering. The crystallization of the films in each method appeared to be the same, so other characterization techniques are required, to make further distinctions between thin films. CONCLUSION The initial hypothesis was correct; in fact different methods originate different results. The thick films were obtained only by EPD technique and the sol-gel and RF magnetron sputtering created thin films. In EPD method, the thickness increased with the deposition time and applied voltage, although not indefinitely. Also the films presented rough surfaces and some cracks. Regarding the XRD patterns, in a green stage, the only phase presented was anatase, and after the sintering process, anatase was converted in rutile. When sol-gel method was employed, the thickness increased with the number of layers, but decreased with the annealing temperature. According to the XRD spectra, it can be concluded that the only phase present was anatase and, with more layers and higher annealing temperatures, the films crystallinity was improved. The films presented smooth surface with some impurities, except for alumina substrates whose surface was rough. The interface between the film and the substrate was imperceptible in SEM images. Finally, in films obtained by RF magnetron sputtering, rutile was the phase present. The thickness of the TiO 2 films increased with the deposition time, but decreased with the annealing temperature. Also, as the deposition time and Advanced Preparation Methods 2011/2012

Figure 15 EPD cell in the suspension.

The EPD cell was made of Teflon and stainless steel and the distance between the electrodes was 20mm and the current applied was, approximately, 2-3mA. It was necessary to put a platinum substrate both electrodes to allow the passage of the current in the suspension. The deposition parameters used for each assay are expressed in Table 3. After deposition, the samples were dried during one day. The thickness of the green films was measured with a micrometer. Finally the films were sintered at 1200C during 3 hours.

Table 3 Different deposition parameters used in EPD method

Table 4 RF magnetron sputtering conditions for TiO2 films deposition.

Assay 1 2 3 4 5

Applied voltage (Volts) 200 300 400 200

Deposition time (Minutes) 2 1 3

RF sputtering conditions RF Power (Density) Target Diameter Target Substrate Distance RF Sputter Gases Ar Flow O2Flow Deposition Temperature Deposition Time Post Deposition Treatment

Values 60W (3W/cm2) 2in 8cm 13,56MHz Ar + O2 15Sccm 5Sccm Room Temperature 3, 5 and 8 hours Annealing at 600C, 700C and 800C

Other technique used was sol-gel. It was used two kinds of precursors to prepare each sol, titanium isopropoxide and titanium butoxide. In order to prepare the first one, with 20 ml of the TiO2 sol whose concentration was nearly 0.4M, 3,02ml of the tetraisopropyl orthotitanate C12H28O4Ti (98%, Merck Germany) was dissolved in 5ml of acetic anhydrate (99%, Riedel-de Han Germany) and 11,98ml of 2-propanol (99,8%, Fluka Germany). Later, the solution was vigorously stirred during 6-8h at room temperature, to obtain a reddish solution, ready to be used for deposition. To make the second one, with the same TiO2 volume and concentration, 2,77ml of the tetra-n-butyl orthotitanate C16H36O4Ti (98% Merck, Germany) was dissolved in 10,57ml of acetic acid AcOH (99%, Merck Germany), 2,8ml of 1,2-propanediol (99,5%, Riedel-de Han Germany) and 5ml of absolute ethanol (99,8%, Merck Germany). 1,2propanediol and acetic acid were positioned in the beaker and mixed for 5-10min, and then the precursor was dropped into diol/AcOH mixture. The solution was maintained under constant stirring for about 12h. Finally, ethanol was added to this transparent and yellowish solution, and continued mixing for another 1h. The substrates used were platinised silicon, alumina and borosilicate glass. They were cut with a diamante cutter with 1cm by 1cm. The substrates were immersed on alcohol or acetone at 80C, in order to clean them. Then they were dried in a heating plate at 200-250C and, after that, they were cooled at room temperature. For both sols, spin coating was used to deposit TiO2 sol onto substrates. The coating conditions were: 4000rpm / 30s. After each coated layer, the wet films were dried on the heating plate at 200-250C for 3min, in order to remove the most volatile organic species prior to the next deposition. Final crystallization of amorphous built-up TiO2 films was done in the tubular furnace at distinct temperatures (500, 600 and 700C) for 1h, with heating and cooling rate 10C/min. The final method used was RF magnetron sputtering. TiO2 films were deposited at room temperature on the same substrates used on sol-gel, by RF in a vacuum system equipped with a turbo molecular pump. The targets were prepared by uniaxially pressing commercial TiO2 powder (Riedel-de Han titanium (IV) oxide 99%) in a 60mm mould with a pressure of 300bar. The compacted green disc was sintered at 1200oC for 1 hour with a heating/ ramp rate of 10oC/min. The dimensions of the substrates were not the same as those of the other techniques, because the dimensions were not important in this case. The substrates were cleaned using a sequential ultrasonic cleaning in isopropyl alcohol and acetone for 2-3min each, and drying under flowing nitrogen. The cleaned substrates were placed at a distance of 80mm from the TiO2 target surface and the sputtering chamber was evacuated to a base pressure of approximately 10-3Pa. All the films were deposited at a fixed power density of 3Wcm-2. A working pressure of 0,35Pa was constantly maintained using a mixture of high pure argon and oxygen while varying the deposition duration. The sputtering conditions are detailed in Table 4.

The final films were then characterized by several techniques: X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS).

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ACKNOWLEDGMENTS The authors gratefully acknowledge to Professor Paula Vilarinho for the possibility to expand our knowledge and the opportunity to acquire useful laboratory experience; also, to the various people of CICECO, specially Ana Ribeiro, Clia Miranda, Maria Joo Bastos, Sebastian Zlotnik, Venkata Saravanan and Ximing Su for the technical support and their availability to answer our questions.

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