# The Photocatalytic Activity and Compact Layer Characteristics of TiO2 Films Prepared Using Radio Frequency Magnetron Sputtering

Authors: H. C. Chang; H. H. Huang; C. Y. Wu; R. Q. Hsu; C. Y. Hsu
Journal: International Journal of Photoenergy
 (2014)

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## Abstract

TiO2 compact layers are used in dye-sensitized solar cells (DSSCs) to prevent charge recombination between the electrolyte and the transparent conductive substrate (indium tin oxide, ITO; fluorine-doped tin oxide, FTO). Thin TiO2 compact layers are deposited onto ITO/glass by means of radio frequency (rf) magnetron sputtering, using deposition parameters that ensure greater photocatalytic activity and increased DSSC conversion efficiency. The photoinduced decomposition of methylene blue (MB) and the photoinduced hydrophilicity of the TiO2 thin films are also investigated. The photocatalytic performance characteristics for the deposition of TiO2 films are improved by using the Grey-Taguchi method. The average transmittance in the visible region exceeds 85% for all samples. The XRD patterns of the TiO2 films, for sol-gel with spin coating of porous TiO2/TiO2 compact/ITO/glass, show a good crystalline structure. In contrast, without the TiO2 compact layer (only porous TiO2), the peak intensity of the anatase (101) plane in the XRD patterns for the TiO2 film has a lower value, which demonstrates inferior crystalline quality. With a TiO2 compact layer to prevent charge recombination, a higher short-circuit current density is obtained. The DSSC with the FTO/glass and Pt counter electrode demonstrates the energy conversion efficiency increased.


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## Body

## 1. Introduction

Dye-sensitized solar cells (DSSCs) have been extensively studied as a promising alternative to conventional solar cells that use a p-n junction because of their reasonable conversion efficiency, low cost, environmentally friendly components, use of a flexible cell design, and simple fabrication process, when compared to silicon solar cells [1]. DSSCs are the next-generation solar cells [2]. If low cost and highly efficient DSSCs can be developed, it will be an important new direction for the development of solar cells. A typical DSSC consists of dye molecules that act as sensitizers, a nanoporous metal oxide film (TiO2 semiconductor material), a transparent conducting oxide (indium tin oxide, ITO), an electrolyte charge carrier, and a counter electrode (Pt or carbon) [3]. The dye and metal oxide, which are used for the sensitizer and the electrode, respectively, are important to the photoelectric conversion efficiency of DSSCs [4].TiO2 is one of the most popular photocatalytic materials, so it has many commercial applications, such as antibacterial applications, waste purification, self-cleaning, and sensors [5]. It is also used for photoelectrodes and in high performance DSSC applications because it has an adequate photoresponse and effective electron transport [6]. A high incident photon to current conversion efficiency is expected for TiO2 films that have a better phase structure and crystallinity and a higher specific surface area [7]. The control of the TiO2 nanostructures is very important for the photovoltaic performance of a DSSC [8]. In order to improve the conversion efficiency of DSSCs, several studies have focused on the structural design, material development, photovoltaic characterization, and analysis of the mechanism of TiO2 nanoparticles [9]. Mesoporous TiO2 is widely used as an electrode in DSSCs to produce a high surface area for the adsorption of a greater density of dye molecules, which produces a significant increase in the photocurrent [10]. However, the highly porous structure of the TiO2 layer can cause an electrical shortage and recombination of the charge/electrons, which interferes with the unidirectional electron transport that takes place at the TiO2 layer/dye molecule and ITO/TiO2 layer interfaces [11]. This leakage by electronic back transfer leads to a decrease in cell efficiency. To avoid this problem, the primary method used to prevent recombination is the use of a TiO2 compact layer (blocking layer) between the ITO and the porous TiO2 layer [11]. This compact layer can be prepared using many growth techniques, such as sputter deposition, dip-coating, chemical vapor deposition, and spray pyrolysis.This study determines the optical, structural, and surface properties of a TiO2 compact layer that is grown by radio frequency (rf) magnetron sputtering on the ITO electrodes, as a function of the deposition parameters that ensure higher photocatalytic activity and greater DSSC conversion efficiency. The nanoporous TiO2 upper layer is coated using the sol-gel process and calcination at 450°C. Moreover, the working electrode which is made of a dye-sensitized TiO2 film that is immobilized onto a fluorine-doped tin oxide (FTO) substrate is also investigated.The Taguchi method is a powerful tool for the design of high quality systems, which can be used to design low cost products, with improved quality [12]. To optimize the deposition process for TiO2 photocatalytic films, a statistical analysis of the signal-to-noise ratio (S/N) is performed, using an analysis of variance (ANOVA). The optimal deposition parameters are obtained by analyzing the results for various experimental permutations [13, 14]. Table 1 shows the effect on the quality of the TiO2 photocatalytic films of four deposition parameters at three levels: the rf power, the sputtering pressure, the Ar-O2 ratio, and the deposition time. An L9 (34, with four columns and nine rows) orthogonal array is used.Table 1
The factor and level settings for sputter deposition of TiO2 compact layers.
Substrate
Soda-lime glass, 20 × 20 × 1 mm3
Target
TiO2 (99.99% purity)
Gas
Ar and O2 (99.99% purity)
Base pressure
5.0 × 10−6 torr
Substrate-to-target distance
80 mm
Substrate temperature
Room temperature
Substrate rotate vertical axis
10 rpm
Symbol
Control factor
Level 1
Level 2
Level 3
A
rf power (W)
100
130
160
B
Sputtering pressure (mtorr)
3
5
7
C
O2/(Ar + O2) (%)
10
30
50
D
Deposition time (hr)
2
3
4


## 2. Experimental

The TiO2 photocatalytic thin films (compact layer) were coated onto ITO/glass substrates (and FTO/glass), using rf magnetron sputtering. The reactive and sputtering gases were O2 (purity: 99.99%) and Ar (purity: 99.99%), respectively. The commercially available, hot pressed, and sintered ceramic target TiO2 had a diameter of 50.8 mm and 99.99% purity (Elecmat, USA).Prior to coating, the target was presputtered for 15 min, in order to remove any contamination, and the substrates were ultrasonically cleaned and degreased in acetone, rinsed in deionised water, and subsequently dried with nitrogen gas. A vacuum, of base pressure 5.0 × 10−6 Torr, was applied before deposition. The distance between the substrate and the target (80 mm) and the rotational speed of the substrate (10 rpm) were constant. By adjusting the experimental permutations, this study determined the effect of each deposition parameter on the deposition rate for TiO2/ITO/glass, the methylene blue (MB) absorbance, the contact angle to a pure water droplet, the surface morphology, and the crystal structure.The porous TiO2 film (p-TiO2) was coated onto the TiO2 compact/ITO/glass (and TiO2 compact/FTO/glass) using a mixture of TiO2 powders (P-25, particle size: <25 nm, 99.7%) with the TiO2 sol-gel component studied in [15]. The TiO2 sol-gel was mixed with 0.3 g of commercially available Degussa P-25, to avoid any cracking of the film. The TiO2 sol-gel was produced using spin coating and blade coating. The gels were predried for 15 min at 50°C and then sintered in a box furnace at 450°C (heating rate 10°C/min) for 30 min in air ambient, to produce the bare TiO2 electrode used in this work to fabricate the DSSC. The porous TiO2 films were immersed into the dye solution (0.4 mM N719 dye solution, Solaronix, Switzerland, Di-tetrabutylammonium cis-bis(isothiocyanato)bis(2,2′-bipyridyl-4,4′-dicarboxylato)-ruthenium(II); chemical formula C58H86N8O8RuS2; Mol Wt: 1188.55) complex for 24 h at room temperature.The Pt counter electrode was coated onto ITO/glass (and FTO/glass) substrates using DC sputtering with pure Ar gas and a DC power of 30 W. The dye-adsorbed TiO2 working electrode and the counter electrode were assembled into a sandwich-type cell and sealed with a hot-melt sealant. Figure 1 shows a schematic diagram of a DSSC with an rf-sputtered TiO2 compact layer/ITO/glass on the ITO electrode. In order to prevent the leakage by electron transfer to the liquid electrolyte, dense TiO2 passivating layers were used.Figure 1
A schematic diagram of a DSSC with an rf-sputtered TiO2 compact layer/ITO/glass on the ITO electrode.The phase identification of the particles produced using various deposition parameters was performed by X-ray diffraction (Rigaku-2000 spectrometer), using Cu-Kα radiation (40 kV, 30 mA, and λ=0.1541 nm). The photoinduced hydrophilicity of the TiO2 thin films was evaluated by measurement of the contact angle to pure water, using a contact angle meter (FACE CAVP150) that is accurate to less than 1°. A black light (UVP UVL-225D) lamp with a principal wavelength of 365 nm (1.5 mW/cm2 at the film surface) was the UV light source. The decomposition of MB aqueous solution (10 μM) was photocatalyzed. An UV-Vis-NIR spectrometer (Jasco V-670) was used to measure the absorption spectra of the MB solution as a function of the UV irradiation time. The film thickness was measured, using a surface profilometer (α-step, AMBIOS XP-1). The surface morphology was analyzed using a field emission scanning electron microscope (FESEM, JEOL JSM-6500F). The crystal structure of the films was characterized by X-ray diffraction (Rigaku-2000 spectrometer), using Cu-Kα radiation (40 kV, 30 mA, and λ=0.1541 nm), with a grazing incidence angle of 1°. The scanning rate was 5°/min.The power used to test the prepared DSSC was a 150 W Xe lamp, which simulates sunlight (AM 1.5). Before the test, the distance between the light source and the sample was adjusted to allow a light source density of 100 mW/cm2. The cell performance parameters, including the short-circuit current density (Jsc), the open-circuit voltage (Voc), the fill factor (FF), and the photoelectronic conversion efficiency (η(%)=Jsc×Voc×FF/totalincidentenergy×100), were measured and calculated using the J-V characteristics of DSSC.


## 3. Results and Discussion

### 3.1. The Photocatalytic Activity of the TiO2 Compact Films

The TiO2 compact films were deposited onto ITO soda-lime glass substrates. The optimization of the parameter settings involved comparing the signal-noise (S/N) ratios, using the Taguchi method. In order to optimize the TiO2 compact films deposition parameters, the water contact angle and the MB absorbance had the smaller the better characteristics and the deposition rate had the larger the better characteristics. The respective S/N ratios for the smaller the better characteristic and the larger the better characteristic are expressed as follows (Taguchi et al. [13]):
(1)(SN)S=-10log⁡1n∑i=1nyi2(SN)L=-10log⁡1n∑i=1n1yi2,
where n is the number of iterations for the experiment and yi is the ith average value of the characteristic measured. Using (1), the S/N ratio values were computed for deposition rate, water contact angle, and MB absorbance in the TiO2 compact layers coatings, as shown in Table 2. The hydrophilicity of the TiO2 films was determined by measuring the water contact angle. The change in the water contact angle is shown as a function of UV irradiation time for the TiO2 films deposited with parameter sets in the orthogonal arrays (Table 2). When the TiO2 film surface is irradiated by UV light for 12 min, the water contact angles of all of the films begin to decrease (less than 63°, sample number 9), which indicates that the film surface becomes more hydrophilic. The absorption spectra for the MB aqueous solution degraded by TiO2 photocatalytic film after 240 min UV irradiation are shown for the orthogonal array settings (Table 2). The TiO2 films deposited using the parameter sets in the orthogonal arrays from number 1 to number 9 show MB absorbance between 1.33 and 1.03.Table 2
The experimental results and theS/N ratios for the deposition rate, the contact angle, and the MB absorbance for the TiO2 compact layer coatings (the experiments were repeated twice).
Exp.
Factors
Deposition rate(Å/min)
S
/
N (dB)
Water contact angle  (degree)
S
/
N (dB)
MB absorbance
S
/
N (dB)
A
B
C
D
T1
T2
T1
T2
T1
T2
1
1
1
1
1
3.35
3.00
9.9953
90.73
91.30
−39.182
1.328
1.332
−2.4770
2
1
2
2
2
2.73
3.04
9.1653
92.13
91.87
−39.275
1.327
1.325
−2.4508
3
1
3
3
3
2.19
2.23
6.8868
73.91
75.40
−37.461
1.296
1.293
−2.2420
4
2
1
2
3
4.85
4.97
13.8197
89.75
90.28
−39.086
1.198
1.187
−1.5292
5
2
2
3
1
4.35
3.95
12.3307
91.01
92.71
−39.262
1.284
1.283
−2.1679
6
2
3
1
2
4.84
4.76
13.6239
93.57
94.68
−39.474
1.205
1.200
−1.6017
7
3
1
3
2
6.38
6.11
15.9046
71.70
72.30
−37.146
1.287
1.284
−2.1814
8
3
2
1
3
7.48
7.25
17.3403
95.35
94.81
−39.561
1.077
1.074
−0.6322
9
3
3
2
1
4.73
4.82
13.5783
63.79
62.39
−35.999
1.031
1.030
−0.2609
Note:A = rf power (W), B = process pressure (Pa), C = O2/(Ar + O2) flow rate ratio (%), and D = deposition time (hr).An analysis of variance (ANOVA) was used to determine the effect of a change in the process parameters on the process response. Table3 shows the ANOVA results for the deposition rate, the water contact angle, and the MB absorbance. Table 3 shows that the variables that most significantly affect the deposition rate, the water contact angle, and the MB absorbance are the rf power (P=84.45%, 33.68%, and 54.36%), the sputtering pressure (P=6.93%, 33.62%, and 14.07%), and the argon-oxygen ratio (P=7.00%, 28.56%, and 20.00%).Table 3
The ANOVA results for the deposition rate, the water contact angle, and the MB absorbance.
Factor
Degree of freedom
Sum of square
Variance
Contribution(P %)
Deposition rate (Å/min)
A
2
74.4166
37.2083
84.45
B
2
6.1132
3.0566
6.93
C
2
6.1644
3.0822
7.00
D
2
1.4211
0.7106
1.62
Total
8
88.1153
100
Water contact angle (degree)
A
2
4.4559
2.22793
33.68
B
2
4.4483
2.22417
33.62
C
2
3.7790
1.88950
28.56
D
2
0.5472
0.27359
4.14
Total
8
13.2304
100
MB absorbance
A
2
2.80223
1.40111
54.36
B
2
0.72560
0.36280
14.07
C
2
1.03120
0.51560
20.00
D
2
0.59634
0.29817
11.57
Total
8
5.15538
100Grey relational analysis (GRA) provides an efficient solution to difficult problems that involve multiple performance characteristics that are uncertain, have multiple inputs, and generate discrete data. The objective of this study is to optimize the deposition parameters for the TiO2 compact films using GRA, which is used extensively in various industries [16].The optimum combination does not yield suitable process parameters with a single performance characteristic (Taguchi method) for the TiO2 compact films coated. In order to optimize the deposition parameters, the deposition rate, the contact angle, and the MB absorbance, multiple performance characteristics (grey relational analysis) must be analyzed. The calculated grey relational grade is taken as the inspected value in the Taguchi method. Table 4 shows the grey relational grade and its ranking for the TiO2 compact layer coatings. A comparison of the experimental results for the orthogonal array (A3B3C2D1) and the photocatalytic activity optimal parameter set (A3B3C2D3) for TiO2 film deposition is shown in Table 5. The multiple performance characteristics for the deposition of TiO2 thin films are greatly improved by using the Grey-Taguchi method. The improvement in the deposition rate is 12.87%, that in the water contact angle is 15.25%, and that in the MB absorbance is 16.06%.Table 4
The Grey relational grade and its ranking for the TiO2 compact layer coatings.
Exp.
Grey relational grade
Rank
1
0.3595
8
2
0.3526
9
3
0.4252
6
4
0.4551
4
5
0.3914
7
6
0.4356
5
7
0.5698
3
8
0.7007
2
9
0.8329
1Table 5
The confirmation test results for the multiple performance characteristics, using the initial and the optimal process parameters.
Level
Initial process parameters
Optimal processparameters
Improvement rate (%)
A
3
B
3
C
2
D
1
A
3
B
3
C
2
D
3
Deposition rate (Å/min)
4.775
5.48
12.87
Contact angle (degree)
63.09
53.47
15.25
MB absorbance
1.0305
0.865
16.06The transmittance spectra are shown as a function of wavelengths in the range between 300 and 800 nm for TiO2 compact layers in Figure 2. The average transmittance in the visible region exceeds 85% for all samples, but transmission in the UV-near visible region decreases abruptly. After annealing treatment, the optical transmittance of the film is increased.Figure 2
The optical transmittance spectra for TiO2 compact layer/ITO/glass.


### 3.2. DSSC Conversion Efficiency

SEM analysis was used to determine the morphology of the sputtered TiO2 compact layers (with photocatalytic activity optimal parameters, A3B3C2D3) on the ITO substrate and the thick TiO2 porous layer produced using the sol-gel method, as shown in Figure 3. The uniform and smooth surfaces of the sputtered compact accumulation film are well covered by spherical particles, which are densely coated with a small grain size (Figure 3(a), TiO2 compact/ITO/glass). This is necessary to prevent charge recombination between the ITO and the porous TiO2 layer [17, 18]. The SEM images show the porous TiO2 film over the sputtered compact layer, produced using the sol-gel with spin coating method (Figure 3(b), porous TiO2/TiO2 compact/ITO/glass) and the sol-gel with blade coating method (Figure 3(c), porous TiO2/TiO2 compact/ITO/glass). The porous TiO2 film structure is not dense and the crystallite size of the TiO2 is increased. DSSC efficiency is improved by producing a TiO2 electrode with a large surface area and optimum pore structure [19, 20].(a) The SEM images for sputtered TiO2 compact layer on ITO/glass, (b) the SEM images for porous TiO2 onto TiO2 compact/ITO/glass, produced using the sol-gel with spin coating method, and (c) the SEM images for porous TiO2 onto TiO2 compact/ITO/glass, produced using the sol-gel with blade coating method.
(a)
(b)
(c)The cross-section of the TiO2 films was observed by SEM. Figure 4(a) corresponds to Figure 3(b) and Figure 4(b) corresponds to Figure 3(c). The TiO2 compact/ITO films produced using the photocatalytic activity optimal deposition conditions (A3B3C2D3) are highly compacted and homogeneous and adhere perfectly to the glass substrate. These results confirm a spongelike structure for the TiO2 layer (Figure 4), which is a prerequisite for a highly efficient DSSC [21]. The characteristics of the TiO2 materials depend significantly upon the surface morphology, the crystal structure, and the crystallization.The SEM cross-sectional image of TiO2 (a) corresponding to Figure 3(b) and (b) corresponding to Figure 3(c).
(a)
(b)Figure5 shows that the XRD patterns of the TiO2 films, produced using the sol-gel with spin coating of porous TiO2/TiO2 compact/ITO/glass, show a good crystalline structure and anatase (101) diffraction peaks that demonstrate a higher crystallinity than the other films. In contrast, without the TiO2 compact layer (only porous TiO2), the peak intensity of the anatase (101) plane in the XRD patterns for the TiO2 film has a lower value, which demonstrates inferior crystalline quality.Figure 5
The XRD patterns for the TiO2 films after being annealed at 450°C.Good performance for the counter electrode requires a low internal resistance and raw material cost. The best material for the counter electrode is Pt, which shows excellent electrochemical activity forI3- reduction at film thicknesses of 2~10 nm [22, 23]. Figure 6 shows the photo current-voltage (I-V) characteristics for the DSSC under AM1.5 solar irradiation with 100 mW/cm2 illumination, with and without the TiO2 compact layer. Figure 6(a) shows a carbon counter electrode and ITO/glass, Figure 6(b) shows a Pt counter electrode and ITO/glass, and Figure 6(c) shows a Pt counter electrode and FTO/glass [24]. The corresponding cell parameters are summarized in Table 6, which shows the performance of the DSSC. With a TiO2 compact layer to prevent charge recombination, a higher Jsc is obtained. The energy conversion efficiency (η) increases if a Pt counter electrode is used instead of a carbon counter electrode.Table 6
The performance of a DSSC prepared using a photoelectrode with and without a TiO2 compact layer, using carbon and Pt counter electrodes, and using ITO/glass and FTO/glass.
V
oc (V)
J
sc (mA/cm2)
Fill factor
Efficiencyη (%)
ITO/sputter/spin coating/carbon
0.54
4.38
0.676
1.59
ITO/sputter/blade coating/carbon
0.53
4.08
0.666
1.44
ITO/spin coating/carbon
0.52
3.18
0.639
1.05
ITO/blade coating/carbon
0.52
3.07
0.572
0.90
ITO/sputter/spin coating/Pt
0.51
12.86
0.678
4.46
ITO/sputter/blade coating/Pt
0.49
10.73
0.675
3.51
ITO/spin coating/Pt
0.58
6.02
0.644
2.24
ITO/blade coating/Pt
0.61
5.10
0.649
2.01
FTO/sputter/spin coating/Pt
0.70
17.22
0.641
7.73
FTO/sputter/blade coating/Pt
0.77
12.79
0.750
7.36
FTO/spin coating/Pt
0.79
12.39
0.692
6.79
FTO/blade coating/Pt
0.79
10.80
0.771
6.53TheI-V characteristics for DSSCs fabricated with and without a TiO2 compact layer, (a) using a carbon counter electrode and ITO/glass, (b) using a Pt counter electrode and ITO/glass, and (c) using a Pt counter electrode and FTO/glass, under AM 1.5 solar irradiation with a density of 100 mW/cm2.
(a)
(b)
(c)For the purposes of comparison, the energy conversion efficiency for the DSSC film deposited on FTO glass is also given. FTO substrates have good optoelectronic performance and higher energy conversion efficiency than ITO substrates. Table6 shows that a FTO/sputter/spin coating/PT setup increases the conversion efficiency of the DSSC, with Voc=0.70 V, Jsc=17.22 mA/cm2, a fill factor = 0.641, and an energy conversion efficiency as high as 7.73%.


## 3.1. The Photocatalytic Activity of the TiO2 Compact Films

The TiO2 compact films were deposited onto ITO soda-lime glass substrates. The optimization of the parameter settings involved comparing the signal-noise (S/N) ratios, using the Taguchi method. In order to optimize the TiO2 compact films deposition parameters, the water contact angle and the MB absorbance had the smaller the better characteristics and the deposition rate had the larger the better characteristics. The respective S/N ratios for the smaller the better characteristic and the larger the better characteristic are expressed as follows (Taguchi et al. [13]):
(1)(SN)S=-10log⁡1n∑i=1nyi2(SN)L=-10log⁡1n∑i=1n1yi2,
where n is the number of iterations for the experiment and yi is the ith average value of the characteristic measured. Using (1), the S/N ratio values were computed for deposition rate, water contact angle, and MB absorbance in the TiO2 compact layers coatings, as shown in Table 2. The hydrophilicity of the TiO2 films was determined by measuring the water contact angle. The change in the water contact angle is shown as a function of UV irradiation time for the TiO2 films deposited with parameter sets in the orthogonal arrays (Table 2). When the TiO2 film surface is irradiated by UV light for 12 min, the water contact angles of all of the films begin to decrease (less than 63°, sample number 9), which indicates that the film surface becomes more hydrophilic. The absorption spectra for the MB aqueous solution degraded by TiO2 photocatalytic film after 240 min UV irradiation are shown for the orthogonal array settings (Table 2). The TiO2 films deposited using the parameter sets in the orthogonal arrays from number 1 to number 9 show MB absorbance between 1.33 and 1.03.Table 2
The experimental results and theS/N ratios for the deposition rate, the contact angle, and the MB absorbance for the TiO2 compact layer coatings (the experiments were repeated twice).
Exp.
Factors
Deposition rate(Å/min)
S
/
N (dB)
Water contact angle  (degree)
S
/
N (dB)
MB absorbance
S
/
N (dB)
A
B
C
D
T1
T2
T1
T2
T1
T2
1
1
1
1
1
3.35
3.00
9.9953
90.73
91.30
−39.182
1.328
1.332
−2.4770
2
1
2
2
2
2.73
3.04
9.1653
92.13
91.87
−39.275
1.327
1.325
−2.4508
3
1
3
3
3
2.19
2.23
6.8868
73.91
75.40
−37.461
1.296
1.293
−2.2420
4
2
1
2
3
4.85
4.97
13.8197
89.75
90.28
−39.086
1.198
1.187
−1.5292
5
2
2
3
1
4.35
3.95
12.3307
91.01
92.71
−39.262
1.284
1.283
−2.1679
6
2
3
1
2
4.84
4.76
13.6239
93.57
94.68
−39.474
1.205
1.200
−1.6017
7
3
1
3
2
6.38
6.11
15.9046
71.70
72.30
−37.146
1.287
1.284
−2.1814
8
3
2
1
3
7.48
7.25
17.3403
95.35
94.81
−39.561
1.077
1.074
−0.6322
9
3
3
2
1
4.73
4.82
13.5783
63.79
62.39
−35.999
1.031
1.030
−0.2609
Note:A = rf power (W), B = process pressure (Pa), C = O2/(Ar + O2) flow rate ratio (%), and D = deposition time (hr).An analysis of variance (ANOVA) was used to determine the effect of a change in the process parameters on the process response. Table3 shows the ANOVA results for the deposition rate, the water contact angle, and the MB absorbance. Table 3 shows that the variables that most significantly affect the deposition rate, the water contact angle, and the MB absorbance are the rf power (P=84.45%, 33.68%, and 54.36%), the sputtering pressure (P=6.93%, 33.62%, and 14.07%), and the argon-oxygen ratio (P=7.00%, 28.56%, and 20.00%).Table 3
The ANOVA results for the deposition rate, the water contact angle, and the MB absorbance.
Factor
Degree of freedom
Sum of square
Variance
Contribution(P %)
Deposition rate (Å/min)
A
2
74.4166
37.2083
84.45
B
2
6.1132
3.0566
6.93
C
2
6.1644
3.0822
7.00
D
2
1.4211
0.7106
1.62
Total
8
88.1153
100
Water contact angle (degree)
A
2
4.4559
2.22793
33.68
B
2
4.4483
2.22417
33.62
C
2
3.7790
1.88950
28.56
D
2
0.5472
0.27359
4.14
Total
8
13.2304
100
MB absorbance
A
2
2.80223
1.40111
54.36
B
2
0.72560
0.36280
14.07
C
2
1.03120
0.51560
20.00
D
2
0.59634
0.29817
11.57
Total
8
5.15538
100Grey relational analysis (GRA) provides an efficient solution to difficult problems that involve multiple performance characteristics that are uncertain, have multiple inputs, and generate discrete data. The objective of this study is to optimize the deposition parameters for the TiO2 compact films using GRA, which is used extensively in various industries [16].The optimum combination does not yield suitable process parameters with a single performance characteristic (Taguchi method) for the TiO2 compact films coated. In order to optimize the deposition parameters, the deposition rate, the contact angle, and the MB absorbance, multiple performance characteristics (grey relational analysis) must be analyzed. The calculated grey relational grade is taken as the inspected value in the Taguchi method. Table 4 shows the grey relational grade and its ranking for the TiO2 compact layer coatings. A comparison of the experimental results for the orthogonal array (A3B3C2D1) and the photocatalytic activity optimal parameter set (A3B3C2D3) for TiO2 film deposition is shown in Table 5. The multiple performance characteristics for the deposition of TiO2 thin films are greatly improved by using the Grey-Taguchi method. The improvement in the deposition rate is 12.87%, that in the water contact angle is 15.25%, and that in the MB absorbance is 16.06%.Table 4
The Grey relational grade and its ranking for the TiO2 compact layer coatings.
Exp.
Grey relational grade
Rank
1
0.3595
8
2
0.3526
9
3
0.4252
6
4
0.4551
4
5
0.3914
7
6
0.4356
5
7
0.5698
3
8
0.7007
2
9
0.8329
1Table 5
The confirmation test results for the multiple performance characteristics, using the initial and the optimal process parameters.
Level
Initial process parameters
Optimal processparameters
Improvement rate (%)
A
3
B
3
C
2
D
1
A
3
B
3
C
2
D
3
Deposition rate (Å/min)
4.775
5.48
12.87
Contact angle (degree)
63.09
53.47
15.25
MB absorbance
1.0305
0.865
16.06The transmittance spectra are shown as a function of wavelengths in the range between 300 and 800 nm for TiO2 compact layers in Figure 2. The average transmittance in the visible region exceeds 85% for all samples, but transmission in the UV-near visible region decreases abruptly. After annealing treatment, the optical transmittance of the film is increased.Figure 2
The optical transmittance spectra for TiO2 compact layer/ITO/glass.


## 3.2. DSSC Conversion Efficiency

SEM analysis was used to determine the morphology of the sputtered TiO2 compact layers (with photocatalytic activity optimal parameters, A3B3C2D3) on the ITO substrate and the thick TiO2 porous layer produced using the sol-gel method, as shown in Figure 3. The uniform and smooth surfaces of the sputtered compact accumulation film are well covered by spherical particles, which are densely coated with a small grain size (Figure 3(a), TiO2 compact/ITO/glass). This is necessary to prevent charge recombination between the ITO and the porous TiO2 layer [17, 18]. The SEM images show the porous TiO2 film over the sputtered compact layer, produced using the sol-gel with spin coating method (Figure 3(b), porous TiO2/TiO2 compact/ITO/glass) and the sol-gel with blade coating method (Figure 3(c), porous TiO2/TiO2 compact/ITO/glass). The porous TiO2 film structure is not dense and the crystallite size of the TiO2 is increased. DSSC efficiency is improved by producing a TiO2 electrode with a large surface area and optimum pore structure [19, 20].(a) The SEM images for sputtered TiO2 compact layer on ITO/glass, (b) the SEM images for porous TiO2 onto TiO2 compact/ITO/glass, produced using the sol-gel with spin coating method, and (c) the SEM images for porous TiO2 onto TiO2 compact/ITO/glass, produced using the sol-gel with blade coating method.
(a)
(b)
(c)The cross-section of the TiO2 films was observed by SEM. Figure 4(a) corresponds to Figure 3(b) and Figure 4(b) corresponds to Figure 3(c). The TiO2 compact/ITO films produced using the photocatalytic activity optimal deposition conditions (A3B3C2D3) are highly compacted and homogeneous and adhere perfectly to the glass substrate. These results confirm a spongelike structure for the TiO2 layer (Figure 4), which is a prerequisite for a highly efficient DSSC [21]. The characteristics of the TiO2 materials depend significantly upon the surface morphology, the crystal structure, and the crystallization.The SEM cross-sectional image of TiO2 (a) corresponding to Figure 3(b) and (b) corresponding to Figure 3(c).
(a)
(b)Figure5 shows that the XRD patterns of the TiO2 films, produced using the sol-gel with spin coating of porous TiO2/TiO2 compact/ITO/glass, show a good crystalline structure and anatase (101) diffraction peaks that demonstrate a higher crystallinity than the other films. In contrast, without the TiO2 compact layer (only porous TiO2), the peak intensity of the anatase (101) plane in the XRD patterns for the TiO2 film has a lower value, which demonstrates inferior crystalline quality.Figure 5
The XRD patterns for the TiO2 films after being annealed at 450°C.Good performance for the counter electrode requires a low internal resistance and raw material cost. The best material for the counter electrode is Pt, which shows excellent electrochemical activity forI3- reduction at film thicknesses of 2~10 nm [22, 23]. Figure 6 shows the photo current-voltage (I-V) characteristics for the DSSC under AM1.5 solar irradiation with 100 mW/cm2 illumination, with and without the TiO2 compact layer. Figure 6(a) shows a carbon counter electrode and ITO/glass, Figure 6(b) shows a Pt counter electrode and ITO/glass, and Figure 6(c) shows a Pt counter electrode and FTO/glass [24]. The corresponding cell parameters are summarized in Table 6, which shows the performance of the DSSC. With a TiO2 compact layer to prevent charge recombination, a higher Jsc is obtained. The energy conversion efficiency (η) increases if a Pt counter electrode is used instead of a carbon counter electrode.Table 6
The performance of a DSSC prepared using a photoelectrode with and without a TiO2 compact layer, using carbon and Pt counter electrodes, and using ITO/glass and FTO/glass.
V
oc (V)
J
sc (mA/cm2)
Fill factor
Efficiencyη (%)
ITO/sputter/spin coating/carbon
0.54
4.38
0.676
1.59
ITO/sputter/blade coating/carbon
0.53
4.08
0.666
1.44
ITO/spin coating/carbon
0.52
3.18
0.639
1.05
ITO/blade coating/carbon
0.52
3.07
0.572
0.90
ITO/sputter/spin coating/Pt
0.51
12.86
0.678
4.46
ITO/sputter/blade coating/Pt
0.49
10.73
0.675
3.51
ITO/spin coating/Pt
0.58
6.02
0.644
2.24
ITO/blade coating/Pt
0.61
5.10
0.649
2.01
FTO/sputter/spin coating/Pt
0.70
17.22
0.641
7.73
FTO/sputter/blade coating/Pt
0.77
12.79
0.750
7.36
FTO/spin coating/Pt
0.79
12.39
0.692
6.79
FTO/blade coating/Pt
0.79
10.80
0.771
6.53TheI-V characteristics for DSSCs fabricated with and without a TiO2 compact layer, (a) using a carbon counter electrode and ITO/glass, (b) using a Pt counter electrode and ITO/glass, and (c) using a Pt counter electrode and FTO/glass, under AM 1.5 solar irradiation with a density of 100 mW/cm2.
(a)
(b)
(c)For the purposes of comparison, the energy conversion efficiency for the DSSC film deposited on FTO glass is also given. FTO substrates have good optoelectronic performance and higher energy conversion efficiency than ITO substrates. Table6 shows that a FTO/sputter/spin coating/PT setup increases the conversion efficiency of the DSSC, with Voc=0.70 V, Jsc=17.22 mA/cm2, a fill factor = 0.641, and an energy conversion efficiency as high as 7.73%.


## 4. Conclusion

TiO2 films (compact layer) are coated onto ITO/glass substrates (and FTO/glass), using rf magnetron sputtering. The reactive and sputtering gases are O2 and Ar, respectively. The multiple performance characteristics for the deposited TiO2 compact films’ photocatalytic activity are greatly improved by using the Grey-Taguchi method. The improvement in the deposition rate is 12.87%, that in the water contact angle is 15.25%, and that in the MB absorbance is 16.06%. The porous TiO2 film that covers the sputtered compact layer produced by the sol-gel method has a structure which is not dense and a crystallite size that is increased. The XRD patterns for TiO2 films produced using sol-gel with spin coating of porous TiO2/TiO2 compact/ITO/glass result in a good crystalline structure and the anatase (101) diffraction peaks demonstrate a higher degree of crystallinity. The energy conversion efficiency (η) for a Pt counter electrode is greater than that for a carbon counter electrode. The experimental results show that FTO/sputter/spin coating/PT setup increases the conversion efficiency of the DSSC, with Voc=0.70 V, Jsc=17.22 mA/cm2, the fill factor = 0.641, and an energy conversion efficiency as high as 7.73%.



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*Source: 786165-2014-05-22.xml*