Accepted Manuscript

Title: Effect of heat treatment to the Rutile based Dye

Sensitized Solar Cell

Author: M.K. Ahmad C.F. Soon N. Nafarizal A.B. Suriani A.

Mohamed M.H. Mamat M.F. Malek M. Shimomura K.
Murakami

PII: S0030-4026(16)00083-8
DOI: http://dx.doi.org/doi:10.1016/j.ijleo.2016.01.034
Reference: IJLEO 57144

To appear in:

Received date: 15-10-2015

Accepted date: 4-1-2016

Please cite this article as: M.K. Ahmad, C.F. Soon, N. Nafarizal, A.B. Suriani, A.
Mohamed, M.H. Mamat, M.F. Malek, M. Shimomura, K. Murakami, Effect of heat
treatment to the Rutile based Dye Sensitized Solar Cell, Optik - International Journal
for Light and Electron Optics (2016), http://dx.doi.org/10.1016/j.ijleo.2016.01.034

This is a PDF file of an unedited manuscript that has been accepted for publication.
As a service to our customers we are providing this early version of the manuscript.
The manuscript will undergo copyediting, typesetting, and review of the resulting proof
before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that
apply to the journal pertain.
*Manuscript

1
2
3
4
5 Effect of heat treatment to the Rutile based Dye Sensitized Solar Cell
6
7
8
9
10
11
1
12 M.K. Ahmad, 1C.F. Soon, 1N. Nafarizal, , 2A.B. Suriani, 2A. Mohamed, 3M.H.

t
13

ip
14 Mamat, 3M.F. Malek, , 4M. Shimomura, 4K. Murakami
15
16

cr
17 1
Microelectronic and Nanotechnology – Shamsuddin Research Centre (MiNT-SRC)
18
19 Faculty of Electrical and Electronic Engineering, Universiti Tun Hussein Onn

us
20
21 Malaysia, 86400
22
23 Parit Raja, Batu Pahat, Johor, Malaysia
24

an
2
25 Nanotechnology Research Centre, Department of Physic, Faculty of Science and
26
27 Mathematics, Universiti Pendidikan Sultan Idris, 35900 Tanjung Malim, Perak,
28 Malaysia
M
29
30 3
Nano-ElecTronic Centre, Faculty of Electrical Engineering, UiTM, 40450 Shah
31
32 Alam, Selangor, Malaysia
33
d
4
34 Department of Engineering, Graduate School of Integrated Science and
35
te

36 Technology, Shizuoka University, Japan

37
38
p

39
40
41
ce

42
43
44
45
Ac

46
47
48
49
50
51
52
53
54
55
56
57 Correspondence should be addressed to M.K.Ahmad, akhairul@uthm.edu.my
58
59
60
61
62 1
63
64 Page 1 of 14
65
 1
2
3
4
5 Abstract
6
7
8 The effect of heat treatment of aligned titanium dioxide (TiO2) nanorods and
9
10 nanoflowers in the application of dye-sensitized solar cell were investigated.
11
12 Both of these nanostructures were deposited on the fluorine-doped SnO2

t
13

ip
14
transparent conducting glass substrate using one step hydrothermal method.
15 Characterizations of dye-sensitized solar cell (DSC) with rutile-phased TiO2
16

cr
17 nanorods and nanoflowers were performed such as surface morphology,
18
19 structural property, dye-adsorption and energy conversion efficiency. In the

us
20
21 DSC preparation, both TiO2 nanorods/nanoflowers, platinum (Pt), ruthenium
22
23 dye N719 and DPMII electrolyte were used as photo electrode, counter
24

an
25
electrode, dye solution and liquid electrolyte, respectively. Concentration of
26 3M cetyltrimethylammonium bromide (CTAB) was added in the preparation
27
28 of rutile-phased TiO2 nanorods and nanoflowers. All of the photo electrodes
M
29
30 were heated at 150°C, 250°C, 350°C, 450°C, respectively. The thickness of
31
32 TiO2 nanorods and nanoflowers-layers were 5 μm and 15 μm, respectively.
33
d

34 Lastly, power conversion efficiency of DSC was performed under the light
35
intensity of 100 mW/cm2. It was found that the highest power conversion
te

36
37 efficiency was 3.27%, and heated at 450°C.
38
p

39
40
41
ce

42
43 Keywords: Titanium Dioxide; TiO2 Nanorods; TiO2 Nanoflower;
44
45 Hydrothermal Method; Rutile phase; Dye-sensitized solar cell;
Ac

46
47
48 1. Introduction
49
50
51 Nanostructured titanium dioxides (TiO2) such as nanorods, nanotubes and
52
53 nanoflowers have been widely studied nowadays due to their excellent properties
54
55 for important applications. Compared to nanoparticle TiO2, nanostructured TiO2 has
56
57 low recombination rate for electron-hole pair and good optical and electrical
58
59
properties. A number of methods have been employed to prepare the nanostructured
60
61
62 2
63
64 Page 2 of 14
65
 1
2
3
4
5 TiO2 films including template assisted method [1], electrochemical method [2],
6
7
hydrothermal method [3], chemical vapour deposition (CVD) [4] and sol–gel
8 process [5]. One of the promising and cost effective methods to prepare a
9
10 homogenous TiO2 film is the hydrothermal method. Hydrothermal method is a
11
12 liquid-deposit process using soft chemistry (bottom-up approach), and gives a

t
13

ip
14 homogeneous thin film assisted with stable temperature and pressure.
15
16

cr
17 It is known that TiO2 has three crystalline phases; rutile phase (tetragonal),
18
19 anatase phase (tetragonal) and brookite phase (orthorhombic). Rutile is stable in

us
20
21 high temperature region, whereas anatase and brookite are metastable and
22
23 transforme to rutile when annealed at high temperature. Most researches have been
24

an
25 performed for anatase phased TiO2 in the DSC applications, even though some of
26
27 the characteristics of these phases are same. There is only a few researches
28 regarding the rutile phased TiO2 nanorod or nanoflower for DSC applications
M
29
30 [6,7,8], which has proven that the rutile phased TiO2 also can be suitable candidate
31
32 for the DSC applications.
33
d

34
35
te

36 Generally, nanorods provided us with good electron mobility which could be use
37
38
in sensor devices application [9] meanwhile nanoflowers give high surface area for
p

39 dye adsorption for dye-sensitized solar cell application. Annealing process is a

40
41 heating process which enhanced the electron transportation in semiconductor
ce

42
43 materials. With the advantages of nanorods and nanoflowers structures and
44
45 annealing process towards rutile phased TiO2, we have prepared the rutile phased
Ac

46
47 TiO2 nanorods (r-TNRs) and nanoflowers (r-TNFs) and used them for the DSC
48
49
application. In this paper, we discuss the effect of annealing process of r-TNRs and
50 r-TNFs for the DSC application. At first, the growth of r-TNRs and r-TNFs with
51
52 different amount of precursor was studied and then, we investigated the advantages
53
54 of hybridization at different annealing temperatures to the performances of DSC.
55
56
57
58
59
60
61
62 3
63
64 Page 3 of 14
65
 1
2
3
4
5 2. Experimental
6
7
8 1. Synthesis of rutile phased nanorods/nanoflowers TiO2 thin film
9
10
11
12
Diagram of the prepared DSC is shown in Fig. 1. Fluorine-doped SnO2 (FTO)

t
13 coated glass was used as a substrate with the thickness of 1.0 mm. Ethanol, acetone,

ip
14
15 hydrochloric acid and titanium butoxide (TBOT) (WAKO chemical) were used as
16

cr
17 received. Deionzed water was used to prepare all the solutions. FTO coated glass
18
19 was cut into dimension of 10 mm x 25 mm and cleaned by sonicating method in

us
20
21 acetone, ethanol and deionzed water with volume ratio of 1:1:1 for 30 min and
22
finally dried in the air. The synthesis of the film was referring to our previous study
23
24 with slight improvement [9]. The chemical solution in the process was obtained by

an
25
26 dissolving 20 ml of concentrated hydrochloric acid (36.5%~38%) in a 20 ml of
27
28 deionzed water. The mixture was vigorously stirred for 5 min before drop wise
M
29
30 amount of TBOT. The solutions were prepared at different concentrations, 0.5 ml,
31
32 0.7 ml, 1.0 ml and 1.5 ml. In order to enhance the film structure 3 M of
33
d
cetyltrimethylammonium bromide (CTAB) was added into the solution as a
34
35 surfactant [10]. The solution was stirred for 10 min before put into the Teflon steel
te

36
37 autoclave for hydrothermal process. The FTO glass substrate was also put into the
38
autoclave (50 ml volume) with facing the conducting side upward. The
p

39
40
41 hydrothermal process was performed at 150˚C for 10 h. After hydrothermal process,
ce

42
43
the autoclave was taken out from oven and cooled down to room temperature.
44 Prepared samples were taken out and immersed into deionized water for a few
45
Ac

46 minutes and then rinsed extensively and dried in oven at 150˚C for 30 min. In order
47
48 to study the effect of annealing temperature, prepared nanostructured films were
49
50 annealing at 150˚C, 250˚C, 350˚C and 450˚C for 30 min.
51
52
53 2.2 Characterization
54
55
56 Surface morphology and cross-section of the prepared TiO2 films were analyzed
57
58 by using field-emission scanning electron microscopy (FE-SEM, JOEL JSM-
59
60 6320F) at accelerating voltage of 20 kV. Thickness of the films was also determined
61
62 4
63
64 Page 4 of 14
65
 1
2
3
4
5 by FE-SEM observation. X-ray diffraction (XRD) was performed by using RINT
6
7
Ultima III (Rigaku) with Cu Kα radiation (α=1.5418Å). The XRD profiles were
8 measured in the 2θ range from 20° to 50° at a 2°/min scanning speed to investigate
9
10 the crystal phases of TiO2 films. The amount of adsorbed dye was determined as
11
12 follows; desorbing the dye from the TiO2 film surface into a mixed solution of 1.0

t
13

ip
14 M NaOH and deionized water (1:1, in volume fraction) and measuring the
15
16 absorption spectra of solution using UV-Vis Spectrophotometer (V-630, Jusco) to

cr
17
18
determine the concentration of adsorbed dye.
19

us
20
21 Photocurrent versus voltage (I-V) characteristics was measured by using solar
22
23 simulator under 1.5 AM (Bunkoh Keiki-Jusco). For photosensitization study, the
24

an
25 prepared TiO2 photoelectrode with working area of 0.25cm2 was immersed in 3 mM
26
27 of N719 dye for about 14 h at room temperature. The Pt counter electrode with
28 mirror finish was prepared by the sputtering method and used as counter electrode.
M
29
30 In order to assemble the DSC, the electrolyte prepared from 0.6 M of 1,2-dimethyl-
31
32 3-propylimidazolium iodide, 0.1 M LiI, 0.5 M of 4-tert-butylpyridine, 0.1 M of
33
d

34 guanidine thiocyanate, 0.85 ml of acetonitrile, 0.5 ml of valeronitrile and 0.05 M of

35
te

36 I2 was inserted between the Pt electrode and the dye-coated r-TNR/r-TNF electrode
37
38 to form a sandwich-type clamped cell for the solar cell measurement.
p

39
40
41
3. Results and discussion
ce

42
43 3.1 Characterization of rutile phased TiO2 nanorods/nanoflowers
44
45
Ac

46 The amount of precursor in the solution is a key factor to grow both r-TNR and
47
48 r-TNF in this study. By using different concentrations, the amount of r-TNF can be
49
50 controlled and optimized for the DSC application. Figures 2(a), (b), (c) and (d)
51
52 show FE-SEM images of the prepared TiO2 films composed of nanorods and
53
54
nanoflowers on the FTO substrates through the hydrothermal method at 150°C for
55 10 h. The inset in each figure shows the corresponding cross-section view. Figure 2
56
57 (a) shows the TiO2 film prepared from 0.5 ml of precursor (TBOT). The film
58
59 consists of mostly the vertically oriented nanorods with some mis-oriented
60
61
62 5
63
64 Page 5 of 14
65
 1
2
3
4
5 nanorods. There are also a few of nanoflowers on top of nanorods layer. When the
6
7
concentration of precursor increases to 0.7 ml, the amount of TiO2 nanoflowers also
8 increases as shown in Fig.1 (b). The amount of nanoflowers continually increases
9
10 and the layer becomes denser with an increase in the concentration until 1.5 ml of
11
12 TBOT. It is found from the cross-section views that the thickness of r-TNR layer is

t
13

ip
14 about 5 μm, which remains same until 1.5 ml of TBOT. On the other hand, the
15
16 thickness of r-TNF layer increases with the concentration of precursor as shown in

cr
17 Fig. 2. From the results, the nanostructured TiO2 film prepared using 1.0 ml of
18
19 TBOT is chosen for further investigations. In order to apply the films to DSC

us
20
21 application they are annealed at different temperatures from 150°C to 450°C for 30
22
23 min.
24

an
25
26
27 XRD profiles of the films annealed at different temperatures, 150°C, 250°C,
28 350°C and 450°C are shown in Fig. 3. The result shows that there are four peaks at
M
29
30 27.40°, 36.04°, 41.20° and 43.90° corresponding to (110), (101), (111) and (210)
31
32 planes of the rutile phase (PDF No.98-000-0090). The main peak at 27.40°
33
d

34 corresponds to [110] plane. As the annealing temperature increases, there is no

35
te

36 additional peak observed in the XRD profiles. The peak intensities do not
37
38 significantly increase either. It is confirmed from the results that the prepared TiO2
p

39 films are single rutile phase and the peak intensities are not affected by the
40
41
ce

annealing temperature up to 450°C due to thermodynamic stability of the rutile

42
43 phase.
44
45
Ac

46
47 3.2 Application of rutile phase TiO2 nanorods/nanoflowers to DSC
48
49
50 Photocurrent-voltage characteristics of the DSCs using r-TNR/r-TNF films are
51
52 shown in Fig. 4 under the simulated full sunlight, 100 mWcm-2. The configuration
53
54 of DSC is FTO/r-TNR/r-TNF+dye+electrolyte/Pt. The r-TNR/r-TNF films are
55
56 annealed at different temperatures, 150°C, 250°C, 350°C and 450°C. Photovoltaic
57
58 performances of the DSCs are summarized in Table 1. It is found from the results
59
60
that the short circuit current density (JSC) and the open-circuit voltage (VOC)
61
62 6
63
64 Page 6 of 14
65
 1
2
3
4
5 increase with an increase in the annealing temperature. The energy conversion
efficiency () of DSCs using the r-TNR/r-TNF films also increases with the
6
7
8 annealing temperature and the DSC with the r-TNR/r-TNF film annealed at 450°C
9
10 gives the highest  of 3.27%. High efficiency is mainly attributed to the increased
11
12 JSC, in other words, amount of the dye adsorption on r-TNR/r-TNF films increases

t
13

ip
14 with the annealing temperature as shown in Table 1. The dye adsorption is closely
15
16 related to surface morphology of the film. Morphology of the r-TNF layer can

cr
17
18 contribute to an increase in the surface area of the film resulting in the higher dye
19
adsorption. Furthermore, surface contamination of the r-TNRs and the r-TNFs can

us
20
21 be removed at higher annealing temperature which is formed during the
22
23 hydrothermal process. Higher annealing temperature also improves interconnection
24

an
25 between the r-TNRs and the r-TNFs resulting in enhancing of the electron mobility.
26
27 Smaller surface area of the r-TNR film can lead to a reduction in the charge
28
recombination [11], which suppresses the dark current and increases the VOC [12].
M
29
30
31
More investigations on mechanism and structure of r-TNR/r-TNF could bring the
32 rutile phased TiO2 film to the same level as anatase phased one in the DSC
33
d

34 application.
35
te

36
37 4. Conclusion
38
p

39
40 In summary, we have successfully prepared the DSCs using r-TNR/r-TNF TiO2
41
ce

42 films annealed at different temperatures and investigated the effect of amount of

43
44 precursor on the structure of r-TNR/r-TNF film. The growth of r-TNF is enhanced
45 by the amount of precursor (TBOT). High density of the r-TNF contributes to
Ac

46
47 higher surface area of the film which could enhance the dye adsorption on the film.
48
49 Better interconnection at r-TNR/r-TNF interface in the film is realized by annealing
50
51 the film at higher temperature to improve the electron mobility. It is concluded that
52
53 the hybridization of r-TNR and r-TNF is one of the promising way to improve the
54
55
efficiency of DSC prepared from the rutile phased TiO2 film.
56
57
58
59
60
61
62 7
63
64 Page 7 of 14
65
 1
2
3
4
5 Acknowledgements
6
7
8
The authors would like to thank to Ministry of Higher Education (MOHE),
9 Malaysia (FRGS 1213) and Universiti Tun Hussein Onn Malaysia (UTHM) for
10
11 financial support.
12

t
13

ip
14
15 References
16

cr
17
18
[1] J. Jiu, F. Wang and M. Adachi, Materials Letters, 58, (2004), 3915.
19 [2] G. Wang, H. Chen, H. Zhang, C. Yuan, Z. Lu, G. Wang and W. Yang, Applied

us
20
21 Surface Science, 135, (1998), 97.
22
23 [3] Z. Y. Yuan and B.L. Su, Colloids and Surfaces A, 241, (2004), 173.
24

an
25 [4] J.H. Chang, A.V. Ellis, Y.H. Hsieh, C.H. Tung and S.Y. Shen, Science of The
26
27 Environment, 407, (2009), 5914.
28
[5] M.Y. Song, D.K. Kim, S.M. Jo and D.Y. Kim, Synthesis Metals. (2005), 635.
M
29
30 [6] P. Charoensirithavorn, Y. Ogami, T. Sagawa, S.Hayase and S. Yoshikawa,
31
32 Journal of Crystal Growth, 311, (2009), 757.
33
d

34 [7] Y. Zhang, Y. Gao, X.H. Xia, Q.R. Deng, M.L. Guo, L. Wan and G. Shao,
35
te

36 Materials Letters, 64, (2010), 1614.

37
38 [8] D.U. Lee, S.R. Jang, R. Vittal, J. Lee, K.J. Kim, Solar Enery, 82, (2008), 1042.
p

39 [9] C. Cao, C. Hu, X. Wang, S. Wang, Y. Tian and H. Zhang, Sens. Actuators B:
40
41
ce

Chem., (2011), (In press).

42
43 [10] M.K. Ahmad and K. Murakami, Advanced Materials Research, 222, (2011),
44
45 24.
Ac

46
47 [11] H. Choi, E. Stathatos and D.D. Dionysiou, Thin Solid Film, 510, (2006), 107.
48
49
[12] D. Kuang, S. Ito, B. Wenger, C. Klein, J.E. Moser, R. Humphry-Baker, S.M.
50 Zakeeruddin and M. Gratzel, J. Am. Chem. Soc., 128, (2006), 4146.
51
52 [13] N.N. Bwana, J. Nanopart. Res., 11, (2009), 1905.
53
54
55
56
57
58
59
60
61
62 8
63
64 Page 8 of 14
65
Figure

Figure captions

Figure 1. Schematic diagram of dye-sensitized solar cell rutile phased TiO2 nanorods
(r-TNR) and rutile-phased TiO2 nanoflower (r-TNF) deposited on top of
FTO coated glass

t
ip
Figure 2. FESEM images of TiO2 nanorods and nanoflowers film prepared at
different amount of precursors; (a) 0.5ml, (b) 0.7ml, (c) 1.0ml and (d) 1.5ml

cr
Figure 3. XRD diffraction patterns of TiO2 nanorods and nanoflowers film prepared
at different annealing temperature; (a) 150°C, (b) 250°C, (c) 350°C and (d)

us
450°C

Figure 4. I-V measurement of r-TNR/r-TNF TiO2 thin film prepared with and without

an
a-TiO2 thin film
M
d
p te
ce
Ac

1
Page 9 of 14
 e-
Glass
Pt

t
e-

ip
Load
I I-
Electrolyte 3
-
Dye

cr
e-

us
r-TNF e-

r-TNR

an
FTO e-
Glass
M
sunlight

Fig. 1 Schematic diagram of dye-sensitized solar cell rutile phased TiO2 nanorods
d

(r-TNR) and rutile-phased TiO2 nanoflower (r-TNF) deposited on top of FTO

te

coated glass
p
ce
Ac

2
Page 10 of 14
 t
ip
cr
us
an
(a) (b)
M
d

(c) (d)
p te
ce
Ac

Fig. 2 FESEM images of TiO2 nanorods and nanoflowers film prepared at different
amount of precursors; (a) 0.5ml, (b) 0.7ml, (c) 1.0ml and (d) 1.5ml

3
Page 11 of 14
 t
ip
cr
us
an
M
d

Fig. 3 XRD diffraction patterns of TiO2 nanorods and nanoflowers film prepared at
te

different annealing temperature; (a) 150°C, (b) 250°C, (c) 350°C and (d) 450°C
p
ce
Ac

4
Page 12 of 14
 o
150 C
8 o
250 C
o

Current density (mA/cm )

350 C
2 o
450 C
6

t
ip
4

cr
us
2

an
0.0 0.2 0.4 0.6 0.8

Voltage (V)
M
Fig. 4 I-V measurement of r-TNR/r-TNF TiO2 film prepared at different annealing
temperature; (a) 150°C, (b) 250°C, (c) 350°C and (d) 450°C
d
p te
ce
Ac

5
Page 13 of 14
Table

Table: 1 I-V measurement of DSC with different annealing temperature

Sample Dye absorption Voc Jsc (mAcm-2) Fill factor Efficiency (%)

t
(x10-8molcm-2)

ip
150°C 3.78 0.64 5.14 0.52 1.72

cr
250°C 3.89 0.70 7.35 0.42 2.14

350°C 7.25 0.78 7.27 0.50 2.83

us
450°C 7.72 0.79 7.75 0.54 3.27

an
M
d
p te
ce
Ac

1
Page 14 of 14