ARTICLE IN PRESS

Dye-sensitized solar cell using natural dyes extracted from rosella and blue pea owers
Khwanchit Wongchareea,, Vissanu Meeyooa, Sumaeth Chavadejb
a

Department of Chemical Engineering, Mahanakorn University of Technology, Nong Chok, Bangkok 10530, Thailand b The Petroleum and Petrochemical College, Chulalongkorn University, Patumwan, Bangkok 10330, Thailand Received 6 November 2006; accepted 7 November 2006 Available online 2 January 2007

Abstract Dye-sensitized solar cells (DSSCs) were fabricated using natural dyes extracted from rosella, blue pea and a mixture of the extracts. The light absorption spectrum of the mixed extract contained peaks corresponding to the contributions from both rosella and blue pea extracts. However, the mixed extract adsorbed on TiO2 does not show synergistic light absorption and photosensitization compared to the individual extracts. Instead, the cell sensitized by the rosella extract alone showed the best sensitization, which was in agreement with the broadest spectrum of the extract adsorbed on TiO2 lm. In case that the dyes were extracted at 100  C, using water as extracting solvent, the energy conversion efciency (Z of the cells consisting of rosella extract alone, blue pea extract alone and mixed extract was 0.37%, 0.05% and 0.15%, respectively. The sensitization performance related to interaction between the dye and TiO2 surface is discussed. The explanations are supported by the light absorption of the extract solution compared to extracts adsorbed on TiO2 and also dye structures. The effects of changing extracting temperature, extracting solvent and pH of the extract solution are also reported. The efciency of rosella extract sensitized DSSC was improved from 0.37% to 0.70% when the aqueous dye was extracted at 50  C instead of 100  C and pH of the dye was adjusted from 3.2 to 1.0. Moreover, DSSC stability was also improved by the changes in conditions. However, the efciency of a DSSC using ethanol as extracting solvent was found to be diminished after being exposed to the simulated sunlight for a short period. r 2006 Elsevier B.V. All rights reserved.
Keywords: Dye-sensitized solar cells; Natural dyes; TiO2 ; Anthocyanin

1. Introduction The dye-sensitized solar cell (DSSC) is a device for the conversion of visible light into electricity, based on the sensitization of wide bandgap semiconductors [1]. The performance of the cell mainly depends on a dye used as sensitizer. The absorption spectrum of the dye and the anchorage of the dye to the surface of TiO2 are important parameters determining the efciency of the cell [2]. Generally, transition metal coordination compounds (ruthenium polypyridyl complexes) are used as the effective sensitizers, due to their intense charge-transfer absorption in the whole visible range and highly efcient metal-toCorresponding author. Tel.: +66 2988 3655; fax: +66 2988 4044.

E-mail address: khwanchit9@yahoo.com (K. Wongcharee). 0927-0248/$ - see front matter r 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.solmat.2006.11.005

ligand charge transfer [3]. However, ruthenium polypyridyl complexes contain a heavy metal, which is undesirable from point of view of the environmental aspects [4]. Moreover, the process to synthesize the complexes is complicated and costly. Alternatively, natural dyes can be used for the same purpose with an acceptable efciency [29]. The advantages of natural dyes include their availability and low cost [3]. The sensitization of wide bandgap semiconductors using natural pigments is usually ascribed to anthocyanins [29]. The anthocyanins belong to the group of natural dyes responsible for several colors in the redblue range, found in fruits, owers and leaves of plants. Carbonyl and hydroxyl groups present in the anthocyanin molecule can be bound to the surface of a porous TiO2 lm. This makes electron transfer from the anthocyanin molecule to

ARTICLE IN PRESS
the conduction band of TiO2 [3]. As reported [29], anthocyanins from various plants gave different sensitizing performances. However, there is no an acceptable explanation behind these results, so far. In this paper, DSSCs were prepared using natural dyes extracted from rosella (Hibiscus sabdariffa L.) and blue pea (Clitoria Ternatea) owers as sensitizers, as these owers are abundant in tropical countries, and rich in anthocyanins [10,11]. The efciency of the solar cells related to dye structures is discussed. This would be an useful information for selecting anthocyanins and also lead to the synthesis of dyes for DSSCs. The performance of DSSCs using the mixed rosellablue pea dye was also investigated. Our hypothesis was that two anthocyanins having different absorption characteristics would give even more synergistic effect compared to the mixed anthocyaninchlorophyll dye reported by Kumara et al. [8]. This is because anthocyanins have advantages over chlorophyll as DSSC sensitizer [3]. Moreover, the effects of extracting temperature, extracting solvent and pH of the dye solution on the DSSC efciency and stability were also determined. 2. Experimental 2.1. Preparation of natural dye sensitizers Fresh rosella or blue pea ower of 1 g was extracted in 100 ml of two different solvents at different temperatures for 30 min. Solid residues were ltrated out to obtain clear dye solutions. A mixed dye was prepared by mixing rosella solution to blue pea solution at a ratio of 1:1 by volume. The effect of extracting temperature was studied at 25, 50, 70 and 100  C, using water as an extracting solvent. The effect of extracting solvent was studied by a comparison of dyes extracted in water and ethanol. The effect of pH of dye solution was studied by adjusting pH from the original pH of 3.2 using 0.1 M HCl solution to four different pHs (0.5, 1.0, 2.0 and 3.0). 2.2. Preparation of TiO2 electrode (photoanode) and counter electrode A TiO2 lm electrode (photoanode) was prepared by blending commercial TiO2 powder (Degussa, P25) of ca. 0.2 g, nitric solution (0.1 M) of 0.4 ml, polyethylene glycol (MW10,000) of ca. 0.08 g and one drop of a nonionic surfactant, Triton X-100. The mixture was well mixed using an ultrasonic bath for 1 h and then the resultant paste was spread over a conductive glass plate having 15 O=cm2 which was purchased from Hartford Glass Co., Inc. The coated plate was then sintered at 450  C for 2 h. The dyes were attached to the TiO2 surface by immersing the coated electrodes in the aqueous solution of each dye for 24 h. The non-adsorbed dye was washed up with anhydrous ethanol. Pt counter electrode was prepared by deposition of Ptcatalyst T/SP paste (purchased from Solaronix SA) on another conductive glass. 2.3. DSSC assembling DSSCs were assembled following the procedure described in the literature [7], the catalyst-coated counter electrode was placed on the top so that the conductive side of the counter electrode faces the TiO2 lm. The iodide electrolyte solution (0.5 M potassium iodide mixed with 0.05 M iodine in water-free ethylene glycol) was placed at the edges of the plates. The liquid was drawn into the space between the electrodes by capillary action. Two binder clips were used to hold the electrodes together. 2.4. Characterization and measurement The absorption spectra of dye solutions and dyes adsorbed on TiO2 surface were recorded using a UVVIS spectrophotometer (Shimadzu, model UV-3101). Solar energy conversion efciency (the photocurrentvoltage (IV ) curve) was measured by using two computerized digital Keithley multimeters under simulated sunlight (AM 1.5, 100 mW cm2 . Based on IV curve, the ll factor (FF) is dened as FF I max V max =I sc V oc , (1) where I max and V max are the photocurrent and photovoltage for maximum power output (Pmax , I sc and V oc are the short-circuit photocurrent and open-circuit photovoltage, respectively. The overall energy conversion efciency (Z is dened as Z I sc V oc FF=Pin , where Pin is the power of incident light. 3. Results and discussion 3.1. Effect of anthocyanin sources and extracting temperature on DSSCs efciency Fig. 1 shows the UVVIS absorption spectra of rosella extract (red), blue pea extract (blue) and rosellablue pea extract mixture (purple). It was found that the absorption peak of rosella extract is about 520 nm while those of blue (2)

Absorbance (a.u.)

(a) (b) (c)

400

500

600 Wavelength (nm)

700

800

Fig. 1. Light absorption spectra of dye solutions of: (a) rosella extract; (b) blue pea extract; and (c) mixed rosellablue pea extract.

ARTICLE IN PRESS
pea extract are about 580 and 620 nm. The difference in the absorption characteristics is due to the different type of anthocyanins and colors of the extracts. It was reported that anthocyanin obtained from blue pea is ternatin while those from rosella are delphinidin and cyanidin complexes [10,11]. An absorption peak at high wavelength of blue pea extract is responsible for its blue color [12]. The combination of rosella extract and blue pea extract did not affect the absorption peaks, three peaks were detected, corresponding to the absorption nature of both extracts. After immersion of the TiO2 -coated electrode (photoanode) in the extracts, observable colors of TiO2 lms turned to deep purple for the rosella extract but the lm turned to light blue for the blue pea extract. The absorption spectra of the photoanode are shown in Fig. 2. In the case of rosella extract, an absorption peak of photoanode is broader than that of the dye solution (Fig. 3(a)), with a shift to a higher wavelength (from 520 to 570 nm). The difference in the absorption peak is due to the binding of anthocyanin in the extract to the oxide surface [13]. This difference, however, was not found in the case of blue pea extract (Fig. 3(b)), as the absorption peaks were found at the same wavelengths for both extract and photoanode. The structure of ternatin (Fig. 4) in blue pea extract has longer R groups compared to that of dephinidin or cyanidin complexes in rosella extract, resulted in a stronger steric hindrance for anthocyanin to form bond with oxide surface and prevents the anthocyanin molecules from arraying on the TiO2 lm effectively [3]. Hence, this leads to a deciency of electron transfer from dye molecules to conducting band of TiO2 . Fig. 5 shows the IV (currentvoltage) curve for the sunlight-illuminated rosella extract sensitized cell. Table 1 presents the performance of the DSSCs in terms of shortcircuit photocurrent (I sc , open-circuit voltage (V oc , ll factor (FF) and energy conversion efciency (Z compared to those of other extracts. Obviously, the efciency of cell sensitized by the rosella extract was signicantly higher than that sensitized by the blue pea extract. This is due to a higher intensity and broader range of the light absorption of the extract on TiO2 (Fig. 2), and the higher interaction between TiO2 and anthocyanin in the rosella extract leads to a better charge transfer. Moreover, anthocyanin in the

Absorbance (a.u.)

(a) (b) (c) 400 500 600 Wavelength (nm) 700 800

Fig. 2. Light absorption spectra of: (a) rosella; (b) blue pea; and (c) mixed rosellablue pea extracts adsorbed on TiO2 .

a
Absorbance (a.u.)

b
Absorbance (a.u.)
500 600 700 Wavelength (nm) 800 400

400

500

600 700 Wavelength (nm)

800

c
Absorbance (a.u.)
400

500

600 700 Wavelength (nm)

800

Fig. 3. Light absorption spectra of dye solutions ( and dyes adsorbed on TiO2 (): (a) rosella; (b) blue pea; and (c) mixed rosellablue pea extracts.

ARTICLE IN PRESS

a
Photocurrent (mAcm-2) cyanidin-3-sambubioside (R1 = OH, R2 = H, R3 = sambubiose) dephinidin-3-sambubioside (R1 = OH, R2 = OH, R3 = sambubiose) cyanidin-3-glucoside (R1 = OH, R2 = H, R3 = glucose)

1.5

0.5

0 0 100 200 300 Voltage (mV) 400

Fig. 5. Currentvoltage curve for a rosella extract sensitized solar cell.

Table 1 Photoelectrochemical parameters of the cells sensitized with natural extracts Extract sources
+

I sc (mA cm2 ) 1.63 0.37 0.82 2.93.2 1.1 0.96 2.1

V oc (mV) 404 372 382 0.440.48 0.55 0.52 0.57

FF 0.57 0.33 0.47 0.52 0.56 0.58

Z (%) 0.37 0.05 0.15

Ref. [2] [3] [5] [5]

Rosella Blue pea Mixed rosellablue pea Authurium owers Black rice Fruit of Calafate Skin of Jaboticaba

Ternatin T-A1 T-A2 T-B1 T-B2 T-D1 T-D2

R -CGCG or CGCG -CGCG or CG -CGCG or CGC -CGC or CG -CGC or CGC -CGC or -C

where C = p-Coumaric acid and G = glucose

Fig. 4. Chemical structures of: (a) cyanidin and delphinidin in rosella dye; (b) ternatin in blue pea dye (reprinted from [10] and [11], respectively).

rosella extract (cyanidin and delphinidin) has a shorter distance between the dye skeleton and the point connected to TiO2 surface compared to that of blue pea extract (ternatin) as shown in Fig. 4. This could facilitate an electron transfer from anthocyanin in the rosella extract to the TiO2 surface and could be accounted for a better performance of rosella extract sensitization [14]. The absorption spectrum of the mixed rosellablue pea extract adsorbed on TiO2 electrodes does not show synergistic characteristics (Figs. 2 and 3(c)) as found in absorption spectrum of the extract solution (Fig. 1), but the spectrum was similar to that of rosella extract with a slightly narrower range and lower intensity. This indicates a dominant inuence of the rosella extract on the TiO2 lm.

A DSSC sensitized by a mixed extract had an efciency of around the average value of those sensitized with rosella and blue pea extracts. This result is in agreement with the absorption spectrum of the extract coated on TiO2 . However, this is rather different from the result by Kumara et al. [8], in which a DSSC fabricated using chlorophyll and shisonin dyes showed synergistic effect of both dyes. The results in this work, are inuenced by low interaction between blue pea extract and TiO2 lm as mentioned above. Under preparation and irradiation conditions, the DSSCs prepared from a rosella extract showed a comparable performance to the DSSCs prepared from other natural dyes (Table 1). Therefore, the rosella extract should be an alternative anthocyanin source for DSSC preparation in geographical regions that rosella is widely available. Rosella extract was chosen for further study since it gave a better sensitizing performance compared to blue-pea extract. The effect of dye extracting temperature on DSSC efciency is shown in Table 2. Obviously, an extraction of anthocyanin above 50  C results in decreasing in the DSSC efciency. This is caused by a decrease in the stability of anthocyanin at elevated temperature [15]. At high temperature, the thermal degradation of anthocyanin could be caused by a loss of glycosyl moieties and a-diketone formation [16]. On the other hand, anthocyanin extracted

ARTICLE IN PRESS
Table 2 Photoelectrochemical parameters of the cells sensitized with rosella dye extracted at various temperature Extracting temperature ( C) 25 50 70 100 I sc (mA cm2 ) 1.24 2.06 1.75 1.63 V oc (mV) FF Z (%) Table 3 Effect of extracting solvent on DSSC efciency and stability (extracting temperature is 50  C) Extracting solvent Water Water Ethanol Ethanol
a

Irradiated time (h)

a

I sc (mA cm2 2.06 1.91 2.51 0.01

V oc (mV) 433 412 488 212

FF

Z (%)

396 433 412 404

0.55 0.59 0.57 0.57

0.27 0.52 0.41 0.37

3
a

0.59 0.55 0.58 0.25

0.52 0.43 0.71 5 103

Just nished assembling.

Absorbance (a.u.)

at 25  C gave even lower DSSC efciency than that extracted at 100  C. This result can be interpreted from the lighter color of the extract at 25  C compared to the others, which is due to limitation of anthocyanin solubility. Here, the optimum extracting temperature was found at 50  C which is in between room temperature and boiling point of water which was performed in the literatures [3,5,6]. 3.2. Effect of extracting solvent on DSSCs efciency and stability It was reported that the extracting solvent has an effect on the efciency of DSSCs [5]. The efciency of the DSSCs was found to increase immensely when ethanol was used for extracting anthocyanin from aged Jaboticaba skin [5]. In this study, similar nding was also obtained. As shown in Table 3, the just nished assembling DSSC using ethanol as a solvent shows a higher efciency than that of using water, reported at 0.71% and 0.52%, respectively. This might owe to the fact that anthocyanin is more soluble in ethanol [17], and hence, the aggregation of dye molecules is less as expected. A good dispersion of dye molecules on the oxide surface could in fact improve the efciency of the system. Unfortunately, the efciency of ethanol system was found to be diminished after being exposed to the simulated sunlight for 3 h while there was only a slight decrease in the efciency for the case of using water as an extract solvent. This might be due to the photocatalytic decomposition of anthocyanin by TiO2 in the presence of ethanol as observed by the color of the anode to become paler after exposed to the simulated sunlight. As shown in Fig. 6, the absorption spectrum of the irradiated TiO2 photoanode adsorbed rosella ethanol extract is rather at showing no light absorption compares to those of other conditions. This makes the DSSC prepared from the rosella ethanol extract unable to function just after a short operating period. Therefore, ethanol is not suitable as an anthocyanin extracting solvent for DSSC application. 3.3. Effect of pH of extract solutions on DSSCs efciency and stability The effect of pH was also investigated in this study. The original pH of rosella extracted anthocyanin was found to

(a) (b) (c) (d)

400

500

600 Wavelength (nm)

700

800

Fig. 6. Light absorption spectra of rosella extract adsorbed on TiO2 : (a) water extract, just nished assembling; (b) water extract, after exposed to the simulated sunlight for 3 h; (c) ethanol extract, just nished assembling; and (d) ethanol extract, after exposed to the simulated sunlight for 3 h.

Table 4 Effect of pH of extract solutions on DSSC efciency and stability (extracting temperature is 50  C) pH 3.2a 3.2a 3.0 2.0 1.0 1.0 0.5
a b

Irradiated time (h)

b

I sc (mA cm2 2.06 1.91 2.18 2.32 2.72 2.68 2.26

V oc (mV) 433 412 429 417 408 406 392

FF 0.59 0.55 0.59 0.60 0.63 0.61 0.52

Z (%) 0.52 0.43 0.55 0.58 0.70 0.66 0.46

3
b b b

3
b

Original pH. Just nished assembling.

be 3.2. As shown in Table 4, the pH of extract solution has a signicant effect on the performance of DSSCs. The efciency was found to increase with decreasing pH and reached a maximum at the optimum pH 1.0. This is might be due to the fact that at pH 1.0, the photoanode made from the rosella extract can absorb more light, indicated by peak intensity as shown in Fig. 7. DSSC stability was also improved by adjusting the pH of the extract from 3.2 to

ARTICLE IN PRESS
adverse effect on the DSSC stability. It was also found that the efciency and stability of DSSCs can be enhanced by adjusting extracting temperature and pH of the extracts. The optimum anthocyanin extracting temperature and pH of the rosella extract were found at 50 and 1:0  C, respectively. At the optimum conditions, the rosella sensitized DSSC showed efciency as high as 0.70%. Acknowledgment This work was supported by the Thailand Research Fund (Contract Number MRG4780074). References
400 500 600 Wavelength (nm) 700 800
[1] M. Gratzel, J. Photochem. Photobiol. C 4 (2003) 145. [2] K. Tennakone, G.R.R.R.A. Kumara, A.R. Kumarasinghe, P.M. Sirimanne, K.G.U. Wijayantha, J. Photochem. Photobiol. A 94 (1996) 217. [3] S. Hao, J. Wu, Y. Huang, J. Lin, Sol. Energy 80 (2006) 209. [4] Y. Amao, T. Komori, Biosensors Bioelectron. 19 (2004) 843. [5] A.S. Polo, N.Y. Iha, Sol. Energy Mater. Sol. Cells 90 (2006) 1936. [6] C.G. Garcia, A.S. Polo, N.Y. Iha, J. Photochem. Photobiol. A 160 (2003) 87. [7] G.P. Smestad, Sol. Energy Mater. Sol. Cells 55 (1998) 157. [8] G.R.A. Kumara, S. Kanebo, M. Okuya, B. Onwona-Agyeman, A. Konno, K. Tennakone, Sol. Energy Mater. Sol. Cells 90 (2006) 1220. [9] N.J. Cherepy, G.P. Smestad, M. Gratzel, J.Z. Zang, J. Phys. Chem. B 101 (1997) 9342. [10] T. Frank, J. Clin. Pharmacol. 45 (2005) 203. [11] N. Terahara, N. Saito, T. Honda, K. Tokis, Y. Osajima, Phytochemistry 29 (1990) 949. [12] J. Oliveira, C. Santos-Buelga, A. Silva, V. Freitas, N. Mateus, Anal. Chim. Acta 563 (2006) 2. [13] K. Vinodgopal, X. Hua, R.L. Dalgren, A.G. Lappin, L.K. Patterson, P.V. Kamat, J. Phys. Chem. 99 (1995) 10883. [14] K. Sayama, S. Tsukagoshi, T. Mori, K. Hara, Y. Ohga, A. Shipou, Y. Abe, S. Suga, H. Arakawa, Sol. Energy Mater. Sol. Cells 80 (2003) 47. [15] M. Rubinskiene, P. Viskelis, I. Jasutiene, R. Viskeliene, C. Bobunas, Food Res. Int. 38 (2005) 867. [16] J.B. Adams, J. Sci. Food Agri. 24 (1973) 747. [17] B. Lapornik, M. Prosek, A.G. Wondra, J. Food Eng. 71 (2005) 214. [18] A. Bakowska, A.Z. Kucharska, J. Oszmianski, Food Chem. 81 (2003) 349. [19] S. Hao, J. Wu, L. Fan, Y. Huang, J. Lin, Y. Wei, Sol. Energy 76 (2004) 745.

(a) (b) (c) Absorbance (a.u.) (d)

Fig. 7. Light absorption spectra of rosella extract: (a) solution at pH 3.2; (b) adsorbed on TiO2 at pH 3.2; (c) solution at pH 1.0; and (d) adsorbed on TiO2 at pH 1.0.

1.0. As can be seen from Table 4, efciency loss of DSSCs decreased with a decreasing pH from 17.3% to 5.7%, after being exposed to the simulated sunlight for 3 h. A reason for the better efciency and stability is that, at pH below 2, anthocyanin existed as avylium ion, which is stable form of anthocyanin, an increasing pH hydrated this ion to quinonoidal bases. These compounds are labile and can be transformed into the colorless carbinol pseudobase and chalcone [18]. It was evident that at low pH the formation of avylium ion form is favorable [18]. However, the cell deterioration by acid leaching is expected as the pH goes lower (pHo1), which results in a lower efciency [19]. 4. Conclusions In conclusion, the rosella extract has higher photosensitized performance as compared to the pea blue extract. This is due to the better charge transfer between the rosella dye molecule and the TiO2 surface which is related to a dye structure. Water is suitable as an anthocyanin extracting solvent for DSSC application while ethanol gave an