Renewable Energy 34 (2009) 17591764

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Effects of paste storage on the properties of nanostructured thin lms for the development of dye-sensitized solar cells
G. Syrrokostas, M. Giannouli*, P. Yianoulis
University of Patras, Renewable Energy Laboratory, Dept. of Physics, 26500 Patras, Greece

a r t i c l e i n f o
Article history: Received 8 July 2008 Accepted 31 December 2008 Available online 30 January 2009 Keywords: Solar energy Dye-sensitized solar cells Nanostructured thin lms Counter electrodes

a b s t r a c t
The effects of paste storage on the properties of nanostructured thin lms were investigated in the present study. To this aim, dye-sensitized solar cells were fabricated using nanostructured TiO2 thin lms and an organic dye as a sensitizer. Aggregation of TiO2 nanoparticles was observed when paste was stored until deposition affecting lms porosity and surface roughness factor and as a consequence, reducing the efciency of the solar cells. On the other hand, fewer cracks were developed during the drying process of the lm when stored paste was used for lm deposition instead of freshly prepared paste. This is due to the presence of large pores on lms with signicant particle agglomeration, which enhance evaporation of acetyl acetone and water, thereby reducing cracks. The development of cracks on the lms surface results to a decrease in the efciency of the cell, albeit a slight one. One of the main aims of the present study was also the investigation of different methods for developing counter electrodes, as the properties of the counter electrodes can affect the efciency of the solar cells considerably. Counter electrodes were prepared by two different methods, namely by electrodeposition using an aqueous solution of H2PtCl6 (0.002 M) and by thermal decomposition of H2PtCl6 from isopropanol (5 mM). Electrodeposited counter electrodes were found to present several advantages over electrodes prepared by thermal decomposition, such as increased photocurrent, reduced sheet resistance, as well improved ll factor for the resulting solar cell. 2009 Elsevier Ltd. All rights reserved.

1. Introduction Photovoltaic cells are considered a promising solution to the continuously growing energy problem by providing a sustainable and, at the same time, clean source of energy. Silicon solar cells have improved considerably in efciency over the past decade and have experienced considerable commercial success. Widespread usage of conventional silicon solar cells however, is still hampered by the high production costs of puried silicon. Dye-sensitized solar cells (DSSC) offer a relatively low-cost alternative to silicon solar cells. The conversion of visible light into electricity in dye-sensitized solar cells is achieved through the sensitization of wide bandgap semiconductors. Nanostructured TiO2 thin lms are commonly used for solar energy conversion in solar cells. Sensitization of these lms with dyes is necessary in order to improve their ability to absorb solar radiation and also to inject electrons into the conduction band of the semiconductor. The

* Corresponding author. Tel.: 30 2610 997449. E-mail address: myrtwg@gmail.com (M. Giannouli). 0960-1481/$ see front matter 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.renene.2008.12.029

performance of dye-sensitized solar cells depends primarily on the properties of the dye which is used as sensitizer [1,2]. Nanostructured TiO2 thin lms can be prepared by spreading a colloidal paste of TiO2 nanoparticles on a glass or a exible substrate. It is known that the synthesis method of the paste affects the efciency of solar cells [1]. Two major methods of TiO2 paste preparation are commonly used. The rst method is the solgel method, starting from the hydrolysis of titanium chloride or a titanium alkoxide [25]. The second method is based on the use of commercial TiO2 nanopowder made by a ame process of titanium tetrachloride [6,7]. The various solgel methods provide better control of the properties of the lms such as particle size, porosity and adherence to the substrate [8], but this may also be a disadvantage, as more factors need to be monitored and improved. Film fabrication using powder, on the other hand, is a less complicated process. Different techniques for spreading the colloidal paste are employed, such as doctor blade, spraying, screen printing, spin coating, as well as a novel compression method. In addition to nanostructured TiO2 thin lm electrodes, counter electrodes comprised of nanosized Pt grains also play an important part in the development of dye-sensitized solar cells. For that

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reason, various methods for their deposition are investigated in the present work. 2. Experimental Nanostructured TiO2 thin lms were deposited on a conducting glass substrate (in this study we used SnO2:F with sheet resistance of 15 U/sq and 80% transmittance in the visible) using a simple doctor blade technique. The most frequently used commercial nanopowder is Degussa P-25 and it consists of 80% anatase and 20% rutile. The TiO2 nanopowder Degussa P-25 was used in this study as a basis for the colloidal paste. The TiO2 powder (3 g) was ground in a porcelain mortar and mixed with a small amount of distilled water (1 ml) containing acetyl acetone (10% v/v) to create the paste [2,6]. Acetyl acetone was used as a dispersing agent, since it prevents coagulation of TiO2 nanoparticles and affects the porosity of the lm [9]. The paste was diluted further by slow addition of distilled water (4 ml) under continued grinding. The addition of water controls the viscosity and the nal concentration of the paste [6,10]. Finally, a few drops of a detergent (Triton X-100) were added to facilitate the spreading of the paste on the substrate, since this substance has the ability to reduce surface tension, resulting to even spreading and reducing the formation of cracks [11,12]. It should be noted here that further addition of water to the mixture after adding Triton X-100 results to the formation of bubbles, which hinder paste deposition. These bubbles disappear after a small amount of distilled water containing acetyl acetone has been added to the mixture. After preparation the paste was stored in a screw-threaded glass bottle until deposition. The paste was spread on the glass surface via the doctor blade method using a glass slide. Adhesive tapes were used on the glass surface in order to dene the area of the TiO2 lm and also to provide uncoated areas on the glass substrate for electrical contacts. The glass slide was applied onto the adhesive tapes, so the thickness of the TiO2 lms was partly controlled by the thickness of the adhesive tapes. It was observed that the lms were thicker at the edge of the adhesive tapes, due to the high concentration of the paste mixture near the edge. After air drying, the electrode was annealed for 30 min at 450 550  C. Sintering enhances the electrical contact between the nanoparticles as well as between the nanoparticles and the conductive substrate but, on the other hand, signicant particle growth occurs [13]. The thickness of the resulting lms was controlled accordingly in order to vary from 5 to 15 mm. The dye molecule Rhodamine B was used as a model sensitizer for all solar cells fabricated during the present study. Coating of TiO2 surface with a monolayer of dye was achieved by soaking the lm in a solution of Rhodamine B (0.01 M) in either methanol or ethanol for at least 12 h. The lm was dipped into the dye solution

while it was still hot (80  C). It was observed that the same dye solution cannot be used to sensitize many TiO2 lms effectively, especially when the solution is stored even for a small period of time. One of the reasons for this effect is contact of the solution with ambient air, which causes the dye colour to fade visibly. Also, it is well known that degradation of Rhodamine B takes place in the presence of TiO2, under visible light illumination. Two different techniques were followed for the preparation of the counter electrode. Counter electrodes were prepared by thermal decomposition of hexachloroplatinic acid solution (H2PtCl6) in isopropanol or by electrodeposition of an aqueous H2PtCl6 solution (0.002 M). For the second method, a few drops of H2PtCl6 solution in isopropanol (5 mM) were spread on a conductive glass substrate, followed by annealing in 400  C for 15 min. After completing the counter electrode preparation by either method, the Van der Pauw method [14] was used to measure the sheet resistance of the counter electrodes. The sensitized TiO2 electrode and the counter electrode were assembled as a sandwich type cell using O-ring and clumps. Finally, redox electrolyte consisting of 0.3 M potassium iodide and 0.03 M iodine in propylene carbonate was used. The electrolyte was inserted in the cell with a syringe, lling the space between the two electrodes. Due to the use of an O-ring, the gap between the two electrodes was relatively large, as was the amount of the electrolyte needed to ll this gap. The aforementioned fabrication process is easy and simple, but results to an increase of the internal resistance of the solar cell and therefore to a reduction of the photocurrent. For the purpose of this study, this simple method of fabrication was adequate.

3. Results and discussion The main disadvantages of using a commercial powder of TiO2 are inefcient control of particle size due to agglomeration during paste preparation, the development of non-pure anatase lms and poor adhesion of the lm to the substrate [12]. In addition, it was observed that signicant particle agglomeration occurs when the paste is stored in a glass-threaded bottle until deposition. The formed large aggregates of TiO2 nanoparticles enhance the porosity of the lm, which means that electrons have to travel a greater distance until they are collected at the conducting substrate, having a greater chance for recombination [15]. The coordination number of nanoparticles is reduced, enlarging the path to the conducting substrate [16]. The adsorption of fewer dye molecules on the lms surface leads to reduced photocurrent and as a result, to lower cell efciency. Moreover, electrical contact is worst, since the area of interconnection is reduced [15,17]. Therefore, the resistance for charge transfer is greater.

Fig. 1. SEM images of a lm prepared by freshly prepared paste (left) and by stored paste (right). The storing time was approximately 2 months.

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20

cell 26 cell 27

0.20 0.18 0.16 cell 27 cell 31 cell 26

Film Thickness (m)

15

I / mA

Film prepared immediately after paste preparation

0.14 0.12 0.10 0.08 0.06 0.04

10

5 Film prepared 2 months after paste preparation 0 4 5 6 7

0.02 0.00 0.0 0.1 0.2 0.3 0.4 0.5

V/V
Fig. 4. IV characteristics of three cells prepared by lms with different pastes.

Scan distance (mm)

Fig. 2. Prolometer data from two different lms, prepared by pastes with different storing intervals. Peaks are due to aggregates.

Although the stored paste was ground again using the mortar and the same quantities of acetyl acetone, water and Triton X-100 were added, lms prepared using the stored paste had larger grains and their surface was rougher. This can be observed from Scanning Electron Microscope (SEM) images (Fig. 1) and also from prolometer data (Figs. 2 and 3). Further addition of the aforementioned organic ingredients and water was required in order to supplement the quantity of the material which was evaporated during storing. The paste thus acquired the appropriate concentration for lm deposition. Also, it is obvious that fewer cracks were developed when the stored paste was used for lm deposition instead of freshly prepared paste. Cracks are developed mainly during the drying process of the lm, before sintering. Larger pores, which are present on lms with signicant particle agglomeration [18], enable evaporation of acetyl acetone and water, thereby reducing cracks. From Figs. 2 and 3 we can observe that lms deposited immediately after paste preparation were thicker than lms deposited from stored paste. Film thickness plays a crucial role for efcient light absorption. Also, lms deposited from a stored paste were less transparent due to larger particle size, even though these lms had lower thickness. Large peaks in the gures correspond to large

nanoparticles in the TiO2 paste, which are formed even after relatively short storing time intervals. Fig. 4 shows the currentvoltage characteristic (IV curves) of three different cells. A 50 W halogen lamp was used as a light source and the illumination intensity was measured to be 660 W/m2. The TiO2 lm on each cell was prepared using paste, which was stored for different time intervals. The TiO2 lm in cell 27 was deposited immediately after paste preparation and the lm in cell 31 was deposited from the same paste as cell 27, after the paste was stored for 20 days. The lm in cell 26 was deposited 2 months after paste preparation. The initial paste used in cell 26 was different than the one used in the two previous cells. This explains the prolometer data from cell 26, which show slightly less prominent aggregates for a lm fabricated 2 months after paste preparation than for the lm fabricated 20 days after paste preparation. From Fig. 4 we can also observe a reduction in the ll factor as the storing time of the paste is increased, indicating an increase in the internal resistance of the cells. More specically, cell 27, which was assembled immediately after paste preparation, has a ll factor of 0.50, while cell 31 and cell 26 have ll factors of 0.47 and 0.46 respectively. From Figs. 2 and 3 it can be observed that the precise amount of storing time of the paste has little effect on particle agglomeration as well as on the stability of the solar cells. Nanoparticles of TiO2 form large aggregates when the paste is stored even when the storing time is relatively short (aggregates are formed after the

20

Film prepared immediately after paste preparation

cell 27 cell 31

0,25

0,5

Film thickness (m)

15 0,20

Voc

0,4

I (mA)

10

0,15

Isc 0,2

5 Film prepared 20 days after paste preparation 0 4 5 6 7 0 10 20 30 40 50 60 0,10

0,1

0,0

Scan distance (mm)

Fig. 3. Prolometer data from two different lms, prepared by pastes with different storing intervals.

Days until film deposition after paste preparation

Fig. 5. Variations of short circuit current and open circuit voltage for cells having lms prepared by a stored paste, for different time intervals.

V (V)

0,3

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Fig. 6. SEM images of lms prepared by different concentrations of acetyl acetone. The concentration was 10% v/v (left) and 20% v/v (right).

paste has been stored for a few days). From Fig. 5 we can observe the reduction of the short circuit current and open circuit voltage, when lms are deposited from both freshly and not-freshly prepared paste. Current is more affected by lm characteristics such as lm morphology, porosity, particle size etc., than voltage. It was also observed that the efciency of the cells was reduced, following the reduction of the current. The lower cell efciency that was observed in cells that were developed using stored paste is due to a number of reasons. The agglomeration of TiO2 nanoparticles results to a reduction of the active surface area for dye adsorption and as a consequence, to reduced photocurrent (Fig. 5). Moreover, electrical contact is worst, since the area of interconnection between nanoparticles is reduced as has also been shown elsewhere in the literature [15,17] and therefore, the resistance for charge transfer is greater, as we have observed from the reduction in the ll factor. Good electrical contact between nanoparticles and between nanoparticles and substrate is essential for electron transport, provided that electrons hop between neighbouring nanoparticles through trap states on the surface of the TiO2 nanoparticles. It is known that those traps are localized energy states just below the conduction band of the semiconductor [10,15,19,20]. Filling of those traps with electrons improves electron transportation [21]. In addition, since the interconnection area becomes smaller when the paste is stored for some time, necking of nanoparticles is reduced. As a consequence, electron recombination, which occurs mainly at grain boundaries, is enhanced, resulting to a reduction in the electron ow. Finally, it is well known that lm characteristics affect the efciency of the cells, since electron transport is mainly due to diffusion and the diffusion coefcient strongly depends on lm properties [2225]. Signicant reduction of the cracks forming on the lms surface was observed when the amount of acetyl acetone in the paste mixture was increased. More specically, an increase in the concentration of acetyl acetone in distilled water from 10% v/v to

20% v/v resulted to the formation of considerably fewer cracks, examples of which are shown in Fig. 6. The lms presented in Fig. 6 were prepared under the same conditions (temperature, air moisture) and were sintered at the same temperature and for the same time in the same oven. As we have observed from Fig. 1, cracks are not developed due to the formation of large aggregates, but rather due to stress during the drying and densication (condensation) process of the lm. The amount of acetyl acetone in the paste mixture affects the lms condensation time. Increasing the amount of acetyl acetone results to an increase in the condensation time, so that the network of TiO2 nanoparticles becomes more resistant to stress. Film thickness also plays an important role in the formation of cracks, as thicker lms tend to have more cracks. It should be mentioned here however, that the lms displayed in Fig. 6 are of similar thickness (approximately 10 mm) and therefore, the difference in the formation of the cracks between the two lms cannot be due to such effects, but rather to the different concentrations of acetyl acetone in the paste mixture. The formation of cracks on the lms surface can reduce the electrical contact between TiO2 nanoparticles. If the cracks formed on the lms surface reach the conducting substrate, electron recombination will be increased due to contact of the electrolyte with the conducting substrate. On the other hand, access of dye molecules is easier during sensitization when cracks are present on the lms surface. As a result, the presence of cracks on the lms surface results to only a slight decrease in the efciency of the cell. The properties of the counter electrode also affect the efciency of the solar cells. We have prepared counter electrodes by two different methods, by electrodeposition using an aqueous solution of H2PtCl6 (0.002 M) [26] and by thermal decomposition of H2PtCl6 from isopropanol (5 mM) [27]. Different conditions for the preparation were tested, in the case of electrodes prepared by electrodeposition. Deposition time was varied from 10 to 30 min, though

Fig. 7. SEM images of electrodeposited lms. Deposition time was 20 min and the current was kept constant at 4 mA.

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0,6 0,5 0,4

0,3 0,2 0,1 0,0 0,00

electrodeposition thermal decomposition 0,05 0,10 0,15 0,20 0,25 0,30 0,35 0,40

and by thermal decomposition. Enhancement in the photocurrent was observed (from 0.525 mA to 0.613 mA) due to the larger area available for the catalytic reduction of triiodide when an electrodeposited counter electrode was used rather than an electrode made by thermal decomposition. The subsequent improvement in the ll factor (from 0.49 to 0.53) is due to the reduction in the internal resistance of the solar cell and particularly in the charge transfer resistance of the electrons at the counter electrode. From Van der Pauw measurements the sheet resistance of electrodeposited counter electrodes was found to be lower than that of electrodes made by thermal decomposition by approximately 2 U/sq. This occurs because sintering at 400  C for thermal decomposition decreases the conductivity of the substrate. Moreover, interconnection of nanoparticles is more efcient in the case of electrodeposited electrode, reducing the sheet resistance.

I / mA

V/V
Fig. 8. IV characteristics of two cells having different counter electrodes.

4. Conclusion Our results indicate that nanoparticle TiO2 lms need to be deposited immediately after paste preparation to avoid agglomeration of the material. It was also observed that, paste characteristics such as viscosity, titanium dioxide concentration, size and nature of nanoparticles, affect lm properties and therefore the efciency of the solar cells, in agreement with ndings presented elsewhere in the literature [3436]. Paste storage may be feasible only under controlled conditions as it is more sensitive to environmental conditions than powder storage, resulting to the formation of large aggregates of TiO2 nanoparticles. Large aggregates of TiO2 nanoparticles enhance porosity but reduce active surface area for dye adsorption and also reduce the transparency of the lm. Two methods of manufacturing counter electrodes were investigated in the framework of this study, namely thermal decomposition and electrodeposition. It was observed that electrodeposited counter electrodes present several advantages over electrodes prepared by thermal decomposition, such as increased photocurrent, reduced sheet resistance of the electrode and improved ll factor of the solar cell. Finally, a major drawback of the thermal decomposition of platinum chloride is that thermal decomposition is achieved at about 400  C. Therefore, this thermal treatment cannot be applied to exible substrates. On the contrary, the method of electrodeposition does not present similar limitations.

the current was kept constant (3 to 4 mA) and lms were electrodeposited from a freshly prepared H2PtCl6 solution. The morphology of the electrodeposited lms was examined via Scanning Electron Microscope (SEM). It was observed that the lm is composed by small Pt nanoparticles and by large sponge like aggregates, as veried by component analysis (Fig. 7). Small Pt nanoparticles are more active catalytically than larger aggregates due to larger density of catalytically active sites [28,29] and in addition, large aggregates may increase conductivity. On the other hand, larger aggregates of Pt particles tend to have lower adherence to the substrate. We have also observed that the amount of Pt deposited by electrodeposition is proportional to the deposition time and the current density. The resulting lms were thicker and became visibly less transparent, having a mirror-like appearance, as the amount of the Pt deposited increased. When a thick layer is deposited, the sheet resistance is reduced up to a point [30] and the interconnection of Pt nanoparticles increases. Charge transfer resistance depends also on the thickness of the Pt layer and the aggregation of the nanoparticles [31], although charge transfer resistance depends primarily on the solvent and the electrolyte used [32]. On the other hand, adherence to the substrate was found to be less satisfactory when counter electrodes were prepared by electrodeposition rather than by thermal decomposition. Sintering of electrodeposited lms improved only slightly the adhesion of the lms on the substrate. Dissolved Pt nanoparticles may be re-adsorbed on the TiO2 electrode and catalyze dark current at the TiO2/ electrolyte interface, enhancing charge recombination. Thicker lms made through electrodeposition were more sensitive when contact was made with the electrolyte, showing more intense dissolution than lms with smaller thickness. It should also be noted that, in thermal deposition, a part of the Pt is deposited with valence 2 and 4, which is less catalytic active than zero valence [33]. The counter electrode should have high conductivity and should be able to catalyze the reduction of triiodide, exhibiting low overvoltage at photocurrent densities up to 20 mA/cm2 [18]. A Pt layer, even a few nm thick, exhibits high electrochemical activity towards triiodide reduction, however is not cost effective. Substitution of platinum with carbon exhibits lower results due to lower catalytic activity of carbon towards triiodide reduction. Recently a dye-sensitized solar cell with a counter electrode prepared by carbon nanotubes (CNT) exhibited higher efciency and better stability [26]. Fig. 8 shows the current voltage characteristics of two cells using two different counter electrodes, prepared by electrodeposition

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