Solar Energy Materials & Solar Cells 73 (2002) 91101

A new method for manufacturing nanostructured electrodes on glass substrates

. Henrik Lindstrom, Eva Magnusson, Anna Holmberg, . Sven Sodergren, Sten-Eric Lindquist, Anders Hagfeldt*
Department of Physical Chemistry, Uppsala University, P.O. Box 532, S-75121 Uppsala, Sweden Received 18 October 2000

Abstract The present paper describes a new method for manufacturing a nanostructured porous layer of TiO2 on a conducting glass substrate for use in a dye-sensitized photoelectrochemical cell. The method involves deposition of a layer of semiconductor particles onto a conducting substrate and compression of the particle layer to form a mechanically stable, electrically conducting, and porous nanostructured lm at room temperature. Photoelectrochemical characteristics and morphology of the resulting nanostructured lms are presented. The potential use of the new manufacturing method in the future applications of nanostructured systems is discussed. r 2002 Elsevier Science B.V. All rights reserved.
Keywords: Nanostructured; Electrode; Solar cell; Photoelectrochemical; Dye

1. Introduction In many applications wherein electrochemical or photoelectrochemical cells are used, such as in solar cells [l] or in displays [24], there is a need to expose an electrolyte to a very large inner electrode area. This could be expressed such that the electrode should exhibit a very high surface to volume ratio. A useful method to achieve a high surface-to-volume ratio is to manufacture an electrode in the form of a nanostructured lm, i.e. a network of interconnected particles of nanometer size. The porosity of such a lm is usually in the range of
*Corresponding author. Fax: +46-18-508-542. E-mail address: anders.hagfeldt@fki.uu.se (A. Hagfeldt). 0927-0248/02/$ - see front matter r 2002 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 7 - 0 2 4 8 ( 0 1 ) 0 0 1 1 4 - 3

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5060%. The particles typically consist of a semiconductor material, such as a metal oxide, and the particle size is within the range of a few nanometers up to several hundred nanometers. The thickness of a nanostructured lm is commonly in the order of 510 mm, but may be up to several hundred micrometers. The electrode lm is normally deposited on a conducting substrate such as a conducting glass. The function of the nanostructured lm depends on the application. For example, in a solar cell the function of the nanostructured lm is to collect the electrons from an excited state produced when light is absorbed in dyemolecules attached to the surface of the nanostructured lm. The electrons are transported through the particle network of the lm to the conducting substrate where the current is collected. In display applications, on the other hand, the nanostructured lm is useful to deliver electrons to the surface attached molecules [24] or to the nanostructured lm itself to accomplish intercalation of for instance, lithium ions [5]. By changing the electrical potential of the conducting substrate the apparent color of the nanostructured lm is controlled. There are several previously known methods for manufacturing nanostructured lms. Common to most of them is that the semiconductor material is applied to the conducting substrate in the form of very small particles, typically with a size of a few nanometers, present in a colloidal solution. These small particles are physically and electrically connected to each other and the conducting substrate, using a ring process. The ring process is normally performed at a temperature of several hundred degrees and for a time period of, typically, half an hour. Actually, in addition to the ring process described above, conventional methods for forming nanostructured lms include several steps, each step is often rather time and cost consuming. For example, a colloidal solution preparation step includes measures to ensure a low degree of particle aggregation, such as adding organic additives. Thus, the ring process is needed not only to connect the particles, but also to remove the anti-aggregating organic additives in the solution by combustion. Furthermore, a lm deposition step may include the use of screens to pattern or limit the extension of the lm. The main purpose of this paper is essentially to introduce a new method [6] to deposit nanostructured electrodes on conducting glass substrates. A layer of nanosized particles is deposited onto a conducting substrate and compressed to form a nanostructured lm electrode. As will be shown, the new deposition method can be varied and performed in a large number of ways.

2. Experimental 2.1. Conducting substrates The conducting glass substrate was a Tec 8 supplied by Hartford glass Co, Inc and consisted of a soda lime glass sheet with a conducting layer of uorine doped tin oxide of 8 O/square resistivity. The glass substrates were cleaned with spectrograde ethanol immediately prior to use.

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2.2. TiO2 suspensions The suspensions were prepared by adding TiO2 powder to spectrograde ethanol. Ethanol was chosen as suspending agent because of its low surface tension resulted in a smooth lm deposition. The TiO2 powder used was P25 (supplied by Degussa and used as received). The P25 consisted of 70% anatase and 30% rutile, and the particle size was 22 and 35 nm, respectively, as obtained by X-ray diraction (Siemens D-5000 powder diractometer). P25 was added to an amount of 20 wt% to ethanol. The suspension was stirred with a magnetic stirrer for a period of, typically, 2 h before deposited on the conducting substrates. 2.3. Deposition and compression The suspension was applied onto the conducting layer by doctor blading using scotch tape as frame and spacer. After the deposition of the suspension, the ethanol was allowed to evaporate to air resulting in a particle layer that will be referred to as the powder lm below. A 50 mm thick lm of aluminum foil was draped on the powder lm. Aluminum was chosen because it has good non-sticking properties. The assembly consisting of substrate, powder lm and separating lm was placed between two planar steel plates. Pressure was applied on the assembly via steel plates using a 150 ton strain rod press with Anataze programmer from PHI. Pressure was applied with a speed of about 2000 kg/(cm2s). 2.4. Film characterization The lm thickness was measured with a Dektak 3 prolometer from Veeco. Porosity was determined by calculating the density of the nanostructured lm (from the lm thickness, lm area and lm weight) and comparing it with the density of compact anatase and rutile, taking into account that P25 contained 30 wt% rutile and 70 wt% anatase. The inner surface area and porosity of the TiO2 lms was examined by BET. Compressed nanostructured lms on conducting glass were red at 4501C in air for 30 min and then scraped o the substrate. 100 mg samples were used for BET characterization. The powders were conditioned in vacuum for 7 days before measurement. The analysis adsorptive was nitrogen. 2.5. Dye-sensitation and electrolyte preparation The electrodes were dye-sensitized by submerging the substrate with the deposited lm for 2 h in a dye-bath consisting of 0.5 mM cisbis(isothiocyanato)bis(2,20 bipyridyl-4,40 dicarboxylato)ruthenium(II) bistetrabutylammonium, i.e. N719 ( dye supplied by Solaronix, in spectrograde ethanol which was dried over 3 A molecular sieves before use. The electrolyte consisted of 0.5 M LiI (99.99%, H2Oo100 ppm, Aldrich), and 0.05 M I2 (99.999%, H2Oo100 ppm, Aldrich) and 0.5 M t-butyl pyridine (99%, Aldrich) in methoxypropionitrile (99%, Fluka). The ( methoxypropionitrile and t-butyl pyridine was dried over 3 A molecular sieves

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before use. The electrolyte and dye-bath were prepared and stored in an argon lled glove box (H2Oo15 ppm, O2o20 ppm). 2.6. Current-voltage and IPCE measurements IV curve measurements were made in a two-electrode sandwich conguration in air and at room temperature. The counter electrode consisted of a thermally platinized conducting glass. It was prepared by covering the conducting glass with a 5 mM solution of H2PtCl6 (99.9%, Aldrich) in isopropanol (99.5%, H2Oo0.005%, Aldrich). After evaporation of the solvent, the glass was heated at 3851C for 15 min in air. The iv curves were monitored and recorded using a computerized Keithley 2400 source meter. To simulate sunlight, a sulfur lamp was used (Lightdrive 1000 from Fusion Lightning). In order to make indoor measurements comparable with measurements performed in direct sunlight (outdoor measurement a cloud free day at 1:00 PM in Uppsala), a pyranometer from Kipp & Zonen was calibrated. This was performed by rst measuring an iv curve of a dye-sensitized solar cell at a certain light power in sunlight. In the next step, the solar cell was exposed to simulated sunlight and the distance to the light source was adjusted such that the same iv characteristics that were obtained in direct sunlight were reproduced. The ratio between the lightpower as measured in sunlight and in simulated sunlight gave a conversion factor for the pyranometer. The IPCE was monitored and recorded using a computerized Keithley 2400 source meter. In the IPCE measurements a xenon lamp was used. Second order harmonics were removed by cuto lters for 400 nm radiation monochromator. The incident monochromatic radiation was monitored in situ using a split beam conguration. The short-circuit currents obtained from iv measurements were veried by the theoretical integral currents, i.e., the product integral of the IPCE spectrum and the solar spectrum at AM 1.5.

3. Results and discussion 3.1. Film preparation The composition of the P25-suspension was adjusted such that the deposition would result in smooth and homogenous powder lms. We found that an addition of (2025) wt% TiO2 powder in the P25 gave satisfactory results with the present deposition methods. After the deposition of the suspension lm, the ethanol was allowed to evaporate in air at ambient conditions. Depending on the thickness of the deposited layer, the evaporation process was completed within 13 min. Generally, the resulting powder lm was strongly light scattering and had poor intrinsic mechanical stability and could therefore be removed easily from the substrate by e.g. scratching. Also depending on the thickness of the deposited suspension layer, macroscopic cracks

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were formed to dierent extent. Typically, for thicker suspension lms, i.e. above 200 mm, macroscopic cracks in the powder lm could be seen by visual inspection. However, when the thickness of the deposited suspension layer was decreased, both the tendency of cracking decreased and the size of the cracks became smaller. It should be noted that although the powder lm contained cracks, the adherence to the substrate was good and the substrate with the deposited lm could therefore easily be handled without peeling o during transport, etc. After evaporation of the ethanol the substrate with the attached powder lm was put between two planar steel press plates. A separating aluminum foil was placed on top of the powder lm to prevent adhesion between the press plate and the lm. Pressure was applied by using a hydraulic press. Fig. 1 shows a SEM picture of a pressed nanostructured TiO2 electrode. The average particle size as determined from the picture was 23 nm, in good agreement with the particle size determined from X-ray measurements (see experimental section). It could be seen that the powder lm became less light scattering and more transparent after the pressing procedure. The transparency increased with higher applied pressures. Furthermore, the lm became more compact (less porous) and the mechanical stability (scratch resistance) of the lm increased. The minimum pressure to achieve a mechanically stable lm was about (200300) kg/cm2. The increase in transparency can be explained by the breakage of particle aggregates in the powder lm: The P25 powder consists of loosely bonded 22 nm particles forming aggregates of roughly 100 nm size. These aggregates are highly light scattering. During the compression of the powder lm, the aggregates are broken up or crushed into smaller particles resulting in reduced light scattering eects due to a smaller eective particle size. It was observed that cracks initially present in the powder lm to a large extent smoothened out and nearly disappeared during the

Fig. 1. SEM picture of a compressed TiO2 powder lm.

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Fig. 2. The porosity of compressed TiO2 powder lms are shown as a function of the applied pressure.

pressing procedure. By varying the applied pressure the transparency, mechanical stability and porosity could be controlled. 3.2. Porosity A 100 mm thick 20 wt% P25 suspension in ethanol was deposited on a conducting glass. The powder lms were compressed at dierent pressures. The results from these experiments are shown in Fig. 2. Each point in the curve is an average value from 3 measurements. The initial porosity at 200 kg/cm2 was 69%. The porosity decreased monotonically in the pressure range from 200 to 2000 kg/cm2. However, the incremental change in porosity decreases with the increasing pressure. Experiments were also performed varying the thickness of the deposited liquid suspension layer (data not shown). No signicant dependence between the initial suspension lm thickness and the porosity of the compressed lm could be observed. 3.3. BET measurements BET measurements were performed on P25 powder and on compressed TiO2 lms. Both samples were sintered at 4501C in air for 30 min. The applied pressure was 1000 kg/cm2. The BET surface area of the compressed lm and the powder were 63.9 and 60.6 m2/g, respectively. The BET pore size distribution in the compressed lm ranged from 5 to 60 nm with a maximum at 23 nm and the average pore diameter was 23 nm. Thus, the pores in the compressed lm have approximately the same diameter as the particle size. The average pore diameter of the un-pressed powder was 27 nm, however, the pore size distribution was much broader, ranging from 5 to 200 nm having a small and broad maximum at (3040) nm. The BET

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porosity value of the compressed lm and the powder was 52% which is in good agreement with that obtained by gravimetric porosity determination (see Fig. 2). The BET porosity of the un-pressed, sintered P25 powder was 61%. 3.4. Selective pressure application In another experiment, we exploited the fact that the nanostructured lm is formed on the substrate on areas of the powder lm where the pressure is applied. Fig. 3 shows a photograph of a nanostructured TiO2 lm produced by compressing selected areas of a powder lm on a glass substrate. Pressure was applied selectively on the powder lm by putting a triangular aluminum foil on top of the powder lm. When pressure was applied on the aluminum foil, the triangular pattern was transferred to the lm which was printed directly on the conducting substrate. The loose powder lm remaining on areas outside the relief areas of the aluminum foil could easily be wiped away. The resolution of the method can be judged by the sharp edges of the printed triangle shown in Fig. 3. 3.5. Surface microstructure It was possible to create a microstructure on the surface of the nanostructured lm by using a brass press plate with a patterned surface. Fig. 4 shows a prolometric

Fig. 3. A nanostructured lm on a conducting glass substrate formed by selectively compressing a powder lm of P25.

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Fig. 4. A: prolometric scan showing the surface structure of a turned brass press platen. B: prolometric scan showing the surface structure of a nanostructured TiO2 lm compressed with a turned brass platen.

Table 1 Non-sintered electrodes, lm thickness: 8 mm, the table shows the average values for 4 electrodes. E=Overall light-to-electric energy conversion eciency. FF=Fill factor, Voc =Open circuit voltage and Isc=Short circuit current Intensity (W/m2) 100 400 700 1000 FF 0.6770.01 0.5870.04 0.5070.06 0.4770.06 E (%) 4.570.3 4.270.l 3.570.3 3.070.4 Voc (V) 0.6670.03 0.7270.03 0.7370.01 0.7370.01 Isc (mA cm2) 1.070.1 4.070.3 6.870.3 8.670.1

scan on the surface of a microstructured brass platen (a), and a prolometric scan on the surface of the nanostructured electrode (b), created with this tool. It can be seen that the amplitude, periodicity and waveform of the press platen and the compressed lm are very similar. Microstructuring of the press tool surface was performed with a lathe. 3.6. Photoelectrochemical measurements The photoelectrochemical properties were investigated by dye-sensitizing the nanostructured electrodes and measuring iv characteristics and IPCE in a sandwich electrode conguration. Tables 1 and 2 shows the averaged data extracted from iv curve measurements on dye-sensitized nanostructured electrodes with equal lm thickness, i.e., all electrodes were 8 mm thick. The manufacturing parameters for all electrodes were kept constant with the only exception that electrodes in Table 1 were not sintered before dyesensitation, and electrodes in Table 2 were sintered at 4501C for half an hour before dye-sensitization. A comparison between the values in Tables 1 and 2 shows that the iv characteristics of the sintered and the un-sintered nanostructured TiO2 electrode to a

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Table 2 Sintered electrodes (4501C, 30 min), lm thickness: 8 mm, the table shows the average values for 7 electrodes. Intensity (W/m2) 100 400 700 1000 FF 0.6470.01 0.5770.02 0.5270.03 0.4870.04 E (%) 4.370.3 4.170.2 3.570.2 3.170.2 Voc (V) 0.6470.01 0.6970.01 0.7170.01 0.7270.01 Isc (mA cm2) 1.070.1 4.170.3 6.670.5 9.170.8

Fig. 5. IV characteristics of electrodes having stacked layers. 1: one deposited layer giving E=5.1%, =0.66, Voc=0.65, Isc=l.2 mA cm2. 2: Two deposited layers giving E=5.2%, =0.66, Voc=0.62, Isc=l.3 mA cm2. 3: Three deposited layers giving E=6.0%, =0.66, Voc=0.62, Isc=l.5 mA cm2. The light intensity was 100 W/m2.

large extent are similar. The linearity of the short circuit current with light intensity shows that the diusion of the redox couple through the nanostructured lm is not limiting for the photocurrent. Thus, the eciency drop at higher light intensities can be attributed mainly to series resistance losses in the conducting substrate. In another experiment several layers of nanostructured lms were stacked on top of each other. Each powder lm layer was compressed separately before the next layer of suspension was applied. The thickness of each separate layer was about 4 mm. Figs. 5 and 6 shows the iv characteristics and IPCE spectra respectively, for l-, 2- and 3-layer electrodes prepared with this method. It can be seen that the overall performance is improved when the number of layers increases. The IPCE spectrum matches well with the absorption spectrum of the dye having a maximum at 540 nm and an absorption tail extending to about 800 nm.

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Fig. 6. IPCE spectra of electrodes having stacked layers. 1: one deposited layer. 2: two stacked layers. 3: Three stacked layers.

4. Summary The method to produce a nanostructured porous electrode by pressing has many advantages with respect to prior art methods. The advantages are mainly due to the fact that the method does not involve the use of additives such as organic detergents, polymers, etc. in the particle suspension. Such additives require a ring step to be removed. The particles are added as a powder commercially available at low cost. The deposition is easily made using simple methods due to the low viscous consistency of the suspension. The step of compressing the deposited lm to achieve a thin but still porous lm is also performed using simple techniques. An especially important feature is that the pressing method gives a mechanically stable and electrically conducting nanostructured lm at room temperature. A structure on the microscale, of the roller surface could be provided, and through the step of compression this structure would then be transferred to the surface of the nanostructured layer. This technique could be useful in achieving optical eects such as light trapping, etc. It is even possible to provide a press platen with a relief pattern to be reproduced on the nanostructured lm. That is, a pattern to be transferred to the nanostructured lm on the substrate is printed directly by the pressure from the press plate, without the need for screens, while the loose particles remaining on at the areas between the relief areas of the roller are wiped or ushed away. The pattern could for instance be segments, digits, or letters, etc, for use in displays or solar cells. Another major advantage is that all the steps of the method are very fast, thereby allowing very high throughput, especially when adopted in an automated process. This paper contains preliminary result from experiments performed on electrodes produced by using P25 as the starting material. However work is in progress in our

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laboratory to include several other metal oxide powders in the study [5]. Additionally, results from experiments performed on plastic substrates will be presented in the near future [6].

5. For further reading The following references may also be of interest to the reader: [1]; [7]; [8].

Acknowledgements The work in this paper has been nanced by the Swedish Foundation for Strategic Environmental Research (MISTRA) and the Swedish National Energy Administration (SEM).

References
[1] B. ORegan, M. Gr. tzel, Nature 353 (1991) 737. a [2] M.O.M. Edwards, G. Boschloo, T. Gruszecki, H. Pettersson, R. Sohlberg, A. Hagfeldt, Electrochemica Acta 46 (2001) 2187. # [3] P. Bonhote, E. Gogniat, F. Campus, L. Walder, M. Gr. tzel, Displays 20 (1999) 137. a [4] A. Hagfeldt, L. Walder, M. Gr. tzel, Proc. Soc. Photo-Opt. Instrum. Eng. 2531 (1995) 60. a [5] A. Hagfeldt, N. Vlachopoulos, M. Gr. tzel, J. Electrochem. Soc. 141 (1994) L82L84. a . . [6] H. Lindstrom, S. Sodergren, S.-E. Lindquist, A. Hagfeldt, International Patent Method for Manufacturing Nanostructured Thin Film Electrodes, No. PCT/SE00/01060. . [7] K. Keis, E. Magnusson, H. Lindstrom, S.-E. Lindquist, A. Hagfeldt, Sol. Energy Mater. Sol. cells, this issue. . [8] H. Lindstrom, A. Holmberg, E. Magnusson, S.-E. Lindquist, L. Malmquist, A. Hagfeldt, Nanolett. 1 (2001) 97.