Thin Solid Films 509 (2006) 123 126 www.elsevier.

com/locate/tsf

Evaluation of treatment effects for high-performance dye-sensitized solar cells using equivalent circuit analysis
Masaki Murayama a,b,*, Tatsuo Mori b
b a Mie Science and Technology Promotion Center, Industrial Division, 5-5-5 Takachaya, Tsu, Mie, 514-0819, Japan Department of Electrical Engineering and Computer Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8603, Japan

Available online 26 October 2005

Abstract Equivalent circuit analysis using a one-diode model was carried out as a simpler, more convenient method to evaluate the electric mechanism and to employ effective treatment of a dye-sensitized solar cell (DSC). Cells treated using acetic acid or 4,t -butylpyridine were measured under irradiation (0.1 W/m2, AM 1.5) to obtain current voltage (I V ) curves. Cell performance and equivalent circuit parameters were calculated from the I V curves. Evaluation based on residual factors was useful for better fitting of the equivalent circuit to the I V curve. The diode factor value was often over two for high-performance DSCs. Acetic acid treatment was effective to increase the short-circuit current by decreasing the series resistance of cells. In contrast, 4,t -butylpyridine was effective to increase open-circuit voltage by increasing the cell shunt resistance. Previous explanations considered that acetic acid worked to decrease the internal resistance of the TiO2 layer and butylpyridine worked to lower the backelectron-transfer from the TiO2 to the electrolyte. D 2005 Published by Elsevier B.V.
Keywords: Dye-sensitized solar cell; Equivalent circuit analysis; Acetic acid treatment; 4,t -butylpyridine

1. Introduction A serious difficulty of the 21st century is the supply of energy resources. Reserves of fossil fuels are confronting depletion: renewable energy resources must be developed in this century. Solar cells present a solution to the predicament because vast energy irradiates the earth as sunlight. The amount of energy coming from the sun to the earth annually is 10,000 times that produced and consumed by humans. However, widely used silicon solar cells require a p n junction comprising high-purity semiconductors. Therefore, production of such cells entails high costs and much energy. Dye-sensitized solar cells (DSC) have been anticipated as a new type of solar cell. They are inexpensive and have high efficiency relative to other photovoltaic devices because they employ nanoporous TiO2 films [1]. In DSCs, nanoporous TiO2 films have a large surface area that adsorbs a large amount of dye. The adsorbed dye absorbs visible light and injects electrons
* Corresponding author. Department of Electrical Engineering and Computer Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8603, Japan. Tel.: +81 59 234 1968; fax: +81 59 234 3982. E-mail address: murayama@mie-iri.tsu.mie.jp (M. Murayama). 0040-6090/$ - see front matter D 2005 Published by Elsevier B.V. doi:10.1016/j.tsf.2005.09.145

into the TiO2 conduction band. Therefore, TiO2 thin films with dyes play an important role as a photoelectrode. Effective treatment of the photoelectrode is important to improve DSC performance. Until now, numerous treatments have been investigated to improve that performance, such as TiO2 electrode treatment with acetic acid [2], 4,t -butylpyridine treatment [3]. Acetic acid treatment increases the short-circuit current (I sc) of DSC. 4,t -butylpyridine effects an increase of open-circuit voltage (Voc) of cells; however, it might decrease I sc. A mutual influence is presumed between these treatments. For evaluation of these treatment effects, it is necessary to analyze how effective the treatment is to the DSC electric mechanism. Advanced methods are often used, such as electrical impedance spectroscopy, to analyze electric mechanisms of cells [4 6]. However, such methods require much time and the obtained data are complicated to interpret and explain. In contrast, the minimum parameter of solar cell performance is generally calculated from the current voltage (I V ) curve, which is measured using a source meter under light irradiation. More than 30 point measurements are carried out to obtain an I V curve. Thereby, only I sc, Voc, fill factor (FF) and energy conversion efficiency (g ) values are calculated. Therefore, we specifically use the I V curve for use in an equivalent circuit

124

M. Murayama, T. Mori / Thin Solid Films 509 (2006) 123 126

Rs

110 105 100 -1/(dI/dV)

Iph

Id

Ish V R sh

95 90 85 80

Fig. 1. Equivalent circuit using a 1-diode model.

75 350

400

450

500 1/(Isc-I)

550

600

650

analysis using 1-diode model, which is well used for analysis of silicon solar cells [7,8]. Electric mechanisms, such as series and parallel resistance in cells, can be estimated by fitting the equivalent circuit to I V curve. Because only the I V curve is used, this analytical method is advantageous in the following respect: it is convenient to evaluate the electric mechanism of a cell quickly. Furthermore, it is comparable to any other cell already reported, even widely used silicon solar cells. This study is intended to evaluate the effect of acetic acid and 4,t -butylpyridine treatment separately through equivalent circuit analysis. Dye-sensitized solar cells were treated by acetic acid or 4-tert -butylpyridine; the I V curve of the cell was measured. First, we discuss fitting the equivalent circuit to the I V curve. Then, we evaluate the effects of treatment on the cell electric mechanism. 2. Experimental procedure Dye-sensitized solar cells were prepared as follows. A TiO2 film was made by extruding a precursor paste onto a F:SnO2 conductive glass substrate (sheet resistance 12 V/sq.; Asahi Glass Co. Ltd.,) and heating it at 500 -C for 30 min. As the precursor paste, 6.0 g TiO2 nano-powder (size 25 nm, p25; Degussa AG), 7.8 ml water, 2.0 g polyethylene glycol (M.W. 200), 0.2 ml acetylacetone, and 0.2 ml Triton-X 100 were mixed using a paint conditioner (Model 5400; Red Devil
2.5

Fig. 3. Plot of 1 / (dI / dV ) versus 1 / (I sc I ) based on Eq. (5). Points derived from measured data were well scattered; it is difficult to fit a straight line.

Equipment Co.). Then, Ru(4,4 V-dicarboxy-2,2 V-bipyridine)2(NCS)2 dye (N3 dye; Kojima Chemicals Co. Ltd.) was adsorbed onto TiO2 film by immersing the film in the 0.3 mM dye ethanol solution. Dye-sensitized solar cells were composed of the dye-adsorbed TiO2 film and a counter electrode (Pt sputtered ITO conductive glass). Between the TiO2 film and counter electrode, a 50 Am space was retained using a PTFE film spacer. Electrolyte was injected into the space. The electrolyte composition was 0.1 M LiI, 0.05 M I2, 0.5 M tetrabutylammonium iodide in acetonitrile solvent. All chemicals used for precursor paste and electrolyte were reagent grade. Acetic acid treatment was carried out similarly to the previously described procedure [2]. Dye-adsorbed TiO2 film was immersed into 1 wt.% acetic-acid toluene solution for 10 h. The film was rinsed with toluene and dried. Then, the cell was composed using the film. Treatment of 4-tert -butylpyridine was carried out by addition of butylpyridine to the electrolyte for 0.5 M 4,t -butylpridine concentration. The current voltage (I V ) curve was obtained using a source measure unit (Model 2400; Keithley Instruments, Inc.) under irradiation (0.1 W/cm2, AM 1.5) using a solar simulator (Module X; Ushio Inc.). The irradiated cell area was 0.25 cm2. The I V curve was used to calculate the short-circuit current (I sc), open-circuit voltage (Voc), fill factor (FF), and the energy conversion efficiency (g ) of DSC. 3. Results and discussion 3.1. Fitting the equivalent circuit to the current voltage curve The equivalent circuit using a 1-diode model is shown in Fig. 1. In this figure, the external current is I Iph Id Ish ; 1

Current [mA]

1.5

0.5

0 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 Voltage [V]

Fig. 2. An example of fitting an equivalent circuit to a current voltage curve. Circles show measured data and the solid line shows the fitting curve base on an equivalent circuit.

where diode current I d and shunt current I sh are written respectively as     V IRs Id Io exp q 1 2 nkT

M. Murayama, T. Mori / Thin Solid Films 509 (2006) 123 126

125

1.5 Current [mA]

Table 1 Short-circuit current (I sc), open-circuit voltage (Voc), fill factor (FF) and energy conversion efficiency (g ) values calculated from current voltage curves of various treated cells I sc [mA] Voc [V] 0.574 0.514 0.701 0.691 FF 0.462 0.478 0.565 0.584 g [%] 2.97 3.16 3.20 3.81

0.5

Non-treated AC tBP AC + tBP

2.80 3.22 2.02 2.36

AC indicates cells treated by acetic acid and tBP denotes cells treated by 4,t -butylpyridine.
0 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 Voltage [V]

estimated from a plot of 1 / ( dI / dV ) versus 1 / (I sc I ) because the plot slope shows nkT / q as Eq. (5) 1 nkT Rs dI qIsc I : dV Next, I o value was calculated from the equation: Io Iph =expq=kT Voc =n; 6 5

Fig. 4. Examples of fitting curves when the diode factor (n ) is changed. Circles show measured data and lines show fitting curves (solid line: n = 1.5, R 2 = 0.0030; bold line: n = 2.0, R 2 = 0.0022; dotted line: n = 2.5, R 2 = 0.0049). The minimum R 2 value corresponds to the best fit. The inset graph shows a magnified section of the curves.

and Ish V IRs : Rsh 3

Therefore, the circuit equation is written in the form of     V IRs V IRs I Iph Io exp q ; 4 1 nkT Rsh where I ph is photo current, Io Rs R sh n q k T initial current, series resistance, parallel (shunt) resistance, diode factor, elementary electric charge, Boltzmann constant, temperature.

derived from Eq. (4) at I = 0 and V = Voc with an approximation I ph I sc. Then, the ideal I V curve was plotted when I ph, R s and R sh values are respectively I sc, 0 and V. The R s value was evaluated from the plot of yV vs. I at high V part, where yV represents the difference of ideal V value and measured V value. In addition, the R sh value was evaluated from the plot of yI vs. V at low V part, where yI is the difference of ideal I value and measured I value. Finally, the fitting curve is plotted from the approximation Eq. (4) using Newton Raphson method for these n , I o, R s and R sh values. Fig. 2 shows an example of fitting this equivalent circuit to the current voltage curve. In this figure, the fitting curve (solid line) coincides well with measured data (circle). 3.2. Estimation of n value and the residual factor (R2) of fitting We examined many DSC samples. Results showed that n values were often over two for dye-sensitized solar cells. It is comparable with n = 2.1, as shown by So dergren et al. for dyesensitized TiO2 thin film solar cells [9]. Especially, n values of cells treated with both acetic acid and 4,t -butylpyridine ranged from 2 to 3. However, it is difficult to estimate the n value because the plot based on Eq. (5) was well scattered, as in Fig. 3. Lower accuracy of n estimation causes worse fitting, and then obtain other parameter I o, R s and R sh is also scattered. We defined a residual factor of fitting as follows to improve the estimation and fitting.
Table 2 Residual factor R 2 values when n values were changed for various treated cells

The procedure of fitting this equation to the current voltage curve is described in the following. First, the n value was
3.5 3 2.5 Current [mA] 2 1.5 1 0.5 0 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 Voltage [V] non-treated AC tBP AC+tBP

n Non-treated AC tBP AC + tBP

1.5 0.0051 0.0122 0.0030 0.0129

2.0 0.0055 0.0094 0.0022 0.0025

2.5 0.0130 0.0474 0.0049 0.0009

3.0 0.0182 0.0460 0.0088 0.0024

Fig. 5. Current voltage curves of various treated dye-sensitized solar cells. Solid line shows the cell treated using acetic acid (AC). Bold-dashed line shows the cell treated using 4,t -butylpyridine (tBP). Both acetic acid and 4,t butylpyridine treated cell (AC + tBP) shown as bold-solid line.

The underlined values are the minimum values of R 2 in the same cell.

126

M. Murayama, T. Mori / Thin Solid Films 509 (2006) 123 126 Table 3 Obtained initial current (I o), series resistance (R s), and parallel (shunt) resistance (R sh) values for n values providing minimum R 2 in Table 2 n Non-treated AC tBP AC + tBP 1.5 2.0 2.0 2.5 I o [nA] 1.0 149.0 2.5 50.5 R s [V] 71.8 47.4 61.0 38.1 R sh [V] 1585 1603 2665 3683

The ideal IV i value was calculated for measured I i and Vi values using the following equation derived from Eq. (4),     Vi Ii Rs Vi Ii Rs 1 ; 7 Ii V Iph Io exp q nkT Rsh where subscript i represents the number of measuring points. The residual factor R 2 is expressed as m X Ii V Ii 2 : 8 m A smaller R 2 value shows better fitting equivalent circuit to measured data (Fig. 4). It is necessary to better estimate the n value taking R 2 as an index to obtain an accurate value of equivalent circuit parameters, I o, R s and R sh. 3.3. Effect of treatments Current voltage (I V ) curves of variously treated dyesensitized solar cells (DSCs) are shown in Fig. 5. The shortcircuit current (I sc), open-circuit voltage (Voc), fill factor (FF) and energy conversion efficiency (g ) values of cells calculated from those curves are shown in Table 1. Acetic acid treatment was effective to increase the I sc value, thereby increasing g . On the other hand, 4,t -butylpyridine was effective to increase Voc and FF values, but it decreased the I sc value. As a whole, DSCs treated by both acetic acid and 4,t -butylpyridine exhibited the best performance of g = 3.81%. Next, we fitted the equivalent circuit of the 1-diode model to these I V curves. As mentioned above, the plot on Eq. (5) was well scattered and n values were widely distributed over the range from under 2 to 3. For instance, n values were changed 1.5, 2.0, 2.5 and 3.0, and the residual factor R 2 values were calculated (Table 2). For non-treated cells, the best fitting equivalent circuit to I V curve was observed at n = 1.5. In contrast, the best fit was observed at n = 2.5 for both acetic acid and 4,t -butylpyridine treated cell. Between these two cells, only acetic-acid treated cell and a 4,t -butylpyridine treated cell showed the intermediate best n value 2.0. Energy conversion efficiency g increased with this n value (see Table 1). In DSC, the higher n value might indicate higher performance. By fitting the equivalent circuit to I V curves using the best n value in Table 2, initial current (I o), series resistance (R s) and parallel (shunt) resistance (R sh) values were obtained (Table 3). Acetic acid treatment decreased the R s value and slightly increased the R sh value; it also increased the I o value (compare non-treated to acetic acid (AC) treated cell and 4,t -butylpyridine (tBP) treated to AC + tBP treated cell). In contrast, 4,t butylpyridine treatment slightly decreased the R s value and increased the R sh value (compare non-treated to tBP treated cell and AC treated to AC + tBP treated cell). It is considered that both acetic acid and 4,t -butylpyridine affect cell performance by chemically modifying the dyeadsorbed TiO2 surface. Sakaguchi et al. indicated that acetic acid treatment decreases interfacial resistances of TiO2 layers [2]. In addition, Huang et al. suggested that 4,t -butylpyridine may lower the back-electron-transfer rate constant by 1 2 R2
i1

orders of magnitude [3]. Results of equivalent circuit analysis mentioned above are suitable to those explanations. That is to say, the decreased resistances of TiO2 layers by acetic acid treatment were shown as the decrease R s value. Namely, a decrease of the back-electron-transfer rate should lower the leakage current from TiO2 surface to electrolyte and it was shown as the increase of the R sh value. It is remarkable that those effects mutually overlapped. It can be said that the acetic acid strongly shows the former effect and 4,t -butylpyridine strongly shows the latter effect. In addition, the large I o value of acetic acid treated cells caused large I d at high V part. It might also have decreased the TiO2 layer resistance. 4. Conclusions Equivalent circuit analysis using a 1-diode model was carried out for dye-sensitized solar cells treated using acetic acid or 4,t -butylpyridine. By introduction of residual factor R 2, most suitable diode factors n , which are difficult to estimate from scatter plots, were obtained. The n values of higher performance dye-sensitized solar cells were often more than two. Acetic acid treatment was effective to increase of shortcircuit current and cell efficiency. It was considered that the acid decreased the respective resistances of TiO2 layers and engendered a smaller series resistance of the equivalent circuit. 4,t -butylpyridine treatment increased the open-circuit voltage and cell efficiency. Butylpyridine lowered the back-electrontransfer from TiO2 to electrolyte; it was shown as larger shunt resistance of the circuit. In conclusion, this equivalent circuit analysis using the 1-diode model is useful to evaluate the effects of treatment for dye-sensitized solar cells. References
[1] B. ORegan, M. Gra tzel, Nature 353 (1991) 737. [2] S. Sakaguchi, H. Ueki, T. Kato, T. Kado, R. Shiratuchi, W. Takashima, K. Kaneto, S. Hayase, J. Photochem. Photobiol., A Chem. 164 (2004) 117. [3] S.Y. Huang, G. Schlichtho rl, A.J. Nozik, M. Gra tzel, A.J. Frank, J. Phys. Chem., B 101 (1997) 2576. [4] R. Kern, R. Sastrawan, J. Ferber, R. Stangl, J. Luther, Electrochim. Acta 47 (2002) 4213. [5] T. Hoshikawa, R. Kikuchi, K. Sasaki, K. Eguchi, Electrochemistry 70 (2002) 675. [6] L. Han, N. Koide, Y. Chiba, T. Mitate, Appl. Phys. Lett. 84 (2004) 2433. [7] Z. Ouennoughi, M. Chegaar, Solid-State Electron. 43 (1999) 1985. [8] K. Nishioka, N. Sakitani, K. Kurobe, Y. Yamamoto, Y. Ishikawa, Y. Uraoka, T. Fuyuki, Jpn. J. Appl. Phys. 42 (2003) 7175. [9] S. So dergren, A. Hagfeldt, J. Olsson, S.-E. Lindquist, J. Phys. Chem. 98 (1994) 5552.