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Japanese Journal of Applied Physics Vol. 45, No. 25, 2006, pp.

L638L640 #2006 The Japan Society of Applied Physics

JJAP Express Letter

Dye-Sensitized Solar Cells with Conversion Eciency of 11.1%


Yasuo CHIBA, Ashraful I SLAM, Yuki W ATANABE, Ryoichi K OMIYA, Naoki K OIDE and Liyuan HAN
Solar Systems Development Center, Sharp Corporation, 282-1 Hajikami, Katsuragi, Nara 639-2198, Japan (Received June 7, 2006; accepted June 9, 2006; published online June 23, 2006)

Dye-sensitized solar cells (DSCs) using titanium dioxide (TiO2 ) electrodes with dierent haze were investigated. It was found that the incident photon to current eciency (IPCE) of DSCs increases with increase in the haze of the TiO2 electrodes, especially in the near infrared wavelength region. Conversion eciency of 11.1%, measured by a public test center, was achieved using high haze TiO2 electrodes. This indicates that raising the haze of TiO2 electrodes is an eective technique for improvement of conversion eciency. [DOI: 10.1143/JJAP.45.L638]
KEYWORDS: dye-sensitized solar cells, haze, internal resistance, TiO2 electrode, IPCE

Dye-sensitized solar cells (DSCs) have been widely investigated as a next-generation solar cell because of their simple structure and low manufacturing cost.1,2) In general, a DSC comprises a nanocrystalline titanium dioxide (TiO2 ) electrode modied with a dye fabricated on a transparent conducting oxide (TCO), a platinum (Pt) counter electrode, and an electrolyte solution with a dissolved iodide ion/triiodide ion redox couple between the electrodes. Although certied conversion eciency using black dye has been reported to be 10.4% by the Swiss Federal Institute of Technology in Lausanne (EPFL),3) eciency of over 10% has rarely been achieved due to insucient understanding of the mechanism of DSCs, which is dierent from that of conventional solar cells. It is well known that the conversion eciency () of solar cells can be represented as follows:4)  FF ISC VOC =Pin ; 1

where FF, ISC , VOC , and Pin are ll factor, short circuit current, open circuit voltage, and incident power, respectively. Equation (1) suggests that it should be necessary to improve these three parameters in order to raise conversion eciency. In our previous studies, we investigated the internal resistance of DSCs using electrochemical impedance spectroscopy (EIS) measurement as a means of investigating DSC mechanisms and proposed an equivalent circuit for modeling DSCs based on the results of EIS analysis.5) We also found that the series resistance of DSCs consists of three resistance elements, namely, the sheet resistance of the TCO, the resistance of ionic diusion in the electrolyte, and the resistance at the interface between the counter electrode and the electrolyte. We discovered that FF increases with decrease in the internal resistance elements and reported a resulting rise in certied conversion eciency to 10.2%.6) In order to further improve the eciency, we then considered ways of elevating the other factors such as short circuit current density (JSC ) and VOC . There are two approaches to improving JSC . One is to develop a new dye which can absorb incident light of longer wavelengths, and the other is to increase the extent of light trapping within the TiO2 electrodes. Many panchromatic dyes have been developed such as -diketonato Ru(II) complex.7,8) Unfortunately, the certied eciency has not been improved as there is no dye superior to black dye. As

for the latter approach, Usami made the theoretical nding that light scattering magnitude in DSCs could be controlled by adding submicron particles to TiO2 electrodes composed of nanocrystalline particles.9) Most related experimental work involves making a rough estimate of the lightscattering magnitude from the light-harvesting eciency (LHE) of the dye-treated TiO2 electrodes.10) However, it is very dicult to obtain the exact magnitude and to elevate it because LHE is aected by the absorption characteristics of the dye. An eective index of the light-trapping eect of TiO2 electrodes is therefore needed. In addition, it is very important to conrm that the JSC obtained from currentvoltage (IV) measurement is consistent with the value estimated from incident photon to current eciency (IPCE) spectra, because JSC can be described by integrating the product of the incident photon ux density [F] and IPCE of the cell over the wavelength () of the incident light, expressed as Z JSC qF1 rIPCEd; 2 where q is the electron charge and r the incident light loss in light absorption and reection by the conducting glass. It is dicult to obtain accurate IPCE spectra of DSCs because IPCE strongly depends on measurement conditions such as chopping frequency and bias light. Recently, Hishikawa et al. reported that IPCE spectra increase with decrease of chopping frequency under AC mode. They suggested that the IPCE of DSCs should be measured under white bias light and in AC mode with low chopping frequency of 1 2 Hz or in DC mode and that JSC measured from the IV curve should be veried with the correct IPCE measurement.11) In the present letter, we attempt to introduce the concept of haze to estimate the optical path length in TiO2 electrodes and discuss the relationship between haze in the infrared region of TiO2 electrodes and IPCE spectra. We veried JSC not only by IV measurement but also IPCE measurement. We also report the achievement of high performance in DSCs. TiO2 electrodes with dierent haze were prepared using a screen-printing method. DSCs were fabricated using a published procedure.6) The TiO2 electrodes on TCO substrates were placed in a mixture solution of tert-butyl alcohol and acetonitrile (1 : 1) at a concentration of 2 104 M of black dye. Deoxycholic acid was added to the dye solution as a coadsorbent at a concentration of 20 mM. Pt-coated

E-mail address: han.liyuan@sharp.co.jp

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100 80
Calculated Jsc (mA/cm2 )

IPCE (%)

60 40 20 0 400 600 800 1000 Wavelength (nm)


Haze 76% Haze 60% Haze 53% Haze 36% Haze 10% Haze 3%

20

76% 60% 53% 36% 10%

15
3%

10
Fig. 1. Dependence of IPCE spectra on haze of TiO2 electrodes. Haze in the gure was measured at 800 nm.

10

15 Measured Jsc

20 (mA/cm 2)

25

glass was used for the counter electrodes. The composition of the electrolyte solution in acetonitrile was: dimethyl propyl imidazolium iodide (0.6 M), lithium iodide (0.1 M), iodine (0.05 M), and tert-butylpryidine (0.5 M). IPCE spectra were measured with monochromatic incident light of 1 1016 photon/cm2 under 100 mW/cm2 white bias light in DC mode (CEP-2000, Bunkoh-Keiki).11) Currentvoltage (IV) characteristics of DSCs were measured using a digital source meter (2400, Keithley) under a standard air mass (AM 1.5) with simulated solar illumination at 100 mW/cm2 (WXS-155S-10, Wacom).12) Haze was controlled by the addition of submicron particles (400 nm diameter) to the TiO2 electrodes. Haze, dened as the ratio of diused transmittance to total optical transmittance, was measured at the wavelength of 800 nm using an integral sphere. Figure 1 shows the dependence of IPCE spectra on haze, which varied in the range from 3 to 76%. Here, the haze at 800 nm was used as an index as this is the wavelength in which we want to improve IPCE. Figure 1 indicates that IPCE is greatly increased by increase in haze, especially in the infrared region, where it increased from 10 to 50% with increase in haze from 3 to 76%. On the other hand, IPCE spectra in the visible region, for example around 600 nm, increased only gradually, from 65 to ca. 80%, with increase in haze from 3 to 53% and reached saturation with further increase in haze. These results suggest that IPCE of 80% in the visible wavelength region is easily obtained using electrodes of medium haze TiO2 because of the large extinction coecient of the dye, while high IPCE in the infrared region demands high haze TiO2 because of the small extinction coecient of the dye. For example, black dye in ethanol has an extinction coecient of about 7 103 mol1 cm1 at around 600 nm, while extinction coefcient is about 200 mol1 cm1 at around 800 nm.3) Experimental evidence was thus found that the IPCE of DSCs is eectively improved by increase in the haze of TiO2 electrodes. Figure 2 shows the relationship between JSC calculated from eq. (2) and JSC measured from IV characteristics at varying haze at 800 nm. In the calculation, F is assumed to be AM 1.5 standard spectrum. A linear relationship between measured JSC and calculated JSC is observed. The slope of the line is very close to 1, suggesting that IPCE could be accurately measured under DC mode. The reason

Fig. 2. Relationship between JSC calculated from eq. (2) and JSC measured from IV characteristics. The solid line shows a good t to the data, y 0:99x 0:008. Percentage values indicate the haze of each TiO2 electrode at 800 nm.

for using DC mode can be explained as follows: in the equivalent circuit model proposed in our previous study,5) there are two large capacitance elements (1 F and 2 mF) parallel to the series resistance. It is these capacitance elements that delay the response of the DSCs. Since it allows the eect of the capacitance elements to be excluded, the DC mode as used here is preferable for IPCE measurement. As a result, the highest JSC of 21 mA/cm2 was achieved when using TiO2 electrodes with haze of 76%. This result indicates that haze is a useful index of the improvement of JSC and energy conversion eciency in DSCs. When using TiO2 electrodes with haze of 76%, we almost always obtained high JSC of 20.8 21.1 mA/cm2 . The cell gap was also investigated. It was found that the resistance of the ionic diusion in the electrolyte decreases when the counter electrode is placed directly on the TiO2 electrode, so that the total series resistance was successfully decreased to 1.6
cm2 . For the sake of fairness, IV characteristics were independently measured by the Research Center for Photovoltaics, the National Institute of Advanced Industrial Science and Technology (AIST, Japan), using a black metal mask with an aperture area of 0.219 cm2 under standard AM 1.5 sunlight (100.0 mW/cm2 ), as shown in Fig. 3. An overall conversion eciency of 11.1% was achieved, which is the highest eciency conrmed by a public test center. In conclusion, we investigated the improvement of DSC performance using TiO2 electrodes with high haze. It was found that the increase of haze in TiO2 electrodes at 800 nm eectively improves the IPCE of DSCs. It is therefore proposed that haze is a useful index of improvement in conversion eciency. Moreover, high JSC was veried not only by IV measurement but also by precise IPCE measurement in DC mode. The highest DSC eciency recorded so far, 11.1% (0.219 cm2 ), was obtained and conrmed by AIST. These ndings appear to emphasize the important role of the haze of TiO2 electrodes in device performance and should aid the further development of DSCs for photovoltaic applications.

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Fig. 3. Currentvoltage characteristics of DSC sensitized with black dye. Results were measured at 25  C with an aperture area of 0.219 cm2 using a black metal mask and irradiance of 100.0 mW/cm2 . Short circuit current ISC 4:57 mA; short circuit current density JSC 20:9 mA/cm2 ; open circuit voltage VOC 736 mV; ll factor FF 72:2%; maximum power voltage VPMAX 583 mV; maximum power current IPMAX 4:16 mA; maximum power PMAX 2:429 mW; eciency = 11.1%. The solid line and dashed line indicate current and power, respectively. This measurement was independently carried out by the Research Center for Photovoltaics, AIST.

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