An Efficient Organic-Dye-Sensitized Solar Cell with in situ Polymerized Poly(3,4-ethylenedioxythiophene) as a Hole-Transporting Material

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1 An Efficient Organic-Dye-Sensitized Solar Cell with in situ Polymerized Poly(3,4-ethylenedioxythiophene) as a Hole-Transporting Material By Xizhe Liu, Wei Zhang, Satoshi Uchida, Liping Cai, Bin Liu,* and Seeram Ramakrishna* Dye-sensitized solar cells (DSSCs) are low-cost photovoltaic devices that have been intensively studied in the last decade. [1,2] Although a high efficiency of 11% has been reported for DSSCs with conventional liquid electrolytes, it remains a problem to fabricate large-area modules with high efficiency and good stability. Conventional liquid electrolyte contains iodine and organic solvents, which leads to difficulties of electrode corrosion and electrolyte leakage. In recent years, researchers have developed several types of hole-transporting materials (HTMs) to replace iodine-based liquid electrolytes. Most research on HTM-based DSSCs is focused on inorganic HTMs and organic small-molecule HTMs. CuI and CuSCN are the most widely used inorganic HTMs in DSSCs. [3 5] By using CuI as the HTM and Ru complex dye N3 as the sensitizer, the highest efficiency for inorganic HTM-based DSSCs is reported to be 4.7%. [3] Up to now, the most effective organic small-molecule HTM for DSSCs is spiro-ometad, which gives the best efficiency of 5% under full sun illumination. [6 12] Conjugated polymers as low-cost organic semiconductors have also been used as HTMs in DSSCs. However, this type of device often gives low efficiency. [13 15] In HTM-based DSSCs, the degree of HTM penetration into the TiO 2 porous electrodes and the photoelectron recombination at TiO 2 /dye/htm interface are two important factors that affect the device efficiency. [16 18] As polymers have a relatively large molecular size, these factors are remarkable for DSSCs with polymers as the HTM. Recently, in situ polymerization of pre-penetrated monomers has been developed to avoid the [*] Prof. B. Liu, Dr. X. Liu, W. Zhang, Dr. L. Cai Department of Chemical and Biomolecular Engineering National University of Singapore 4 Engineering Drive 4 Singapore (Singapore) cheliub@nus.edu.sg Prof. S. Uchida Research Center of Advanced Science and Technology The University of Tokyo 4-6-1, Komaba, Meguro, Tokyo, (Japan) Prof. S. Ramakrishna Nanoscience and Nanotechnology Initiative National University of Singapore 9 Engineering Drive 1 Singapore (Singapore) DOI: /adma difficulty of polymer penetration into the TiO 2 porous electrodes. [19] By using Ru complex dye Z907 as the sensitizer and in situ polymerized poly(3,4-ethylenedioxythiophene) (PEDOT) as the HTM, the light-to-electrical conversion efficiency for polymer- HTM-based DSSCs has been improved to 2.8%. [20] However, this efficiency is still much lower as compared to that of DSSCs based on small-molecule HTMs or inorganic HTMs. [3,8] To further improve the efficiency of polymer-htm-based DSSCs, good polymer penetration and low photoelectron recombination are highly desirable. For in situ polymerized HTM-based DSSCs, the polymerization is initiated by the photocreated holes at the HOMO level of the dyes. Therefore, dye sensitizer plays an important role in the polymerization process, which determines the properties of the TiO 2 /dye/polymer interface and the penetration of polymer in the TiO 2 layer. Recently, several highly efficient organic dyes have been developed. [21 23] Our preliminary study shows that some organic dyes facilitate the in situ polymerization of 2,2 0 -bis(3,4-ethylenedioxythiophene) (bis-edot) as compared to that with Z907, [24] which motivates us to study in situ polymerized HTM-based DSSCs with organic dyes as sensitizers. In this Communication, we report an indoline D149 dye-sensitized solar cell with in situ polymerized PEDOT prepared in a specially designed thin-layer electrolytic cell to serve as the polymer HTM. These devices give an average light-to-electrical efficiency of 6.1% under full sun illumination (AM1.5, 100 mwcm 2 ), which represents a remarkable improvement for polymer-htm-based DSSCs. A similar device with Z907 as the sensitizer was also fabricated for comparison. The photoelectrical properties of both devices were studied, and the photoelectron recombination and polymer penetration in each device are discussed. The chemical structures of D149 dye and Z907 dye are shown in Figure 1a and b, respectively. Z907 is a hydrophobic Ru complex dye, which has been widely used in HTM-based DSSCs. [20] D149 dye belongs to the indoline dye series, which is a highly efficient organic dye for DSSCs. [21] Figure 1c shows the specially designed thin-layer electrolytic cell for in situ polymerization of PEDOT. This cell only requires several tens of microliters of monomer solution per square centimeter for polymerization. In addition, it can be easily sealed to separate air and prevent the electrolyte from evaporation, which facilitates in situ polymerization. Figure 1d shows the device structure. In these devices, the iodine-based electrolyte is replaced by in situ polymerized PEDOT, which works as the HTM. Detailed E150 ß 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2010, 22, E150 E155

2 Figure 1. The chemical structures of a) D149 dye and b) Z907 dye. c) The structure of the thin-layer electrolytic cell for in situ polymerization. From bottom to top: FTO glass, TiO 2 dense film, dye-sensitized TiO 2 layer, bis-edot solution sealed by parafilm, and pyrolyzed Pt/FTO glass. d) The structure of the DSSC based on in situ polymerized PEDOT. From bottom to top: FTO glass, TiO 2 dense film, dye-sensitized TiO 2 layer, PEDOT layer, Au layer, and FTO glass. polymerization and device fabrication procedures are shown in the experimental section. Figure 2a and b show the surface morphology of the dye-sensitized TiO 2 layer before and after in situ polymerization of bis-edot. A porous layer of PEDOT is clearly observed on the surface of the dye-sensitized TiO 2 film in Figure 2b. Such a porous layer structure favors the post treatment of the TiO 2 /dye/ PEDOT layer with Li salt/propylene carbonate solution. The performance of DSSCs with different TiO 2 layer thicknesses is shown in Tables 1 (D149) and 2 (Z907). The current voltage (I V) curves of D149- and Z907-sensitized DSSCs with optimized TiO 2 layer thickness (5.8 and 4.2 mm, respectively) are shown in Figure 2c. Under 100 mwcm 2 AM1.5 illumination, the D149-sensitized devices have a short-circuit photocurrent of 9.3 ma cm 2 and efficiency of 6.1%, which are much higher than for devices with Z907 as the sensitizer (3.6 ma cm 2, 1.7%). This result even outperforms the best record for HTM-based DSSCs. [8] The performance of both DSSCs under different light intensity is shown in Tables S1 and S2 in the Supporting Information, respectively. Figure 2d shows the corresponding incident photon-to-current efficiency (IPCE) spectra for devices used in Figure 2c. IPCE spectra reflect the light response of photovoltaic devices, which is directly related to the short-circuit current. For both devices, the IPCE values decrease at the long wavelength region ( nm). The wavelength at the half maximum of the IPCE value is thus used to reflect the lightresponse range of the solar cells. For Z907-sensitized devices, the half maximum of the IPCE value occurs at 597 nm, which is 39-nm shorter as compared to that for D149-sensitized devices. Therefore, D149-sensitized devices have a broader light response than that of Z907-sensitized ones in the red-light region. On the other hand, the IPCE value of D149-sensitized devices (65.5% at 500 nm) is more than twice that of Z907-sensitized ones (25.7% at 500 nm). These data indicate that D149-sensitized devices not only absorb more solar energy, but also utilize solar energy more effectively relative to those devices with Z907 as the sensitizer. As only the absorbed photons can generate photoelectrons, the light absorption is directly related to the IPCE, which is reflected by the transmittance spectra (1 T%) of dye-sensitized TiO 2 layers shown in Figure 2d. The half-maximum value of transmittance for D149-sensitized TiO 2 layer is at 655 nm, which is 41-nm longer than that for Z907-sensitized ones. This agrees with the IPCE spectra and, therefore, the broad light-response range of the IPCE spectrum for D149-sensitized devices can be attributed to the broad light-absorption range of the D149-dye-sensitized TiO 2 layer. Although the light absorption for D149- and Z907-sensitized TiO 2 layers at 500 nm is similar (99.8% and 90.0%, respectively), the IPCE value of D149-sensitized devices at 500 nm is 150% higher than that for Z907-sensitized ones. We also note that the competing light absorption from PEDOT is less than 15% and 6% at 500 nm for Z907- and D149-sensitized DSSCs, respectively, based on the light absorption for PEDOT (35%) and that for both dyes at 500 nm. This implies that some other factors exist that should account for the difference in the IPCE spectra. The main possible recombination and charge-collection processes in a typical DSSC are illustrated in Figure 3a. [25] Electrochemical impedance is a widely used method to study the recombination in DSSCs. The impedance for PEDOT-based DSSCs with 4.2 mm TiO 2 thickness was measured under different bias voltages. [10,12] The spectra were analyzed by fitting with equivalent circuit in the literature to yield chemical capacitance (C m ) and charge transfer resistance (R ct ) for each device. [20] Figure 3b shows the C m as a function of bias voltage, which indicates the distribution of electron state density in the TiO 2 electrode. The C m of D149-sensitized DSSCs is lower than that of Z907-sensitized ones, indicating that the energy gap between TiO 2 conduction-band edge and PEDOT Fermi level is larger for D149-sensitized DSSCs than that for Z907-sensitized ones. On the other hand, the sheet resistance of the in situ polymerized PEDOT layers was measured to be 6.57 kv sq 1 for D149-sensitized DSSCs and 6.45 kv sq 1 for Z907-sensitized ones. The resistivity of the PEDOT layers in both devices is similar, which implies that the PEDOT layers have a similar Fermi level position. Therefore, the TiO 2 conduction band is upward shifted (0.1 V) for D149-sensitized DSSCs relative to Adv. Mater. 2010, 22, E150 E155 ß 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim E151

3 Figure 2. SEM images of the dye-sensitized TiO 2 photoelectrode before (a) and after (b) polymerization to form a PEDOT layer. c) The photocurrent photovoltage curves of PEDOT based DSSCs with D149 (solid squares) and Z907 (open triangles) as sensitizers under 100 mw cm 2 AM1.5 illumination. The active area is 0.15 cm 2, which is controlled by a mask. d) The IPCE spectra of PEDOT-based DSSCs with D149 dye (solid squares) and Z907 dye (open triangles) as sensitizers. Transmittance spectra of D149- and Z907-sensitized TiO 2 layers are shown in the solid line and dashed line, respectively. Table 1. The performance of D149-sensitized devices with different TiO 2 layer thickness under 100 mw cm 2 AM1.5 illumination (average of three devices). Thickness [mm] I sc [ma cm 2 ] V oc [V] Fill factor Efficiency [%] Table 2. The performance of Z907-sensitized devices with different TiO 2 layer thickness under 100 mw cm 2 AM1.5 illumination (average of three devices). Thickness [mm] I sc [ma cm 2 ] V oc [V] Fill factor Efficiency [%] that for Z907-sensitized ones. The upward shift of TiO 2 conduction band is beneficial to the device performance for increased photovoltage and decreased recombination. [12,26] Figure 3c shows the R ct as a function of bias voltage. The R ct in D149-sensitized DSSCs is higher than that in Z907-sensitized ones at each bias voltage. As R ct at the TiO 2 /HTM interface is a widely used parameter to evaluate the recombination velocity at the TiO 2 /HTM (or electrolyte) interface, this result indicates that the recombination velocity in D149-sensitized DSSCs is lower than that in Z907-sensitized ones under the same bias voltage. Figure 3d is the intensity-modulated photocurrent spectra (IMPS) of PEDOT-based DSSCs with D149 and Z907 as sensitizers. The intensity of the IMPS shows that the D149-sensitized devices have a larger light response than that for Z907-sensitized ones in the measured frequency range, which agrees with the IPCE measurement shown in Figure 2d. The inverse of the frequency (1/2pf min ) at the minimum of the IMPS arch represents the typical time interval from photoelectron injection to photoelectron arrival at fluorinated tin oxide (FTO) glass. [16] The calculated time interval is 0.15 ms for D149-sensitized devices, which is faster than that for Z907-based ones (0.32 ms). Therefore, the photoelectron collection process (process 5 in Fig. 3a) in D149-sensitized devices is faster than that E152 ß 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2010, 22, E150 E155

4 Figure 3. a) Charge collection and recombination process in the DSSCs. It includes photoelectron injection from the LUMO level of the dye to the conduction band of TiO 2 (process 1), the recombination of the photoelectrons in TiO 2 by reaction with PEDOT (process 2) and oxidized dye (process 4), electron transfer from HTM to the oxidized dye (process 3), photoelectrons diffuse in the TiO 2 phase toward FTO glass (process 5), and holes diffuse to Au electrode in the HTM (process 6). b) The C m in D149- (solid squares, solid line) and Z907- (open triangles, dashed line) sensitized DSSCs as a function of bias voltage. c) The R ct at the TiO 2 /PEDOT interface in D149- (solid squares, solid line) and Z907- (open triangles, dashed line) sensitized DSSCs as a function of bias voltage. d) The IMPS of PEDOT-based solar cells with D149 (solid squares, solid line) and Z907 (open triangles, dash line) as the sensitizers. Both devices have a TiO 2 thickness of 4.2 mm. in Z907-based ones. Since the recombination fraction of photoelectrons in the TiO 2 electrode comes from the competition between the electron collection process and the recombination process, the slow photoelectron recombination (Fig. 3c) and fast photoelectron collection (Fig. 3d) in D149-sensitized devices should result in a relatively lower recombination fraction of photoelectrons as compared to that for Z907-based devices. On the other hand, the recombination of photoelectrons in TiO 2 with the oxidized dye on TiO 2 could also occur (process 4 in Fig. 3a). Since reduction of oxidized dyes by HTM (process 3 in Fig. 3a) is much faster than that by electrons in TiO 2, [25,27,28] the recombination from process 4 is generally small. In this case, the short-circuit current (I SC ) of HTM-based DSSCs should increase with increased TiO 2 layer thickness, because a thicker TiO 2 layer can absorb more dye molecules. However, if the TiO 2 layer is too thick to be well penetrated by the HTM, the holes will have difficulties to be transported to the counter electrode and the oxidized dye will not be reduced in time by the HTM. [17,18] In this case, the recombination from process 4 will increase remarkably, and the performance of DSSCs will decrease with increased TiO 2 layer thickness. The TiO 2 -thickness-dependent I SC for both devices is shown in Figure 4a. The I SC reaches the maximum at a TiO 2 film thickness of 5.8 and 4.2 mm for D149- and Z907-sensitized devices, respectively. Further increasing the TiO 2 film thickness leads to decreased device performance for both dyes. The TiO 2 -film-thickness-dependent device performance indicates that the sensitizers could affect the polymer penetration depth and the effective penetration depth in D149-sensitized devices should be longer than that in Z907-sensitized ones. As the optimized thickness of the TiO 2 layer for spin-coating HTM-based DSSCs is usually mm, [18,29,30] these results indicate that in situ polymerization is a promising method to improve polymer penetration. To further understand the difference in polymer penetration depth, the impedance spectra of PEDOT-based DSSCs in the absence of a TiO 2 dense film at 0 V bias are studied, and the results are shown in Figure 4b. In the absence of a dense film, the electrons are not blocked and the PEDOT is able to make direct contact with FTO glass. At zero-bias voltage, the resistance of PEDOT is much smaller than that of TiO 2, and as a Adv. Mater. 2010, 22, E150 E155 ß 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim E153

5 These results indicate that polymer-htm-based DSSCs are a promising generation of HTM-based DSSCs, which deserve further studies. By comparing with Z907-sensitized devices, the excellent light response of D149-sensitized devices is attributed to the broad light absorption, low photoelectron recombination, and good polymer penetration. It is important to note that for in situ polymerized HTM-based devices, the dye sensitizer determines not only the light absorption, but also the polymerization process, which could greatly affect the properties of the TiO 2 /dye/polymer interface and the polymer penetration depth in the TiO 2 porous layer. Further improvement in dye sensitizers and in situ polymerization methods is likely to yield devices with further improved efficiency. Experimental Figure 4. a) Relationship between the short-circuit current and TiO 2 layer thickness for D149- (solid squares, solid line) and Z907- (open triangles, dashed line) sensitized solar cells. b) The resistances of D149- (solid squares, solid line) and Z907- (open triangles, dashed line) sensitized solar cells in the absence of TiO 2 dense film at 0 V bias voltage for different TiO 2 layer thickness. The inset is a zoomed-in image of the bottom left corner. consequence, the impedance is mainly determined by the distribution of PEDOT in the TiO 2 porous layer. For both D149-and Z907-sensitized devices, the impedance increases with increased TiO 2 layer thickness. The slope of the increase is faster for Z907-sensitized devices than for D149-sensitized ones, which indicates that in situ polymerization of bis-edot on D149-sensitized TiO 2 layers gives better penetration than on Z907-sensitized ones. This agrees with the I SC TiO 2 thickness curves in Figure 4a. Figure 4b shows the relationship between the resistance obtained from the impedance spectra and the TiO 2 layer thickness for D149- and Z907-sensitized solar cells. The resistances of PEDOT from the foremost of the TiO 2 layer (FTO side) throughout the device to the Au electrode are 36 ohm cm 2 for a 5.8-mm D149-sensitized TiO 2 layer and 25 ohm cm 2 for a 4.2-mm Z907-sensitized TiO 2 layer. These values are sufficiently low for hole transportation in the devices. In conclusion, we fabricated efficient polymer-htm-based DSSCs by in situ polymerization of bis-edot in a thin-layer electrolytic cell using D149 dye as the sensitizer. The devices have shown an average efficiency of 6.1%, which represents a remarkable improvement for polymer-htm-based DSSCs. The dye-sensitized TiO 2 photoelectrode is prepared as follows. Firstly, the TiO 2 dense film was prepared by spraying 0.2 M Ti(OPr) 2 (acac) 2 on cleaned FTO/glass (TEC15, LOF) at 450 8C. After the TiO 2 paste (Solaronix T/SP) was diluted to the desired concentration by 5 wt% ethyl cellulose in terpineol solution, it was doctor-bladed on the surface of the dense film. The film was sintered at 125 8C for 20 min, 325 8C for 15 min, 375 8C for 15 min, and 450 8C for 20 min. The film was then treated with 40 mm TiCl 4 aqueous solution at 70 8C for 30 min and sintered again at 450 8C for 30 min. After cooling to 80 8C, the film was immersed into a D149 dye solution or a Z907 dye solution (0.3 mm D149 and 0.3 mm deoxycholic acid or 0.3 mm Z907 and 0.6 mm deoxycholic acid in a mixture of acetonitrile and tert-butyl alcohol, v/v ¼ 1:1). The films were kept for 2 h at room temperature and 4 h at 65 8C, respectively, which were followed by rinsing with acetone and drying under nitrogen gas flow. For in situ polymerization, the dye-sensitized TiO 2 photoelectrode and pyrolyzed Pt/FTO electrode were clipped together to assemble the thin-layer electrolytic cell as shown in Figure 1c. Parafilm was used as the spacer and sealant. Saturated bis-edot and 0.1 M lithium perchlorate in acetonitrile solution were used as the precursor solution (N 2 bubbled). A filtered ( nm) Xe lamp light of 25 mw cm 2 was used to illuminate the thin-layer cell from the Pt/FTO side. The polymerization lasted for 1500 s with the current density maintained at 10 macm 2.For PEDOT-based DSSCs in the absence of TiO 2 dense film, the polymerization conditions are the same. The dye-sensitized TiO 2 photoelectrode with PEDOT layer was then treated with 25 mm lithium bistrifluoromethanesulfonimide in propylene carbonate solution for 1 day. Then the photoelectrode was dried under strong N 2 gas flow and clipped with the counter electrode to form DSSCs (the clipping force was 3kgcm 2 ). The counter electrode was Au-coated FTO/glass (Asahi Glass), which was made by sputtering Au at 20 ma for 300 s (Auto fine Coater JFC-1600, JEOL). The devices were assembled in air with no redox couple used. The photocurrent photovoltage measurements were recorded by the electrochemical workstation (PGSTAT30, Autolab). A solar simulator (XES-151S, San-EI Electric) was used as the light source for measuring the solar cells (<385 nm was cut off by XUL0385 filter, Asahi Spectra). The intensity of incident light was calibrated using a reference cell (OptoPolymer, ISE CalLab) before each experiment. The IPCE was measured using a 300 W Xe light source (MAX-310, Asahi Spectra) and a monochromator (TMS300, Bentham). All the measurements were performed in air. SEM measurements were performed on a Quanta 200 FEG SEM. UV-Vis transmittance spectra of dye-sensitized TiO 2 layers were collected with a Shimadzu UV-1700 spectrophotometer. The impedance of DSSCs was measured with an Autolab (PGSTAT30) electrochemical workstation. The experiments were performed under different bias voltage in the dark. The IMPS were measured following the autolab application note [31]. E154 ß 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2010, 22, E150 E155

6 Acknowledgements The authors are grateful to the A-Star of Singapore (R ) for financial support. We also thank Dr. Z. Fang and Dr. J. B. Shi for providing the thiophene dimer and Dr. R. Zhu and Dr. Y. Xiong for valuable discussion. Supporting Information is available online from Wiley InterScience or from the author. Received: December 5, 2009 Published online: April 6, 2010 [1] B. O Regan, M. Grätzel, Nature 1991, 353, 737. [2] F. Gao, Y. Wang, D. Shi, J. Zhang, M. Wang, X. Jing, R. Humphry-Baker, P. Wang, S. Zakeeruddin, M. Grätzel, J. Am. Chem. Soc. 2008, 130, [3] G. Kumara, M. Okuya, K. Murakami, S. Kaneko, V. Jayaweera, K. Tennakone, J. Photochem. Photobiol. A 2004, 164, 183. [4] B. O Regan, D. T. Schwartz, S. M. Zakeeruddin, M. Grätzel, Adv. Mater. 2000, 12, [5] Q. Meng, K. Takahashi, X. Zhang, I. Sutanto, T. Rao, O. Sato, A. Fujishima, H. Watanabe, T. Nakamori, M. Uragami, Langmuir 2003, 19, [6] U. Bach, D. Lupo, P. Comte, J. E. Moser, F. Weissortel, J. Salbeck, H. Spreitzer, M. Grätzel, Nature 1998, 395, 583. [7] P. Chen, J. Yum, F. Angelis, E. Mosconi, S. Fantacci, S. Moon, R. Baker, J. Ko, M. Nazeeruddin, M. Grätzel, Nano Lett. 2009, 9, [8] H. Snaith, A. Moule, C. Klein, K. Meerholz, R. Friend, M. Grätzel, Nano Lett. 2007, 7, [9] S. Moon, J. Yum, R. Humphry-Baker, K. Karlsson, D. Hagberg, T. Marinado, A. Hagfeldt, L. Sun, M. Grätzel, M. K. Nazeeruddin, J. Phys. Chem. C 2009, 113, [10] F. Fabregat-Santiago, J. Bisquert, L. Cevey, P. Chen, M. Wang, S. Zakeeruddin, M. Grätzel, J. Am. Chem. Soc. 2009, 131, 558. [11] H. Snaith, A. Petrozza, S. Ito, H. Miura, M. Grätzel, Adv. Funct. Mater. 2009, 19, [12] M. Wang, C. Grätzel, S. Moon, R. Humphry-Baker, N. Rossier-Iten, S. M. Zakeeruddin, M. Grätzel, Adv. Funct. Mater. 2009, 19, [13] S. Spiekermann, G. Smestad, J. Kowalik, L. M. Tolbert, M. Grätzel, Synth. Met. 2001, 121, [14] N. Ikeda, T. Miyasaka, Chem. Commun. 2005, [15] Y. Wang, K. Yang, S. Kim, R. Nagarajan, L. Samuelson, J. Kumar, Chem. Mater. 2006, 18, [16] J. Kruger, R. Plass, M. Grätzel, P. J. Cameron, L. M. Peter, J. Phys. Chem. B 2003, 107, [17] J. Kroeze, N. Hirata, L. Schmidt-Mende, C. Orizu, S. Ogier, K. Carr, M. Grätzel, J. Durrant, Adv. Funct. Mater. 2006, 16, [18] I. Ding, N. Tetreault, J. Brillet, B. Hardin, E. Smith, S. Rosenthal, F. Sauvage, M. Grätzel, M. McGehee, Adv. Funct. Mater. 2009, 19, [19] Y. Saito, N. Fukuri, R. Senadeera, T. Kitamura, Y. Wada, S. Yanagida, Electrochem. Commun. 2004, 6, 71. [20] J. Xia, N. Masaki, M. Lira-Cantu, Y. Kim, K. Jiang, S. Yanagida, J. Am. Chem. Soc. 2008, 130, [21] T. Horiuchi, H. Miura, K. Sumioka, S. Uchida, J. Am. Chem. Soc. 2004, 126, [22] M. Wang, M. Xu, D. Shi, R. Li, F. Gao, G. Zhang, Z. Yi, R. Humphry-Baker, P. Wang, S. M. Zakeeruddin, M. Gratzel, Adv. Mater. 2008, 20, [23] N. Koumura, Z. Wang, S. Mori, M. Miyashita, E. Suzuki, K. Hara, J. Am. Chem. Soc. 2006, 128, [24] When in situ polymerization of bis-edot is conducted under constant voltage, the D149-sensitized TiO 2 layer gives a higher polymerization current than that from the Z907-sensitized TiO 2 layer (Figure S1 in the Supporting Information). On the other hand, when polymerization is conducted at constant current, the D149-sensitized TiO 2 layer requires a lower polymerization voltage than the Z907-sensitized TiO 2 layer (Figure S2 in the Supporting Information). [25] A. Hagfeldt, M. Grätzel, Chem. Rev. 1995, 95, 49. [26] D. Kuang, S. Uchida, R. Humphry-Baker, S. Zakeeruddin, M. Grätzel, Angew. Chem. Int. Ed. 2008, 47, [27] U. Bach, Y. Tachibana, J. Moser, S. Haque, J. Durrant, M. Grätzel, D. Klug, J. Am. Chem. Soc. 1999, 121, [28] D. Kuang, C. Klein, J. Snaith, J. Moser, R. Humphry-Baker, P. Comte, S. Zakeeruddin, M. Grätzel, Nano Lett. 2006, 6, 769. [29] H. Snaith, L. Schmidt-Mende, Adv. Mater. 2007, 19, [30] R. Zhu, C. Jiang, B. Liu, S. Ramakrishna, Adv. Mater. 2009, 21, 994. [31] Characterization of photovoltaic energy conversion device by DC and frequency resolved techniques (IMPS/IMVS), com/download/content/appl050.pdf (accessed March 2010). Adv. Mater. 2010, 22, E150 E155 ß 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim E155