CopyrightWILEYVCHVerlagGmbH&Co.KGaA,69469Weinheim,Germany,2012.

SupportingInformation

forAdv.Mater.,DOI:10.1002/adma. 201200003

A Large-Area Light-Weight Dye-Sensitized Solar Cell based on All Titanium Substrates with an Effi ciency of 6.69% Outdoors Jihuai Wu, * Yaoming Xiao, Qunwei Tang, Gentian Yue, Jianming Lin, Miaoliang Huang, Yunfang Huang, Leqing Fan, Zhang Lan, Shu Yin, and Tsugio Sato

CopyrightWILEYVCHVerlagGmbH&Co.KGaA,69469Weinheim,Germany,2012.

ADVANCED MATERIALS
Supporting Information
for Adv. Mater., DOI: 10.1002/adma. 201200003

A Large-Area Light-Weight Dye-Sensitized Solar Cell Based on All Titanium Substrates with an Efficiency of 6.69% Outdoors

Jihuai Wu*, Yaoming Xiao, Qunwei Tang, Gentian Yue, Jianming Lin, Miaoliang Huang, Yunfang Huang, Leqing Fan, Zhang Lan, Shu Yin and Tsugio Sato

Results and discussion

Morphology and compositions of the Ti foils Figure S1 (a) shows the SEM image of the Ti foil cleaned in the 0.20 mM HF solution. It is obvious that the surface of the cleaned Ti foil is roughened after immersed in the HF solution. As shown on the Figure S1 (b), TiO2 nanofibers (TNFs) were produced on the cleaned Ti foil after a NaOH hydrothermal treatment, and this Ti foil has a higher void space than the Ti foil only cleaned in the HF solution. From Figure S1 (c-1) to Figure S1 (c-7), the SEM images show that the HF post-treatment changed the surface morphology of the Ti foils. Figure S1 (c-4-0), (c-4-1), (c-4-2), and (c-4-3) show the TNFs treated by the HF solution with the time of 400 s, it can be seen that the surface morphology like a honeycomb. This honeycomb surface could improve the superficial area of the TiO2 anode, and the TNFs could provide 1

direct pathways for the rapid collection of photogenerated electrons, resulting in quick and efficient transport for electrons in the film, and the enhancement of photocurrent.[S1] Figure S1 (c-6-0), (c-6-1), (c-6-2), and (c-6-3) show the TNFs treated by the HF solution with the time of 600 s, it can be seen that the honeycomb surface was corroded by the HF solution after 600 s, leaving honeycomb trace and TiO2 nanoparticles (TNPs) behind. The EDS (Figure S1 (d)) spectrum shows that the Sample C-4 is consisted of C, Au, Ti and O, however, Au in which comes from the spray gold processing, and C from the conducting resin. Therefore, the Ti foil honeycomb surface is consisted of Ti and O.

Figure S1. SEM images of the Samples A (a), B (b), C-1 (c-1) , C-2 (c-2), C-3 (c-3), C-4 (c-4-0, c-4-1, c-4-2, c-4-3), C-5 (c-5), C-6 (c-6-0, c-6-1, c-6-2, c-6-3), C-7 (c-7), and EDS (d) of the Sample C-4 TiO2/Ti foil anodes

Figure S2 (a), (b), and (c-4) show the SEM images of the light-weight TiO2 anodes prepared on the Sample A, B and C-4. Compared to the three light-weight TiO2 anodes, the anode prepared on the Sample C-4 has the largest void space to harvest the most light, this could be confirmed by the Figure 2S (d). Figure 2S (d) shows the reflectance of the three light-weight dye-sensitized TiO2 anodes, the wavelength at the 535 nm comes from the dye absorption,
[S2,S3]

the reflectance of the Sample A is the highest, and the lower are the Sample B, and the

smallest is the Sample C-4. This is due to that the surface of the cleaned Ti foil is flat with little rough, this structure leading to the highest reflectance. The Sample C-4 with a honeycomb surface structure could use to catching the light, resulting in the smallest reflectance. The lower reflectance means less light reflecting off the space, which resulting in more light is utilized. As well known, the more incident light is harvested, the larger photocurrent occurs. According to our experiments, the light-weight TiO2 anode prepared on the Sample C-4 can harvest most light and produce largest photocurrent.

Figure S2. SEM images of light-weight TiO2 anodes on the Sample A (a), B (b), C-4 (c-4), and reflectance of the three dye-sensitized TiO2 anodes (d)

The photovoltaic performances of DSSCs with the same Pt/Ti CE and different light-weight TiO2 anodes on the Sample A, B, C-2, C-4, and C-6, are shown in the Table 1. It can be found that the ISC value increases firstly and then decreases with the increase of the HF post-treatment time, this trend is due to the reflectance of the light-weight TiO2 anodes. In other words, the reflectance reduces after the NaOH treatment and the HF post-treatment, because of the honeycomb surface, which is advantageous to harvest and utilize more light, leading to higher ISC. However, the honeycomb surface was corroded by the HF solution after 600 s, therefore, the reflectance increases, resulting in a lower ISC. The VOC values of the cells based on the NaOH treatment and HF post-treatment, have comparatively similar VOC (0.720 V), this is due to the VOC is mainly determined by the energy level difference between the Fermi level of the electron in TiO2 and the redox potential of the electrolyte,[S4,S5] since these light-weight DSSCs have the same compositions, their VOC are close. However, their VOC are higher than that of the Sample A, this is due to the TNFs could provide direct pathways for the rapid collection of photogenerated electrons, resulting in quick and efficient transport for electrons in the film, and the enhancement of photocurrent. [S1] The fill factor (FF) values are little changed. Therefore, the and Pmax values of the DSSC increase firstly and then decreases with the increase of the HF post-treatment time. Table 1. The photovoltaic performance of DSSCs with different HF post-treatment times Samples A B C-2 C-4 C-6
*

HF post-treatment time (second) 0 0 200 400 600

(A) 0.629 0.641 0.652 0.665 0.643

SC

J 6.29 6.41 6.52 6.65 6.43

(mAcm-2)

SC

(V)

OC

FF 0.711 0.715 0.713 0.715 0.714

(%) 5.81 6.00 6.10 6.23 5.99

(W) 0.320 0.330 0.336 0.343 0.330

max

0.715 0.720 0.722 0.721 0.718

Pmax = Isc Voc FF

Electrochemical impedance spectroscopy (EIS) Electrochemical impedance spectroscopy (EIS) was measured with the large-area (100 cm2) light-weight DSSCs, based on the same light-weight TiO2 anodes on the Sample C-4 and different CEs (shown in Figure S3), where RS is the series resistance mainly related to the counter electrode, and RCT is the charge-transfer resistance at the interface between electrolyte and the electrode for the I3/I redox reaction.[S6,S7] The results of the RS and RCT are shown in the table accompanying the Figure 3S. It can be found that the RS and RCT of the PEDOT/Ti CE are higher than that of the Pt/Ti CE, this is unfavorable to electron transport.[S8-S10] The RS of the PEDOT-Pt/Ti CE is in between of the other two CEs, however, the RCT is the smallest one among the three CEs, this is favorable to increase the fill factor of the large-area light-weight DSSC.

Figure S3. EIS (measured in the dark) of light-weight DSSCs based on the Pt/Ti CE, PEDOT/Ti CE, and PEDOT-Pt/Ti CE

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