28th European Photovoltaic Solar Energy Conference and Exhibition

ACCELERATED AGING TEST FOR CARBON COMPOSITE COUNTER ELECTRODES BASED DYE SENSITIZED SOLAR CELLS
Authors: Syed Ghufran Hashmi, Janne Halme and Peter Lund Email: ghufran.hashmi@aalto.fi New Energy Technologies Group, Department of Applied Physics, Aalto University, P.O. BOX 15100, FI-00076 Aalto (Espoo), Finland ABSTRACT: We report here an accelerated aging test for carbon composite catalyst layer based dye sensitized solar cells (DSSCs) that was performed under artificial light intensity (1000 W/m2) equivalent to 1 Sun and at 60 C for 1000 hours in the presence of significant fraction of UV light intensity. The performance of the reference DSSCs with thermally platinized counter electrodes degraded almost completely due to severe electrolyte bleaching, which is an expected result of UV light induced degradation of DSSCs. The performance loss was also accompanied by an increase in the counter electrode charge transfer resistance (RCT). However, DSSCs with counter electrodes based on carbon composite catalyst layers exhibited markedly more stable photovoltaic performance, showed no visible bleaching of the electrolyte, and their catalytic activity even improved with a gradual decrement in RCT (from 6 cm2 to 2.6 cm2). The efficiency of the carbon composite based DSSCs was reduced by 35% from the initial efficiency due to a slight degradation in N719 dye and the corrosion at the silver contacts which caused a small increase in the total cell resistance in both types of DSSCs. The resistance of these carbon composites counter electrode based DSSCs against UV light may potentially reduce the overall manufacturing cost by partially or completely relaxing the need for UV filters in complete DSSC assembly, but this hypothesis as well as the physical and chemical origin for the effect should be investigated and verified by further studies. Keywords: Dye sensitized solar cells, stability, carbon composites and counter electrodes. 1. INTRODUCTION Dye sensitized solar cells (DSSCs) propose variety of cheap materials to be tested in different combinations [1]. However, long term operation of these inexpensive materials in the cell is critical for the reliable commercialization of DSSCs [2]. The composites of carbon have been tested as an alternative to replace the expensive platinum (Pt) catalyst layer in several studies [3-7]. Nevertheless accelerated aging tests for these composites are rarely reported [8, 9] and more precisely, their long term electrochemical impedance performance is mostly missing in the literature. In this contribution, we present an accelerated aging test that was performed under artificial light intensity (1000 W/m2) equivalent to 1 Sun and at 60 C to see the potential of carbon composites catalyst layers to be implemented in the durable DSSCs. The illumination of the solar cells in the aging test included also significant UV light component, which is known to be significant aging factor of DSSCs. The performance of these carbon catalyst layers in an accelerated aging test was evaluated in terms of photovoltaic parameters (IV), electrochemical impedance spectroscopy (EIS measurements) and incident photon to collected electron efficiency (IPCE) and compared with reference thermally platinized counter electrodes (TPCE).

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2. EXPERIMENTAL SETUP 2.1 Measurements setup Photovoltaic performance of all the cells was measured by a source meter (Keithley 2420) in the light intensity (1000 W/m2) of an artificial solar simulator which is equivalent to 1 Sun. (IPCE) measurement was performed (from PE side) with Spectral Response/QE/IPCE (model QEX7, PV measurements Inc) measurement system from a wavelength range of 300900 nm. The electrochemical impedance spectra were obtained by Zahner-Elektrik IM6 potentiostat. All the cells were aged in the light soaking (projector lamps from Philips, type 13117 were employed) at 60 C with 20% Humidity in the weather chamber (Arctest, Model 400). The cells were kept under open circuit voltage condition. 2.2 Fabrication of the test cells Two types, i.e. traditional thermally platinized counter electrode (TPCE) and carbon composite counter electrode (CCE) based DSSCs were fabricated for the study. The details of complete fabrication process are given below. 2.2.1 Fabrication of counter electrodes The counter electrodes (CE) were prepared as follows: Details of carbon composite paste and carbon composite counter electrode (CCE) Screen-printable carbon composite paste was prepared by mixing 0.4 g of carbon furnace black particles (20 nm Printex L6), 0.4 g of TiO2 nanoparticle (Degussa) and 0.4 g of Sb:SnO2 (Zelec ECP 3010-XC, Milliken Chemicals) and 1.2 g of graphite powder (particle size 1-5 m (Sky Spring

Nanomaterials Inc). This composite was first milled (2 hours) in 15-20 ml of ethanol solution (99.9% purity) and collected in a glass flask in the form of viscous paste. Then 20-30 ml of ethanol was added to the paste and sonicated with a tip-sonicator (Branson model 450D) for 30 minutes. To improve the viscosity and printability, 6 g of Ethyl cellulose was dissolved in the mixed solution of terpineol (9 ml) and ethanol (5 ml) solvents. This ethyl cellulose based solution was added to the sonicated carbon solution and was thoroughly mixed with an ultra turrex mixer (IKA) for 20 minutes. As a final step, ethanol was completely removed from the carbon composite solution through a rotary evaporator (Buchi-Rotavap) and highly viscous paste was obtained. This paste was deposited on FTO glass (Sheet resistance = 15 /) through screen printing (T61-mesh). Thickness of printed layers was 20-30 m whereas the area of carbon electrodes was 0.54 cm2 which is slightly larger than the PE area (0.4 cm2) to avoid the mismatch. The layers were then sintered at 500 C and were chilled down to room temperature. Thermal platinization on FTO glass substrate 4 l of 5 mM solution of Choloro platinic acid hydrate (H2PtCl4.6H2O) in 2-Propanol was spread on FTO glass (Area =16x20 mm2) substrates, fired at 390 C for 20 minutes in a preheated oven and then substrates were cooled down to room temperature. 2.2.2 Fabrication of photo electrodes First the cleaning step was performed for Fluorine doped tin oxide (FTO) coated glass substrates (Sheet resistance 15 /, Pilkington) by washing them with the mild detergent and followed by sonication in the

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ethanol and acetone solutions (5 min each). All the substrates were dried via compressed air before placing them in a UV-O3 Chamber (Bio-force nano sciences UV Ozone Pro Cleaner, 20 minutes) for further cleaning. After UV-O3 cleaning step, the substrates were immersed into a 40 mM TiCl4 solution container box and placed for 30 minutes in a preheated oven at 70 C. After that the substrates were again washed with deionized water (DIW) and ethanol solution sequentially and dried with compressed air. Sequential screen printing steps of commercial nano crystalline TiO2 paste (18NR-T Dyesol) and TiO2 scattering paste (WER2-0 Dyesol) were performed to get 9-10 m and 2-4 m thick films respectively with mesh T-61. Each layer was dried at 110C for 5-10 minutes after the deposition. The TiO2 printed layers were then sintered at 500 C for 30 minutes and were cooled down to room temperature in the oven. After sintering the TiCl4 treatment step was again performed (with above mentioned sequence till the drying with compressed air) and the substrates were resintered at 500 C (for 30 minutes) and were again cooled down to room temperature to complete the process. These TiCl4 treated substrates were sensitized in the 0.32 mM cis bis (isothiocyanato) bis (2, 20-bipyridyl4, 40-dicarboxylato)-ruthenium (II) bis tetrabutyl ammonium (N-719, Solaronix) and ethanol (99.5 wt %) solution for 16 hours before the cell assembly. 2.2.3 Cell assembly Both PE and CE were assembled in sandwich type fashion by separating them through a 50 m thick Bynel foil (Dupont). The (I/I3) redox based electrolyte (HSEDyesol) was injected into the cell channel via drilled holes at PE side. Finally these cell holes were sealed with a 25 m thick Bynel foil (Dupont) and a thin glass cover

piece. The cell contacts were made by applying the conductive copper tape and spreading silver ink at the in-active area of the cell. The contacts were then protected with a slow drying epoxy. All the cells were soaked for 1 day in 1 Sun light intensity (1000W/m2) for initial stabilization before the initial measurements. 3. RESULTS AND DISCUSSIONS 3.1 Initial photovoltaic performance Table 1 represents the initial photovoltaic performance of both thermally platinized counter electrodes (TPCE) and carbon composite counter electrodes (CCE) based DSSCs. The sample to sample variations are presented in the form of standard deviation for each type of DSSCs (Table 1). Both types of DSSCs exhibited almost equal efficiencies (Avg ~ 6.5%) however, the TPCE based DSSCs showed ~ 8% higher currents (JSC), 3% higher fill factor (FF) and ~ 20% lower cell resistance (RCELL). Nevertheless the CCE based DSSCs exhibited 8% higher open circuit voltage (VOC). Additionally the high fill factors in each type of DSSCs suggest good adhesion of catalyst layers over the substrates. Table 1: Initial photovoltaic performance of 4-5 cells of each type of DSSC along with their standard deviations.
Cell type* GPEGTPCE GPEGCCE JSC VOC (mA/cm2) (mV) 15.6 0.2 690 4 14.4 0.4 750 14 FF RCELL (%) (%) (cm2) 61 2 6.6 0.2 11 0.8 59 1 6.3 0.2 14 0.4

* GPEGPTCE = Glass photo electrode Glass thermal platinum counter electrode. GPE GCCE = Glass photo electrode Glass carbon composite counter electrode.

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3.2 Initial electrochemical impedance response

W/m2) as was used for measuring the photovoltaic parameters. The measured frequency range was from 100 mHz to 100 kHz. In this frequency range, the traditional TPCE exhibits three semi circles [10, 11] (Figure 1a). Each semicircle can be distinguished according to its unique peak position (Figure 1b). The first semicircle for TPCE is associated with charge transfer resistance (RCT) which appears at very high frequency (> 1 kHz) range [10, 11] (Figure 1b). Additionally the second adjacent semicircle corresponds to the recombination resistance of the photo electrode (RPE) and its characteristic frequency appeared around 20-30 Hz [10] (Figure 1b). The third small semicircle that appeared at very low frequency (~ 1 Hz, Figure 1a-b) is associated with the diffusion resistance (RD) of the cell [10, 11]. The case is different for CCE in which a large semi-circle results from the overlapping of RCT and RPE responses at lower frequency (10-20 Hz, Figure 1b) range. Hence it is difficult to estimate the exact value of RCT for CCE. One possibility is to subtract the RPE value of TPCE based DSSC since the same photo-electrode geometry was employed in fabrication of the each type of DSSCs [12, 13]. Based upon this assumption, the RCT values of CCE are calculated and presented in Table 2. In addition to that one small semicircle adjacent to the large semicircle (Figure 1a) can be seen in the CCE spectrum which appears at very high frequency (~10 kHz, Figure 1b) and is distinguished as in-pore diffusion resistance (RPORE) or contact resistance [13, 14]. The value of RPORE was added in the RCT values to calculate the total charge transfer resistance (RCT-TOTAL) of CCE [12, 15]. Table 2 summarizes the EIS parameters of each type of DSSCs.

Figure 1: Typical EIS spectra of each type (*GPEGTPCE and **GPEGCCCE) DSSCs used in this study. a) Nyquist plot, as b) imaginary impedance Z as a function of frequency f. *GPEGTPCE = Glass photo electrode Glass thermally platinized counter electrode. **GPE GCCE = Glass photo electrode Glass carbon composite counter electrode. The initial measurement results regarding electrochemical impedance response of each type of DSSCs are summarized in Table 2. These measurements were performed at open circuit voltage and in the solar simulator with same light intensity (1000

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The main conclusion that can be drawn from initial EIS performance is; almost equal series resistance (Avg RS = 4.6 0.4 cm2) for each type of DSSCs due to the same FTO Glass substrate (RSHEET = 15 /) however, the TPCE exhibited lower RCT (2.2 0.5 cm2) than CCE (6.0 0.2 cm2). Table 2: Initial average values of 4-5 cells of each type along with their standard deviations representing electrochemical impedance performances.
Cell type* RS (cm2) RCT (cm2) RREC (cm2) RPORE (cm2) RREC+RCT (cm2) RCT-TOTAL (cm2) *GPEGPTCE 4.7 0.6 2.2 0.5 2.7 0.4 **GPE GCCE 4.5 0.2 5.2 0.5 0.8 0.2 7.9 0.5 6.0 0.2

UV blocking filter is used to prevent the reaction. Since in this work no UV blocking filter was employed we assume the aforementioned cause is responsible for the loss of tri-iodide ions here as well. Figure 4 shows the photon flux spectrum of the lamps used in the light soaking system (Philips 13117), confirming the presence of UV light (below 400 nm). Surprisingly, no visible bleaching of electrolyte occurred in CCE based DSSCs and the JSC values were only fractionally (~ 8%, Figure 2 a) decreased from the initial value. It should be noted again that in each type of DSSCs, the same photo electrode and electrolyte composition was used and the only difference was in the catalyst layer i.e. thermal platinum and carbon composite. This raises a hypothesis that the irreversible reaction between the electrolyte and UV light was minimized or stopped by the carbon composite. In addition to that, a continuous drop in open circuit voltage (VOC) for CCE based DSSCs was observed whereas it was recovered up to 90% in case of TPCE based DSSCs (Figure 2b). The drop in open circuit voltage is mainly associated with the resistance of photo electrode (RPE) which is investigated and further discussed in section 3.4. Nevertheless, over the whole 1000 h period, the voltage decreased by 13% and 7% in case of CCE and TPCE based DSSCs respectively (Figure 2b). Also the FF did not remain stable but decreased by 11% in case of TPCEs and 19% for CCE based DSSCs (Figure 2 c). These drops in FFs are resulted due to an increase in total cell resistance (RCELL 74% increase for TPCE and 26% increase for CCE based DSSCs) of the cells (Figure 5 a). The RCELL depends upon various factors for instance charge transfer resistance at counter

* GPEGPTCE = Glass photo electrode Glass thermally platinized counter electrode. ** GPE GCCE = Glass photo electrode Glass carbon composite counter electrode. 3.3 Photovoltaic performance of DSSCs with accelerated aging Figure 2 represents the short circuit current density (JSC), open circuit voltage (VOC), fill factor (FF) and overall efficiency () recorded for each type of DSSC during this study (from 0 h to 1000 h). During the entire period of study, both types of DSSC exhibited different trends compared to each other. During the whole study, JSC of TPCE based DSSCs was continuously decreased (Figure 2a) due to the bleaching of the electrolyte (Figure 3 b-c). The bleaching of the electrolyte solution is well known problem in traditional TPCE based DSSCs when exposed to real or artificial sunlight and is mainly associated with loss of triiodide ion in the electrolyte solution [16-20]. This loss of tri-iodide ion has further been associated with a reaction between UV light and the electrolyte solution that generates an irreversible reaction for iodine [21, 22] unless a

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electrode (RCT), ideality factor of photo electrode, contact resistance of the contacts, sheet resistance (RSH) of the substrates and electrolyte diffusion. These parameters are investigated in detail in section 3.4. Due to the decrease in FF and VOC, the efficiency of CCE based DSSCs was reduced from 6.3 0.2% to 4.1 0.2 (i.e. by 35 %) whereas the efficiency of the TPCE based cells dropped linearly by 85% mainly due to the UV induced, electrolyte bleaching reaction (Figure 2 d).

(black circles) cells. a) Short circuit current density (JSC) (b) Open circuit voltage (VOC) (c) Fill factor (FF) and (d) Efficiency () of the cells. *GPE GTPCE = Glass photo electrode Glass thermally platinized counter electrode. **GPE GCCE = Glass Photoelectrode Glass carbon composite counter electrodes.

Figure 3: Bleaching of the electrolyte in *TPCEs based DSSCs was observed during the entire period. a) Fresh electrolyte with dark yellow color. b) Semi bleached electrolyte losing yellow color. c) Completely colorless/bleached electrolyte. * Thermally platinized counter electrodes.

Figure 4: Spectrum of lamps used in the light soaking system. 3.4 Electrochemical performance of DSSCs with accelerated aging Some of the critical factors which determine the performance of counter electrodes are also investigated with electrochemical impedance spectroscopy (EIS). These parameters are presented in Figure 5 b-d. As discussed in earlier section, both types of DSSCs exhibited almost equal initial series resistance (RS). However, the TPCE based

Figure 2: Photovoltaic parameters of *GPE GTPCE (red squares) and **GPE GCCE

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DSSCs was not found stable and RS was drastically increased from 4.7 0.6 cm2 to 9.2 2.8 cm2 (Figure 5 b). The high standard deviation values result from the bleaching of the electrolyte that started in some cells already after a few (~ 50) hours and caused variations from cell to cell whereas these huge variations were not observed in CCE based DSSCs since no bleaching occurred. Nevertheless, RS in case of CCE was also increased up to 30% of the initial value (Figure 5 b). The RS mainly depends upon the sheet resistance of the substrate which could in principle be increased by degradation in the conducting Fluorine doped tin oxide (FTO) layer. However, there were no direct indications of FTO failure. Instead, clear corrosion of the silver contacts appeared during the aging test (Figure 3 b-c) which most likely explains at least part of the 30% increase in RS. There was a severe increase (82%) in the charge transfer resistance (RCT) at the thermally platinized counter electrodes (Figure 5 c). Although degradation of Pt catalyst layers prepared with different techniques has been reported in the literature [23-25] , the thermal platinization method used here has provided good stability results with no loss of catalytic activity [26]. Here, analysis of the catalyst stability is complicated by the fact that RCT depends not only on the catalytic activity of the catalyst, but also on the concentration of the redox species in the electrolyte [11]. Since the loss of tri-iodide concentration was not quantified in the present work, it is not possible to conclude whether the increase of RCT in the TPCE DSSCs was due to the triiodide depletion only or also additionally due to catalyst degradation. Nevertheless, in the CCE based DSSCs that did not show -

Figure 5: Average EIS responses of 4-5 samples of *GPEGTPCE (red squares) and **GPE GCCE (black circles) cells along with their standard deviations. a) Total cell resistance, b) Series resistance, c) Charge transfer resistance and d) Resistance of photo electrode as a function of time. *GPE GTPCE = Glass photo electrode Glass thermally platinized counter electrode. **GPE GCCE = Glass photo electrode Glass carbon composite counter electrode.

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- visible bleaching, the carbon composite counter electrodes exhibited improving catalytic performance: their RCT gradually decreased (down to 58%) throughout the study (Figure 5 c). In addition to that, gradual increase in the resistance of photo electrode (RPE) has also been observed (Figure 5 d). This confirms the reason for the degradation in the open circuit voltage (VOC) that was discussed in section 3.2). The possible factor of these deviations in the RPE can be the degradation in the photo electrode. This hypothesis was further studied with incident photon to collected electron efficiency (IPCE) measurements and discussed in the next section. 3.5 Incident photon to collected electron efficiency (IPCE) of DSSCs.

final IPCE spectrum of TPCE based DSSCs due to the complete bleaching of the electrolyte as shown in Figure 3 b-c. However an idea can be obtained from the initial IPCE spectrum of TPCE based DSSCs since the same photo electrode geometry was used in each type of DSSCs. Both types of DSSCs revealed almost equal (~ 72 - 74%) initial peak IPCE values however these efficiencies were reduced to ~ 65% confirming degradation in photo electrodes. The possible hypothesis can either be desorption of N719 dye molecules which has been observed at high (60-80 C) temperatures [2, 27] or penetration of water inside the cell. Here the aging was performed at 60 C and 20% humidity and N719 dye is known to be hydrophilic dye [2]. 3.6 Short comparison of thermally platinized counter electrodes and carbon composite counter electrodes based DSSCs. An interesting comparison between TPCE and CCE based DSSCs has been obtained at the end of the study. The reference TPCE based DSSC exhibited higher initial performance in terms of ~ 8% higher JSC, 3% higher FF, ~ 5% higher efficiency and 270% lower RCT than CCEs based DSSCs. However in the accelerated aging test, TPCE based DSSCs were unable to maintain the above mentioned performance and their efficiency dropped below that of CCE based cells due to almost complete failure via electrolyte bleaching. Despite of lower initial performance, the CCE based DSSCs were able to retain ~ 92% of initial JSC, 87% VOC, 81% FF and 65% overall efficiency and thus showed clear superiority over TPCE based DSSCs in this aging experiment. Interestingly, the RCT also was remarkably decreased from 6 0.2 cm2 to 2.6 0.1 cm2.

Figure 6: Average IPCE spectra of *TPCE and *CCE based DSSCs. *Thermally platinized counter electrodes. **Carbon composite counter electrode. The in-situ IPCE measurements of TPCE and CCE based DSSCs was also performed to investigate the possibility of degradation in N719 dye used in this work. The initial and final average IPCE spectra of CCE based DSSCs are presented in Figure 6 whereas it was not possible to present the

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The key observation of this study was the absence of electrolyte bleaching in the CCE based DSSCs under halogen lamp light without a UV filter. At the same time, equally prepared but TPCE based DSSCs degraded due to complete loss of tri-iodide. It is also noteworthy that the CCE showed stable catalytic performance. In fact, their RCT was significantly reduced from its initial value which means no degradation at these counter electrodes. The study raises interesting questions such as why bleaching did not occur in CCE based DSSCs. It is important to verify and investigate it with more sophisticated techniques such as camera imaging [16], limiting current density analysis [28] and selective application of UV filters. The degradation at the photo electrode was established here through IPCE measurement; however, more sophisticated setup for instance Raman Spectroscopy [2] or IR spectroscopy [2] is suggested for a future study. 4. CONCLUSIONS Stability of carbon composite based catalyst layers was tested under artificial light intensity (1000 W/m2) equivalent to 1 Sun at 60 C. The efficiency of these carbon composite based dye sensitized solar cells were only reduced by 35% from the initial efficiency compared to the reference thermally platinized counter electrodes based DSSCs which completely degraded due to severe bleaching of the electrolyte. On the other hand, no bleaching of the electrolyte occurred in carbon composite counter electrode based DSSCs. The catalytic activity of the carbon composite counter electrodes was also improved with a gradual decrement in their charge transfer resistance (from 6 0.2 cm2 to 2.6 0.1 cm2). Moreover, the critical reasons for 35% reduction of efficiency in CCE based DSSCs was not the carbon composite counter electrodes themselves but a slight

degradation in the N719 dye at the photoelectrode and the corrosion at the silver contacts which occurred in both types of DSSCs. These results speak for the viability of inexpensive carbon composite as an alternative to expensive platinum catalyst layer for stable high performance dye sensitized solar cells. 5. ACKNOWLEDGEMENT Ghufran Hashmi thanks Fortum Foundation and Tekniikan edistmissti (Finnish Foundation for Technology Promotion) for travel grants. 6. REFERENCES [1] G. Hashmi, K. Miettunen, T. Peltola, J. Halme, I. Asghar, K. Aitola, M. Toivola, and P. Lund, Renew. Sust. Energ. Rev 15 (2011) 3717-3732. [2] M. I. Asghar, K. Miettunen, J. Halme, P. Vahermaa, M. Toivola, K. Aitola, Energy Environ Sci 3 (2010) 418-426. [3] Y. Jo, J. Y. Cheon, J. Yu, H. Y. Jeong, C. H. Han, Y. Jun, S. H. Joo, Chem. Commun 48 (2012) 8057-8059. [4] S. J Thompson, J. M. Pringle, X. L. Zhang, Y. B. Cheng, J. Phys. D: Appl. Phys 46 (2013) 024007. [5] D. Y. Kim, J. Kim, J. Kim, A. Y. Kim, G. Lee, M. Kang, J. Indus. Eng. Chem 18 (2012) 1-5. [6] X. Miao, K. Pan, Q. Pan, W. Zhou, L. Wang, Y. Liao, G. Tian, G. Wang, Electrochimica Acta 96 (2013) 155-163. [7] C. T. Hsieh, B. H. Yang, W. Y. Chen, Int. J. Photo. Energ, (2012) doi:10.1155/2012/709581

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