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Materials Letters 70 (2012) 193–196

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

A new anode material of silver photo-deposition on TiO2 in DSSC
Zhiyue Han a, Jingchang Zhang a, b,⁎, Yue Yu a, Weiliang Cao a, b
a b

Institute of Modern Catalysis, Beijing University of Chemical Technology, State Key Laboratory of Chemical Resource Engineering, Beijing 100029, China Hainan Institute of Science and Technology, Haikou 571126, China

a r t i c l e

i n f o

a b s t r a c t
A series of nano-scaled Ag/TiO2 anode was prepared by photo deposition method with different light time. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) confirmed that Ag deposited on TiO2 surface mainly in zero valent successfully. Electrochemical Impedance Spectroscopy (EIS) measurements showed that the Rct2 corresponding to the TiO2/dye/electrolyte interface decreased 10.4 Ω. Deposition of Ag on TiO2 surface can transmit the carriers produced by photo excited dye better than pure TiO2. This improved the electrons transmission efficiency of anode. Therefore, the photoelectric conversion efficiency of dye-sensitized solar cell (DSSC) was improved. There is an optimum light time. That is the 10 min measured by experiment. © 2011 Elsevier B.V. All rights reserved.

Article history: Received 22 November 2011 Accepted 30 November 2011 Available online 8 December 2011 Keywords: Photo deposition XPS Dye sensitized solar cell Solar energy materials

1. Introduction Dye-sensitized solar cells (DSSCs) have attracted increasing attention for their high efficiency, low-cost, flexibility, and fine-tuned materials, since Professor M. Grätzel and O'Regan first introduced DSSCs in 1991 [1,2]. In order to improve the photoelectric conversion efficiency of DSSC, there are some reported methods, such as chemical surface modification, compound with other semiconductor and design morphology [3,4]. However, there is no report about silver photodeposition on TiO2 anode in DSSC to improve the current density. In this paper, nano-scaled Ag/TiO2 anode was prepared by photodeposition method. Deposition of Ag on TiO2 surface can transmit the carriers produced by photo excited dye better. This improved the photoelectric conversion efficiency of dye-sensitized solar cell (DSSC). 2. Experimental 2.1. Preparation of TiO2 by supercritical fluid drying method according to Ref. [5] Surfactant AEO-3 (0.3 v%) was added to TiCl4 (0.3 mol/L) and stirred vigorously at ambient temperature. The pH of the solution was adjusted to 8–9 with aqueous ammonia. After aging for 16 h, the solution was filtered and washed until all chloride ions were removed. The water in the solution was replaced with absolute ethanol. The

resulting alcogel was transferred into the high-pressure autoclave with ethanol (three-fifths of the volume of autoclave) as a supercritical fluid. The autoclave was sealed, and the temperature was increased at the heating rate of 100 °C/h. The ethanol was maintained in the supercritical state for 30 min at 243 °C. The fluid was released. The autoclave was purged with nitrogen to remove residual ethanol and water and cooled to room temperature. The powders of titanium oxide aerogels were finally prepared.

1000
TiO2 anatase rutile

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Ag-TiO2

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⁎ Corresponding author at: Institute of Modern Catalysis, Beijing University of Chemical Technology, State Key Laboratory of Chemical Resource Engineering, Beijing 100029, China. Tel.: + 86 1 64434904; fax: + 86 1 64434898. E-mail address: zhangjc1@mail.buct.edu.cn (J. Zhang). 0167-577X/$ – see front matter © 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2011.11.120

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2θ(Ο)
Fig. 1. XRD patterns for the TiO2 and Ag–TiO2.

2. a small amount of viscous liquid residue was slowly added to methanol (200 mL) and the product precipitated.01 mol) in chloroform (20 mL) gradually was added drop wise to the solution.2. Preparation of TiO2 anode 0. . The monomer (0. A chloroform solution remained. The precipitate was vacuum dried at room temperature and subjected to Soxhlet extraction with methanol for 20 h. and the mixture was stirred for 15 min. After precipitation with methanol (200 mL) and vacuum drying at room temperature. the final polymer was obtained. and dropped evenly on the above FTO using spinning at the rate of 3000 rmin− 1 for (a) 1000000 (b) Survey TiLMM Ag3p1 Ag3p3 O1s Ag3d 100000 Ti 2p 80000 800000 OKLL Ag3s Intensity (CPS) Intensity (CPS) Sn3d Ti2p 600000 60000 Ag-TiO2 40000 N1s C1s Ag4s Ag4p 400000 Ti3s Ag4d Ti3p 200000 20000 TiO2 0 1000 0 800 600 400 200 0 468 466 464 462 460 458 456 Binding Energy (eV) Binding Energy (eV) (c) Ag 3d 120000 (d) 120000 O 1s 100000 Intensity (CPS) 90000 Intensity (CPS) 80000 Ag-TiO2 60000 60000 40000 30000 20000 0 360 364 368 372 376 380 TiO2 0 538 536 534 532 530 528 526 Binding Energy (eV) Binding Energy (eV) (e) 160000 O1s 140000 Ag-TiO2 Intensity (CPS) 120000 100000 80000 60000 40000 536 534 532 530 528 526 Binding Energy (eV) Fig.1 M TiCl4 solution was dropped on the clean FTO glass using spinning at the rate of 3000 rmin− 1 for 20 s. [6] Under a N2 atmosphere.194 Z.01 g) prepared in Section 2. The product was slowly added to methanol (300 mL). separated from the solvent.03 mol) were added to a 100 mL flask. After removing the chloroform by distillation.3. TiO2 (0. and filtered. Han et al. / Materials Letters 70 (2012) 193–196 2. The remaining black solid was added to chloroform (50 mL) in the conical flask and was stirred for 60 min with gentle heating at 40 °C. Synthesis of poly (3-octylthiophene) according to Ref. XPS spectra of TiO2 and Ag–TiO2.1 was respectively suspended in ethanol (2 mL). chloroform (20 mL) and anhydrous FeCl3 (0. The reaction temperature of system was controlled at 25 °C for 7 h. 2.

Testing DSSCs Electrochemical Impedance Spectroscopy (EIS) measurements were carried out at the Potentiostiostat/Galvanostat (EG&GPARModel283). 2. 14 12 10 8 0 min 5 min 10 min 15 min Z//(Ω) 6 4 2 0 25 30 35 40 45 50 55 60 65 Z/(Ω) Fig.86 2.78 Voc(V) 0. After drying at room temperature and calcination at 450 °C for 30 min. 2.73 eV of the Ag–TiO2. 370.531 0. This indicates that the Ti atoms loss electronics after silver deposition. 54. This suggests that Ag was highly scattered on the surface of TiO2 and a little partly doped into the lattice of TiO2.60 2.69 8. 48. 0 5 10 15 . Current–voltage (I–V) measurements were taken in air at room temperature (25 °C) using a Keithley236 high current source power meter under white-light illumination from a 500 W Xenon lamp.36 0 0. Ag mainly exists in Ag0 in Ag–TiO2. 1 shows the XRD patterns of pure TiO2 and Ag/TiO2 anode films.6.576 0. In TiO2.535 0.58 eV of the TiO2. It is seen that Ti is mainly tetravalent in Ti–O. which is consistent with the data found in Ref.48°.543 Pmax (mW) 0. The impurities are not evident in the sample. 2. 3. 2e).96°are assigned to the (101). The method of sensitization and pack is the same with that in Ref.0 mA).22 Jsc (mA/cm2) 7. but it mainly existed in anatase phase.0 kV. Compared to TiO2.23 0.78 eV of the Ag–TiO2. 11 W) for 5. The oxygen peak of the O on surface shifts to low binding energy and becomes smaller after deposition. XPS analysis was conducted by an ESCALAB 250.49 7. Silver photo-deposition on TiO2 anode The TiO2 anodes prepared in Section 2.547 0.3 0.2. three Ag–TiO2 anodes were prepared. [7]. 2a–e is the high-resolution XPS of the pure TiO2 and Ag/TiO2 anode films.4 0. very small part of the silver-promoted compound (Ag–TiO2) mainly contains the Ag grains which deposited on the TiO2 surface along with fraction of Ag2O.7 eV were found in the spectra of Ag–TiO2 (see Fig.22 0. 2a).68 Rct2 (Ω) 26. XRD Fig. voltage 40. 367. XRD.55 8. Two oxygen peaks at 530 eV and 531. dried at 25 °C and calcined at 380 °C for 30 min to prepare Pt electrode. There were a little parts of rutile phase in TiO2. 2c shows the narrow scans for Ag3d3/2 peaks locate at 367. [3]. C.23 0. a high binding energy-shift has taken place. XPS XRD measurements were performed using a Shimadzu HR6000X (Cu target X tube. Han et al. and the latter is attributed to the O on surface.72 2. Preparation of Pt electrode H2PtCl6 was evenly dropped on another FTO. Then the solutions were irradiated by UV light (main wavelength 254 nm.7. The former is attributed to Ti–O in bulk. 2d).2 0.545 0.546 0. Fig. 37. 2.4. In the Ag/TiO2 sample (Fig. 3. After drying at room temperature. XPS Fig. This results from the chemical adsorption of Ag on the surface of TiO2. which are attributed to the signals of the anatase phase. 2.6 Voc (V) Fig.Z. current 30. Two oxygen peaks at 530 eV and 533 eV were found in the spectra of TiO2 (see Fig.24°.3 were soaked in the 10− 4 mol/L AgNO3 solution. Ag promotes the accumulation and transmission of electrons. (004).98 19. The former is attributed to Ti–O in bulk.571 0.6 eV) in the Ag 3d5/2 XPS peaks [7]. Sensitization and pack of anode Prepare dye: mixture of 5 mmol/L N719 ethanol solution and 5 mmol/L P3OT chloroform solution with the volume ratio 2:1.5 0.589 FF 0. the XPS shows Ti. diffraction peaks located at 2θ = 25.53 21. (200).5. TiO2 anodes were prepared. O and Ag.561 η(%) 2. EIS spectrums of dye-sensitized solar cells. Results and discussion 3.64 16. which lead 8 Jsc (mA/cm2) 6 0 min 4 5 min 10 min 15 min 2 Table 1 Performance parameters of the dye-sensitized solar cells. Ti2p3/2 peaks locate at 458.659 0.625 0. / Materials Letters 70 (2012) 193–196 195 20 s. As seen from XRD spectra of Ag/TiO2. and the latter is attributed to Ti–O on surface. (106) and (215) lattice planes of TiO2.1 0. 4. no bands of Ag 0 and Ag2O were discerned.08°.8. and 62.96°. Photochemical study of dye-sensitized solar cells. 2b shows the narrow scans for Ti2p3/2 peaks locate at 458. Time (min) S (cm2) 0.1.3 eV) and Ag (Ag0.0 0. 10 and 15 min separately. In terms of the respective chemical bonding states of Ag2O (Ag+. Fig. 3.

3. Fu CY.136:293–7. Han et al. Zhang JC. there is an optimum light time. Inc. Cao WL. Conclusion Nano-scaled Ag/TiO2 anode was prepared by photo-deposition method. This improved the electrons transmission efficiency of anode. Similar results were previously observed in the Pb–TiO2 and Pt–TiO2 systems by Rahmana and Linsebigler [8. the amount of Ag deposited on the surface of TiO2 is little. J Photochem Photobiol. Nature 1991. When the light time is 10 min. the photoelectric conversion efficiency of DSSC increases significantly. [5] Han ZY. Physical Electronics. Yu-Lin Kuo also conducted some research on this issue [10]. it is inferred that the Ag–O–Ti local structure was presently formed. Therefore. C 2003.14:3866–73. Synthesis and photoelectric property of poly (3-octylthiophene)/ferric oxide composite. . [2] Grätzel M. Zhu H. ZDXM20100062. Zhu H. / Materials Letters 70 (2012) 193–196 to the high shift of Ti2p binding energy and the reduction of O on surface. This is consistent with XRD discussion. [6] Han ZY. N/TiO2 anode film and co-sensitization in DSSC.515:3461–7. the amount of Ag deposited on the surface of TiO2 is more.118: 5284–9. Thin Solid Films 2007. J Inorg Organomet Polym 2010. the highest photoelectric conversion efficiency and the highest current density were obtained. which becomes the recombination center of photo-electron and hole. J Solid State Chem 1998. Yang XY. 3.4:145–53. J Am Chem Soc 1996.9]. The change of chemical environment around partly O and Ti results in the change of crystalline form. Zhang JC. Ku Y. IV and EIS Current density–voltage curves for the DSSCs based on the thin film electrodes are shown in Fig. Deposition of Ag on TiO2 surface can transmit the carriers produced by photo excited dye better. Sol Energy Mater Sol Cells 2010. Cao WL. Bomben KD. [7] Moulder JF. J Mater Sci 2010. Synthesis and photoelectric property of poly (3-methoxythiophene)/titanium dioxide complexes. This is because when the light time is shorter. In addition. Yates Jr JT. That is the 10 min measured by experiment. After silver deposition. Stickle WF.353:737–40. References [1] Regan BO. Zhang JC. Preparation of PZT thin films on stainless steel using electrochemical reduction. Sobol PE. Yang XY. The XPS peaks of O 1s and Ag 3d were in agreement with the existence of a small amount of Ag2O particles on TiO2 substrate. [3] Zhang JC. [10] Kuo YL. high-efficiency solar cell based on dye-sensitized colloidal TiO2 films. Chen HW. Fujioka Y. 1995. [4] Han ZY. Study on the performance of Zn. 4. Handbook of X-ray photoelectron spectroscopy. Yang XY. the Rct2 is the smallest. At this moment. Therefore.94:755–60. Rusu C. 4 shows the EIS results of the DSSCs. Matsumoto Y.Mater Electron 2010. J Mater Sci . Zhu H. The estimated performance parameters are summarized in Table 1.196 Z. Cao WL. Fig.6:554–61. the photoelectric conversion efficiency of dye-sensitized solar cell (DSSC) was improved. Acknowledgments This work was supported by the Key Science Planning Program of Hainan under grant no. When the light time is longer. Analysis of silver particles incorporated on TiO2 coatings for the photodecomposition of o-cresol. Ohmura H. Grätzel M.3.1:43–9. [9] Linsebigler A. Yamada S. [8] Koinuma M. A low-cost. In short. so it cannot play a very good optical carrier transport effect. Yang XY. The XPS confirms that Ag deposited on the surface of TiO2 anode mainly in zero valent and a little part in Ag2O. Cao WL. Absence of platinum enhancement of a photoreaction on TiO2–CO photooxidation on Pt/TiO2(110). Synthesis and photoelectric property of poly (3-octylthiophene)/titanium dioxide nano-composite material.