Journal of Materials Chemistry

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A facile synthesis of anatase N,B codoped TiO2 anodes for improved-performance dye-sensitized solar cells
Huajun Tian, Linhua Hu, Wenxin Li, Jiang Sheng, Shuangying Xu and Songyuan Dai*
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Received 26th February 2011, Accepted 2nd April 2011 DOI: 10.1039/c1jm10853k

A facile process to fabricate highly crystalline mesoporous N,B codoped TiO2 is introduced. The N,B codoped TiO2 nanomaterial, which has controlled crystallographic phase, size and unique nanoshape, is successfully applied to an enhanced device for dye-sensitized solar cells (DSCs) with an open-circuit photovoltage of 0.823 V and yielding a high overall energy conversion of 8.4%. A DSC based on the N,B codoped TiO2 electrode shows a competitive photovoltaic performance compared with the undoped DSC, which is attributed to the ideal combination of superior energy band structure and retarded electron recombination from the unique N,B codoped TiO2 particle structure. In recent years, growing attention has been paid to the design and fabrication of ne-structured titania on the nanoscale because of its unique potential applications in renewable energy (solar cells,1,2 photo electrochemical splitting of water into hydrogen and oxygen3,4) and photocatalysis for degradation of organic pollutants.5,6 TiO2, in its anatase phase, has been intensively investigated, especially as an electrode in dye-sensitized solar cells (DSCs) over the past decade since Grtzel and co-workers reported their breakthrough work.7 In a those studies, liquid-junction DSCs, which exhibit the high shortcircuit photocurrent densities (Jsc) and good ll factors (FF), have been widely researched by exploring novel photosensitizers and electrodes.810However, the low open-circuit photovoltage (Voc) has always been an urgent problem to be solved. Especially, electron recombination in DSC plays a critical role because of the extremely large TiO2/dye/electrolyte interface area and the proximity of electrons to the oxidized redox species (the hole carriers), which can limit the photovoltaic performance.1113 Moreover, high crystallinity of the TiO2 lm, which favours the injected electrons, is not always obtained. According to these technical problems, many methods to improve the Voc have been adopted, including retarding the electron recombination,14 shifting the conduction band edge of TiO2 to more negative potentials15 and nding appropriate novel organic dyes, which have much higher lowest unoccupied molecular orbitals

Key Lab of Novel Thin Film Solar Cells, Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, Hefei, Anhui, 230031, Peoples Republic of China. E-mail: sydai@ipp.ac.cn; Fax: +86 (0)551 5591377; Tel: +86 (0)551 5591377 Electronic supplementary information (ESI) available. See DOI: 10.1039/c1jm10853k

(LUMOs) as compared to Ru complex dyes.16Undoubtedly, doping is a widely applied technological process in nanomaterials science that involves incorporating atoms or ions of appropriate elements into host lattices to yield hybrid materials with desirable properties and functions.1719 In DSCs, the technology of doping has been widely adopted to tailor the properties of TiO2 electrodes, such as forming barrier layers for prohibiting the recombination reaction,20 or modulating the band gap and conductivity.21 Meanwhile, the doping could inuence the particle growth process to give simultaneous control over the crystallographic phase, size and optical emission properties of the resulting nanocrystals. Especially, codoping as a good pair has charge compensation on the basis of different ions through an internal charge transfer with a large stabilization effect resulting in a less defective codoped TiO2 system.22 We report here the preparation and characterization of one kind of nonmetal-doped titania nanoparticlethe highly crystalline mesoporous N,B doped TiO2 nanomaterial, which shifts the conduction band edge of TiO2 to more negative potentials and simultaneously retards the electron recombination at the dyed TiO2 electrode/electrolyte interface. Herein, a major advancement in the enhancement of Voc of DSCs by using this highly crystalline mesoporous N,B codoped TiO2 nanomaterial based electrode is reported, and to the best of our knowledge, this is the rst application of this highly crystalline N,B codoped TiO2 material, which has controlled crystallographic phase, size and unique particle structure, into enhanced devices for dye-sensitized solar cells with a high open-circuit photovoltage of 0.823 V and yielding a high overall energy conversion of 8.4%. Anatase mesoporous N,B codoped TiO2 nanomaterials containing various concentrations of N and B dopants were synthesized by a facile modied solgel method (the experimental details of synthesis are provided in the ESI). Fig. 1a, b, c shows cross-sectional eldemission scanning electron microscopy (FESEM) images and SEM top-surface images of a typical N,B codoped anatase TiO2 lm sample at both low and high magnication. It can be seen that the N, B codoped anatase TiO2 lm has equal particle size. Compared with the undoped TiO2 lm, a more uniform and porous lm is obtained (see ESI, Fig. S1), with an average size of approximately 20 nm as shown in Fig. 1c. After the addition of B,N dopants, some cubic-like nanoparticles appear. This demonstrates that the doping could inuence the particle growth process. The result is shown to be well consistent with the TEM image, as illustrated in Fig. 1d. High-resolution transmission electron microscopy (HRTEM) images (Fig. 1e, f) show that N,B codoped nanocrystals exhibit
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Fig. 2 XRD for N,B codoped and undoped titania powder.

conversion efciency (h) can be obtained from the JV curve through the relationships (eqn (1,2)): FF
Fig. 1 a, b, c) Cross-sectional and top-surface FESEM images of the N, B codoped TiO2 lms deposited on a TCO substrate at low and high magnication, respectively. d, e, f) High-resolution TEM images of N,B codoped TiO2 powder. Inset of (f): the corresponding fast Fourier transform (FFT) pattern.

Jmax Vmax Jsc Voc

(1)

h%

Jmax Vmax Jsc Voc FF 100% 100% Pin Pin

(2)

approximately cubic shapes. Simultaneously, it is clearly showed that the N,B codoped nanocrystals are highly crystallized with wellresolved lattice structure, and the observed spacing between the lattice planes of the sample is obtained as 0.35 nm for the (101) plane of the anatase crystal. Furthermore, the crystal lattice is very clear, indicating no obvious defects. The inset of Fig. 1f shows the fast Fourier transform (FFT) pattern of the N,B codoped TiO2, which indicates a high crystallinity of the anatase TiO2. Moreover, the crystallization of N,B codoped mesoporous TiO2 nanoparticles is further identied by the X-ray diffraction (XRD) pattern. In Fig. 2, the (101) anatase peak intensity of the N,B codoped TiO2 is denitely stronger than that of undoped TiO2, which conrms that the crystallinity of TiO2 was improved by N,B codoping.23 Meanwhile, XRD patterns indicate the absence of peaks corresponding to the N,B phase, owing to the low doping concentration of the N,B doping(0.43 at.% N, 0.51 at.% B) (see ESI, Fig.S2), or that the impurities are uniformly dispersed among the anatase crystallites. Solar cells with working electrodes consisting of the undoped and N,B codoped anatase TiO2 lms were tested under illumination with 100 mW cm2 intensity. The response of the solar cells to the illumination in the form of a JV curve is shown in Fig. 3 and the performances of the solar cells such as open circuit voltage (Voc), short circuit current density (Jsc), ll factor (FF), and overall
This journal is The Royal Society of Chemistry 2011

where Pin is the illumination power density and Jmax and Vmax are maximal photocurrent density and photovoltage in the JV curve, respectively. The liquid-state DSCs using the N,B codoped electrodes give high photovoltages of 0.823 V, 0.792 V which are enhanced signicantly, by about 7% and 3%, respectively (see ESI, Table S1). The overall efciency of the DSC using the N,B codoped TiO2 (0.43 at.% N, 0.51 at.% B) electrode is improved to 8.4% due to the signicant improvement of photovoltage.

Fig. 3 JV characteristics of DSCs based on the undoped and N,B codoped TiO2 photoanodes measured in the dark and under simulated AM 1.5 sunlight at an intensity of 100 mW cm2.

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It is well known that the measured Voc values under high light intensities can give a rough estimate of the Fermi level position.24 Fig. 4 shows the changes in the Voc of undoped and N,B codoped TiO2 electrode based DSCs with increasing Jsc by modifying the light intensity. The Voc, which is determined by the difference between the Fermi level of the TiO2 electrode and the redox potentials of I/I3, of all the electrodes increased with the increased light intensities, assuming that it is not limited by the charge injection from the dye. In the measured intensity range, Fig. 4 shows that the maximum value of Voc of the N,B codoped TiO2 electrode based DSC is 40 mV higher than the undoped electrode based DSC. Moreover, the spectroelectrochemical measurements for undoped and N,B codoped TiO2 are shown in Fig. 5 in order to further investigate the cause of the enhancement of Voc in DSC. The at-band potential Vfb of TiO2 samples with and without N,B codoping are determined as 2.25 V and 2.20 V (vs. Ag/AgCl), respectively. So, a higher quasi-Fermi level closer to the conduction band is denitely achieved, which can lead to the larger Voc for liquid-state DSCs employing an N,B codoped TiO2 electrode. Meanwhile, this negative movement of Vfb at the same time decreases the electron injection rate from the excited dyes resulting in the decrease of Jsc, and at the same time the increase of the titania crystallite size and the BET also could inuence the dye N719 absorption of TiO2 lm (see ESI, Table S2, Fig. S3). But increased crystallinity of the doped porous TiO2 lm could favour the injected electrons, which is consistent with the result of IPCE (see ESI, Fig. S4). As we known, light absorption in TiO2 is mainly determined by the band structure and the dipole matrix elements. It is concluded from the UV-vis spectra for undoped and N,B codoped TiO2 (inset of Fig. 5) that the band gaps of undoped and N,B codoped TiO2 are almost identical because only a negligible blue shift in the UV-vis spectrum is observed. Thus, an upward movement of the conduction band edge of N,B codoped TiO2 would not have to be accompanied by an upward shift in the valence band (VB) edge as well. On the other hand, electrochemical impedance spectroscopy (EIS) was measured to reveal the appreciable difference in the charge transfer resistance at the conducting layer/TiO2, Pt/electrolyte, dyecoated TiO2/electrolyte interface and diffusion of the I3/I redox electrolyte. Especially, EIS techniques were applied in order to

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Fig. 5 Absorbance measured at 780 nm as a function of applied potential for nanostructured undoped and N,B codoped TiO2 electrodes at 298 K in 3 M KCl solution (Ag/AgCl reference electrode). Inset : UV-visible absorption and reection spectra of undoped and N,B codoped TiO2 (0.43 at.% N, 0.51 at.% B) lms.

understand the recombination dynamics at the dyed TiO2/electrolyte interface. The dark reaction impedance represents electron transfer from the conduction band of the mesoscopic TiO2 lm to triiodide ions in the electrolyte, which is shown by the semicircle in the intermediate frequency regime in the Nyquist plots.25The typical EIS Nyquist plots of TiO2 lms with and without N,B codoping were measured in the dark at the same forward bias. It is obvious that the charge transfer resistance attributed to the electron transfer at the dyed TiO2/electrolyte interface (denoted as R2, Fig. 6a) increases apparently with the introduction of N,B codoping. The bigger the diameter of the middle frequency semicircle in the Nyquist plots, the slighter is the electron recombination at the dyed TiO2/electrolyte interface. In Fig. 6b, the Bode phase plots likewise indicate that the middle-frequency peak of the DSC based on N,B codoped TiO2 electrode shifts to lower frequency relative to the undoped one, indicating a longer electron lifetime for the N,B codoped device. Overall, the DSC device based on the N,B codoped TiO2 electrode shows a competitive photovoltaic performance compared with the undoped one, which is attributed to the ideal combination of superior energy band structure, retarded charge recombination and high crystallinity derived from the unique TiO2 particle structure. So the whole process for DSCs could be optimized through the N,B codoping by shifting the conduction band edge and retarding the charge recombination (see ESI, Fig. S5).

Fig. 4 Open circuit potential measurements at different light intensities for DSCs based on undoped and N,B codoped TiO2 (0.43 at.% N, 0.51 at. % B) electrode. Cell active area: 0.25 cm2.

Fig. 6 (a) Nyquist plots for the dye-sensitized solar cells based on undoped and N,B codoped TiO2 (0.43 at.% N, 0.51 at.% B) electrode. Inset is equivalent circuit. (b) Bode impedance plots of the undoped and N,B codoped DSCs.

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In conclusion, we have provided a facile route for the fabrication of highly crystalline mesoporous N,B codoped TiO2 nanomaterial based electrodes. This method can be used to improve the crystallinity of TiO2 nanoparticles and tune the at-band potential of highly crystalline mesoporous TiO2 electrodes and at the same time retard the electron recombination in the dye-coated TiO2/electrolyte interface of DSCs. As a novel and low-cost photoelectrode material for DSCs, liquid-state DSCs employing this N,B codoped highly crystalline mesoporous TiO2 nanomaterial as electrode achieve a rather high open circuit voltage of 0.823 V and a high efciency of 8.4%, which provides valuable insight for the design of high-performance DSCs.
Downloaded by CHONNAM NATIONAL UNIVERSITY on 14 June 2011 Published on 18 April 2011 on http://pubs.rsc.org | doi:10.1039/C1JM10853K

Acknowledgements
This work was nancially supported by the National Basic Research Program of China under Grant No. 2011CBA00700, the National High Technology Research and Development Program of China under Grant No. 2009AA050603, Funds of the Chinese Academy of Sciences for Key Topics in Innovation Engineering under Grant No. KGCX2-YW-326 and the National Natural Science Foundation of China (Grant No. 20703046).

Notes and references

1 U. Bach, D. Lupo, P. Comte, J. E. Moser, F. Weissrtel, J. Salbeck, o H. Spreitzer and M. Grtzel, Nature, 1998, 395, 583585. a 2 Y. J. Kim, Mi H. Lee, H. J. Kim, G. Lim, Y. S. Choi, N. G. Park, K. K. Kim and W. I. Lee, Adv. Mater., 2009, 21, 36683673. 3 A. Fujishima and K. Honda, Nature, 1972, 238, 3738. 4 H. Van Damme and W. Keith Hall, J. Am. Chem. Soc., 1979, 101, 43734374. 5 J. W. Tang, Z. G. Zou and J. H. Ye, Angew. Chem., Int. Ed., 2006, 43, 44634466. 6 E. Obuchi, T. Sakamoto and K. Nakano, Chem. Eng. Sci., 1999, 54, 1525.

7 B. O. Regan and M. Grtzel, Nature, 1991, 353, 737740. a 8 S. Iwamoto, Y. Sazanami, M. Inoue, T. Inoue, T. Hoshi, K. Shigaki, M. Kaneko and A. Maenosono, ChemSusChem, 2008, 1, 401 403. 9 M. K. Nazeeruddin, P. Pchy, T. Renouard, S. M. Zakeeruddin, e R. Humphry-Baker, P. Comte, P. Liska, L. Cevey, E. Costa, V. Shklover, L. Spiccia, G. B. Deacon, C. A. Bignozzi and M. Grtzel, J. Am. Chem. Soc., 2001, 123, 16131621. a 10 M. K. Nazeeruddin, F. De Angelis, S. Fantacci, A. Selloni, G. Viscardi, P. Liska, S. Ito, B. Takeru and M. Grtzel, J. Am. a Chem. Soc., 2005, 127, 1683516847. 11 M. Grtzel, Inorg. Chem., 2005, 44, 68416851. a 12 L. M. Peter, Phys. Chem. Chem. Phys., 2007, 9, 2630. 13 J. Bisquert, A. Zaban and P. Salvador, J. Phys. Chem. B, 2002, 106, 87748782. 14 H. J. Tian, L. H. Hu, C. N. Zhang, W. Q. Liu, Y. Huang, Lie. Mo, L. Guo, J. Sheng and S. Y. Dai, J. Phys. Chem. C, 2010, 114, 1627 1632. 15 X. J. Feng, K. Shankar, M. Paulose and C. A. Grimes, Angew. Chem., Int. Ed., 2009, 48, 80958098. 16 K. Hara, T. Sato, R. Katoh, A. Furube, T. Yoshihara, M. Murai, M. Kurashige, S. Ito, A. Shinpo, S. Suga and H. Arakawa, Adv. Funct. Mater., 2005, 15, 246252. 17 D. J. Norris, A. L. Efros and S. C. Erwin, Science, 2008, 319, 1776 1779. 18 H. J. Queisser and E. E. Haller, Science, 1998, 281, 945950. 19 N. Manyala, J. F. DiTusa, G. Aeppli and A. P. Ramirez, Nature, 2008, 454, 976980. 20 E. Palomares, J. N. Clifford, S. A. Haque, T. Lutz and J. R. Durrant, J. Am. Chem. Soc., 2003, 125, 475482. 21 X. J. Lu, X. L. Mou, J. J. Wu, D. W. Zhang, L. L. Zhang, F. Q. Huang, F. F. Xu and M. Huang, Adv. Funct. Mater., 2010, 20, 509515. 22 H. Xu and L. Z. Zhang, J. Phys. Chem. C, 2010, 114, 940946. 23 G. Liu, C. H. Sun, L. N. Cheng, Y. G. Jin, H. F. Lu, L. Z. Wang, S. C. Smith, G. Q. Lu and H. M. Cheng, J. Phys. Chem. C, 2009, 113, 1231712324. 24 S. Gubbala, V. Chakrapani, V. Kumar and M. K. Sunkara, Adv. Funct. Mater., 2008, 18, 24112418. 25 Q. Wang, S. Ito, M. Grtzel, F. Fabregat-Santiago, I. Mora-Sero, a J. Bisquert, T. Bessho and H. Imai, J. Phys. Chem. B, 2006, 110, 2521025221.

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