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Directly Hydrothermal Growth of Single Crystal Nb3O7(OH) Nanorod Film for High Performance Dye-Sensitized Solar Cells
Haimin Zhang, Yun Wang, Dongjiang Yang, Yibing Li, Hongwei Liu, Porun Liu, Barry J. Wood, and Huijun Zhao*
As a promising alternative to conventional silicon-based solar cells, dye-sensitized solar cells (DSSCs) have attracted extensive interest in recent years due to their potential low-cost and high-efciency.[16] The photoanode is an essential component of DSSCs that plays a key role to determine the dye loading and photoelectron transfer, hence the light conversion efciency.[15,7,8] Although nanostructured TiO2 has been the most widely used photoanode material, much effort has also been paid to develop alternative photoanode materials such as Nb2O5, ZnO, SnO2, SrTiO3, and other composites.[914] A main objective of these research activities is to develop alternative photoanode materials that possess one or combined advantages of large surface area and/or rich surface functionality to improve the dye loading capacity; suitable structure and good crystallinity to facilitate the photoelectron transfer and enhance the current collection efciency; and more negative conduction band (CB) edge positions versus TiO2 to achieve high opencircuit voltage (Voc).[5,7,15,16] Development of new photoanode materials which can be used for assembly of the exible DSSCs is also an important aspect of such research activities.[17,18] As a wide bandgap semiconductor, Nb2O5 has been widely investigated for photocatalysis, lithium-ion battery, and solar cells.[1924] A higher Voc is expected for a DSSC assembled with Nb2O5 photoanode because of its more negative CB edge position relative to TiO2.[21,22] Le Viet et al. recently investigated the CB edge potentials of different Nb2O5 crystal structures.[22] Their investigation suggests that the CB edge potentials of H-Nb2O5 (pseudohexagonal), O-Nb2O5 (orthorhombic) and M-Nb2O5 (monoclinic) are of 0.82, 0.78 and 0.87 eV more negative than that of TiO2. For DSSC application, 3.05% conversion efciency can be obtained for H-Nb2O5 photoanode, which is signicantly higher than that of DSSCs made from O-Nb2O5 and M-Nb2O5 photoanodes due to the high surface area of H-Nb2O5 nanowires.[22] To date, Nb2O5 with various nanostructures including nanoparticles, nanobelts, nanowires and nanoforests have been synthesized by hydrothermal method, electrospinning technique and pulsed laser deposition (PLD).[21,22,2527] However, as the photoanode materials for DSSCs using these nanostructures, the obtained light-to-electricity conversion efciencies are still unsatisfactory (5.0%).[21,22,2527] The low efciency has mainly been attributed to the insufcient surface area for dye loading.[21,22] Therefore, development of niobium oxide nanostructure with high surface area is highly desired. In 1978, Kodama et al. reported the synthesis of Nb3O7(OH) nanorods by hydrothermally treating niobic acid or triniobium chloride heptaoxide with sulfuric acid at 250350 C and 15 MPa.[28] However, no detailed structure information was given in their study. Herein, we report a facile, one-pot hydrothermal method to directly grow the three-dimensional (3D) high crystallinity Nb3O7(OH) single crystal nanorod lm on FTO substrate. The obtained 3D nanorod lm possesses a high surface area of 104 m2/g with an average pore size of 19.5 nm. The lm composes of Nb3O7(OH) single crystal nanorods with an average diameter of 22 nm and an average length of 230 nm. In addition to the large surface area, the as-synthesized Nb3O7(OH) nanorod lm displays an excellent crystallinity, which can be directly used as the photoanode for DSSCs without need for further calcination to achieve an impressive overall efciency of 6.77%, the highest among all reported DSSCs assembled with niobium oxidebased photoanodes.[21,22,2527] Such a distinctive feature of the as-synthesized Nb3O7(OH) nanorod lm makes it a promising candidate for fabrication of exible photoanodes.[17,18] To the best of our knowledge, this is for the rst time a directly grown 3D Nb3O7(OH) single crystal nanorod lm photoanode is used for DSSCs without the calcination. Additionally, the crystal structure of Nb3O7(OH) has been precisely identied based on the experimental data and theoretical calculations. The XRD pattern of the as-synthesized sample (Figure 1A) can be indexed to an orthorhombic Nb3O7(OH) structure with lattice parameters of a = 20.74 , b = 3.823 and c = 3.936 (JCPDS, Card No. 31-0928).[28] The SEM image of the assynthesized Nb3O7(OH) shown in Figure 1B displays a uniform nanorod lm. High magnication SEM image indicates that the obtained nanorods with an average diameter of 22 nm and an average length of 230 nm (inset in Figure 1B). The crosssectional SEM image reveals that the as-synthesized nanorod lm has an average thickness of 11.5 m, with uniform porous structure across the entire lm (Figure 1C and inset). TEM image of an individual Nb3O7(OH) nanorod is given in Figure 1D.
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Dr. H. M. Zhang, Dr. Y. Wang, Dr. D. J. Yang, Y. B. Li, Dr. H. W. Liu, Dr. P. R. Liu, Prof. H. J. Zhao Centre for Clean Environment and Energy and Grifth School of Environment Grifth University Gold Coast Campus, QLD 4222, Australia E-mail: h.zhao@grifth.edu.au Dr. B. J. Wood Centre for Microscopy & Microanalysis The University of Queensland Brisbane, QLD 4072, Australia

DOI: 10.1002/adma.201104650
Adv. Mater. 2012, DOI: 10.1002/adma.201104650

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2

insightful knowledge on the atomic structure, especially the H atom in the atomic structure, is specially interested. The density functional theory (DFT) is therefore performed to gain such insight information. The locations of Nb and O atoms can be readily derived from XRD data for building the atomic structure model. However, the precise H atom location in the Nb3O7(OH) atomic structure cannot be conrmed by the XRD data. Four structural congurations based on the symmetry of the systems involving possible H atom locations are therefore considered for DFT model (Figure S1, Supporting Information). The calculation results suggest that the intramolecular hydrogen bonds play a critical role capable of reducing the system energy by 0.20.3 eV. After the lattice constants and atomic coordinates are fully optimized, the most stable structure (Figure 1E) is found to be congured by the H atom bonding to one O atom at the (002) plane and interacting with another nearest O atom at the same plane via a hydrogen bond to form OHO (Figure S1A, Supporting Information).[29] The effect of thermal treatment on the morphology and crystal structure of the Nb3O7(OH) nanorods was investigated. The XRD pattern of the calcined sample can be indexed to Nb2O5, suggesting a structural transformation from orthorhombic Nb3O7(OH) to monoclinic Nb2O5 (JCPDS, Card No. 71-0005) has occurred (Figure S2A, Supporting Information).[28] Despite the crystal structural changes during the calcination process, the obtained SEM image shows no obvious dimensional and morphological changes after calcination, except the formation of some nanorod bundles (Figure S2B, Supporting Information). The TEM image of an individual Nb2O5 nanorod is given in Figure S2C (Supporting Information). The SAED data indicate that the obtained Figure 1. (A) XRD pattern of the as-synthesized sample obtained at 210 C for 24 h. (B) SEM Nb2O5 nanorods are single crystals with high image of the as-synthesized Nb3O7(OH) nanorod lm (low magnication) and inset of high crystallinity (top inset in Figure S2C, Supmagnication SEM image. (C) Cross-sectional SEM image of the obtained Nb3O7(OH) nanorod lm (low magnication) and inset of high magnication SEM image. (D) TEM image of an indi- porting Information). The fringe spacings of vidual Nb3O7(OH) nanorod with insets of SAED pattern (top) and HRTEM image. (E) Atomic 0.374 nm and 1.02 nm are consistent with structure models of Nb3O7(OH). Atom colour code: greenNb, redO, blackH. the d values of (110) and (101) planes of the monoclinic Nb2O5, respectively (bottom inset in Figure S2C, Supporting Information). In order to transform Nb3O7(OH) to Nb2O5 during calcination, the The SAED pattern (top inset in Figure 1D) and HRTEM image OH groups in the (002) plane are removed via a dehydration (bottom inset in Figure 1D) reveal a good single crystalline process, leading to a serious deformation of the Nb3O7(OH) nature of the as-synthesised Nb3O7(OH) nanorods. The SAED crystal structure along z axis. However, the deformation along data conrm a preferred growth along [010] direction, while x and y directions are minor, as shown in Figure 2. Indeed, the HRTEM image conrms the fringe spacings of 0.376 nm and obtained lattice constants changes when the Nb3O7(OH) is con1.04 nm, which are consistent with the d values of (110) and verted to Nb2O5 do support the theoretical prediction (Table S1, (200) planes of the orthorhombic Nb3O7(OH), respectively.[28] Supporting Information). The structure transformation caused Known precise atomic structure of crystals is critical for underby the calcination is also conrmed by the FT-IR spectra. The standing their properties. For the single crystal Nb3O7(OH), the

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FTO substrate was observed, due to the completely suppressed NbCl5 hydrolysis. In the absence of HCl (water was used as reaction solution), NbCl5 precursor rapidly hydrolyzed to form Nb(OH)5, which is subsequently dehydrolyzed to form Nb2O5 precipitates (Figure S5B, Supporting Information). The formation of Nb3O7(OH) could occur only when the rate of hydrolysis of NbCl5 is precisely controlled by a suitable concentration of HCl (Figure 1B).[28] The as-synthesized Nb3O7(OH) single crystal nanorod lms on FTO substrate without calcination were dyed and directly used as the photoanodes for DSSCs. For comparison, Nb2O5 single crystal nanorod lms and Nb2O5 nanoparticle lms were also used as photoanodes for DSSCs measurement. The Nb2O5 single crystal nanorod lms with an average thickness of 11.2 m (Figure S6A, Supporting Information) were obtained by thermal treatment of Nb3O7(OH) single crystal nanorod lms at 450 C for 2 h. The Nb2O5 nanoparticle lms with an average thickness of 12.1 m (Figure S6B, Supporting Information) were fabricated Figure 2. Schematic illumination of atomic structure transformation from orthorhombic Nb3O7(OH) to monoclinic Nb2O5 during calcination. (A) orthorhombic Nb3O7(OH); (B) on FTO substrates by combining sol-gel [21] monoclinic Nb2O5. The locations of OH groups are highlighted by blue cycles in Figure 2A. method and screen-printing technique. Atom colour code: greenNb, redO, blackH; green octahedron: [NbO6]. All photoanodes were sensitized with dye N719 (3 104 mol/L) for 24 h before DSSCs measurement.[34] as-synthesized Nb3O7(OH) exhibits a strong absorption peak at The performance of DSSCs assembled with the dye sensitized 3400 cm1 due to the stretching vibration of NbOH,[28,30,31] photoanodes was evaluated under the standard AM 1.5 simua peak at 1680 cm1 attributed to OH in-plane bending vibralated sunlight (100 mW/cm2). Figure 3 shows typical photocur[28,30] 1 1 tion, and two peaks at 873 cm and 530 cm assigned to rent density-photovoltage curves (JV curves) of the resulting NbO stretching and NbONb angular vibrations, respectively (curve a in Figure S3, Supporting Information).[31] The disappearance of absorption peaks at 3400 cm1 and 1680 cm1 for 16 the calcined sample (curve b in Figure S3, Supporting Information) conrms the removal of OH groups.[28] Importantly, 14 the peak resulting from the NbO stretching vibration is blueshifted from 873 cm1 to 912 cm1 after calcination, suggesting 12 the existence of theoretically predicted OHO hydrogen bond 10 in Nb3O7(OH).[29] The crystal structure change was also conrmed by XPS data. The XPS spectra of Nb 3d can be assigned 8 to the binding energy of Nb 3d5/2 and Nb 3d3/2 electrons, respec[20,30] For O 1s, a tively (Figure S4A, Supporting Information). 6 Nb3O7(OH) nanorod film main peak at 530.2 eV due to the oxygen anions (O2) bound to Nb2O5 nanorod film the niobium in the lattice is recorded for both Nb3O7(OH) and 4 Nb2O5 nanoparticle film Nb2O5, but an additional peak at 532.8 eV is obtained from the as-synthesized Nb3O7(OH) sample, conrming the presence of 2 OH groups (Figure S4B, Supporting Information).[20,32,33] 0 When NbCl5 is used as the precursor, a precise controlled 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 hydrolysis rate is the key for direct growth of single crystal Voltage (V) Nb3O7(OH) nanorod lm on FTO substrate. In this work, HCl is used to control an apt acidic reaction environment. With high concentration HCl (e.g., 10.2 M), a porous structure resulted Figure 3. Photocurrent as a function of photovoltage for DSSCs assemfrom the substrate etching was observed (Figure S5A, Supbled with single crystal Nb3O7(OH) and Nb2O5 nanorod and Nb2O5 porting Information). No formation of niobium oxide on the nanoparticle lm photoanodes.

Current Density (mA/cm )

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DSSCs. The Nb3O7(OH) photoanode possesses a highest shortcircuit current densities (Jsc) of 15.00 mA/cm2 that is almost 1.3 times of both Nb2O5 nanorod and nanoparticle photoanodes. A 740 mV of open-circuit voltages (Voc) was obtained from the Nb3O7(OH) photoanode, which is 9 mV less than that of the Nb2O5 nanorod photoanode, but 78 mV greater than that of the Nb2O5 nanoparticle photoanode. The Nb2O5 nanoparticle photoanode exhibits a lower Voc than that of the Nb2O5 nanorod photoanode could be attributed to a number of reasons such as the higher electron transport resistance of the nanoparticles and larger dark current resulting from the reduction of triiodide at the nanoparticle photoanode.[35] The similar Voc values obtained from the single crystal Nb3O7(OH) and Nb2O5 nanorod photoanodes could be due to the similarity in their conduction band edge positions, which deserves a further investigation. The measured ll factor of 61.0% from the Nb3O7(OH) photoanode is the same when compares to the Nb2O5 nanoparticle photoanode but 8% lower than that of Nb2O5 nanorod photoanode. As a result, the Nb3O7(OH) photoanode exhibits a highest conversion efciency ( = 6.77%) that is 12% and 45% higher than that of the Nb2O5 nanorod and nanoparticle photoanodes, respectively. The key characteristics of these photoanodes are summarized in Table 1. It is obvious that the highest Jsc is the main attribute for the dramatically improved DSSCs performance using the Nb3O7(OH) photoanode, which could be ascribed to the attributes such as dye loading capacity, light utilization efciency and photoelectron transport. A higher dye loading on photoanodes normally leads to a higher photocurrent density.[15,34] The Nb3O7(OH) photoanode shows a highest dye loading of 1.62 107 mol/cm2, which is 16.6% and 44.6% higher than that of Nb2O5 nanorod and Nb2O5 nanoparticle photoanodes, respectively (Table 1). This superior dye loading capacity of the Nb3O7(OH) nanorod lm could be attributed to its large surface area as demonstrated in Figure S7 (Supporting Information). A specic surface area of 104 m2/g with a narrow pore size distribution centered at 19.5 nm was obtained from the Nb3O7(OH) nanorod lm, which is 1.46 and 3.97 times higher than that of Nb2O5 nanorod (71.0 m2/g) and nanoparticle (26.2 m2/g) lms, respectively (Table 1). The decreased specic surface area for the Nb2O5 nanorod lm resulted from the calcination of the Nb3O7(OH) nanorod lm could be due to the formation of nanorod bundles during the calcination process (Figure S2B, Supporting Information). These conrm the high amount of dye loading beneted from

(A) 80
Diffuse Reflectance (%)
70 60 50 40 30 20 10 0 200 300
Nb3O7(OH) nanorod film Nb2O5 nanorod film Nb2O5 nanoparticle film

400 500 600 Wavelength (nm)

700

800

(B) 80
70 60 50 40 30 20 10 0 400
Nb3O7(OH) nanorod film Nb2O5 nanorod film Nb2O5 nanoparticle film

IPCE (%)

500

Wavelength (nm)

600

700

800

Figure 4. (A) Diffusive reectance spectra and (B) Incident photon to current conversion efciency (IPCE) curves of the single crystal Nb3O7(OH) and Nb2O5 nanorod and Nb2O5 nanoparticle lms with similar thickness.

Table 1. Photovoltaic properties of the DSSCs assembled by using photoanodes made of Nb3O7(OH) and Nb2O5 nanorods and Nb2O5 nanoparticles with similar thickness.
Photoanodes Thickness Surface Area Jsc Voc [m] [m2/g] [mA/cm2] [mV] Nb3O7(OH) Nanorod Nb2O5 Nanorod Nb2O5 Nanoparticle 11.5 11.2 12.1 104 0.6 71.0 0.3 26.2 0.1 15.00 12.20 11.57 740 749 662 FF [%]

[%]

Adsorbed Dye [107 mol/cm2] 1.62 1.39 1.12

61.0 6.77 66.0 6.03 61.1 4.68

the high specic surface area is a major contribute for the improved performance of DSSCs assembled with Nb3O7(OH) nanorod photoanode. However, the presence of the surface functional group OH in Nb3O7(OH) could also be a attribute for the high dye loading capacity. A high Jsc could also be resulted from enhanced light utilization efciency.[8,9,15,34,36] Figure 4A shows the diffuse reectance spectra of the three photoanode lms with similar thickness. Among the three lms, the Nb2O5 nanorod lm exhibits the highest light reectance ability over the entire visible and near-infrared regions, indicating a superior light scattering property of the Nb2O5 nanorod lm.[8,9,15,34,36] This could be due to the formation of nanorod bundles during the calcination process (Figure S2B, Supporting Information). Although the Nb2O5 nanorod photoanode exhibits higher light utilization efciency, the signicantly lower surface area makes its dye loading capacity much lower than that of the Nb3O7(OH) nanorod photoanode, leading to a lower conversion efciency, as conrmed by the measured incident photon to current conversion efciency (IPCE) spectra (Figure 4B).

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The electron transport inside photoanode is also a key factor affecting the Jsc that can be investigated by an electrochemical impedance spectroscopy (EIS) technique.[22,37] The Nyquist plots of DSSCs assembled by the three photoanodes display a small and a large semicircle within low and high frequency regions, attributing to the electron transfer at the oxide/dye/electrolyte interfaces and the redox reaction of I/I3 at the Pt/electrolyte interface, respectively (Figure S8, Supporting Information).[10,37] The measured semicircular radius within the low frequency region suggests a charge transfer resistance order of Nb2O5 nanoparticle lm>Nb3O7(OH) nanorod lm>Nb2O5 nanorod lm. The electrons lifetime (n) was calculated from the Bode plots (inset in Figure S8, Supporting Information) using n = 1/(2fmax), where fmax refers to the peak frequency.[22,38] The calculated n values for Nb3O7(OH) nanorod, Nb2O5 nanorod and nanoparticle photoanodes are 17.7, 22.7 and 7.98 ms, respectively. The n value of the Nb2O5 nanorod lm is slightly higher than that of the Nb3O7(OH) nanorod lm, attributing to the high crystallinity of single crystal nanorods. These results also suggest that the high dye loading capacity of the Nb3O7(OH) nanorod photoanode beneted from the large surface area is the decisive factor for the obtained high DSSCs efciency. In summary, the Nb3O7(OH) single crystal nanorod photoanode with high surface area of 104 m2/g have been successfully synthesized onto FTO substrates via a facile hydrothermal method. An overall light conversion efciency of 6.77% can be obtained from a DSSC assembled with the Nb3O7(OH) single crystal nanorod lm photoanode without the need for further calcination. The high DSSCs performance is attributed to the high dye loading capacity of the photoanode resulted from the high specic surface area. This work demonstrates a feasibility of assembly high performance DSSCs using alternative metal oxide photoanode materials such as Nb3O7(OH) single crystal nanorod lm.

Experimental Section
Synthesis of single crystal Nb3O7(OH) nanorod lm. In a typical synthesis, 0.5403 g of niobium (V) chloride (NbCl5, Aldrich) was dissolved in a 40 mL of 5.1 M hydrochloric acid (HCl, 32%, SigmaAldrich) solution. After stirring for 2 min, the resulting reaction solution was transferred into a Teon-lined stainless steel autoclave with an volume of 100 mL. Subsequently, a piece of pre-treated FTO conducting glass (15 /square, Nippon Sheet Glass, Japan) with conductive facing up was immersed into the above solution. The hydrothermal reaction was performed at 210 C for 24 h. After hydrothermal reaction, the autoclave was cooled to room temperature and then FTO substrate was taken out, rinsed adequately with deionized water and allowed to dry in a nitrogen stream. The dried Nb3O7(OH) nanorod samples were further characterized and tested in DSSCs. The single crystal Nb2O5 nanorod lms were obtained by thermal treatment of single crystal Nb3O7(OH) nanorod lms at 450 C for 2 h. The Nb2O5 nanoparticle lm was fabricated by combination of sol-gel method and scree-printing technique.[21] Nb2O5 nanoparticles were rst obtained by sol-gel method and calcination at 450 C for 2 h. Subsequently, the fabricated Nb2O5 nanoparticles were scree-printed on FTO substrates. After annealing at 450 C for 1 h, the Nb2O5 nanoparticle lm was used as photoanode for DSSC measurement. Characterization: SEM (JSM-6300F), TEM (Philips F20), and XRD (Shimadzu XRD-6000 diffractometer) were employed for characterizing the prepared samples. FT-IR analysis of the samples was performed

using a Nicolet Nexus 870 FT-IR spectrometer with a smart Endurance single-bounce diamond ATR cell. Chemical compositions of the samples were analyzed by X-ray photoelectron spectroscopy (XPS, Kratos Axis ULTRA incorporating a 165 mm hemispherical electron energy analyzer). Nitrogen adsorption-desorption isotherms of the samples were obtained on a Quantachrome Autosorb-1 surface area and pore size analyser. The pore size distributions of the samples were derived from the adsorption branches of the isotherms based on the BarettJoynerHalenda (BJH) model. Diffuse reectance spectra of the lms were recorded on a Varian Cary 5E UV-vis-NIR spectrophotometer. Dye loading measurements were conducted by desorbing the dye molecules from the dye-anchored photoanode lms in NaOH ethanolic solution (104 M).[39] The loading amount was calculated from the absorbance of the completely desorbed dye solutions by the spectrophotometer (Varian, Cary 4500). Theoretical Calculations: All computations are performed using the Vienna ab initio simulation package (VASP) based on the all-electron projected augmented wave (PAW) method.[40,41] A plane-wave basis set is employed to expand the smooth part of wave functions with a kinetic energy cut-off of 520 eV. For the electron-electron exchange and correlation interactions, the functional of PBE,[42] a form of the general gradient approximation (GGA), is used throughout. The Brillouin-zone integrations were performed using Monkhorst-Pack grids of special points, with gamma-point centered (2 8 8) k-points meshes used for the bulk cells. When the geometry is optimized, all atoms are allowed to relax. A variable cell technique is employed to simultaneously optimize the lattice constant and the atomic structure to encounter the complexity and low-symmetry of the Nb3O7(OH) crystals. And the lattice constants and geometric structure are optimized until the residual forces were below 0.001 eV/. Measurements: A series of DSSCs were fabricated with traditional sandwich type conguration by using a dye-anchored nanostructured lm and a platinum counter electrode deposited on FTO conducting glass. A mask with a window area of 0.15 cm2 was applied on the niobium oxide photoanode lm side to dene the active area of the cells. A 500 W Xe lamp (Trusttech Co., Beijing) with an AM 1.5G lter (Sciencetech, Canada) was used as the light source. The Light intensity was measured by a radiant power meter (Newport, 70260) coupled with a broadband probe (Newport, 70268). The photovoltaic measurements of DSSCs were recorded by a scanning potentiostat (Model 362, Princeton Applied Research, US). The IPCE as a function of wavelength was measured with QE/IPCE measurement kit (NewSpec). Impedance measurements were performed with a computer-controlled potentiostat (CHI660D, CH Instruments). The frequency range is 0.1 Hz to 1 M Hz and the magnitude of the modulation signal is 10 mV.

Acknowledgements
This work was nancially supported by Australian Research Council (ARC) Projects. Received: December 5, 2011 Revised: January 29, 2012 Published online:

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