Electrochimica Acta 54 (2008) 821828

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Size effects on the photoelectrochemical activities of single wall carbon nanotubes

Chen-Zhong Li a, , Won-Bang Choi b , Cheng-Hsin Chuang c
a Nanobioengineering/Bioelectronics Lab, Department of Biomedical Engineering, Florida International University, EC 2612, 10555 W. Flagler Street, Miami, FL 33174, USA b Department of Mechanical & Materials Engineering, Florida International University, 10555 W. Flagler Street, Miami, FL 33174, USA c Department of Mechanical Engineering & Institute of Nanotechnology, Southern Taiwan University, Taiwan

a r t i c l e

i n f o

a b s t r a c t
This paper reveals an improved photoelectrochemical activity of single wall carbon nanotube (SWNT) with respect to enhanced photo-induced currents as they are shortened at a few nanometer sizes. Raman spectroscopy, photoelectrochemistry and scanning electronic microscopy (SEM) characteristics indicate a uniform nite-sized SWNT lm with distinct physical and photochemical properties. Unlike p-type semiconductive pristine SWNTs, both cathodic photocurrent and anodic photocurrent are observed on shortened SWNT formed thin lms. The incident photon conversion efciency is eight-fold higher compared to the longer SWNTs, suggesting the electronic structure and photoelectrochemical properties of SWNTs are signicantly altered by shortening the length of SWNT. The improved photoelectrochemical activities open a new perspective to use nite-sized SWNTs in combination with other semiconducting materials for fabrication of efcient optoelectronic devices, nanotube optical detectors or emitters that can be operated across a wide range of optical wavelengths. 2008 Elsevier Ltd. All rights reserved.

Article history: Received 4 April 2008 Received in revised form 19 June 2008 Accepted 19 June 2008 Available online 4 July 2008 Keywords: Single walled carbon nanotubes Photoelectrochemistry Solar cell Photo energy Photocurrent Size effects Finite

1. Introduction The remarkable electronic and mechanical properties of nanoscale carbon-based materials (fullerene and carbon nanotubes) with strong covalent sp2 carbon bonds have a tremendous potential application for nanoelectronic devices. One of the key features of nanoscale carbon-based materials (fullerene and carbon nanotubes) is their photoactivity and potential to function as optoelectronic device elements [14]. The extraordinary electronacceptor properties of fullerenes have resulted in noteworthy advances in the application of the carbon material as a basic building block for the conversion of solar to electrical energy. Single wall carbon nanotubes (SWNTs) can be viewed as an extension in one dimension of different fullerene molecular clusters or as a strip cut form an innite graphene sheet that rolls up to form a tube. Fundamental research of band gap uorescence from individual SWNTs provides a basis for applications of SWNT as optical materials for the solar to electrical energy conversion system [5]. Unlike semiconducting material, silicon, SWNTs have a direct band gap in the momentum space, which induces interband transitions

Corresponding author. Tel.: +1 305 3480120; fax: +1 305 3486954. E-mail address: licz@u.edu (C.-Z. Li). 0013-4686/$ see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.electacta.2008.06.059

and direct light absorption and emission without photon intervention. In particular, the seemingly ideal features of optical excitation together with the recombination across pairs of van Hove peaks lead to the potential use of carbon nanotubes in the areas of light-reduced electron-transfer chemistry and solar energy conversion [68]. Indeed, photo-generated currents from CNTs have been reported by several groups [9,10]. Notably, individual semiconducting SWNTs in a eld-effect transistor (FET) can emit polarized light, while illumination of the FET devices generates signicant photocurrent, in agreement with theoretical estimation by Steward et al. [11]. Unlike fullerene-based lm with n-type (photo-induced oxidation) photoactivity [2], a p-type photoelectrochemical feature has been reported by Kamat and co-workers on a SWNT lm-based opto-system [12,13], wherein they deposited unformed SWNT lms on optically transparent electrodes electrophoretically and measured the resulting photoactivity under excitation by visible light. The large photo-current generation of multi wall carbon nanotubes has also been reported [14]. Despite the signicant improvement of photon-to-current conversion efciencies achieved using SWNT conjugated polymer materials [15,16], only very low efciency was obtained on pure SWNT lms. It has been reported that the electronic structure of SWNTs is largely relied on the CNTs diameter, chirality, and length. Besides the electrical properties, the optoelectronic properties of

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nanotubes may also be tailored by selecting the length accordingly. Venema et al. [17] have prepared carbon nanotubes into segments of a few tens of nanometers in length and proved that the band gap increased with a decrease in the tube length. Conceptually, as the length of a SWNT is reduced, the size of SWNT eventually approaches the limit of a fullerene molecular cluster with a band gap from 1.5 to 2.3 eV [18,19]. Based on this basis, nite-sized SWNTs might be considered as promising materials, which are similar to fullerene for manufacturing optoelectronic devices with better photon-to-current conversion efciencies. This paper presents a novel photoelectrochemical property of nitesized SWNT in term of an enhanced photoactivity when the length of SWNT is decreased. An improved photocurrent on nite-sized SWNT modied gold electrodes; with energy conversion efciency eight-fold higher compared to pristine SWNT modied electrodes. In particular, diode-like characteristics of nite-sized SWNTs are observed in terms of the generation of both cathodic (electron current) and anodic (hole current) photocurrent upon the different applied potentials. The structure and the physical properties of the nite-sized SWNT lm derived by electrophoretic deposition are further characterized by Raman and scanning electronic microscopy (SEM). 2. Instruments and methods 2.1. Instruments Photoelectrochemical measurements were conducted in a home-made three electrode cell with a round (5 mm diameter) quartz window at oxygen-free condition. An Oriel arc lamp source (Newport Oriel Instruments, Irvine, CA) with an Osram XBO 150-W xenon lamp was used for UV illumination. A grating monochromator (Oriel) was introduced into the path of the excitation beam for selecting the wavelengths. The light intensity was measured with a Melles Griot hotometer (Melles Griot Optics, Irvine, CA). Currentvoltage characteristics were measured using an EG&G potentiostat (PerkinElmer, Princeton Applied Research, Oak Ridge, TN). AC impedance characterization was performed using the same EGG potentiostat. Impedance obtained at 220 mV versus Ag/AgCl in the presence of 1 mM ferro/ferri cyanide redox electrolytes was superimposed on a sinusoidal potential modulation of 5 mV. The data was measured and collected for 31 harmonic frequencies from 100 kHz to 100 MHz. The impedance data obtained from the bare gold electrode, pristine SWNTs and nite-sized SWNTs modied gold electrodes was analyzed using the ZSimpWin software (Princeton Applied Research). In all impedance spectra, symbols represent the experimental data and the solid lines represent the tted curves. 2.2. Materials SWNTs obtained from Carbon Nanotechnologies (Houston, TX) are synthesized by a modied gas phase process and remove large catalyst particles with a purity of about 99%. The shortened SWNTs are prepared from pristine SWNTs (Carbon Nanotechnologies) according to the previous report [20]. Finite-sized SWNTs were made following an ultrasonic process for over 3 h in dilute ceric sulfate (CS) at room temperature. Mid-sized SWNTs with 100500 nm in length were obtained by controlling the sonication times. The main by-products in this process were amorphous carbon and graphitic nanoparticles. Resulting samples were centrifuged (10,000 rpm for 30 min), followed by the removal of the supernatant. The CNTs were neutralized, dispersed in NaOH and washed with water followed by recentrifugation. In order to com-

pletely remove CS from the samples, this procedure was repeated 10 times until no UV characteristics (peak at 264 nm) of CS were observed. The SWNT suspension was further ultraltered using 0.1 m pore sized membrane lters (Schleicher-Schuell; cellulose nitrate, diameter 90 m) to remove amorphous carbon impurities. The acid-treated product was puried by gas phase oxidation at a heating rate of 5 C/min in air from room temperature to 600 C, leaving the SWNTs with a weight of 40% of the initial raw materials. 2.3. Electrode preparation The SWNT lm was electrodeposited on electrode surfaces according to Kamat and co-workers [12]. Briey, SWNTs were negatively charged by mixing with tetraoctylammonium bromide (TOAB) in tetrahydrofuran (THF). Sonication of the mixture for 30 min yields a stable dark suspension. Then the solution was washed with THF by several cycles of centrifugation and resuspension to remove unbound TOAB in the solution. After the solvent removal, the charged SWNTs were dried. The dried materials consisting of TOAB modied SWNTs was re-suspended in 10 mL of THF and sonicated for 20 min. A home-made electrophoretic deposition cell, including two 8 mm 42 mm gold coated silicon plates, a quartz cuvette and a voltage source, was used to deposit SWNTs on the gold substrate. A 50 V/cm dc voltage was applied on the two conducting gold plates and SWNTs started to move towards the positive electrode. Under the inuence of a dc electric eld, SWNTs assembled as stretched bundles were anchored on the positive electrode within a few minutes. Similarly, the electrophoretic deposition approach was also employed to cast the carbon black or graphite lm on gold substrates. 3. Results and discussions The size control of carbon nanotubes would allow the investigation of the electronic properties at different length scales, towards the advanced utilization of nanotubes in device applications. In this experiment, appropriate conditions for the treatments were found to depend greatly on the nature of the starting material. Accordingly, the reaction conditions and production of each step was carefully examined and characterized by Raman and TEM to avoid over destruction of SWNTs. To date, numerous methods to cut SWNTs into shorter segments have been reported including acidic or uorinating treatment. We have recently reported that ceric sulfate (CS) treatment with sonication leads to the transformation of SWNTs to nanocrystalline carbon materials. By combining the wet chemical oxidation process (acidic treatment) and dry purication process (high temperature oxidation), most impurities including carbonaceous materials and the metal catalyst have been removed. By carefully controlling the experimental conditions, nite-sized carbon nanotubes could be obtained, which are relatively unscathed with a tubular structure. In addition, carbon black and graphite powder-based electrodes have been investigated as control samples to better understand the photoelectrochemical properties of carbon nanotubes. 3.1. Characterization of SWNT-based lm By varying the sonication time in acid solution, selected length of SWNTs were obtained. AFM and TEM (Fig. 1) enabled us to monitor the progressive decrease in SWNT length with different sonication time. The longer distribution of SWNTs (>1 mm) shown in Fig. 1A1 and B1 was the pristine SWNTs. After 1 h treatment by CS, the tubes were cut into shorter segments with length from 200 to 400 nm (Fig. 1A2 and B2). Further sonication for 3 h resulted

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Fig. 1. AFM (A) and TEM (B) images showing the pristine SWNTs (A1 and B1); middle-sized SWNTs (A2 and B2); and nite-sized SWNTs (A3 and B3). Magnications used in each case are shown on the respective images.

in carbon nanotubes ranging from 10 to 100 nm, which still displayed a good tubular structure as indicated in Fig. 1A3 and B3. A closer inspection of some isolated tubes showed the tendency of the nite-sized SWNTs to aggregate to form super ropes in order to minimize the newly exposed surfaces. Although some of SWNTs might be completely destroyed at this stage, most remained as onedimensional structures after being ultra-shortened (Fig. 1B3), and their tubular structure was evidenced further by Raman measurements as discussed later. Under the applied dc eld (50 V), the TOBE-capped SWNTs were assembled on the positive gold electrode. After only 10 min, the black SWNTs suspension became transparent due to the depo-

sition of SWNT onto the gold substrate, while a uniform SWNT layer was formed on the gold surface. The estimated amount of the deposited SWNTs was 0.2 mg cm2 by weighting the solution in the deposition cell before and after deposition. SEM was also used to characterize the SWNT lms formed by pristine SWNTs and shortened SWNTs. As shown in Fig. 2A, many SWNTs bundles and SWNTs loops several micrometers in size were assembled as a uniformed but rough layer on the electrodes. In contrast, the deposition of shortened SWNTs resulted in a much smoother lm due to the nite size of the SWNTs (Fig. 2B). An articial physical defect contained SWNT lm was selected to measure the lm thickness. The average thickness of the SWNT lm was determined

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Fig. 2. The SEM images of pristine SWNT-based lm (A), and the nite-sized SWNT formed lm (B). The inset of (A) shows an enlarged view of pristine SWNT bundles on the surface.

up to 50 m according to the surface prole of SEM image. Fig. 3 shows the Raman spectrum of the pristine SWNT lm, the nitesized SWNT lm and two control samples; graphite and carbon black powders. Fig. 3 shows a comparison over a broad frequency range from 0 to 3500 cm1 , between the spectrums of these carbonbased lms on gold substrates with the same excitation laser source (531 nm, 2.31 eV). As expected, the Raman spectrum of pristine SWNTs (Fig. 3a) exhibits the radial breathing mode (RBM) frequencies in the range 150190 cm2 . However, the lineshape change at the radial breathing mode of the nite-sized SWNT was noted as a broadened and suppressed feature, corresponding to the retained tubular structure and the enrichment of defects [21]. The tangential stretch G band in terms of a narrow Lorentzian lineshape 1585 cm1 with a broad Bret-Wigner-Fano shoulder at 1574 cm1 further conrms that the pristine SWNT retains its intact morphology after the process of electrodeposition, in agreement with the literature data [22]. Different from the over destructed SWNTs as we previ-

ously reported [20], in which a complete disappearance of the RBM was obtained, the lineshape change at the radial breathing mode of the nite-sized SWNT was noted as a broadened and suppressed feature, corresponding to the retained tubular structure and the enrichment of defects. After the shorten process, the most obvious effect is the appearance of a strong band at ca. 1364 cm1 with an increased 1364 cm1 /1585 cm1 intensity ratio compared with longer SWNTs. The increased intensity of the D-band at 1364 cm1 reects the nanoscale structure of nite size SWNTs that exhibit higher photon density [23]. Furthermore, the weak Raman intensity at intermediate frequency (5001200 cm1 ) and the lack of the other semiconduction associated Lorentzian feature, could be contributed from the vibrations along the direction of the nanotube axis, indicating the SWNTs are ultra-shortened by the shortening process. It has been known that an increase of the order in carbonaceous materials is reected by an increase in the frequency of the G mode as well as a decrease of its bandwidth [24]. Fig. 3b shows the Raman spectrum of the nite-sized SWNT deposited on gold substrate in comparison with the two reference materials of graphite powders, sp2 hybridized carbon atoms in a multi-planar hexagonal structure (Fig. 3c) and the carbon black, amorphous carbon with a disorder carbon structure (Fig. 3d). The band frequencies of the graphite lm and the carbon black-based lm are quite similar to previously published spectrums of graphite and carbon black powder [25,26]. Clear differences can be extracted from Fig. 3ac when comparing the bandwidth at the G band of the amorphous carbon black (Fig. 3d). The narrower G modes indicate a retained polycrystalline graphitic structure of SWNTs when they are shortened to a nite size. Similar to our previously reported data, over 10 h of sonication in CS resulted in the total destruction of SWNTs and no tubular features were observed. 3.2. Photoelectrochemical measurements Photocurrent measurements with the electrodes modied with different carbon materials were performed in an electrolytic aqueous phosphate buffer solution (0.1 M, pH 8.5) containing a ferri/ferro cyanide redox couple. The regenerative Fe2+ /Fe3+ redox couple facilitates the charge transporter at the electrode surfaces and thus enables the delivery of photocurrent. As a ferro/ferricyanide electrolyte is effectively transparent in the 300900 nm region, the deleterious effect in terms of losing incident photons through competitive electrolyte light absorption will be prevented. Photocurrents with white light were recorded, conrming the photoactivity of the SWNT lm on the gold electrodes.

Fig. 3. Raman comparison of (a) pristine SWNT lm; (b) nite-sized SWNT lm; (c) graphite-based lm; and (d) carbon black taken with 532.1 nm (2.31 eV) laser excitation on gold substrates. Inset shows the enlarged G-bond for comparison.

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Fig. 4. (A) Potential dependence of photocurrent, obtained on a nite-sized SWNT modied gold device in the dark (black) and under illumination of white light (red). (B) Time traces of the cathodic photocurrent at 0.75 V (vs. Ag/AgCl) applied electric eld; and (C) Time traces of the anodic photocurrent at +0.75 V (vs. Ag/AgCl) with a monochromatic incident light chopped, respectively. In (B) and (C), the upper two traces (a) are taken at pristine SWNT lms, the middle two (b) are taken at middle-sized SWNT (200500 nm) formed lms, and the lower two (c) are taken at nite-sized SWNT modied electrodes in phosphate buffer solution (0.1 M, pH 8.5) that contained 1 mM Fe(CN)6 3/4 redox species. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of the article.)

p-Type features of the pristine SWNTs were evident by the cathodic photocurrent generation because only the photo-generated holes of SWNTs were able to migrate from the gold substrate to the counter electrode. However, with the positive bias on the SWNT modied surface, no photo-induced anodic current was observed. Fig. 4A presents photocurrentvoltage curves for the nite-sized SWNT lm measured under dark (dark current) conditions and light illumination (photocurrent). With a positive bias, a manifest increased anodic current (electron current) was obtained with increasing pos-

itive potentials. In both cases, a steady ow of cathodic currents (photo-induced) was observed, and the photocurrent magnitude was dependent on the applied potential with respect to a decreasing of cathodic photocurrent (hole current) when the applied potential becomes negative. The current spikes are visible with chopping of the incident light. When the light was turned on, in all three cases the cathodic currents decreased (Fig. 4B), while only the nite-sized SWNT modied electrode displayed the anodic current spikes in the opposite direction (Fig. 4B, c).

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CNTs on the gold electrodes. The surface characterization results showed that both carbon black and graphite power can form a uniformed thin lm with comparable surface coverage and the thickness of CNT. However, the carbon black-based lm was not photoactive and the graphite formed lm only produced very small or negligible photocurrents indicating the unique photo-electro activities of efcient generation of photocurrents of nite-sized SWNTs. 4. Discussions We have shown experimentally the size effects of SWNTs on their optical properties and photoactivities. Generally, the mechanism for the photocurrent generation of carbon-based materials involves photo-excitation of hot carriers (electron and hole) and a so-called charge separation process in terms of the migration of the hot electrons to the electrode surface (or supply of electrons from electrode to the valence-band holes) [7]. The hot electrontransfer rate associated with the conductivities of the SWNT thin lm plays an important role for photocurrent generation. Therefore, it is essential to understand how the conductivity will be alternated by chemically shortening the SWNT. SWNTs have been reported to signicantly enhance the photocurrent generation in a photo system based on SWNT-Cds nanoparticle composite [36], in which SWNT acted as a transport path of the conduction-band electrons. Therefore, the assumptions of conductivity effects and electronic structure changes, which are directly related to the hot carriers and charge separation process, can be made to interpret the improved photoactivities of SWNTs. Electrochemical impedance spectroscopy (EIS) has been extensively used to characterize various thin lms [28,29] as is has the capability of giving interfacial information on capacitance and resistance, charge properties and the disorder of the lm [30]. The impedance method is based upon a measurement of the response of the electrochemical cell to a small-amplitude alternating potential. The length changes of the SWNT lm on the gold surface must affect a change in the AC response, such as charge-transfer resistance and lm capacitance. Data analysis of EIS characterization requires modeling the electrode kinetics with an equivalent circuit consisting of electrical components. For thin lm measurements, a commonly accepted equivalent circuit is based on the Randles model [31] as shown in inset of Fig. 6A. Fig. 6 compares Nyquist plots of impedance spectroscopy on gold surfaces modied with SWNTs and shortened SWNTs in the presence of equimolar (1 mM) Fe(CN)6 4/3 and measured at the formal potential. For the nite-sized SWNT modied surface, the charge-transfer resistance RCT , the diameter of the semicircle at high frequency, is clearly greater than RCT of the pristine SWNT modied surface. In addition, the low frequency linear-mass-transfer region is not observed on the nite-sized SWNT lm due to the electron-transfer reaction which is under kinetic control over the entire frequency range. Notice that the semicircle measured at the pristine SWNT modied electrode is poorly dened which is due to a fast electrode reaction, while it is well dened at the pristine SWNT modied electrode. The charge-transfer resistance RCT increases from 60 to 3378 cm2 , and the double-layer capacity C drops to 2.49 F cm2 . This data indicates that the improved photoactivities are not the consequence of the conductivity alternation since the lowered conductivity will decrease hot electron transfer. Thus, the enhanced photocurrent generation of shorten SWNTs is more likely related to the photo-excitation of hot holeelectron pair rather than the charge separation process. Research predictions have pointed out that the electronic structure of SWNTs plays a major role in the hot electronhole generation and the mechanical deformation and a high electrostatic eld can

Fig. 5. Photoaction spectrum of gold electrodes modied with ( ) nite-sized SWNTs and ( ) and pristine SWNTs, respectively.

The effect of the lengths of the SWNTs on the generation of photocurrent was further investigated by using different sized SWNTs. Fig. 4 also shows time-resolved traces of the photocurrent at 1.0 and +1.0 V applied potential on the gold electrodes modied with pristine SWNTs (Fig. 4B, a), middle-sized SWNTs (200 nm < 400 nm) (Fig. 4B, b) and nite-sized SWNTs (<40 nm) (Fig. 4B, c), respectively. An increase in photocurrent as the length of SWNTs decreased was clearly identied, although precise estimation of the size effect on the photocurrent generation was difcult due to the separation and purication of shortened SWNTs. As the electrochemical cells were not optimized for the best possible photocurrent generation in terms of the lm thickness, the impurities of SWNTs, the substrate materials and composition of the electrolyte, the monochromatic incident photon-to-current conversion efciency (IPCE) was generally low compared to many semiconductor lms. The IPCE is dened as the number of electrons collected per incident photon and this quantity is dened as IPCE (%) = 100 (Isc 1240)/Linc , where Isc is the short circuit photocurrent (A cm2 ), Linc is the incident light intensity (W cm2 ), and is the excitation wavelength (nm) [27]. The photocurrent action spectrum of pristine SWNT lm, i.e., a plot of the observed IPCE% as a function of the incident wavelength, was compared with the nite-sized SWNT lm (Fig. 5). In contrast to the range of incident light that enables the generation of a measurable photocurrent on the pristine SWNT formed lm, the photocurrent response resulting from the nite-sized lm covered a relatively broader visible window (350650 nm) of the incident light. The wavelength near 450 nm appeared to be most effective in producing photo-current on the nite-sized SWNT lm, whereas the pristine SWNT coated electrode showed the maximum IPCE% upon irradiation at 400 nm light. The IPCE of the nite-sized SWNT lm was estimated as 0.6% under 1 mW cm2 illumination at = 450 nm, i.e., eight-fold higher compared with pristine SWNT formed lm (IPCE 0.08%). At a constant applied voltage, for both cases the larger photocurrents were measured as the light intensity increased, as expected by an increase in the formation of electronhole pairs. The spectral and light power dependence of photocurrents also ruled out the possibility that electrode heating by the light beam was a source of the observed photocurrents. For potential application of using SWNT as a photoelectrode material, the possible contaminations of amorphous carbon may affect the photoelectrochemical properties. Despite the efforts on the development of sufcient purication of SWNT, the understanding of the photoactive properties of these impurities (such as graphite nanocrystalline and amorphous carbon) will be helpful for design and processing CNT-based photoelectrodes with optimized activities. Therefore, the photoelectrochemical activities of carbon black and graphite thin lms were investigated and then compared with

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IPCE of pristine SWNTs probably could be attributed to the band gap of SWNT (from 0.3 to 0.7 eV) [34], just outside of the optical light range. It has been shown that the nite size effects on the electronic structure of SWNTs results in a reversely increasing band gap with reducing SWNT length. Considering the dependence of electronic band structures of SWNTs on diameter, length and chirality, the enhanced photocurrent nite-sized SWNTs probably could be attributed to the band gap shifting closer to the range of incident light, which is more energetically feasible for sufcient excitation of electrons from the valence band into the conduction band. Therefore, the enhanced photocurrent generation is more likely related to the photo-excitation of hot holeelectron pair rather than the charge separation process. 5. Conclusion Our results have clearly demonstrated an efcient generation of photocurrents by using nite-sized SWNT lm modied electrodes. We observe both anodic photocurrent and cathodic photocurrent on the photoelectrochemical cell with visible light illumination. The results present a new concept for the future design of SWNTbased optoelectronics. The assembly of nite-sized SWNT with other semiconducting solid materials or polymers as solar cell architecture is of interest for further investigation. Experiments using SWNTs with different lengths and different substrates are underway to characterize the photoactivities. Acknowledgments
Fig. 6. Nyquist plots with 1 mM Fe(CN)6 3/4 as redox probe for the pristine SWNT (A) and the nite-sized SWNT (B) modied electrodes. The electrode potential was 0.22 V vs. Ag/AgCl. The solid line is the experimental raw data, and the symbol ( ) represents the tted curves by using the equivalent circuit model shown as inset of (A). The frequency range was 100 kHz to 100 mHz.

This research work is partially supported under grant FA955006-1-0467 and FA9550-07-1-0344 of Department of Defense/Air Force Ofce of Scientic Research and 2008 FIU Faculty Research Award and Wallace H. Coulter Foundation. References

remarkably affect the electronic properties of the tube [7,17,23]. The electronhole pair could be generated in a high energy azimuthal sub-band of SWNTs by photo-excitation, followed by a decay into the lowest sub-band, from which the pair recombines with the emission of a photon. Photo-excited electronhole pairs can be separated and expected to be driven to the electrode interface by an applied electric eld to generate cathodic or anodic photocurrent. The so-called at band potential associated with the kinetics of electrolyte charge transfer has been predicted and corresponds to the change of the photocurrent sign [32]. In this case, the depressed kinetics of charge transfer of ferri/ferro cyanide on the nite-sized SWNT layer probably could negatively shift the at band potential to produce the measurable anodic photocurrent, whereas pristine SWNT lm under the same range of applied potentials would not produce a photo-induced anodic current. A quantitative estimate of the at band potential values for the two cases is a subject of future studies. Research predictions have pointed out that mechanical deformation and a high electrostatic eld can remarkably affect the electronic properties of the tube and could be used for engineering a band gap in nanotube-based molecular scale electronics [33,34]. Considering the dependence of electronic band structures of SWNTs on diameter, length and chirality [35], we could suggest a possible explanation for the improved photocurrent and IPCE of the nite-sized SWNT. Ideally, the optimal values of the band gap of semiconducting materials are from 1.2 to 3.3 eV, which are comparable to the energies of photons whose frequencies lie within the visible light, making them have the potential of creating high efciency photovoltaic devices. Therefore, the lower photocurrent and

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