Communications

[8] J. Pan, W. J. D. Shaw, Microstruct. Sci. 1994, 21, 95. [9] M. P. Farrell, R. G. Kander, A. O. Aning, J. Mater. Synth. Proc. 1996, 4, 151. [10] A. R. Nesarikar, S. H. Carr, K. Khait, F. M. Mirabella, J. Appl. Polym. Sci. 1997, 63, 1179. [11] C. B. Bucknall, Toughened Plastics, Applied Science, London 1977. [12] M. Fischer, G. P. Hellmann, Macromolecules 1996, 29, 2498. [13] I. K. Partridge, in Multicomponent Polymer Systems (Eds: I. S. Miles, S. Rostami), Longman, Harlow 1992, Ch. 5. [14] C. B. Bucknall, I. K. Partridge, M. V. Ward, J. Mater. Sci. 1984, 19, 2064. [15] P. A. Lovell, Trends Polym. Sci. 1996, 4, 264. [16] F. Vazquez, M. Schneider, T. Pith, M. Lambla, Polym. Int. 1996, 41, 1. [17] F. S. Bates, Science 1991, 251, 898. [18] Y. Lyatskaya, D. Gersappe, A. C. Balazs, Macromolecules 1995, 28, 6278. [19] I. Piirma, Polymer Surfactants, Marcel Dekker, New York 1992. [20] J. Sthr, NEXAFS Spectroscopy, Springer, Berlin 1992. [21] H. Ade, X. Zhang, S. Cameron, C. Costello, J. Kirz, S. Williams, Science 1992, 258, 972. [22] H. Ade, in Vacuum Ultraviolet Spectroscopy I, Vol. 32 (Eds: J. Samson, D. Ederer) Academic, San Diego, CA 1998, Ch. 11. [23] A. P. Smith, C. Bai, H. Ade, R. J. Spontak, C. M. Balik, C. C. Koch, Macromol. Rapid Commun. 1998, 19, 557. [24] H. Ade, D. A. Winesett, A. P. Smith, S. Anders, T. Stammler, C. Heske, D. Slep, M. H. Rafailovich, J. Sokolov, J. Sthr, Appl. Phys. Lett. 1998, 73, 3775. [25] S. Spector, C. Jacobsen, D. Tennant, J. Vac. Sci. Technol. B 1997, 15, 2872.

Composites of Carbon Nanotubes and Conjugated Polymers for Photovoltaic Devices**

By Hiroki Ago,* Klaus Petritsch, Milo S. P. Shaffer, Alan H. Windle, and Richard H. Friend It has been shown that composites of p-conjugated polymers and C60 have promise for application in photovoltaic devices, owing to efficient electron transfer from the conjugated polymer to C60 under visible light.[13] In this respect, composites of p-conjugated polymers and carbon nanotubes are of great interest in terms of the novel electronic interaction between these two elements and the mechanical reinforcement of the polymer film. Here, we report on
[*] Dr. H. Ago[+] Department of Molecular Engineering, Kyoto University Kyoto, 606-8501 (Japan) Dr. H. Ago, [+] K. Petritsch, Prof. R. H. Friend Cavendish Laboratory Madingley Road, Cambridge, CB3 0HE (UK) Dr. M. S. P. Shaffer, Prof. A. H. Windle Department of Materials Science and Metallurgy University of Cambridge Pembroke Street, Cambridge, CB2 3QZ (UK) [+] Present address: National Institute of Materials and Chemical Research (NIMC), Tsukuba, 305-8565, Japan. [**] This work was supported by the Engineering and Physical Sciences Research Council (EPSRC). We acknowledge Cambridge Display Technology and, under a contract with AHW, Hyperion Catalysts Inc. for supplying the PPV precursor and raw MWNT, respectively. HA acknowledges the JSPS Research Fellowships for Young Scientists. KP acknowledges the European Commission (TMR network, SELOA). The authors also thank B. Weir and D. Mackenzie for help with the measurements. Adv. Mater. 1999, 11, No. 15

the preparation and optical properties of a composite of multi-walled carbon nanotubes (MWNTs) and poly(pphenylene vinylene) (PPV). We obtained thin and uniform MWNT films by spin-coating the highly concentrated MWNT dispersion, which had been stabilized by chemical oxidation. Composites were realized by introducing the polymer precursor onto the surface of the MWNT film, followed by conversion at high temperature. We fabricated a photovoltaic device from the composite by using MWNTs as a hole-collecting electrode and obtained twice the quantum efficiency of the standard device with an indiumtin oxide (ITO) electrode. This result suggests that the MWNTs, being different from C60, act as a good electrode owing to the formation of a complex interpenetrating network with the polymer chains. The combination of carbon nanotubes with polymers offers an attractive route not only to reinforce polymer films but also to introduce new electronic properties based on morphological modification or electronic interaction between the two components. In particular, the combination of carbon nanotubes with p-conjugated polymers is of interest because their p-conjugation enables the polymers to be used as an active material for light-emitting diodes (LEDs),[4] field-effect transistors (FETs),[5] and photovoltaic devices.[6] The potential interaction between the highly delocalized p-electrons of carbon nanotubes and the p-electrons correlated with the lattice of the polymer skeleton is intriguing. It is noteworthy that the addition of C60 improves the quantum efficiency of p-conjugated polymerbased photovoltaic devices.[13] This effect is a consequence of the efficient exciton dissociation due to electron transfer from the photo-excited polymer to the C60, whose electron affinity is high. These considerations provide the motivation for studying the optical and electronic properties of composites of carbon nanotubes and p-conjugated polymers. The carbon nanotube and polymer composites were initially reported by Ajayan et al., where they mechanically mixed the purified MWNTs with epoxy resin.[7] Since then, attention has been paid to composite materials with uniform and high nanotube loading, mainly focusing on their mechanical properties. Recently, Curran et al. prepared composites of arc-grown MWNTs and the meta-linked poly(p-phenylene vinylene) (PPV) derivatives.[8] They claim that the helical structure of the polymer chain helps the MWNTs disperse in the polymer solution, and that LEDs made with this composite are five times more stable in air compared with devices without the MWNTs. However, when one utilizes the composites for electronic devices, the nanotubes can cause a short-circuit due to their high conductivity. Therefore, we think that lamination or separation of the nanotube and polymer layers is useful when one utilizes the nature of nanotubes. Romero et al. fabricated diodes with double layers of PPV and MWNTs, but the MWNT film, which was prepared by filtration, was so rough that a very thick PPV layer was needed to avoid a
0935-9648/99/1510-1281 $ 17.50+.50/0

WILEY-VCH Verlag GmbH, D-69469 Weinheim, 1999

1281

Communications

short-circuit.[9] In the diode, no photocurrent was observed, probably due to the thick PPV active layer. In this communication, we report the preparation of composites of PPV and MWNTs and photovoltaic devices utilizing the composite. We have oxidized the surface of the MWNTs to attach a hydrophilic or polar surface and obtained a MWNT dispersion, as previously reported by Hiura et al.[10] For this treatment, a MWNT is more suitable than a single-walled nanotube (SWNT) because the inner graphene layers can remain unreacted and the essential electronic structure can be retained. We have employed catalytically grown MWNTs because they are more realistic for the present purpose, i.e., susceptibility to chemical oxidation (they form a dispersed solution with higher concentration and viscosity compared to arc-grown MWNTs[11]) and availability in mass production. From the dispersion of the catalytically grown MWNTs, we have succeeded in obtaining thin and uniform films of MWNTs through spin-coating. The obtained MWNT films were relatively flat but showed a significant degree of roughness, which promises a very high surface area. The composite of MWNTs and PPV was obtained by adding a layer of pure precursor and subsequently converting it at 210 C. We show that the photoluminescence (PL) spectrum of PPV is greatly affected by MWNTs and that the composite may find application in photovoltaic devices owing to the high contact area with the polymer and high work function of the MWNTs. The MWNT films produced by spin-coating appear black and become reflective, depending on thickness and uniformity. In Figure 1a we show the field-emission scanning electron microscopy (FE-SEM) image of the surface of the

spin-coated MWNT film with a thickness of 210 nm. The average outer and inner diameters of the MWNTs were determined to be 10 and 5 nm, respectively, using high-resolution transmission electron microscopy (HR-TEM) measurements.[11] One can see some evidence of bundle formation, suggesting an attractive force between the MWNTs. The MWNTs form a complex network at a nanometer scale, which has an increased surface area compared with the relatively smooth surface of ITO.[12] We note that our spin-coated MWNT film is much flatter and denser compared to films obtained by the filtration of arc-grown MWNTs.[9] In the latter film, some nanotubes were aligned almost vertically to the film because they stuck in the pores of a filter membrane. It should be noted that the quality of films is crucial for device fabrication because MWNTs protruding from a film could cause a short-circuit. In Figure 2,

Fig. 2. A tapping-mode AFM image of the surface of a MWNT film.

we present an atomic force microscopy (AFM) image of the surface of a MWNT film obtained in tapping mode. It was found that the MWNT film possesses an effective thickness of more than 50 nm. We will discuss the roughness of the MWNT film later. Fabrication of the PPV MWNT composite was successfully achieved; Figure 1b shows the cleaved surface of the composite imaged in the region near the bottom of the MWNT layer. It can be seen that PPV covers the surface of the MWNTs and forms a well-mixed composite, indicating a very high contact area between the two components. The interaction between MWNTs and PPV was investigated by means of PL measurements. Results are shown in Table 1 and Figure 3. The thickness of the PPV layer on a MWNT film was taken to be that of a PPV layer deposited
Table 1. PL efficiencies of PPV films spin-coated on quartz, MWNT, and ITO. The excitation wavelength is 458 nm. The values in parentheses indicate the film thicknesses. Fig. 1. a) SEM micrograph of the surface of a spin-coated MWNT film. b) The cleaved surface of a PPVMWNT composite near the bottom of the MWNT layer. The small particles seen in the composite are evaporated gold particles used to avoid a charging effect because the composite is less conducting than the pure MWNT film.

1282

WILEY-VCH Verlag GmbH, D-69469 Weinheim, 1999

0935-9648/99/1510-1282 $ 17.50+.50/0

Adv. Mater. 1999, 11, No. 15

Communications

tivity of a MWNT film was reported to be 1020 % in the visible region),[15] were the main cause of the observed spectral change. We have fabricated and studied photovoltaic devices based on the composite. The structure of the photovoltaic devices is shown in Figure 4a, where PPV and MWNT layers have 210 and 140 nm thickness, respectively. The MWNT layer was used as the hole-collecting electrode, be-

Fig. 3. Normalized PL spectra of the PPV films on a thin MWNT film (solid line), ITO substrates (dashed line), and quartz (dotted line). The thickness of each film is shown in Table 1.

separately on a quartz substrate. From Table 1, one can see that the PL efficiency of PPV was remarkably reduced by the presence of the MWNT layer, much more so than for an ITO substrate. Although scattering and absorption by the MWNTs are probably the main contribution to the reduction of PL efficiency in this composite, we also suspect that electronic interactions at the PPV/MWNT interface quench the radiative recombination. This suggestion is supported by the fact that even a PPV film deposited on a thin MWNT film (60 nm) showed a drastic reduction in PL efficiency. A possible quenching mechanism is considered to be the transfer of electronhole pairs (excitons) generated in PPV chains to MWNTs (in other words, energy transfer), because the present MWNTs are small-gap semiconductors as shown by the temperature dependence of the electrical conductivity.[13] However, hole transfer from the photo-excited PPV to the MWNTs is also possible as a result of the enhanced photovoltaic effect described below. The effects are quite different from that observed for the interface between PPV and C60, in which C60 acts as an electron acceptor.[13] In addition to the drastic reduction of the PL efficiency, a clear difference was found in the vibronic structure of the PL spectrum between the composite and the pure polymer (Fig. 3). In spite of the original yellow color of PPV, the composite appeared to be green or blue depending on the thickness of each layer. The peak at 2.41 eV was intense for the composite, whilst PPV on an ITO or a quartz substrate had its strongest peak at 2.25 eV. It is noted that a similar effect was reported for composites of arc-grown non-oxidized MWNTs and meta-linked PPV.[14] This fact suggests that the observed change is not due to catalytic impurities or surface-oxidized groups possibly existing in the catalytically grown MWNTs. Therefore, based on the fact that the intensity of the peak at 2.4 eV depends on the thickness of the MWNT film, we concluded that optical effects, such as interference due to reflection by the MWNTs (the reflecAdv. Mater. 1999, 11, No. 15

Fig. 4. a) Structure of the photovoltaic devices employed for the present study. Visible light is shone through a semi-transparent Al electrode. The film thickness of PPV and MWNT is 210 nm and 140 nm, respectively. b) Energy diagram of the MWNT/PPV/Al device before and after contact. Since the work function of ITO (4.5 eV [12]) is smaller than that of the MWNT (5.1 eV [16]), a higher photovoltaic efficiency can be expected for an MWNT/PPV/Al device than for an ITO/PPV/Al device.

cause of its relatively high conductivity (8 S/cm at room temperature)[13] and high work function (5.1 eV)[16]. For comparison, the standard device with an ITO substrate was also studied. We expect a very high contact area between PPV and MWNT layers and a lower barrier to hole-collection for the MWNTs compared to ITO (Fig. 4b). Since the spin-coated MWNT film is essentially free from protruded MWNTs (see Fig. 1), a much thinner PPV film has been achieved in comparison with the previous report of an arcevaporated MWNT/PPV/Al (or Au) device (the MWNT and PPV films were about 2 mm and 600 nm thick, respectively[9]). Figure 5 shows the currentvoltage (IV) characteristics of the MWNT/PPV/Al device. This device showed a clear diode characteristic with a rectification ratio of 3 103 at  2 V in the dark. Although a previous paper reported a much lower operational voltage,[9] our MWNT/PPV/Al composite device showed a similar IV curve to that of the standard ITO/PPV/Al device. We suspect that the previously reported IV curve[9] may be ascribed to the consid0935-9648/99/1510-1283 $ 17.50+.50/0

WILEY-VCH Verlag GmbH, D-69469 Weinheim, 1999

1283

Communications

Fig. 5. The currentvoltage (IV) characteristics of an MWNT/PPV/Al device in the dark (closed circles), and under illumination at a wavelength of 485 nm and intensity of 37 mW/cm2 (open circles). Inset: same data with a logarithmic current axis.

erable reduction of the effective thickness of the PPV layer due to the number of protruding MWNTs. The present result demonstrates that the chemically treated MWNTs can be an effective and highly processible anode material. Upon illumination through the Al electrode, a clear photocurrent was observed. Light with a wavelength of 485 nm and an intensity of 37 mW/cm2 gave an open- circuit voltage (VOC) and short-circuit current (ISC) of 0.90 V and 0.56 mA/cm2, respectively. This VOC is close to the difference in the work functions of the two electrodes, which are 4.3 eV and 5.1 eV for Al and MWNTs, respectively.[16] The fill factor (FF) and power conversion efficiency were calculated to be 0.23 and 0.081 %, respectively. The ITO/PPV/ Al device showed similar VOC and FF (0.80 V and 0.24) under similar conditions. The external quantum efficiency (EQE) for both devices is shown in Figure 6. The EQE observed for the MWNT/ PPV/Al device was twice that of the ITO/PPV/Al device. We have examined several samples and obtained typically 1.5 to

Fig. 6. External quantum efficiencies of MWNT/PPV/Al (open circles) and ITO/PPV/Al (closed circles) devices. The broken line indicates the absorption spectrum of a pure PPV film. Both devices were illuminated through a semi-transparent Al layer.

2 times greater EQE for the composite device. This result can be interpreted as the consequence of the complex network of MWNTs and PPV chains and a stronger built-in electric field due to the higher work function of MWNTs than ITO. From the observed EQE, it is probable that the holes are preferentially accepted by MWNTs at the PPV/ MWNT interface. Therefore, we think that the PL quenching observed in Figure 3 stems from hole transfer to MWNTs in addition to the main energy transfer Further investigation, for example, by means of a photo-induced absorption (PIA) measurement, is necessary to clarify the interfacial interaction between MWNTs and PPV[13] and is underway. The effect of light reflection by MWNTs[15] on the enhanced photocurrent is denied because the reflection would produce a photocurrent at an absorption edge (ca. 2.4 eV for PPV) due to a filter effect:[6] if the reflected light were to contribute to the photocurrent, the reflected light would be absorbed by a PPV layer and only non-absorbed light would give an enhanced photocurrent at the absorption edge. From the AFM image (Fig. 2), the MWNT layer can be seen to have an effective thickness of 5090 nm. Assuming that the MWNTs align in a parallel, closed packed manner, eight MWNTs (10 nm diameter) could stack in the 70 nm thickness. Under this simple assumption, it can be deduced that the surface area of the electrode increases by about 24. This roughness factor of 24 is much smaller than that of a film made with TiO2 particles whose roughness is 780,[17] which act as an efficient electron acceptor for dye-sensitized Grtzel-type photovoltaic devices. This increased roughness factor for TiO2 particles is due to their spherical shape and the much thicker layer (10 mm) used for dye-sensitized photovoltaic devices.[17] A direct comparison of the present MWNT layer with TiO2 in terms of the photovoltaic efficiency is difficult; the MWNTs have been applied as a hole-collecting electrode and PPV has a certain range of exciton diffusion lengths (510 nm[3]) owing to the p-conjugation length along the polymer chains. We note that the EQE of our MWNT devices is still lower than that of an ITO/PPV/C60/Al device (EQE is ca. 9 %[3]). Moreover, the enhancement of EQE obtained for the MWNT/PPV/Al device is not as high as expected from the surface roughness. These facts can be accounted for by considering that holes have a much higher mobility than electrons in a PPV film. Even if holes are accepted by MWNTs, the remaining electrons cannot reach the Al electrode. In the case of the electron-accepting C60, the electron mobility is relatively high so that both electrons and holes can reach the electrodes, thereby increasing the EQE remarkably. In this sense, it would be very interesting to study the combination of a nanotube electrode with a donoracceptor polymer[18,19] as a means of improving photovoltaic efficiency. In summary, we have studied the optical and photovoltaic properties of a composite of MWNTs and PPV. The composite was realized by spin-coating the PPV precursor on thin MWNT films and subsequent conversion at high
0935-9648/99/1510-1284 $ 17.50+.50/0 Adv. Mater. 1999, 11, No. 15

1284

WILEY-VCH Verlag GmbH, D-69469 Weinheim, 1999

Communications

temperature. A drastic reduction of the PL efficiency and a change in the vibrational structure of the PL spectrum were effected by MWNTs. The reduction of the PL efficiency can be a result of energy transfer and partial hole transfer from PPV chains to MWNTs, together with scattering and absorption by MWNTs. Using the composite, photovoltaic devices have been fabricated by employing MWNT as a hole-collecting electrode. We obtained good quantum efficiency (1.8 % at 2.93.2 eV), about twice that of the standard ITO device. It is considered that the high efficiency arises from a complex interpenetrating network of PPV chains with MWNTs and the relatively high work function of the MWNT film. The present results suggest the possible application of carbon nanotubes as a new interesting electrode material in macroscale devices.

Experimental
The MWNTs were synthesized by the catalytic pyrolysis of hydrocarbons in the presence of a transition metal [20]. These catalytically grown MWNTs are essentially free from carbon impurities, such as tetrahedral carbons, fullerenes, and nanoparticles. Although they suffer from a greater concentration of structural defects than arc-evaporated MWNTs and, thus, are not perfect one-dimensional conductors, they are suitable for the present study because their nanoscale diameter allows the production of nanoscopically mixed composites. In order to obtain a concentrated dispersion of MWNTs, the raw MWNT sample was oxidized in acid solution (HNO3 and H2SO4 mixed 1:3) for 2 h and then filtered and washed thoroughly with distilled water. After the oxidation, no traces of catalytic metals were observed by X-ray microanalysis [11] and X-ray photoelectron spectroscopy (XPS) [16] measurements. The surface groups generated by this treatment, such as carboxyl and alkoxyl groups, form a hydrophilic surface on the MWNTs and stabilize dispersions in water without surfactant. Details of the structure of these MWNTs as well as the oxidation method are reported elsewhere [11]. Thin films of MWNT were spin-coated onto a glass or quartz substrate from dispersions with concentrations of 0.52.0 wt.-%. The thickness of films can be controlled (from 20 to 300 nm) by altering the concentration or the spinning speed. For PL measurements and photovoltaic devices, we spin-coated the PPV precursor (sulfonium salt) onto MWNT films, ITO, or quartz, followed by thermal conversion at 210 C for 10 h in vacuum [4]. This heat treatment stimulates the penetration of PPV into the MWNT layer and forms a good composite as described below. Finally, semi-transparent Al (with a transparency of about 40 % in the absorption range of PPV) was evaporated on top of the PPV layer to act as a second contact for the photovoltaic devices. Since the light was shone through the Al electrode during the photovoltaic measurements, we evaporated Al from the same batches for both MWNT/PPV/Al and ITO/PPV/Al devices to ensure the validity of any comparisons. Film thickness was measured with a Dektak IIA profilometer. The morphology of MWNT and PPVMWNT films was investigated by FE-SEM using a JEOL JSM-6340F operating at 10 keV. In order to study the morphology, we mechanically cleaved the composite with a microtome after encapsulation in epoxy resin. AFM was also applied to the surface of a MWNT film to investigate the depth profile using a Nanoscope IIIa. The absolute PL efficiency was obtained using an integrated sphere connected to an Oriel Instaspec IV spectrophotometer through a liquid light guide. The 458 nm line of an Ar ion laser was used as an excitation source. The device characteristics were evaluated with a Keithley 237 source-measure unit under a vacuum of 105 torr. The device was illuminated through a semi-transparent Al electrode using a tungsten halogen lamp dispersed by a Bentham M300 single-grating monochromator. Received: April 12, 1999 Final version: July 28, 1999 [1] S. Morita, A. A. Zakhidov, K. Yoshino, Jpn. J. Appl. Phys. 1993, 32, L873. [2] N. S. Sariciftci, D. Braun, C. Zhang, V. I. Srdanov, A. J. Heeger, G. Stucky, F. Wudl, Appl. Phys. Lett. 1993, 62, 585. Adv. Mater. 1999, 11, No. 15

[3] J. J. M. Halls, K. Pichler, R. H. Friend, S. C. Moratti, A. B. Holmes, Appl. Phys. Lett. 1996, 68, 3120. [4] J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, K. Mackay, R. H. Friend, P. L. Burns, A. B. Holmes, Nature 1990, 347, 539. [5] H. Koezuka, A. Tsumura, T. Ando, Synth. Met. 1987, 18, 699. [6] R. N. Marks, J. J. M. Halls, D. D. C. Bradley, R. H. Friend, A. B. Holmes, J. Phys.: Condens. Matter 1994, 6, 1379. [7] P. M. Ajayan, O. Stephan, C. Colliex, D. Trauth, Science 1994, 265, 1212. [8] S. A. Curran, P. M. Ajayan, W. J. Blau, D. L. Carroll, J. N. Coleman, A. B. Dalton, A. P. Davey, A. Drury, B. McCarthy, S. Maier, A. Stevens, Adv. Mater. 1998, 10, 1091. [9] D. B. Romero, M. Carrard, W. de Heer, L. Zuppiroli, Adv. Mater. 1996, 8, 899. [10] H. Hiura, T. W. Ebbesen, K. Tanigaki, Adv. Mater. 1995, 7, 275. [11] M. S. P. Shaffer, X. Fan, A. H. Windle, Carbon 1998, 36, 1603. [12] J. S. Kim, M. Gransrm, R. H. Friend, N. Johansson, W. R. Salaneck, R. Daik, W. J. Feast, F. Cacialli, J. Appl. Phys. 1998, 84, 6859. [13] H. Ago, M. S. P. Shaffer, D. S. Ginger, A. H. Windle, R. H. Friend, unpublished. The activation energy for the MWNT film was estimated to be 314 meV. [14] A. B. Dalton, H. J. Byrne, J. N. Coleman, S. Curran, A. P. Davey, B. McCarthy, W. Blau, in Proc. NANOTECH 98 (Nanotechnology in Carbon and Related Materials), Brighton, UK, Sept. 911, 1998. [15] F. Bommeli, L. Degiorgi, P. Wachter, W. S. Bacsa, W. A. de Heer, L. Forro, Synth. Met. 1997, 86, 2307. [16] H. Ago, T. Kugler, F. Cacialli, W. R. Salaneck, M. S. P. Shaffer, A. H. Windle, R. H. Friend, J. Phys. Chem. B, in press. [17] B. O'Regan, M. Grtzel, Nature 1991, 353, 737. [18] J. J. M. Halls, C. A. Walsh, N. C. Greenham, E. A. Marseglia, R. H. Friend, S. C. Moratti, A. B. Holmes, Nature 1995, 376, 498. [19] M. Granstrm, K. Petritsch, A. C. Arias, A. Lux, M. R. Andersson, R. H. Friend, Nature 1998, 395, 257. [20] C. Niu, E. K. Sichel, R. Hoch, D. Moy, H. Tennet, Appl. Phys. Lett. 1997, 70, 1480.

Patterned Films of Nanotubes Using Microcontact Printing of Catalysts**

By Hannes Kind,* Jean-Marc Bonard, Christophe Emmenegger, Lars-Ola Nilsson, Klara Hernadi, Eliane Maillard-Schaller, Louis Schlapbach, Lszl Forr, and Klaus Kern There is increasing experimental and theoretical evidence that carbon nanotubes[1] have remarkable physical
[*] H. Kind, Dr. J.-M. Bonard, Dr. L. Forr, Prof. K. Kern Dpartement de Physique, cole Polytechnique Fdrale de Lausanne CH-1015 Lausanne (Switzerland) C. Emmenegger, L.-O. Nilsson, Dr. E. Maillard-Schaller, Prof. L. Schlapbach Physics Department, University of Fribourg Prolles, CH-1700 Fribourg (Switzerland) Dr. K. Hernadi Applied Chemistry and Environment Department Jozsef Attila University H-6720 Szeged, Rerrich B. ter.1 (Hungary) Prof. K. Kern Max-Planck-Institut fr Festkrperforschung Heisenbergstrasse 1, D-70569 Stuttgart (Germany) [**] We thank E. Delamarche, M. Geissler, H. Schmid, and B. Michel for providing us with masters and stamps and A. Bietsch and A. M. Bittner for helpful discussions. We are grateful to CIME-EPFL for access to SEM and TEM facilities. K. Hernadi thanks the National Science Foundation of Hungary for financial support (OTKA-T025246). 0935-9648/99/1510-1285 $ 17.50+.50/0

WILEY-VCH Verlag GmbH, D-69469 Weinheim, 1999

1285