碳纳米管膜中自组装大范围的微米尺度图案检测方案(接触角测量仪)

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Carbon Nanotubes Angewandte Self-Assembly of Large-Scale Micropatterns onAligned Carbon Nanotube Films** Huan Liu， Shuhong Li， Jin Zhai， Huanjun Li，Quanshui Zheng， Lei Jiang，*and Daoben Zhu The fabrication of well-defined structures with nanoscalematerials is a key technology，" and self-assembly is anefficient and often preferred process to build micro-andnanoparticles into ordered macroscopic structures.2 Ascarbon nanotubes are attractive materials for nanotechnologybecause of their interesting physicochemical properties andmolecular symmetries，3-6] it is necessary to control thearchitecture of carbon nanotubes on the substrates. Mostpatterned carbon nanotubes are formed on prepatternedsubstrates or prepatterned catalysts during the fabricationprocess. 7-9l Herein we report the first use of a long-rangeforce (capillary force) in the self-assembly of three-dimen-sional (3D) micropatterns on aligned carbon nanotube filmsthrough a water-spreading method after the growth of thecarbon nanotube. It is considered that low-density regions orvacancies of carbon nanotube films play an important role inthe formation of the pattern. Therefore different kinds ofhighly ordered micropatterned structures have been built in acontrolled fashion by introducing vacancies artificially. Hydrophobic aligned carbon nanotube films were grownon quartz substrates by pyrolysis of iron(II) phthalocyanine(FePc) by methods described in the literature. 10-12] Interestingly， when a water droplet was placed on thefresh carbon nanotube film， the color of the water regionchanged from black to grey. Water permeates slowly into thefilm， accompanied by a change in the height and shape of thedroplet， but its contact area with the film is almost unchanged(See Supporting Information Figure S1). Detailed scanningelectron microscopic (SEM) observations show that thestructures in the grey color region are micropatterns com-posed of honeycomb-like polygons with sizes ranging from 30to 60 um (Figure1a). An oblique view shows that these ( [ *] Dr. H. L i u， D r . S. Li，* Dr. J. Zhai， Dr . H. Li ， L. J ia n g， D. Zhu C enter of M olecular Sciences， Institute of Chemistry， Chinese Academy of SciencesBeijing 100080 (P. R. C hina) Fax： (+86)10-8262-7566 E-mail： jianglei@infoc3.icas.ac.cn Prof. Q. Zheng T singhua UniversityBeijing 100084 (P. R . China)[t] PhD students of the Graduate School of the Chinese Academy ofSciences. They contributed e q ually to this work.[**] The a uthors thank the State Key Project F u ndamental Research(G1999064504) and t h e Special R esearch Foundation of the National Nature Science Foundation of China ( 2 9992530) fo r continuing financial support. The Chinese Academy of Sciences isgratefully acknowledged. ) ( Supporting i n formation for this article is available on the WWWunder http：//www.angewandte.org or from the author. ) Figure 1. a) The SEM image of patterned carbon nanotubes induced bywater spreading. These patterns are mostly honeycomb-like structureswith the sizes ranged from 30 to 60 um. b) Enlarged oblique view ofan individual honeycomb structure with the honeycomb“wall" verticalto the substrate. honeycomb-like patterns have 3D structures in which the“walls” are vertical to the substrate. Figure 1b is a high-resolution SEM image of an individual polygon. All carbonnanotubes inside this polygon are bent radially toward the“walls” from the center. In particular， all carbon nanotubesoriginally on the substrate of thee “cave" region wereflattened， bundled， and eventually formed the cave (SeeSupporting Information Figure S2). The height and thicknessof the “walls”are 6-10 um and ca. 0.5 um， respectively， in thisimage. All these phenomena can be explained as the self-assembly of carbon nanotubes as a result of the capillaryaction of water. A variety of strategies for self-assembly havebeen proposed and employed to fabricate two- and three-dimensional structures，[13-18] and the driving forces are usuallyvan der Waals forces，19 hydrogen bonding， 20l and Coulombicforces.21，22] However， these short-range forces can only act ona molecular level， whereas longer-range forces， such assurface tension， capillary force， convection， etc.， can be usedfor constructing microstructures with nanostructured materi-als. Although carbon is hydrophobic， it is known that flatgraphite surfaces are hydrophilic， with a water contact angle中 of~86°122 Transmission electron microscopy images (SeeSupporting Information Figure S3) of carbon nanotubesdispersed from the film show their bamboolike structure，with diameters ranging from 40 to 60 nm. We have not foundmeasurement water contact angle values of carbon nano-tubes. However， it is believed that the water contact angle ofperfect carbon nanotubes of large diameters (40-60 nm)would be almost the same as that of the graphite plane. Thebamboo structures should lead to better hydrophilicity thanthat of perfect nanotubes， as generally observed for that ofrough surfaces. This means that the water contact angles nt ofthe bamboolike carbon nanotubes are generally smaller than86°. The SEM image of the film surface (See SupportingInformation Figure S4) shows that thinner tubes extend fromthicker aligned tubes and grovel on the film surface. Thesehydrophilic flattened tubes guide the water droplet along thecorresponding aligned carbon nanotubes into the film. Once the water is guided into the spaces between thealigned tubes， the resulting capillary action forces the waterdown to the quartz substrate. The water then spreads over thesubstrate because the quartz is hydrophilic. All interspacesamong aligned tubes over the water-spread region become tobe soaked due to the capillary force. The capillary force supplied by a single nanotube of radius r can be estimated tobe 2strywcosont through the water surface tension or surfaceenergy23yw=72.8mNm- and the water contact angleThe capillary force thus generates a hydrostatic dilation stressp to the water. To have an estimate of p， we modeled analigned carbon nanotube cluster by a hexagonal distributionof their cross-section (Figure 2a，b)， with diameter 2r anddistance 2R of tubes， which gives rise to Equation (1)， inwhich c=(r R-)2is the density of carbon nanotubes. Figure 2. a) Top view and b) side view of the model of the alignedcarbon nanotube cluster with tubes of diameter 2r at a distance 2 R.The blue lines represent the water surface， the dark green dots andpillars are the carbon nanotubes. c) The relationship between hydro-static dilation stress p and the volume fraction of nanotubes. Using the values yw=72.8 mNm-，r=40 nm， dnt<中=86° yields p>(0.25c)(1-c)- in MPa. The relationshipbetween the dilation stress p and the volume fraction ofnanotubes c is shown in Figure 2c， indicating the nonlinearincrease in p as the carbon nanotube density increases. Thishydrostatic dilation stress alone causes the nanotubes toflatten. SEM images of the grown carbon nanotube films showthat the carbon nanotube densities are not homogeneous.There are both low-density and high-density regions in allcarbon nanotube films. With the above estimate of hydro-static dilation stress p， the nanotubes along the boundarybetween a lower-density -cand higher-density -Ch regionsare subjected to a load q per unit tube length toward thehigher-density region (Equation (2)). From Equation(2) it can be concluded that alignednanotubes may be bent， flattened， or even burst throughfrom lower- toward higher-density regions. For example， withthe observed typical values R，r-=2and Rr-=3， we haveq=3.7×10-Nm-. The bundling force and bending momentexperienced by a single nanotube of length L=19 um nearthe substrate areqL=70.3 nN and (qL2)/2=6.7×10-4nNm，respectively. If the axial Young modulus of the carbonnanotubes is assumed to be 1TPa， then the maximumbending strain is 11%， that is， much larger than the criticalrippling strain of ≈0.6%.24.25] It means that the estimatedload q experienced by a single carbon nanotube can evenforce a dozen carbon nanotubes to be severely bent. Duringthe above bending and bundling procedures， -c decreasesand -C increases further. This leads to a stronger andstronger q， until micropatterns are formed in which nanotubesare very closely aligned so that the van der Waals repulsiveforces between the nanotubes become effective and balanceq. That is， the hydrostatic dilation stress at higher densities islarger than that at lower densities， so this difference leads tothe flattening of the nanotubes， while the “wall”is formedwhen the collapsing nanotubes from opposite directions meetbetween two regions of lower density. The lower-densityregion is the center of the micropatterns. Therefore， it is possible to control the patterns artificially，for example， to etch the regular vacancies by pulse laser. Thevacancy etched by laser is 2-3 um in diameter and variouspatterns with different vacancy distances were prepared whena water droplet was placed on the surface. Figure 3 shows thatthe morphologies after the water has spread are dependent onthe etching distance. There are two kinds of areas in the samefilm. One is the controlled assembling region in which theetching vacancy is the center； the other is the freelyassembling region， which is determined by the density ofthe carbon nanotube film. The freely assembling region is Figure 3. SEM images of micropatterned carbon nanotubes induced bywater spreading on the laser-etched films with different etching distan-ces： a) 150， b) 100， and c) 30 um. decreased as the etching vacancy distance decreases (theetching distance is 150 um and 100 um in Figures 3 a and 3b，respectively). When the etching distance approaches≈40 um， highly ordered aligned micropatterns are obtainedwithout the freely assembling region because of the interfer-ence of the etching vacancies (Figure 3c)， suggesting that ifvacancies are arranged artificially， then various desired highlyordered polygon micropatterns may be fabricated. According to the above idea， ordered micropatterns weredesigned and obtained successfully by designing the positionof the etching vacancies. The “wall" of the polygon issupposed to stand up approximately at the vertical bisectorof two adjacent vacancies. Some designs of the etchingpositions are given in the inserts of Figure 4a-d，in which the a) Figure 4. Highly ordered aligned patterns (a) cubic， b) hexagon，c) pentagon and d) parallel lines) are prepared by adjusting thearrangement of the vacancies. The inserts are the designs， the bluedots represent the laser etched vacancies and the blue lines the“walls”of carbon nanotubes. blue dots represent vacancies and the lines represent“walls”.In terms of these designs， the cubic， pentagonal， andhexagonalaligned micropatterns were fabricated (Fig-ure 4a-c) by water spreading on the etched carbon nanotubefilm， and parallel lines were also formed in Figure 4d. Allthese demonstrate that large-scale aligned micropatternedstructures can be obtained in a controlled fashion by waterspreading and capillary force. In summary， the present results provide evidence for self-assembly of carbon nanotubes to form large-scale 3D micro-patterns through the water-spreading effect， and highlyordered patterned structures can be built controllably byadjusting the density of carbon nanotubes films artificially.Two-dimensional carbon nanotube films can be easily trans-formed into three-dimensional architectures after the growthof the film. This method might not only be extended to bothinorganic nanotube/wire arrays26，27] and organic nanotubes/fibers28-30] to realize the transformation of 1D and 2D to 3Darchitectures， but also useful in fabricating microelectricaldevices as well. Experimental Section Aligned carbon nanotubes films were prepared on cleaned quartzglass plates by pyrolysis of iron(II) phthalocyanine (FePc)， whichcontains both the carbon source and the iron catalyst required. FePc(0.23 g) in a quartz boat was decomposed at approximately 550°C，and the carbon nanotube film was prepared at approximately 900℃in a flow reactor consisting of a quartz tube and a tube furnace fittedwith a temperature controller under Ar/H. The growth time of thecarbon nanotube films in this case was 5 min. After that， a water dropwas carefully placed on the films. The artificial vacancies wereinduced by the Pulse Laser Etching System with 355 nm (New WaveResearch Inc. in California)， the size of the facula was 35×35 (2-3 um) and the energy was 1.8-2.9 uW. Optical microscope images were obtained on Olympus TH3optical microscopy equipped with a CCD camera. SEM images wereobtained on a JEOL JSM-6700F scanning electron microscope at3.0 kV. 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