Colloids and Surfaces A: Physicochem. Eng.

Aspects 272 (2006) 6367

Rose-like superhydrophobic surface based on conducting dmit salt

Guanglei Cui a , Wei Xu a , Xinhong Zhou b , Xunwen Xiao a , Lei Jiang a, , Daoben Zhu a,
a

Laboratory of Organic Solids, Center for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, North 1st Street, Zhongguancun, 100080 Beijing, PR China b College of Chemistry and Molecule, Qingdao University of Sciences and Technology, Qingdao, PR China Received 9 March 2005; received in revised form 29 June 2005; accepted 11 July 2005 Available online 24 August 2005

Abstract The rose-like crystalline microstructures of the dmit (dmit = C3 S5 2 = 2-thioxo-1,3-dithiole-4,5-dithiolato) salt were assembled using the combination of template method and electrochemical deposition. XRD pattern and scanning electron microscopy (SEM) show that the growth of rose-like crystals follows parabolic law and it is resulting from the anisotropic growth of the crystals which was under the inuence of diffusion-limited aggregation. These special rose-like structures can be used to fabricate a superhydrophobic surface after coating a gold lm and assembling a monolayer of n-dodecanethiol on these microstructures. 2005 Elsevier B.V. All rights reserved.
Keywords: Crystal growth; Electrochemistry; Wettability; Surface chemistry

1. Introduction The chemical composition and geometrical structures control the properties of the solid surfaces. For example, the superhydrophobic property of the lotus leaf is due to its surface topography and a hydrophobic wax-like material [1]. A superhydrophobic surface is one exhibiting a water contact angle of more than 150 and a very low hysteresis. This is a surface on which a water droplet can easily roll off. Owing to its potential in both fundamental investigation and practical applications, synthetic superhydrophobic surfaces with interesting topography have come up with many surprises in recent years [27]. Among them, a superhydrophobic surface based on the conducting materials is attracting more attentions due to potential applications in the fabrication of microuidic devices, uid microchips and microreactors. However, to the best of our knowledge, there are few reports on a superhydrophobic surface based on conducting materials [6d,7c]. Herein, we reported the fabrication of a superhydrophobic surface using electrically conducting materials. The superhydrophobic surface was fabricated in two steps. Firstly,

rose-like crystalline microstructures based on a dmit salt were electrochemically deposited on the surface of anodic aluminum oxide template (AAO) and it resulted in a surface with uniform roughness. Then a superhydrophobic surface can be achieved after coating a gold lm and self-assembling a monolayer of n-dodecanethiol on these rose-like microstructures. 2. Experimental section 1. [(CH3 )4 N][Ni(dmit)2 ] (structural formula is shown in Scheme 1) was prepared according to the literature [8]. Its purity was characterized by Element Analyzer (CarloErba-1106 instrument). Anal. Calcd. for C10 H12 NS10 Ni: C, 22.85; H, 2.30; N, 2.66; S, 61.01. Found: C, 22.88; H, 2.36; N, 2.66; S, 61.23. 2. All galvanostatic experiments were carried out in an acetonitrile solution of 0.0015 M [(CH3 )4 N][Ni(dmit)2 ] and 0.01 M [(CH3 )4 N][ClO4 ] using EG&G Potentiostat/Galvanostat Model 283 instruments. The electrodeposition was performed at 25 C. Rose-like microstructures were produced by electrochemical deposition using a thin gold lm (ca. 100 nm) on one side of the AAO template

Corresponding authors. Tel.: +86 10 82621396. E-mail address: jianglei@iccas.ac.cn (L. Jiang).

0927-7757/$ see front matter 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.colsurfa.2005.07.011

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G. Cui et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 272 (2006) 6367

Scheme 1.

(pore diameter of 15 4 nm) as the working electrode with platinum wire (1 mm) as the counter electrode and the saturated calomel electrode as reference electrode. The solution was deaerated by a nitrogen stream and maintained at a slight overpressure during the experiment. Finally, the template was rinsed with CH3 CN and dried under N2 before it was analyzed under SEM. All the potentials were referenced to a saturated calomel electrode (SCE). 3. Characterization of rose-like microstructures: SEM (Jeol JSM 6700F) was employed to assess the structure of the templates as well as the microstructures. To avoid charging effects while imaging, a thin layer of gold was sputtered onto the surface and the images were acquired at 3.0 kV electron voltage. XRD results were recorded using a Dmax 2000 spectrometer (Rigaku, Cu K ). 4. The fabrication of the superhydrophobic surface on the rose-like microstructures. A gold lm (ca. 50 nm) was evaporated in high vacuum (3 105 Pa) on the surface of the rose-like microstructure on AAO lm using High Vacuum Evaporator (HUS-5GB, HITACHI). After cooling to room temperature, this AAO lm was immersed in an ethanol solution containing 1.0 103 M

n-dodecanethiol overnight. The template was then thoroughly rinsed with pure ethanol. 5. Contact angles (CAs) were measured on a Dataphysics OCA20 contact-angle system at ambient temperature. Water droplets (about 3 L) were dropped carefully onto the surfaces. The average CA value was determined by measuring at ve different positions of the same sample.

3. Results and discussion The growth of the dmit salt was carried out using a conventional galvanostatic method for the crystalline growth of an organic conductor [9]. After electrochemical deposition with a constant current density of 0.15 A mm2 for about 7 h, the surface of the AAO membrane was coated with rose-like microowers of the dmit salt as observed in SEM investigations (Fig. 1a). It can be seen that these microowers have a hemispherical three-dimensional structures with diameters ranging from 5 to 10 m and densely aligned. As shown in an enlarged image of an individual microower (Fig. 1d), the microowers were made up of several dozens of crystalline nanopetals. These platelet crystals are about 50100 nm thick and 15 m wide. To understand the formation mechanism of the microowers, the growth process of the dmit salt on AAO membrane has been observed carefully. It has been found that the shape and size of dmit salt deposited on the AAO membrane surface are strongly depended on the pore diameter

Fig. 1. The SEM images of rose-like dmit salt microstructure formed on the surface of AAO template by electrochemical deposition at a current density of 0.15 A mm2 . (a) The arrays of nanowires developed from the AAO template and a lm formed on them after 4 h deposition. (b) The rudiment of rose-like microstructure and its enlarged image developed from the lm on the top of the arrays of nanowires after 5 h deposition. (c and d) The rose-like microstructures formed and its enlarged image after 7 h.

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of AAO membrane, the value of applied current density and growth time. The AAO membrane with right pore diameter is the key for the growth of microowers. It was found that the microowers can be obtained when an AAO membrane with a pore diameter of 15 4 nm was used. The applied AAO template was made according to a reported procedure [10]. Close-packed arrays of parallel cylindrical pores were normal to the template surface. The side view of AAO template shows that the cavities stand upright on the substrate straight and separate from each other. The holes are about 28 m deep, corresponding to the thickness of the AAO template. There is a small distance between the adjacent pores (1020 nm) in the template. After 4 h deposition, the dmit salt nanocrystals grew up to the surface from different pores. And they connected with each other and resulted in a lm covered on the AAO surface (Fig. 1a). Because part of pores were not lled with the dmit salt, the lm was not continuous. Then this lm served as a conducting substrate for the further growth of the crystals. After 5 h deposition, a few crystalline islands interlarded and developed on top of the lm (Fig. 1b). Every crystalline island grew from the same growth point (the enlarged image in Fig. 1b). These crystalline islands can lead to rose-like microowers. The kinetic of these microstructures involves instantaneous nucleation and subsequent three-dimensional growth. This is to say, it follows parabolic law. During electrodeposition process, the similar dendritic fractal morphology was reported [1114]. The formation of dendritic microstructures during deposition of metal particle was under the inuence of diffusion-limited aggregation (DLA) [1517]. For example, Debasis et al. reported that the growth of dendritic palladium nanocrystallites was limited by diffusivity of bulky palladium tetrachloro square-planar complex from bulk solution to near the electrode surface [13]. Moreover, dmit salt crystal is anisotropic organic crystals. The growth of rose dmit microstructures was also limited by diffusion [18]. So, it is under the inuence of diffusion-limited aggregation. The preferential orientation of dmit salt electrodepositions was attributed to the competitive crystal growth as an aftermath of crystal hemi-

spherical electrodeposits. The rose-like microstructures were resulting from the anisotropic competitive growth of the crystals which was under the inuence of diffusion-limited aggregation. It can be seen that the lm of the dmit salt on the AAO membrane is critical for the fabrication of the microowers. And this lm just can be obtained using the AAO membrane (pore diameter of 15 4 nm) as the working electrode. When a conventional bulk electrode, such as a platinum plate electrode, was used for the electrochemical deposition of the dmit salt, only densely packed microcrystals can be obtained under the similar conditions [19]. When an AAO membrane with larger pore diameters of 100200 nm was used, needle or ber-like nanocrystals (depend on the current density) can be obtained after the dmit salt grew up to the surface. And neither the lm nor microowers can be observed. Gimeno et al. [20] have investigated the electrodeposition of two-dimensional branched Pd islands on highly oriented pyrolitic graphite. This result of such study strongly suggest that the shape and aspect ratio of palladium island deposits are a function of the cathodic overpotentials. Similar to two-dimensional branched Pd islands, the overpotentials can possibly inuence above results. Under a higher current density, such as 1.5 A mm2 , only protuberance-like microstructures would be deposited on the AAO membrane with pore diameters of 15 4 nm. As shown in Fig. 2, these protuberance-like microstructures are more sparsely populated on the AAO surface, and these structures are more like amorphous structures in contrast with rose-like crystal microowers. This is due to the fact a higher current density can result in poorer crystals. These rose-like microstructures were further characterized with XRD. XRD pattern of the as-deposited rose-like microstructures on the AAO template is shown in Fig. 3. XRD peaks are all indexed to [(CH3 )4 N][Ni(dmit)2 ]2 in a mono clinic crystal system with cell parameters of a = 13.654 A, b = 6.426 A, c = 35.709 A, and = 93.94 . These cell parameters were obtained from the single crystal harvested from the standard bulk electrode under the identical electrochemical deposition conditions. The XRD pattern indicates rose-like

Fig. 2. (a) The protuberance-like microstructure of dmit salt image on the template surface. It was developed in a solution of 0.0015 M [(CH3 )4 N][Ni(dmit)2 ] in acetonitrile containing [(CH3 )4 N][ClO4 ] at a current density of 1.5 A mm2 . (b) The enlarged image of a protuberance like microstructure.

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G. Cui et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 272 (2006) 6367

Fig. 3. The XRD pattern of the rose-like microstructure formed on AAO template surface. The position for [(CH3 )4 N][Ni(dmit)2 ]2 (2 1 1), (2 3 3), (1 1 1), (3 5 5) in monoclinic crystal system are marked.

Fig. 4. The contact angle measured on the surface of rose-like microstructure modied by a self-assembly lm of n-dodecanethiol using water droplet as an indicator. The contact angle reached 152 1.7 .

microstructures are polycrystalline. The macroscopic conductivity property of the rose-like surface was characterized by two-probe method by slower evaporating another gold lm electrode on the opposite side of the as-prepared sample. The conductivity was in the range from 0.08 to 0.004 S cm1 which indicates the interface is electrically conducting. Compared with the nanowire of dmit salt, the conductivity of the rosy microstructure is much lower [18]. This is because the lm on the surface of the template may be amorphous. These rose-like microowers are made up of platelets of nanocrystals that intersected and overlapped each other. Between these micro-crystals platelets there are nano-scale apertures and more air trapped among them. The contact angle (CA) of this surface reached 65.3 1.5 . The surface with rose-like microowers can be fabricated into a superhydrophobic surface by converting it with lower surface energy molecules. First a gold lm can be evaporated in vacuum (ca. 50 nm) onto these rose-like surfaces. At this time the contact angle increased to 118.7 1.3 . There was no distinct change in topography after evaporation of a gold lm. Then these surfaces were immersed in an ethanol solution of n-dodecanethiol (1 103 M) overnight, a self-assembled monolayer can be formed on the gold-coated surface [7d]. After rinsing with pure ethanol, we have studied the wetting property of the modied surface by contact angle measurements using water. The contact angle can reach as high as 152 1.7 suggesting the formation of a superhydrophobic surface (Fig. 4). Further evidence for the superhydrophobicity of the surface is given by its low tilt angle, which reects the difference between the advancing and receding contact angles. The tilting angle of the surface is around 4 , indicating that water droplets can roll off easily. This superhydrophobicity based on conducting is very important for conductors with self-cleaning and special interfacial properties. To further understand the superhydrophobicity of the intersurface, a contrast experiment for the measurement of

contact angle on a smooth surface was performed. The contact angle in terms of the Cassie equation is described [21]: cos r = f1 cos f2 , where r (152 ) and (95 ) are the contact angles on the selfassembled monolayer of n-dodecanethiol on a rough surface with rose-like microstructure covered with gold lm and on a smooth gold surface, respectively; f1 and f2 are the fractional interfacial areas of the rose-like microstructures and of the air in the voids among the rose-like microstructures, respectively (f1 + f2 = 1). According to the equation, the f2 value of the rose-like surface is estimated to be 0.87. Through this f2 value we realize that trapped air within the microstructures is important to produce superhydrophobicity. In other words, the unusual rose-like topography, which have a hierarchical micro-, and nanostructure plays a very important role in fabricating the superhydrophobic surface [22]. In conclusion, unusual rose-like crystalline microstructures were prepared based on dmit salt by template directed electrodeposition. XRD pattern and SEM show that the roselike crystal was a polycrystalline material resulting from the anisotropic and competitive growth of the crystals which was under the inuence of diffusion-limited aggregation. Moreover, a hydrophobic surface based on conducting materials can be achieved after coating a gold lm and self-assembling a monolayer of n-dodecanethiol on these microstructures. The unusual rose-like topography plays a very important role in the fabrication of the superhydrophobic surface.

Acknowledgments This work was nancial supported by the Chinese Academy of Sciences, NSFC and the State Basic Research Development Program.

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References
[1] (a) W. Barthlott, C. Neinhuis, Planta 202 (1997) 1; (b) C. Neinhuis, W. Barthlott, Ann. Bol. 79 (1997) 667. [2] (b) L. Jiang, R. Wang, B. Yang, T.J. Li, D.A. Tryk, A. Fujishima, K. Hashimoto, D.B. Zhu, Pure Appl. Chem. 72 (2000) 73; (b) P. Aussillous, D. Qu r , Nature 411 (2001) 924; ee (c) L. Feng, S. Li, Y.S. Li, H. Li, L. Zhang, J. Zhai, Y.L. Song, B.Q. Liu, L. Jiang, D.B. Zhu, Adv. Mater. 14 (2002) 1857; (c) J.C. Love, B.D. Gates, D.B. Wolfe, K.E. Paul, G.M. Whitesides, Nano Lett. 2 (2002) 891. [3] (a) T. Sun, G. Wang, H. Liu, L. Feng, L. Jiang, D. Zhu, J. Am. Chem. Soc. 125 (2003) 14996; (b) J. Genzer, K. Emenko, Science 290 (2000) 2130; (c) P.S. Swain, R. Lipowsky, Langmuir 14 (1998) 6772; (d) H.Y. Erbil, A.L. Demirel, Y. Avci, O. Mert, Science 299 (2003) 1377; (e) Z.Z. Gu, H. Uetsuka, K. Takahashi, R. Nakajima, H. Onishi, A. Fujishima, O. Sato, Angew. Chem. Int. Ed. 42 (2003) 894. [4] (a) H. Tada, H. Nagayama, Langmuir 11 (1995) 136; (b) K. Tadanaga, N. Katata, T. Minami, J. Am. Ceram. Soc. 80 (1997) 1040; (c) A. Nakajima, A. Fujishima, K. Hashimoto, T. Watanabe, Adv. Mater. 11 (1999) 1365; (d) K. Tsujii, T. Onda, S. Shibuichi, Angew. Chem. Int. Ed. 36 (1997) 1011; (e) Kenneth K.S. Lau, J. Bico, Kenneth B.K. Teo, M. Chhowalla, Gehan A.J. Amaratunga, William I. Milne, Gareth H. McKinley, K. Karen, K Gleason, Nano Lett. 3 (2003) 1701. [5] (a) S. Hermingghaus, Europhys. Lett. 52 (2000) 165; (b) S. Shibuichi, T. Onda, N. Satoh, K. Tsujii, J. Phys. Chem. 100 (1996) 19512; (c) J.T. Han, D.H. Lee, C.Y. Ryu, K. Cho, J. Am. Chem. Soc. 126 (2004) 4796; (d) S. Minko, M. Muller, M. Motornov, M. Nitschke, K. Grundke, M. Stamm, J. Am. Chem. Soc. 125 (2003) 3896; (e) A. Lafuma, D. Qu r , Nat. Mater. 2 (2003) 457; ee (f) J. Bico, C. Marzolin, D. Qu r , Europhys. Lett. 47 (1999) 220. ee [6] (a) M. Thieme, R. Frenzel, S. Schmidt, F. Simon, A. Hennig, H. Lunkwitz, K.D. Scharnweber, Adv. Eng. Mater. 3 (2001) 691;

[7]

[8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20]

[21] [22]

(b) J.P. Youngblood, T.J. McCarthy, Macromolecules 32 (1999) 6800; (c) K. Tadanaga, J. Morinaga, A. Matsuda, T. Minami, Chem. Mater. 12 (2000) 590; (d) M. Li, J. Zhai, H. Liu, Y. Song, L. Jiang, D. Zhu, J. Phys. Chem. B 107 (2003) 9954. (a) M. Morra, E. Occhiello, F. Garbassi, Langmuir 5 (1989) 872; (b) J.-Y. Shiu, C.-W. Kuo, P. Chen, C.-Y. Mou, Chem. Mater. 16 (2004) 561; (c) X. Zhang, F. Shi, X. Yu, H. Liu, Y. Fu, Z.Q. Wang, L. Jiang, X.Y. Li, J. Am. Chem. Soc. 126 (2004) 3064; (d) H. Gau, S. Herminghaus, P. Lenz, R. Lipowsky, Science 283 (1999) 46. S. Sun, D. Wu, D. Zhu, Chin. Chem. Lett. 11 (1996) 1054. H. Kim, A. Kobayashi, Y. Sasaki, R. Rato, H. Kobayashi, Chem. Lett. (1987) 1799. A.L. Prieto, M. Sands, T.S. Sander, M.S. Martin, R. Gronsky, A.M. Stacy, J. Am. Chem. Soc. 123 (2001) 7160. D. Barkey, F. Oberholtzer, Q. Wu, Phys. Rev. Lett. 75 (1995) 2980. H. Martin, P. Carro, A.H. Creus, S. Gonz lez, R.C. Salvarezza, A.J. a Arvia, Langmuir 13 (1997) 100. B. Debasis, C.K. Suresh, S. Sudipta, J. Phys. Chem. B 108 (2004) 556562. J. Amblard, M. Froment, G. Maurin, N. Spyrellis, E. TrevisanSouteyrand, Electrochim. Acta 28 (1983) 909. (a) T.A. Witten, L.M. Sander, Phys. Rev. Lett. 47 (1981) 1400; (b) T.A. Witten, L.M. Sander, Phys. Rev. Lett. 27 (1983) 5686. P. Meakin, Phys. Rev. Lett. 51 (1983) 119. R.Q. Hwang, J. Schr der, C. G nther, R.J. Behm, Phys. Rev. Lett. o u 67 (1991) 3279. G.L. Cui, W. Xu, C.W. Guo, X.W. Xiao, H. Xu, D.Q. Zhang, L. Jiang, D.B. Zhu, J. Phys. Chem. B 36 (2004) 1363813642. R. Shen, W. Xu, D.Q. Zhang, D.B. Zhu, Solid State Commun. 130 (2004) 401. (a) Y. Gimeno, A.H. Creus, S. Gonz lez, R.C. Salvarezza, A.J. Arvia, a Chem. Mater. 13 (2001) 1857; (b) Y. Gimeno, A.H. Creus, S. Gonz lez, R.C. Salvarezza, A.J. Arvia, a J. Phys. Chem. B 106 (2002) 4232. A.B.D. Cassie, Trans. Faraday Soc. 44 (1948) 11. T.L. Sun, L. Fin, X.F. Gao, L. Jiang, Acc. Chem. Res. (2005), ASAP.