Materials Science and Engineering C 15 2001. 269271 www.elsevier.

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Preparation of polymeric and metallic nanostructures using a template-based deposition method

S. Demoustier-Champagne ) , M. Delvaux
Unite de Physique et de Chimie des Hauts Polymeres, ` Uniersite catholique de Louain, Croix du Sud, 1, B-1348 Louain-la-Neue, Belgium

Abstract Arrays of micro- and nanoscopic Ag and Au tubes with different thicknesses were prepared by electroless deposition of the corresponding metal within the pores of polycarbonate particle track-etched membranes. q 2001 Elsevier Science B.V. All rights reserved.
Keywords: Polycarbonate membrane; Electroless deposition; Template method

1. Introduction Nanomaterials constitute an emerging subdiscipline of the chemical and materials science that deals with the development of methods for synthesizing nanoscopic particles of a desired material and with specific characterization of the properties of the obtained nanomaterial. Nanomaterials have a wide-range of possible commercial and technological applications, including uses in chemistry, physics, electronics, optics, materials and biomedical sciences. Among the different strategies to synthesize nanoscopic materials reported in the literature, the use of nanoporous host materials as templates is an elegant approach w1x. Though there now exists a huge range of hosts, many studies were performed using commercial particle tracketched membranes PTM. and alumina membranes. Martin et al. w25x have used these commercial membranes as templates to prepare nanofibrils composed of metals, semiconductors and conducting polymers. Although particle track-etched membranes are commercially available, the technology has recently been improved in our lab in order to produce reliable and reproducible nanoporous particle track-etched membranes nano-PTM. w6x. These lab-scale samples exhibit controlled properties: mean pore size in the range of 151000 nm, low pore size distribution, perfectly cylindrical pores with smooth walls and a parallel arrangement across the membrane. With

such optimized properties, nano-PTM are excellent templates for the preparation of controlled nanoscale materials. In parallel with the development of preparation processes and characterization techniques of nano-PTM, we have performed chemical and electrochemical syntheses of polypyrrole PPy. and polyaniline PANi. within the pores of these nano-PTM. The studies on the morphology, structure and electrical properties of these template-synthesized PPy and PANi nanotubes and nanowires have been reported elsewhere w79x. In particular, we have shown that the electrical conductivity of conducting polymer nanotubes could be one or two orders of magnitude higher than in the bulk form of the polymer. In this paper, we report on the preparation of arrays of metallic micro- and nanotubes by electroless deposition of Ag and Au within the pores of micro- and nanopores. 2. Experimental 2.1. Materials SnCl 2 UCB., AgNO 3 Aldrich, 99q%., trifluoroacetic acid Acros, 99%., formaldehyde Acros., methanol and NH 4 OH Acros, 2838 wt%., KNaC 4 O6 H 4 Acros., MgSO4 P 7H 2 O Acros. and Na 2 SO 3 Merck. were used as received. A commercial solution of Na 3 AuSO 3 . 2 Oromerse Part B, Technic. was used after dilution in water 40 times.. Polycarbonate micro-PTM and nano-PTM with pore density ranging from 2 = 10 7 to 10 9 pores cmy2 , and different pore diameters ranging from 100 to 1000 nm were used as templates for electroless plating of silver and gold.

Corresponding author. Tel.: q 32-10-474-015; fax: q 32-10-451-593. E-mail address: demoustier@poly.ucl.ac.be S. Demoustier-Champagne..

0928-4931r01r$ - see front matter q 2001 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 8 - 4 9 3 1 0 1 . 0 0 2 1 7 - X

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S. Demoustier-Champagne, M. Delaux r Materials Science and Engineering C 15 (2001) 269271

2.2. Electroless deposition The procedure used for electroless plating of silver and gold was based on a report by Martin et al. w10,11x. First, a AsensitizerB Sn2q . was adsorbed to the substrate surface by immersion of the membrane into a solution of 0.026 M SnCl 2 and 0.07 M trifluoroacetic acid for 3 min. The solvent used was 50:50 methanolrwater. The membrane was then thoroughly rinsed with methanol. Electroless silver was deposited using a two-part A and B. bath. Part A consisted of 2.3 g AgNO 3 , 1.9 ml NH 4 OH and 22.7 ml of milli-Q water. Part B consisted of 7.95 g KNaC 4 O6 H 4 , 0.57 g MgSO4 and 18.2 ml of milli-Q water. Equal volumes of A and B were mixed with 14.1 parts of milli-Q water. The Sn2q-sensitized membrane was placed in a freshly prepared electroless silver plating solution. The working temperature of the electroless silver plating bath was 358C. The membrane was left in the plating solution for various times, ranging from 20 min to 48 h. This caused Ag to deposit on the activated surfaces and pore walls of the membrane. Electroless plating of gold consisted of three principal steps. First, adsorption of a AsensitizerB Sn2q . to the membrane surfaces pore walls and faces. as described above. Second, this Sn2q-sensitized membrane was then activated by immersion in an aqueous solution of ammoniacal AgNO 3 0.029 M. for 2 min, resulting in the formation of nanoscopic Ag particles on the pore walls and membrane faces. Then the membrane was again thoroughly rinsed with methanol. Finally, the Ag-coated membrane was immersed into a gold-plating solution containing Na 3 AuSO 3 . 2 7.9 = 10y3 M, diluted from Oromerse Part B, Technic., Na 2 SO 3 0.127 M. and HCHO 0.625 M.. The temperature of the gold-plating solution was 48C. The Ag particles are galvanically displaced by Au since Au is a more noble metal. As a result, the pore walls and faces become coated with Au particles. These particles are excellent catalytic sites for the oxidation of formaldehyde and the concurrent reduction of AuI. to Au0.. Thus, gold plating continues on gold particles with HCHO as a reducing agent, leading to the deposition of Au tubes into the pores and gold films onto the membrane faces. Plating times varied between 20 min and 48 h.

2.3. Characterization Scanning electron microscopy FE-SEM. was performed using a high resolution FEG Digital Scanning Microscope 982 Gemini from Leo.

3. Results and discussion Electroless metal deposition involves the use of a chemical reducing agent to plate a metal from solution onto a surface. The key requirement of an electroless deposition bath is to arrange the chemistry, such that the kinetics of homogeneous electron transfer from the reducing agent to the metal ions is slow. This is essential because otherwise the metal ion would simply be reduced in the bulk solution. A catalyst that accelerates the rate of metal ion reduction is thus applied to the surface to be coated. In this way, metal ion is reduced only at the surface and the surface becomes coated with the desired metal. Electroless deposition of silver and gold within the pores of PTM with different pore sizes ranging from 100 nm to 1 m m, and pore densities ranging from 2.2 = 10 7 to 10 9 cmy2 have been carried out. As the metal deposition proceeds from the activated pore wall, rather than from a base layer of metal, as in the electrochemical method, micro- or nanotubes that span the entire thickness of the membrane are obtained. The metal tubes have monodispersed length since the template membrane has uniform thickness. Dissolving away the polycarbonate template membrane in CH 2 Cl 2 allows us to observe by FE-SEM ensemble of silver or gold tubes Fig. 1.. Different experimental parameters affect the tubes thickness. In gold electroless deposition, increasing the temperature of the plating bath leads to an increase of the rate of deposition but also leads to less homogeneous and regular Au microtubes. A careful evolution of the tubes thickness in terms of the plating time was carried out. As shown in Fig. 2, Ag and Au tubes thickness increase with metal plating time. However, even after 48 h of reaction, the pores of the membrane are not completely filled with Au and Ag, thus microtubes are still obtained. This surely

Fig. 1. FE-SEM images of Au tubes obtained after dissolution of the PC membrane, a. plating time s 1 h, b. plating time s 48 h.

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Acknowledgements S.D-C thanks the Belgian National Fund for Scientific Research FNRS. for her Research Associate position. Thanks also go to the AServices Federaux des Affaires Scientifiques Techniques et CulturellesB for their financial support in the frame of the APole dAttraction InteruniversitairesB.
Fig. 2. Evolution of Ag and Au tubes thickness in terms of electroless plating time outer diameters of Au and Ag tubes s 1 m m..

References results from a limited diffusion of the reagents within the pores. We are currently investigating the possibility of preparing narrower Au nanotubes and to immobilize biological components at their surface, using a method based on self-assembling of functionalized thiols on Au.
w1x G.A. Ozin, Adv. Mater. 4 1992. 612. w2x Z. Cai, J. Lei, W. Liang, V. Menon, C.R. Martin, Chem. Mater. 3 1991. 960. w3x C.R. Martin, Science 266 1994. 1961. w4x C.R. Martin, Chem. Mater. 8 1996. 1739. w5x V.M. Cepak, C.R. Martin, Chem. Mater. 11 1999. 1363. w6x E. Ferain, R. Legras, Nucl. Instrum. Methods B 131 1997. 97, results to be patented. w7x J. Duchet, R. Legras, S. Demoustier-Champagne, Synth. Met. 98 1998. 113. w8x S. Demoustier-Champagne, P.-Y. Stavaux, Chem. Mater. 11 1999. 829. w9x M. Delvaux, J. Duchet, P.-Y. Stavaux, R. Legras, S. DemoustierChampagne, Synth. Met., in press. w10x C.J. Brumlik, V.P. Menon, C.R. Martin, J. Mater. Res. 9 1994. 1174. w11x V.P. Menon, C.R. Martin, Anal. Chem. 67 1995. 1920.

4. Conclusion In this paper, we have described a template method for preparing metallic micro- and nanotubes. Due to their high surface area, these materials present potential applications in different areas, in particular, in chemical and biochemical sensing devices.