NANO LETTERS

Palladium Wire-Shaped Nanoparticles from Single Synthetic Polycation Molecules

2002 Vol. 2, No. 8 881-885

Werner Jaeger
Department of Water Born Polymers, Fraunhofer-Institut fur Angewandte Polymerforschung, Geiselbergstr. 69,14476 Golm, Germany
Received May 3, 2002; Revised Manuscript Received May 29, 2002

ABSTRACT
Here we described simple chemical route to fabricate wire-shaped metallic nanoparticles of about 5 nm in a diameter and of 1000 nm in a length from single synthetic polycations. The preparation is based on the deposition of Pd-clusters on single poly(methacryloyloxyethyl dimethylbenzylammonium chloride) molecules adsorbed on Si-wafers from aqueous solution. The length and the diameter of nanowires are determined by the length and the diameter of the underlying polymer chains.

Introduction. Due to the considerable success in modern supramolecular1 and polymer2 chemistry various molecular objects of different shapes and functionalities are available now. Using complimentary building blocks and employing chemical reactions or self-assembling methodology3 it is possible to design complicated structures at molecular level.4 These approaches provide the development of the modern field of molecular electronics.5 For the further miniaturization of electronic devices it would be a challenging task to develop simple methods to fabricate nanoparticles of dedicated shape and desired properties incorporated in a supermolecular construction assembled from single functional molecules. One-dimensional (1D) sequences of nanoparticles (nanowires) are important elements of the nanotechnology toolbox because they provide interconnects between functional devices and even can be used as elementary units of optoelectronic devices. They also have been attracting increasing attention due to unique optical,6 magnetic,7 and catalytic8 properties. Several routes have been developed for synthesis of metallic nanowires, including template synthesis,9 step-edge decoration,10 vapor-liquid-solid condensation,11 as well as several other wet chemical techniques based on reduction of metals in the presence of protecting polymers or surfactants.12 Template-based methods involve deposition of metals into cylindrical pores of a host material, so-called 1D nanotemplates, e.g., carbon nanotubes,13 rod-like micelles,14 etc. Recently, DNA has been successfully used as
* Corresponding author: [email protected]. 10.1021/nl025603i CCC: $22.00 Published on Web 06/14/2002 2002 American Chemical Society

a biotemplate for the fabrication of metallic nanowires from single molecules.15 The synthesis is based on a two-step procedure that involves binding of metals (Pd or Ag) to DNA followed by chemical reduction. This procedure results in 20-100 nm thick metallic wire-shaped particles, which are, however, much larger than 2 nm assumed for the diameter of a single DNA molecule. Vacuum evaporation was used to deposit gold on single extended DNA strands to produce wires of width <10 nm and of length up to 60 nm.16 Recently, we reported about the visualization of different conformations of single flexible polyelectrolyte (PE) molecules of poly(2-vinylpyridine) with atomic force microscopy (AFM) and conditions to deposit fully stretched PE chains on the mica substrate.17 Here we describe a simple chemical route to fabricate metallic palladium wire-shaped nanoparticles which are 3-7 nm in a diameter and up to 1000 nm in a length based on mineralization of single poly(methacryloyloxyethyl dimethylbenzylammonium chloride) (PMBCl)18 molecules deposited on solid substrates. Experimental Section. Materials. Polycation PMB-Cl (below) was synthesized by free radical polymerization in aqueous solution.18

Methacryloyloxyethyl dimethylbenzylammonium chloride (MB-Cl) from Atochem (aqueous solution) and water soluble initiator 2,2-azobis (2-amidinepropane) hydrochloride (AAP) from Wako were used without further purification. Aqueous solutions of MB-Cl (0.68 M) and AAP (0.01 M) were mixed at 50 C during 1 h. Then the reaction mixture was cooled and resulting polymer was precipitated by addition of the concentrated NaCl solution. The further purification and fractionation was done by a sequential precipitation into acetone. Number average (Mn) moleculear weight, weight average (Mw) molecular weight, and polydispersity index (PDI) were evaluated from ultracentrifugation (MnUC ) 370 kg/mol; MwUC, ) 550 kg/mol; PDI ) 1.5) and light scattering data (Mn ) 450 kg/mol; MwLS ) 720 kg/mol; PDI ) 1.6). Highly polished silicon (Si) wafers (obtained from WackerChemitronics) were first cleaned three times in a ultrasonic bath for 5 min with dichloromethane (DCM), placed in the cleaning solution (prepared from NH4OH and H2O2) at 60 C for 1 h. (Note: NH4OH/H2O2 solution reacts Violently with organic compounds. Caution should be used when handling this solution.) Samples were finally exposed to 50% sulfuric acid for 15 min and then rinsed several times with Millipore water (18 MQxcm). Pd(OAc)2 (PA), dimethylamine borane (DMB), and DCM were used as received from Aldrich. To obtain a saturated PA aqueous solution, 5 mg of PA in 30 mL of water was placed in an ultrasonic bath for 30 min and then the unsolved PA was precipitated by centrifugation for 5 min at 2000 g. Sample Preparation. PMB-Cl was deposited on the surface of a carefully precleaned Si wafer or freshly cleaved mica from the 0.0005 g/L aqueous solution. The substrate was immersed in the solution for 1 min at ambient conditions to adsorb PMB-Cl and afterward it was rinsed several times in water. The substrate with deposited PMB-Cl was then dipped into PA solution (0.05 g/L) in acidic (HCl, pH 2.0) water19 for 1 min at ambient temperature and afterward rinsed in water again. In the final step Pd(+2) was reduced by treatment with 1.0 mg/mL aqueous solution of DMB. Atomic Force Microscopy. The adsorbed PMB-Cl molecules before and after Pd deposition are investigated in dry state with an AFM instrument Multimode (Digital Instruments, Santa Barbara) operating with an amplitude feedback in a light tapping mode (amplitude setpoint in the range of 0.99-0.95). Silicon tips with spring constant of 0.3 N/m and resonance frequency of 250-300 kHz were used after calibration with gold nanoparticles (diameter of 5.22 nm, Pelco AFM gold standard kit) to evaluate the tip radius (R). The tips with R ) 14.9 ( 1.9 nm were used for most measurements. The dimensions of structures obtained from AFM images were corrected (decreased) by the tip radius according to the standard procedure.20 Results. PMB-Cl molecules adsorbed onto mica from extremely diluted aqueous solution (see Experimental Section) appear in AFM images as worm-like chains (Figure 1a, c). PMB-Cl single molecules deposited on Si wafers (root mean roughness 0.5 nm) display the same conformation
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Figure 1. Representative AFM topography images (Z range 3 nm) of PMB-Cl: (a) on mica, (b) on Si wafer, (c) zoom of the image a, and (d) its cross-section, taken along the chain as shown by the dash line in the image c. Here and below we present original AFM images (without deconvolution) in which lateral dimensions of the structures are overestimated. The dimensions of the structures corrected using the value of the tip radius are shown in Table 1.

but the resolution of the images is much poorer because of the larger roughness of the Si wafers (Figure 1b).
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Table 1: Average Size of PMB-Cl Molecules and Pd Nanowires

sample PMB-CL Pd-PMB-Cl

Figure 2. Contour length (a, d), height (b, e), and width (c, f) distributions for PMB-Cl molecules (a, b, c) and Pd metallized wire-shaped nanoparticles (d, e, f).

The statistical analysis of number average (Ln) and weight average (Lw) contour length, height (H), and width (W) was done for 150 structures (Table 1, Figure 2 a-c). The values of contour length were used to calculate the number average MnAFM ) 362 kg/mol and the weight average MwAFM ) 516 kg/mol molecular weights, and polydispersity index PDI ) 1.42 of the polymer using the following equation (for example for number average molecular weight): Mn ) Ln mmon 2 l sin(/2)

Figure 3. Representative AFM topography images (Z range 7 nm) of Pd-PMB-Cl wire-shaped nanoparticles on Si wafer (a, b) and cross-sectioned along the long axis of the nanowires on image b (c).

where l ) 0.154 nm is the length of the C-C bond in the backbone, ) 109 is the valence angle between C-C bonds in the backbone, and mmon ) 284 g/mol is molecular mass of the monomer unit. After Pd deposition the resulting nanowires appear in AFM images as a 1D sequence of interconnected Pd clusters (Figure 3a, b). The wire-shaped Pd nanoparticles are visualized in profiles of AFM images as undulations interconnected by bridging strings. We performed the statistical analysis of parameters extracted from the AFM images and profiles: height, width, and contour length of nanowires (Table 1,
Nano Lett., Vol. 2, No. 8, 2002

Figure 2 d-f). For the representative series of experiments we obtained the same average values of height (2.6 ( 0.7 nm) and width (4.1 ( 1.5 nm). The number-average contour length of metallized PMB-Cl deposited onto Si wafers (Ln.met ) 251 nm) is only slightly smaller than the length of starting PMB-Cl. The same images and quantitative characteristics of the structures were obtained before and after reduction of Pd(+2) coordinated by PMB-Cl. It suggests that morphology of the metallic nanowires is determined by the conformation of Pd-PMB-Cl hybrid worm-like chains adsorbed on Si wafers. In contrast, nanowires produced by the same procedure onto the surface of mica display a considerably more coiled conformation (Figure 4).
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Figure 4. Representative AFM topography image (Z range 7 nm) of Pd-PMB-Cl nanoparticles on mica.

Pd(OAc)2 + 4HCl h H2PdCl4 + 2HOAc

(1)

Figure 5. Representative AFM topography image of Pd-PMBCl nanoparticles on Si wafer (Z range 7 nm) prepared from PMBCl of Mw ) 6300 Kg/mol.

PMBnxnClQ + 1/2n H2PdCl4 f PMBnx[PdCl42Q]n/2 (2) PMBnx[PdCl42Q]n/2 9 PMB-Cl Pd0 8

(3)

The lengths of the resulting Pd nanowires are determined by the length of underlying polymer chains. To prove this point, we synthesized the sample of PMB-Cl of much larger molecular weight (for this sample we evaluated Mw ) 6300 kg/mol with gel permeation chromatography). The number average contour length of the nanoparticles fabricated from this sample was Ln.met ) 1000 nm (Figure 5). Discussion. In aqueous salt-free solution, molecules of PMB-Cl adopt an extended conformation due to the strong long-range Coulomb repulsive forces between positively charged monomer units. The quantitative statistical analysis shows very good agreement between molecular dimensions of PMB-Cl obtained from the AFM images with those obtained from unltracentrifugation and light scattering data (Table 1). In this state single molecules of PE could serve as convenient 1D templates to produce wire-shaped metal nanoparticles. Such a strategy may be successful only for rigid PE, for example, for double stranded DNA.12 A stiffness of DNA molecules is effected not only by the electrostatic repulsion but additionally by a bare stiffness of the backbone and secondary structures stabilized by hydrogen bonds. Reaction of PMB-Cl with palladium acid19 (which is formed from PA in HCl solution, eq 1) results in waterinsoluble organic-inorganic composite (eq 2). Thus the addition of the palladium acid compensates positive charges on PE molecules and effects the collapse transition of flexible PMB-Cl chains to a globular conformation. To overcome the collapse of PMB-Cl chains by PA we developed the special experimental procedure. In the first step the extended worm-like conformation of PMB-Cl chains in aqueous solution was frozen during adsorption onto the surface of Si wafer. The following deposition of PA only slightly changes the initial extended conformation. Finally, the reduction step leads to nanowires (eq 3) (Figures 3-5). In contrast, the metallization of PMB-Cl on mica results in partially collapsed nanoparticles (Figure 4). An origin of this difference is still unknown, but probably, it is due to the poorer adsorption of PMB-Cl chains on mica than on Si wafers. The study of details of the chemical transformations involved in the fabrication of nanowires as
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well as determination of their exact structure and conductivity are in progress now. In conclusion, single flexible synthetic polyelectrolyte molecules PMB-Cl deposited on mica and Si wafers from aqueous solution were visualized with AFM. The single chains were found in worm-like conformations. The deposition of palladium clusters onto the PE molecules results in wire-shaped nanoparticles of about 5 nm in the diameter and number-average contour length equal to 251 or 1000 nm, depending on molecular weight of PE. Those metallized nanoparticles thus reflect the conformation and the length of original adsorbed PE molecules. We believe that the presented strategy to fabricate nanowires is universal and can be readily adapted to the preparation of organicinorganic nanoparticles of desired shape and size from appropriate polyelectrolytes and metals. This concept might be a route to a nanomachine consisting of a single molecule with different functions at different locations. Acknowledgment. This work was supported by Institut fur Polymerforschung Dresden and DFG foundation. We acknowledge helpful discussions with Prof. W. Pompe at Technical University Dresden. References
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