Appl. Phys. A 70, 365376 (2000) / Digital Object Identier (DOI) 10.

1007/s003390000440

Applied Physics A
Materials Science & Processing

Invited paper
Template-based synthesis of nanomaterials
A. Huczko
Department of Chemistry, Warsaw University, 1 Pasteur, 02-093 Warsaw, Poland (Fax: +48-22/822-5996, E-mail: ahuczko@chem.uw.edu.pl) Received: 27 May 1999/Accepted: 27 October 1999/Published online: 8 March 2000 Springer-Verlag 2000

Abstract. The large interest in nanostructures results from their numerous potential applications in various areas such as materials and biomedical sciences, electronics, optics, magnetism, energy storage, and electrochemistry. Ultrasmall building blocks have been found to exhibit a broad range of enhanced mechanical, optical, magnetic, and electronic properties compared to coarser-grained matter of the same chemical composition. In this paper various template techniques suitable for nanotechnology applications with emphasis on characterization of created arrays of tailored nanomaterials have been reviewed. These methods involve the fabrication of the desired material within the pores or channels of a nanoporous template. Track-etch membranes, porous alumina, and other nanoporous structures have been characterized as templates. They have been used to prepare nanometer-sized brils, rods, and tubules of conductive polymers, metals, semiconductors, carbons, and other solid matter. Electrochemical and electroless depositions, chemical polymerization, sol-gel deposition, and chemical vapour deposition have been presented as major template synthetic strategies. In particular, the template-based synthesis of carbon nanotubes has been demonstrated as this is the most promising class of new carbon-based materials for electronic and optic nanodevices as well as reinforcement nanocomposites. PACS: 61.46.+w; 61.48.+c; 61.82.Rx In 1959 Richard Feynman, the future Nobel Laureate, suggested in his famous lecture, entitled Theres Plenty of Room at the Bottom, a variety of tests that might be achieved at very small scales. Three decades later Feynmans vision has become the greatest scientic frontier of the century. It opened a new eld of Nanostructures having dimensions of about 10 to 1000 , a size that is small by engineering standards, common by biological standards, and large to chemists. The central thesis of nanotechnology is that almost any chemically stable structure that can be specied can actu-

ally be built. Nature has plenty of proof that nanotechnology works, from the liposomes in cells that manufacture proteins atom by atom, to the chloroplasts of plants that turn sunlight, carbon dioxide, and water into copies of themselves. Since biological machines exist, and work, and since biology follows the same laws of physics and chemistry applied by engineers, theres no question the nanostructural machines will work. Scientists have to gure out, however, how to build them. Of particular signicance is the size dependence of many properties in nanomaterials, for example, an enhancement in the strength and hardness of solids; the possibility of modications of their electrical properties by control of the arrangement within the constituent nanoclusters and of their assembly; the control of chemical reactivity by the attachment of functional side-groups; the control of optical properties by variation of the size and microstructure of the nanoclusters; the possibility of creating nanostructures of metastable phases with non-conventional properties, including superconductivity and magnetism [1]. If a nanocrystal is fabricated such that at least one of its dimensions is smaller than the length scale of some property, then that property is conned and becomes dependent on the size and shape of what is now called a quantum crystal [2, 3]. Material structures of reduced size or dimensionality may exhibit quantized conductance [46], localization phenomena in lowdimensional systems [7], and mechanical properties for the creation and propagation of dislocations in small metallic samples [8, 9]. In fact, the technology of nanostructures is driven largely by the urge to make ever smaller and faster electronics [10]. Another example of the nano-world at work is the photoelectric conversion property of nanostructured materials [11] which represents an alternative approach to efcient and economical solar energy conversion. For nanocrystalline particles quantum size effects may be manifested in the photophysical properties. Examples of improved photoelectrochemical cells include nanocrystalline: TiO2 [11, 12], CeSe [13], and ZnO [14]. Traditional materials for photoelectrochemical applications have been single-phase and composite compounds with 3-D structures. More recently, articially

366

structured and low-dimensional materials containing intricate, nanometer-scale structures have been developed. They frequently exhibit novel, highly anisotropic, enhanced properties, directly related to the dimensionality and the extra degrees of freedom of the nanostructure. A recent progress in quantum structure materials, physics, and devices was reviewed by Sakaki [15] and Barbara and Wernsdorfer [16] reported on the quantum tunneling effect in magnetic nanoparticles. The new perspectives in future nanoelectronics related to metal nanosized clusters were presented by Schmid and Hornyak [17]. Obviously, nanotechnology is not a single discipline. It requires the collaboration of physicists, chemists, biologists, computer scientists, and engineers. The coming nanometer age can, therefore, also be called the age of interdisciplinarity [18]. Synthesis, manipulation, modication, and control on the nanometer or even atomic scale have made tremendous progress in the past couple of years [1922]. These works require the use of multiple experimental techniques. Among the most popular are electron spectroscopies (XPS, AES), electron microscopies (SEM, TEM, BEEM), ion- and neutral spectroscopies (SIMS, SNMS, ISS), and scanning probe microscopies (SXM) such as atomic force microscopy (AFM) [23]. Many methods for preparing nanomaterials have been developed, ranging from milling techniques to chemical and lithographic methods [24]. Their main weakness is, however, attributed to the poor control of nal morphology of the produced nanostructures although some specic properties (for example, the enhanced electronic conductivities) are exhibited only with enhanced molecular and supermolecular order [25, 26]. A method termed template synthesis entails the preparation of a variety of micro- and nano-materials of a desired morphology and, therefore, provides a route for enhancing nanostructure order. In the broadest sense, a template may be dened as a central structure within which a network forms in such a way that removal of the template creates a lled cavity with morphological and/or stereochemical features related to those of the template. Various porous templates are employed and the nanostructures are synthesized within the pores. If the templates that are used have cylindrical pores of uniform diameter, monodisperse nanocylinders of the desired material are obtained within the voids of the template material. Depending on the operating parameters, these nanocylinders may be solid (a nanorod) or hollow (a nanotubule). The nanostructures can remain inside the pores of the templates or they can be freed and collected as an ensemble of free nanoparticles. Alternatively, they can protrude from the surface like the bristles of a brush. Thus, with the template approach, one is able to prepare monodisperse nanorods and nanotubules of almost any desired geometry. The method has been used to prepare both nanotubules and nanobrils composed of conductive polymers, metals, semiconductors, carbon, and other materials. The object of this paper is to review the template synthesis of nanomaterials. Various nanoporous structures used as the templates are described and the methods developed to do the synthesis within these materials are reviewed. The fundamental features of these novel nanostructures are also discussed. Finally, the applications of template-synthesized nanobrils and nanotubules are presented.

One should mention that an entire issue of Chemistry of Materials (volume 8, issue 8) has been dedicated to reviewing nanocluster chemistries including the use of templates to prepare nanostructures of various materials. The May 1999 issue of Accounts of Chemical Research is devoted to recent advances in this multidisciplinary eld. The template-based technique has also been explored and mastered for years by the research group at Colorado State University, USA, lead by Prof. Charles R. Martin [2637]. 1 Template synthesis of nanomaterials Nanotubules and nanorods of various materials can be synthesized using a template-based approach. Polymers, metals, semiconductors, carbons, and other materials have been deposited within pores of previously characterized templates [31, 32]. 1.1 Polymeric nanostructures The electronically conductive polymers, presented in Fig. 1, polypyrrole [35, 38, 39], poly(3-methylothiophene) [34], and polyaniline [40] were template-synthesized by electrochemical or oxidative polymerization. By controlling the polymerization time, conductive polymer tubules with thin or thick walls can be obtained. For polypyrrole, the tubules ultimately form solid brils. In contrast, the polyaniline tubules will never close up, even at long polymerization times [31]. Following the dissolution of the template polypyrrole nanotubules were freed. The SEM and TEM observations showed that the tubules are all 10 m long, which is equivalent to the thickness of the template and their diameter being larger than the nominal pore diameter [35]. Using the same technique, one-dimensional Au-polypyrrole nanoparticle arrays were obtained [38]. Conducting polyaniline laments were stabilized in the ordered, 3-nm-wide hexagonal channels of the mesoporous aluminosilicate [40]. The structural data

Fig. 1. Some of the template-synthesized electronically conductive polymers, adapted from [31]

367

show that about 20 aligned polyaniline chains could t in the template channels. Nishizawa et al. [39] described template synthesis of polypyrrole-coated spinel LiMn2O4 nanotubules. The outer diameter of these tubules agreed with the diameter of pores (200 nm) of the template, and the thickness of the tubule wall was about 50 nm. Nanoscopic polyacetylene brils were template-synthesized by polymerizing acetylene within 200-nm pores of ltration membrane [27]. The brils show good monodispersity of both length and diameter. Radical polymerization of acrylonitrile within the pores of zeolites produced polyacrylonitrile (PAN) [41]. On pyrolysis, PAN was transformed into nanometer-size conducting carbon laments. Tang and Xu [42] prepared carbon nanotube-containing poly(phenylacetylenes) (NT/PPAs) by in situ catalytic polymerizations of PPAs in the presence of the nanotubes. The short nanotubes thickly wrapped in the PPA chains exhibit a strong photostabilization effect, protecting the PPA chains from photodegradation. Such a stabilization effect may not only trigger basic research on the understanding of electronic properties of the nanotubes but also help nd technological applications for the nanotubes in electronic and optical systems. 1.2 Nanometals Through connement of metals to a nanosized dimension, a variety of changes in their characteristics are induced [29, 31, 32, 4245]. The gold nanoparticles were electrodeposited as shown in Fig. 2. First, a thin layer of Ag is sputtered (Fig. 2a) followed by plugs electrochemically grown into the pores (Fig. 2b). From those nanoposts Au nanoparticles are grown (Fig. 2c), and nally, the Ag foundations are chemically removed resulting in an array of Au nanorods (Fig. 2d). Depending on the pore diameter of the template, Au nanoparticles with different diameter can be obtained. A TEM analysis made possible the determination of aspect ratios of the nanoparticles. The hollow Au tubules that run the complete thickness of the template can also be obtained if the deposition is stopped before the pores

are completely lled [31]. Brumlik et al. [29] also prepared Au and Ag microtubules using various procedures. With the evaporation/electroplating method the smallest diameter tubules had outer diameters of 400 nm with the maximum tubule length about 1 m. Using the pore-wall-modication electrochemical method, longer Au tubules (around 3 m) were grown. 400-nm-diameter silver microtubules as long as 10 m were obtained via the electroless deposition method. However, tubules with extremely small diameters (30 nm) can also be prepared [29]. The potentiostatic electrochemical template synthesis yielded different metal nanowires (Ni, Co, Cu, and Au) with nominal pore diameters between 10 and 200 nm [42]. The wires produced were true replicas of the pores. Whitney et al. [43] fabricated the arrays of nickel and cobalt nanowires by electrochemical deposition of the metals into track-etched-templates. The morphology of the arrays was studied by using SEM and TEM techniques after removal from the template. The nanowires were narrow (30 nm) and continuous, with length equal to that of the matrix thickness. Tomassi and Buczko [44] obtained the nanorods of the following metals: Ni, Cu, Sn, Fe, Co, Zn, Cd, Au, and Pt, using the electrodeposition template technique. The diameter of metal particles depended on pore diameter and was found to be between 5 and 30 nm. Braun et al. [45] proposed a two-step procedure that allow the application of DNA as a template for the vectorial growth of a 12-m-long, 100-nm-wide conductive silver nanowire. The study show that the recognition capabilities of DNA can be exploited for the targeted attachment of functional nanostructures. 1.3 Carbon nanotubes Iijimas [46] discovery of novel carbon tubes of nanometer dimensions has greatly stimulated studies in the eld of carbon ber growth. The large-scale synthesis of carbon nanotubes, CNTs, based on an arc-discharge method similar to the synthesis of fullerenes, was later developed by Ebbesen and Ajayan [47]. In fact, this unusual form of carbon was already reported almost 50 years ago as minute vermicular growths (from 10 nm up to about 0.2 m in thickness) which can penetrate the brickwork of blast furnaces [48]. General methods commonly used to produce carbon nanotubules (both single-walled SWCNTs and multi-walled MWCNTs) carbon arc and laser plasma techniques [46, 47, 49], catalytic pyrolysis of hydrocarbons [5052], lowpressure condensation of carbon vapors [5355], and condensed-phase electrolysis [56, 57] suffer from the drawbacks that polyhedral carbon particles are also formed, the dimensions of the nanotubes are highly variable and they have a disordered and bundle structure. Thus, growing organized CNTs on large-scale surfaces is important for their possible various applications. Templating methods have been successfully applied to produce ensembles of aligned and monodisperse tubules of graphitic carbon with diameters as small as a few nm. CVD technique was commonly applied and hydrocarbons were pyrolyzed in alumina templates yielding graphitic carbon nanober and nanotube ensembles (with diameters as small as 20 nm and lengths around 50 m) [33, 36, 37, 58]. Massive arrays of self-oriented monodispersed carbon nanotubes

Fig. 2. Fabrication procedure for Au nanoparticle-alumina composite, adapted from [32]

368

were also prepared by CVD decomposition of hydrocarbons on patterned porous silicon [59, 60] or within the pores of activated silica [61, 62]. Both single- and multi-walled tubules were formed with diameters from 13 nm and lengths up to tens of m. SWCNTs were also synthesized in 1-nm channels of porous crystallites [63]. Tang et al. [64] fabricated mono-sized and parallelaligned SWCNTs in 0.73-nm-sized channels of microporous aluminophosphate crystallites by pyrolysis of tripropylamine molecules in the channels. The electric transport properties for the nanotubes were also studied and their conductivity was shown to monotonically increase with increasing temperatures, indicating that the SWCN had semiconductor characteristics. The formation of patterned CNTs (having the specic size of 3080 nm) can be also catalyzed by annealed FeNi islands (deposited on the Ag lm) in the process of CVD of carbon from acetylene decomposition [65]. Terrones et al. [66] described a method for generating aligned CNTs from hydrocarbons over thin lms of Co catalyst patterned on a silica substrate by laser etching. This method offered control over length (up to around 50 m) and fairly uniform diameters (3050 nm) of the nanotubules. 1.4 Other nanomaterials In addition to conductive brils, metal and carbon nanorods and nanotubules, a variety of other nanostructure have been succesfully synthesized by using a template technique. Hulteen and Martin [32] developed chemical strategies for preparing composite tubular nanostructures for which one can imagine a host of applications. Thus, a semiconductor conductor (TiO2 polypyrrole or TiS2 polypyrrole) tubular nanocomposites (60 m long and 200 nm diameter) as well as conductorinsulatorconductor (CPANAu) composite structures were fabricated with template synthesis. Also, 15-nm-diameter semiconductor (TiO2 ) nanotubules and nanobers were deposited into the pores of a template membrane [32, 67]. A variety of applications for tailored composites in the nanometer-size range from 1 to 100 nm, including structural materials, high-performance coatings, catalysts, electronics, photonics, and magnetic and biomedical materials have been recently reviewed by Dagani [68]. Near-monodisperse hollow nanotubules of MoS2 (about 30 m long with diameters of 50 nm and wall thickness of about 10 nm) were prepared by thermal decomposition of molecular precursors, (NH4 )2 MoS4 and (NH4 )2 Mo3 S13 , within the pores of Al2 O3 membrane template [69]. Template-based approaches to the preparation of amorphous, nanoporous silicas (using the removable organic templates) were described by Raman et al. [70]. Pt- or Fe-metal-enclosed carbon tubes were obtained by using the electrochemical template technique [71, 72]. These composite nanotubes are uniform and their outer diameter and wall thickness could be estimated to be 30 nm and about 5 nm, respectively. Carbon nanotubes have been widely applied as removable templates for fabrication oxide nanocomposites (PbO, Bi2 O3 , V2 O5 , SiO2 , Al2 O3 , MoO3 , MnO2, Co3 O4 , ZnO, and WO3 ) [34, 73, 74]. Metal (Ag, Au, AuCl3 )-lled carbon

nanotubes were obtained by Chu et al. [75] and individual crystals located within the hollow cavity of nanotubes were studied by FEGTEM technique with a 0.7-nm probe for the EDS data. Galium nitride nanorods (with a diameter of 4 to 50 nm and a length of up to 25 m) were prepared through a carbon nanotube-conned CVD reaction [76, 77]. The GaN nanorods were solid in contrast to the hollowcore structure of CNTs. The nanostructure of GaN (a single crystal with fewer defects) and SiC (a -SiC crystal with heavy layer sequence faults) nanowires produced by carbon nanotube-conned reaction has been studied by means of HRTEM, microanalysis, and microdiffraction [78]. Silicon nitride nanorods were also fabricated through the hightemperature reaction of carbon nanotubes with SiO under nitrogen atmosphere. Han et al. [79] prepared boron-doped carbon nanotubes and crystalline nanorods (with typical diameters between 6 and 30 nm) through a template substitution of some carbon atoms of CNTs by boron atoms. Boron nitride nanotubes were also successfully synthesized by CNTsubstituted reaction method [80]. Solid carbide nanoscale rods of TiC, NbC, Fe3 C, SiC and BCx with typical diameters of between 2 and 30 nm were prepared by the conversion of carbon nanotubes to carbide rods by reaction with respective volatile oxide and/or halide species [81, 82]. The growth of the nanorods involved a template mechanism in which the carbon nanotubes dened the overall morphology of the produced nanostructures. The template-based organization of buckminsterfullerene C60 in one-dimensional array was achieved by using various approaches: fullerene incorporation (by wet chemistry) into the channels of zeolites [83], surface adsorption on the monolayers of the Au chain structures acting as adsorption templates [84], or C60 trapping in situ during carbon nanotube formation, following pulsed laser vaporization of graphite [85]. DNA could be also used as a framework for the assembly of fullerene nanomaterials through electrostatic interactions with the phosphate groups along the DNA backbone [86]. Other forms of carbon nanostructures were prepared by using the template-assisted growth process. Thus, a highly oriented graphite was synthesized in a two-dimensional opening between the lamellae of montmorillonite as the eld of carbonization [87, 88] Fig. 3. The carbon was then released from MONT and its crystallite size (L c and L a were around

Fig. 3. Schematic diagram of graphitization process of the nanocarbon derived from intercalated polymer (IPC) and free polymer (FPC), adapted from [87]

369

40 nm and > 1 m, respectively) determined by XRD and SEM analyses. Carbonmineral nanocomposites and microporous carbons (about 80% of micropore volume is in pores smaller than 1.2 nm) were obtained by in situ carbonization of organic compounds in the inorganic matrixes [89]. 2 Template synthetic techniques Nearly any solid matter can in principle be synthesized within nanoporous templates, provided a suitable chemical pathway can be developed. There are, however, some concerns that need to be considered, for example (1) does the deposited material wet the pore; (2) how to avoid the pore blockage; (3) is the template stable with respect to the reaction conditions? There are essentially ve representative strategies to carry out template synthesis of nanostructures [31, 32]. 2.1 Electrochemical deposition Electrodeposition of a material within the pores of the matrix is preceded by coating one face of the template with a metal lm and using this metal lm as a cathode for electroplating [28, 29, 32, 4244]. The volume of the pore is continuously lled up beginning from the pore bottom. Thus, the length of a nanostructure can be controlled by varying the amount of material deposited. Both metal and conductive polymer nanorods and nanotubules can be sythesized using this method. Arrays of Ni and Co nanowires were electrodeposited from sulfate solutions as shown in Fig. 4. The process was carried out at constant potential so that the deposition could be monitored from the current response. Large arrays of uniform and continuous Co and Ni nanowires (diameter in the range of 3060 nm) were obtained after dissolving the polycarbonate template [43]. The electrochemistry of the template synthesis of nanowires was studied by

comparing the potentiostatically measured currenttime characteristics obtained during wire growth for different pore dimensions and a pore-size dependence of the diffusion coefcient for the metal ions was found [42]. Another example of the vacuum/electroplating method is shown in Fig. 5. A gold lm is rst vacuum evaporated on the surface of a membrane yielding extremely thin-walled (about 20 nm) gold tubules (Fig. 5a) which can be further strengthened by electrochemical deposition of silver (Fig. 5b). Finally, the membrane is dissolved away to expose an ensemble of free-standing tubules with outer diameters as small as 200 nm (Fig. 5c) [29]. 2.2 Electroless (i.e., chemical) deposition Electroless deposition involves the use of a chemical agent to plate a material from the surrounding phase onto a template surface [29, 39, 40, 73, 77, 82]. This method differs from the previous one in that the surface to be coated need not be electrochemically conductive. The material deposition in the pores starts at the pore wall. Therefore, after short decomposition times, a hollow tubule is obtained within each pore, whereas long deposition times result in solid nanowires. Unlike the electrochemical deposition method where the length of the metal nanowire can be controlled at will, electroless deposition yields structures that run the complete thickness of the template membrane. The inside diameter of the tubules

Fig. 4. Schematic illustration of the electrode arrangement for electrodeposition of Ni and Co nanowires, adapted from [43]

Fig. 5. Schematic of the evaporation/electroplating procedure for forming metal microtubules, adapted from [29]

370

Fig. 7. Schematic of the electroless deposition for forming metal tubules, adapted from [29]

Fig. 6. Schematic illustration of the electroless method for LiMn2 O4 tubule array, adapted from [39]

Fig. 8. Reaction scheme used to prepare carbide nanorods, adapted from [82]

can be controlled by varying the deposition time. Of course the outside diameter is determined by the dimensionality of the pores in the matrix. Figure 6 shows a scheme of this method applied for a LiMn2 O4 tubule array [39]. First, a porous alumina membrane was plugged with Pt nanoposts (Fig. 6a). An aqueous solution of Li and Mn nitrates was then applied to ll the pores of the template (Fig. 6b). The membrane was heated at 500 C for 5 h, resulting in formation of tubules of LiMn2 O4 within the pores of the template (Fig. 6c). Finally, the alumina membrane was dissolved using NaOH solution yielding the tubular arrays of lithium-manganese-oxide (Fig. 6d). Electroless silver was deposited as shown in Fig. 7 [29]. A strip of Scotch-brand tape was attached to the smooth face of a polycarbonate membrane (Fig. 7a) which was then activated with a tin (II) chloride solution (Fig. 7b). The tape was removed (Fig. 7c) and the Sn2+ activated membrane was placed in a freshly prepared electroless silver plating solution. This caused Ag to deposit on the activated pore walls (Fig. 7d) yielding silver nanostructures. Another approach to chemically synthesize nanorods is shown schematically in Fig. 8 [81, 82]. Here, formerly obtained carbon nanotubes are consumed in the reaction with volatile metal halide or oxide species to form solid carbide nanorods with diameters between 2 and 30 nm and lengths up 20 m. As a matter of fact, carbon tubules have been recently commonly used as templates in the synthesis of nanorods and nanotubes [75, 9095]. Various materials were introduced to the internal nanotube cavities by a variety of methods. Cook

et al. [90] reviewed the arc-evaporation of metal-doped carbon rods for a number of transition metals and lanthanides. With the exception of cobalt and copper, the encapsulated materials are always transition metals or lanthanide carbides. The arc-evaporation of manganese compounds yielded the nanotubes lled with various manganese carbides [91]. Demoncy et al. [96] showed that the presence of sulfur in catalytic quantity is crucial for the production by this technique of abundant metal (Cr, Ni, Yb, Dy) containing encapsulated nanowires. In addition to this in situ method, carbon nanotubes can also be lled using a one-step chemical method by boiling a sample in HNO3 in the presence of metal nitrates [90, 92]. A more versatile two-step method uses pre-opened nanotubes which can be lled using standard wet-chemistry techniques. Green et al. [90, 93] used this method to encapsulate a wide variety of inorganic compounds, including RhCl3 , AuCl3 , PdCl2 , SnO2 , pure metals (Fe, Ni), and oxides (Sm2 O3 ). As was rst observed for molten lead and bismuth, the nanotubes can also be lled simply by capillary action [94, 95]. Thus, they act as moulds for the fabrication of metalic wires, some of which can be less than 2 nm in diameter [95]. 2.3 Chemical polymerization Different conductive polymers (see Fig. 1) can be templatesynthesized by the polymerization of the corresponding monomer to yield tubular nanostructures [27, 31, 33, 35, 38, 41, 63, 70, 8789]. The process can be accomplished by simply immersing the membrane into a solution containing the

371

Fig. 9. Scheme of methods for synthesis of enzyme-loaded nanocapsule arrays, adapted from [31]

Fig. 10. Schematic of the organic-template approach to prepare nanoporous amorphous silica, adapted from [70]

desired monomer and a polymerization reagent. The polymer preferentially nucleates and grows on the pore walls, resulting in tubules at short deposition times and bers at long times. For electronically insulating plastics (i.e., polyacrylonitrile, PAN) the nanostructures can be further thermally processed to create conducting graphitic carbon tubules and brils [32, 97]. Figure 9 shows an interesting example of synthesis of the enzyme-loaded nanocapsule arrays. The surface of the polycarbonate template membrane is rst sputtered with a thin layer of gold (Fig. 9a) which is followed by the electropolymerization a polypyrrole lm to yield short plugs within the pores (Fig. 9b). Polypyrrole tubules are then chemically polymerized within the pores of the plugged template (Fig. 9c). The capsules are then lled with the desired enzyme (Fig. 9d). Torrseal epoxy is applied to the upper surface of the membrane (Fig. 9e), and nally the template is dissolved to yield the array of enzyme-loaded nanocapsules (Fig. 9f). The organic-template approach to prepare nanoporous silica is shown in Fig. 10. Here, the supramolecular templating was used to synthesize inorganic nanomaterials. There is a direct correlation of the templating surfactant array size and shape to the nal morphology in the silica mesophase. 2.4 Sol-gel deposition Sol-gel synthesis within the pores of templates can be conducted to create both tubules and brils of a variety of materials [32, 34, 38, 74]. The process typically involves preparation of a solution of a precursor molecule to obtain rst a suspension of colloid particles (the sol) and then a gel composed of aggregated sol particles is thermally treated to yield the desired nanostructure within the pores of the tem-

Fig. 11. Synthetic protocol for the synthesis of alkyldithiolate-linked Au colloids, adapted from [38]

plate. Figure 11 presents a scheme for the synthesis of wellorganized 1-D Au colloids. The Ag was electroplated inside the pores of the membrane and the pore side of the Ag lm was derivatized with 1,6-hexanedithiol. The membrane was subsequently immersed in a solution containing Au colloids. They diffuse down the pore and bind to the free end of the dithiol at the base of the pore. Any unbound colloid was removed and the cycle is repeated by alternately soaking the membrane in solutions of the dithiol and Au. Silver coating and the template were nally dissolved yielding the supernanostructure in which the number of colloids is controlled by the number of immersion cycles. 2.5 Chemical vapor deposition (CVD) Chemical vapor deposition has long been applied in the commercial production of solid thin lms. The technique entails surface solidication of desired reactants resulting from their gas-phase chemical transformations. The method has successfully been developed for the template synthesis of

372

carbon nanotubules [32, 36, 66]. The starting reactants, i.e. ethylene and pyrene [37, 59], acetylene [61, 62, 65], tripropylamine [63], methane [60], propylene [58], or 2-amino-4,6dichloro-s-triazine [66], were thermally activated and decomposed to solid carbon within porous templates while traversing the length of the pore. Thermal decomposition of the gas occurs throughout the pores, resulting in the deposition of carbon lms along the length of the pore walls and formation of carbon tubules within the pores. The thickness of the

walls of tubules is dependent on total reaction time and precursor pressure. The method offers control over length (up to 100 m) and fairly uniform diameters in nanometer range, as well as efcient-producing carbon tubules. Figures 12 and 13 illustrate the formation process of carbon tubes by the template thermal decomposition of ethylene (at 700 C) and propylene (at 800 C), respectively. The CVD technique can also be utilized to templatesynthesize other nanostructures such as Au/TiS2 composites [32, 98]. 3 Template materials used Most of the studies in template synthesis, to date, have entailed the use of two types of nanoporous materials, tracketch polymeric membranes and porous alumina or silica membranes. However, there are a variety of other, both natural and synthetic, materials that could be utilized as templates. Formerly synthesized nanostructures can also be used as templates. 3.1 Track-etch membranes The track-etch method entails bombarding a nonporous sheet of the desired material (standard thickness range from 6 to 20 m) with nuclear ssion fragments to create damage tracks in the material, and then chemically etching these tracks into pores [32]. The resulting porous materials contain randomly distributed nanochannels of uniform diameter (as small as 10 nm). Pore densities approaching 109 pores cm2 can be obtained. Such membranes are also often called nuclear track lters or screen membranes. These commercially available (Nuclepore, Poretics, Cyclopore, Osmonics, and Millipore) ltration membranes are usually prepared from polycarbonate or polyester [2932, 38, 43, 99, 100]. Other materials (for example mica [101]) are also amenable to the track-etch process [32, 102]. The structure of track-etched membranes can be modied by a high-frequency discharge plasma in air [103]. 3.2 Anodic aluminum oxide (AAO) Alumina membranes with uniform and parallel porous structure are obtained by anodic oxidation of aluminum metal in solutions of sulfuric, oxalic, or phosphoric acid [2734, 36 38, 44, 104]. Dimensions of the pores are tunable in the range of 4 to several hundred nanometers, which render it an ideal template material for creating arrays of cylindrical nanostructures. Unlike the track-etch membranes, the pores in AAO templates have little or no tilt with respect to the surface normal resulting in an isolating, non-connecting pore structure [3032]. Pore densities as high as 1011 pores cm2 can be obtained, and typical membrane thickness can range from 10 to 100 m [3032, 105]. Li et al. [106] reported recently on the growth of highly oriented pores in anodized aluminum oxide. The AAO membranes have a porosity of 40% to 65% [29], and are commercially available (Whatman Anapore, Anotech Separations) [28, 37, 38, 99].

Fig. 12. Schematic process for the synthesis of oriented carbon nanotubes on porous silicon by catalyst patterning and CVD of ethylene, adapted from [59]

Fig. 13. Schematic drawing of the formation process of carbon tubes by template CVD of propylene, adapted from [58]

373

Organized nanostructures can be also grown on porous silicon obtained by electrochemical etching of Si wafers [59]. The resulting porous structure has a thin nanoporous layer (with pore diameters of 3 nm) on top of macroporous layer [107]. 3.3 Other nanoporous materials Various other synthetic and natural nanoporous materials have been used in the template synthesis. Mesoporous silica were prepared by a sol-gel process from tetraethoxysilane (TEOS) hydrolysis followed by the calcination of a soft material called an alcogel [61, 62]. Silica aerogels have a high porosity (90% or higher) and high surface area (8001000 m2 /g), an ideal matrix for the chemical vapor inltration of a desired material on an extremely ne scale. The zeolite-related aluminophosphates VPI-5 [81] and AlPO4 -5 (AFI) [63], and aluminosilicates MCM-42 [40] and zeolite Y [41] were used as microporous inorganic host materials. The intracrystalline space of layered minerals was also employed for in situ template formation of nanocomposites. Thus, Bandosz et al. [89] used the synthetic mineral, taeniolite TL-0. The lithium form of this mineral has the following chemical formula: Li(Mg2 Li)(Si4 )O10 F2 nH2 O. Carbon nanostructures were also prepared by using a two-dimensional opening between the lamellae of montmorillonite (MONT) [87, 88]. Modication of the porous structure of alumina ceramics by chemical vapor deposition (CVD) of nanoscaled SiC and Si3 N4 led to a new family of composites [108]. Nanotechnological syntheses could also rely upon selfassembling strategies using natural scaffolds as templates for the construction of synthetic nanostructures. DNA is particulary well suited for such applications due to its structural regularity, its ability to reversibly assemble through hydrogen bonding, and the relative ease in obtaining materials of precise length within the nanometer regime [45, 86]. Nanoscale templating was also carried out to produce 1- and 2-dimensional elongated carbon nanostructures using Au/Ni (110) [84] and layered cobalt [66] as patterned catalysts. The interchain separation of obtained nanostructures was dictated by the surface modication of adsorption templates. Kong et al. [60] described a strategy for making highquality individual single-walled carbon nanotubes on silicon wafers patterned with m-scale islands of catalytic material (Fe). The control of external dimensionality of NTs was also achieved by the diameter (about 3080 nm) of the round alloy particles prepared by annealing FeNi islands deposited on the silica substrate during the catalytic decomposition of acetylene [65]. A template-based approach to prepare controlled porosity materials was demonstrated by Raman et al. [70] in the synthesis of organic template-derived amorphous silicas. Ramans scheme was inspired by the chemical specicity inherent to biological systems observed earlier by Dickey [109]. Dickeys 1949 publication appears to be, in fact, the rst documented demostration of molecular imprinting or templating to control pore size and shape. The inner dimensionality of produced structures was also controlled using Ta tubes as templates to synthesize TaC and graphite microtubules [110].

3.4 Nanostructures as templates Using carbon nanotubes as templates, various ceramic oxide (silica, vanadium pentoxide, molybdenum oxide, zirconia, and yttria-stabilized zirconia) nanotubes were prepared [111]. Multi-walled carbon nanotubes are usually obtained by the arc-discharge method [7375] or from metal-catalyzed decomposition of ethylene in the presence of hydrogen [76, 77, 81, 82]. The carbon template can be later removed by heating the coated or lled nanotubes in air at elevated temperatures [111]. Thus, the nanoscale rods or tubules with typical diameters of between 2 and 30 nm and lengths of up to 20 m are separated [81, 82]. The carbon nanotube acted as a removable template in the synthesis of silicon and boron nitride nanorods [76]. In the course of preparing Si3 N4 nanorods the silicon/silica mixture was covered with carbon nanotubes and the endothermal reaction 3SiO(g) + 3C(s) + 2N2(g) = Si3 N4(s) + 3CO(g) was carried out at 1673 K in Al2 O3 crucible under owing nitrogen. The total transformation of carbon nanotubes into silicon nitride nanorods (diameter between 440 nm) was observed. The Pt nanorods and nanoparticles were also prepared using carbon nanotubes formerly obtained by a template carbonization technique and an anodic aluminum oxide lm [71]. Produced by pulsed laser vaporization of graphite, SWCNTs contained self-assembled chains of C60 molecules, resembling a nanoscopic peapod [85]. 4 Examples of fundamental and applied studies The reason for research interest in nanowires and nanotubules of various materials is manifold. Efforts to create electronic functions and devices based on nanostructures (having superior electronic properties) instead of bulk materials are inspired by the anticipated enormous increase in computing speed and storage density. Thus, the conductivity of polymer brils, laments, and tubules has been extensively investigated [27, 35, 3941]. The nanoscopic brils of heterocyclic polymers show electronic conductivities (along the bril axis) that are substantially higher than conductivities of bulk lms of the analogous polymer [112]. Also the template-synthesized polyacetylene brils show enhanced supermolecular order and higher electronic conductivity [27]. Wu and Bein [40] demonstrated that the polyaniline laments have signicant conductivity while encapsulated in nanometer channels as measured by microwave absorption at 2.6 GHz. For polypyrrole brils the conductivity increases with decreasing diameter: values higher than one order of magnitude larger than the bulk value were deduced for nanostructures with diameters of around 30 nm [113]. Intrazeolite polyacrylonitrile can be pyrolyzed to form conducting material consisting of nanometer-size laments; these systems are promising candidates for low-eld conductivity at nanometer-scale dimensions [41]. The investigation of the galvanostatic charge-discharge characteristics of the polypyrrole-coated LiMn2O4 nan-

374

otubule electrodes showed their several times higher capacities than the polypyrrole-coated LiMn2 O4 thin-lm electrode [39]. Nanometals have interesting optical, electronic, electrochemical, and magnetic properties [31]. The colloidal suspensions of gold differ in color depending on the size of the spherical Au particles. This results from shape-induced changes in the plasmon resonance band of the Au nanoparticle which corresponds to the wavelength of light that induces the largest electric eld on the nanoparticles. Thus, the Al2 O3 templates with imbedded gold nanocylinders may nd decorative and protective applications [31, 32, 44]. The Au nanodisk electrodes prepared by using the template method offer in fundamental and applied electrochemistry the opportunities to study the kinetics of charge-transfer processes that are too fast to measure at conventional macroscopic electrodes [114]. The ultratrace levels of electroactive species can be detected with ensembles of nanoscopic electrodes [31] and electrochemistry can be performed in highly resistive media [115]. Quantum phenomena are observed in the electron transport of thin metal wires when the wire diameter becomes comparable or smaller than some scaling lengths [116118]. Spin-polarized transport leads to interesting phenomena in nanostructured materials composed of magnetic transition metals [99]. Among these, the so-called giant magnetoresistance (GMR) effect discovered in 1988 [119], has attracted a great deal of interest recently. The study of magnetic order and reversal processes on nanostructured magnets may create the possibility of synthesis of new devices and highdensity data storage materials [99]. Membranes lled with Co, Ni, or Fe are magnetic nanocomposites that have a strong perpendicular magnetic anisotropy suitable for perpendicular recording [120]. Arrays of template-synthesized ferromagnetic Ni and Co nanowires display the preferred magnetization direction perpendicular to the lm plane with enhanced coercivities as high as 680 oersteds and remnant magnetization up to 90% [43]. DNA-templated synthesis of conducting silver nanowires allows for the construction of functional circuits since the difculties of achieving inter-element wiring and electrical interfacing to macroscopic electrodes may be overcome [45]. DNA-templating routes lead to hybrid nanoarchitectures in size regimes inaccessible by traditional synthetic methods [86]. The superconducting properties of lead nanowires exhibit some differences compared to those of large specimens: the external critical eld parallel to the nanowire axis is about one order of magnitude larger for the sample with diameter 120 nm than for the bulk [99]. Carbon nanotubes represent a very distinctive group of nanostructures owing to remarkable properties suggesting a range of new technologies. Discussing the likely utility of carbon nanotubes, nanotube researcher Alex Zettl of the University of California, Berkeley, said: If I were to write down all the different applications, Id have a book for nanotubes. [121]. CNTs can be used as catalysts and catalyst supports, selective adsorption agents, composite materials in reinforcement applications, in energy storage [122]. Polymerized nanotube structures may form new zeolites [123], CNTs can be transferred to diamond by laser irradiation [124] or applied for electrochemical capacitors [125]. They are

well suited for use as nm-sized probe tips in applications such as atomic force microscopy (AFM) [126] and scanning probe microscopy [127] or the worlds smallest gas cylinders [128] for storing gases (hydrogen!) [129]. Hyperion Catalysis International is already manufacturing MWCNTs in bulk (300 kg every day) for use in electrically conducting plastics [121]. CNTs constitue a new class of materials with fascinating electronical applications. They behave as ideal 1D quantum wires [130] and quantum resistors [131]. A high-intensity electron gun based on eld emission from a lm of aligned carbon nanotubes has been made [132]. Cathode ray tubes (as lighting elements) equipped with eld emitters composed of MWCNTs have been already manufactured [133]. However, the conventional techniques to produce carbon nanotubes yield unsorted, web-like products. Obviously, for both fundamental studies and applications the alignment of the carbon nanotubes is particularly important. Although some progress in this respect has been made already [134 137], the template-based approach to synthesize aligned and tailored carbon nanotubes, as shown above [33, 36, 37, 58, 60, 62, 65, 66], seems to be the best technique. There are several other specic potential applications of various template-synthesized nanostructures. The polycarbonate template membranes were loaded with enzymes (glucose oxidase, catalase, subtilisin, trypsin, and alcohol dehydrogenase have been tested to date) or drugs to make a new type of enzymatic bioreactor or in drug delivery [31]. 1D Aunanoparticle arrays linked by organic conductive polymers and alkyldithiolates may be useful in optimizing electromagnetic enhancements in surface-enhanced Raman spectroscopy (SERS) and in developing functional nanoscale electronic circuit elements [38, 137, 138]. Monodisperse gold nanotubules deposited in pores of polymeric membranes, with inside diameter of molecular dimension (less than 1 nm), were used in a simple membrane-permeation test to cleanly separate small molecules on the basis of molecular size [139]. Such a molecular lter was used to separate pyridine (molecular weight 79) and quinine (molecular weight 324). The MoS2 nanoclusters and tubules are known to be a useful catalyst for hydrodesulfurization, an electrode in high-energy-density batteries, and an intercalation host to form new materials [140]. The organization of C60 in 1D channels of the microporous zeolites leads to a nanocomposite which exhibits novel interesting optoelectronic properties [83]. Template-derived amorphous silicas with tailormade pore sizes and shapes are important in many applications, such as shape-selective catalysis, molecular sieving, chemical sensing, and selective adsorption [70]. Carbide [81, 82] and silicon nitride [76] nanorods may nd technological applications in solid-state physics and nanostructured composite materials. GaN nanorods have promising applications for blue and ultraviolet opto-electronic devices (blue lightemitting diodes) [77]. In addition to carbon nanotubes other new forms of carbon (for example highly oriented nanographite) are expected to have various interesting physical properties such as high conductivity, optical anisotropy, and high radiation resistance, and, therefore, can be applied as a new material in the elds of advanced technology [8789]. Semiconductor (TiO2 , MnO2 , Co3 O4 , ZnO, WO3 , and SiO2 ) tubules and brils were synthesized by a template tech-

375

nique [32, 34]. TiO2 in particular is an excellent photocatalyst for the decomposition of organic pollutants [141]. The rate of decomposition of salicylic acid on an array of immobilized TiO2 nanobers was an order of magnitude higher than for the thin-lm TiO2 catalyst [32, 34], mostly due to the increased surface area and corresponding increase of the decomposition reaction rates. 5 Summary The general methodology described here allows the design and synthesis of a wide range of nanostructures with specied geometry and surface characteristics, and with a wide range of potential applications. For example, such tailored nanomaterials could be used in inclusion chemistry and electrochemistry, materials and biomedical sciences, electron microscopy, molecular storage and separation technology, novel optical and electronic devices. The presented approach, termed template-synthesis, entails using the pores and channels in the nanoporous template structures for forming the desired nanomaterials.
Acknowledgements. The work was supported by the Committee for Scientic Research (KBN) through the Department of Chemistry, Warsaw Uniwersity, under Grant No. 3 T09A 058 16.

References
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. M.S. Dresselhaus: Mater. Sci. Eng. 354, 192 (1993) J.R. Heath: Science 270, 1315 (1995) C.B. Murray, C.R. Kagan, M.G. Bawendi: Science 270, 1335 (1995) R. Landauer: J. Phys. Condens. Matter 1, 8099 (1989) C.W.J. Beenakker, H. Van Houten: Solid State Phys. 44, 1 (1991) J.I. Pascual, J. Mendez, J. Gomez-Herrero, A.M. Baro, N. Garcia, U. Landman, W.D. Luedtke, E.N. Bogachek, H.-P. Cheng: Science 267, 1793 (1995) P.A. Lee, T.V. Ramakrishnan: Rev. Mod. Phys. 57, 287 (1985) R.W. Siegel: Mater. Sci. Eng. B 19, 37 (1993) U. Landman, W.D. Luedtke: J. Vac. Sci. Technol. 9, 414 (1991) L.L. Sohn: Nature 394, 131 (1998) G.J. Meyer, P.C. Searson: The Electrochemical Society Interface 23 (Winter 1993) N. Vlachopoulos, P. Liska, J. Augustynski, M. Gratzel: J. Amer. Chem. Soc. 110, 1216 (1988) G. Hodes, I.D.J. Howell, L.M. Peter: J. Electrochem. Soc. 139, 3136 (1992) S. Hotchandani, P.V. Kamat: J. Electrochem. Soc. 139, 1630 (1992) H. Sakaki: Solid State & Materials Science 1, 17 (1996) B. Barbara, W. Wernsdorfer: Solid State & Mater. Sci. 2, 220 (1997) G. Schmid, G.L. Hornyak: Solid State & Mater. Sci. 2, 204 (1997) H. Rohrer: Il Nuovo Cimento A107, 989 (1994) R. Garcia: Appl. Phys. Lett. 60, 1960 (1992) I.-W. Lyo, P. Avouris: Science 253, 173 (1991) M. Crommie, C.P. Lutz, D.M. Eigler: Science 262, 218 (1993) C.J.A. Monty: High Temp. Chem. Processes 3, 467 (1994) K. Reihs: Thin Solid Films 264, 135 (1995) G.C. Hadjipanayis, R.W. Siegle: In Nanophase Materials: SynthesisProperties Applications. Series E: Applied Sciences (Kluwer, Dordrecht 1994) p. 260 S. Kivelson, A.J. Heeger: Synth. Met. 22, 371 (1988) J. Lei, Z. Cai, C.R. Martin: Synth. Met. 46, 53 (1992) W. Liang, C.R. Martin: J. Am. Chem. Soc. 112, 9666 (1990) C.J. Brumlik, C.R. Martin: J. Am. Chem. Soc. 113, 3174 (1991) C.J. Brumlik, V.P. Menon, C.R. Martin: J. Mater. Res. 9, 1174 (1994) C.R. Martin: Science 266, 1961 (1994) C.R. Martin: Chem. Mater. 8, 1739 (1996) J.C. Hulteen, C.R. Martin: J. Mater. Chem. 7, 1075 (1997)

33. R.V. Parthasarathy, K.L.N. Phani, C.R. Martin: Adv. Mater. 7, 896 (1995) 34. B.B. Lakshmi, C.J. Patrissi, C.R. Martin: Chem. Mater. 9, 2544 (1997) 35. S. De Vito, C.R. Martin: Chem. Mater. 10, 1738 (1998) 36. G. Che, B.B. Lakshmi, E.R. Fisher, C.R. Martin: Nature 393, 346 (1998) 37. G. Che, B.B. Lakshmi, C.R. Martin, E.R. Fisher, R.S. Ruoff: Chem. Mater. 10, 260 (1998) 38. S.M. Marinakos, L.C. Brousseau, III, A. Jones, D.L. Feldheim: Chem. Mater. 10, 1214 (1998) 39. M. Nishizawa, K. Mukai, S. Kuwabata, C.R. Martin, H. Yoneyama: J. Electrochem. Soc. 144, 1923 (1997) 40. C.-G. Wu, T. Bein: Science 264, 1757 (1994) 41. P. Enzel, J.J. Zoller, T. Bein: Chem. Commun. 633 (1992) 42. B.Z. Tang, H. Xu: Macromolecules 32, 2569 (1999) 43. T.M. Whitney, J.S. Jiang, P.C. Searson, C.L. Chien: Science 261, 1316 (1993) 44. P. Tomassi, Z. Buczko: XIth Seminar Tempus JEP 09032-95, Athens, 7-9.05.1998 45. E. Braun, Y. Eichen, U. Sivan, G. Ben-Yoseph: Nature 391, 775 (1998) 46. S. Iijima: Nature 354, 56 (1991) 47. T.W. Ebbesen, P.M. Ajayan: Nature 358, 220 (1992) 48. W.R. Davis, R.J. Slawson, G.R. Rigby: Nature 171, 756 (1953) 49. H. Lange, A. Huczko, P. Byszewski, E. Mizera, H. Shinohara: Chem. Phys. Lett. 289, 174 (1998) 50. X.B. Zhang, X.F. Zhang, D. Bernaerts, G. Van Tendeloo, S. Amelinckx, J. Van Landuyt, V. Ivanov, J.B. Nagy, Ph. Lambin, A.A. Lucas: Europhys. Lett. 27, 141 (1994) 51. V. Ivanov, J.B. Nagy, Ph. Lambin, A. Lucas, X.B. Zhang, X.F. Zhang, D. Bernaerts, G. Van Tendeloo, S. Amelinckx, J. Van Landuyt: Chem. Phys. Lett. 223, 329 (1994) 52. K. Hernadi, A. Fonseca, J.B. Nagy, D. Bernaerts, J. Riga, A. Lucas: Synth. Met. 77, 31 (1996) 53. L.A. Chernozatonskii, Z.Y. Kosakovskaya, E.A. Fedorov, V.I. Panov: Phys. Lett. A 197, 40 (1995) 54. M. Ge, K. Sattler: Science 260, 515 (1993) 55. M. Ge, K. Sattler: Appl. Phys. Lett. 64, 710 (1994) 56. W.K. Hsu, J.P. Hare, M. Terrones, H.W. Kroto, D.R.M. Walton, P.J. Harris: Nature 377, 687 (1995) 57. W.K. Hsu, M. Terrones, J.P. Hare, H. Terrones, H.W. Kroto, D.R.M. Walton: Nature 262, 161 (1996) 58. T. Kyotani, L.-F. Tsai, A. Tomita: Chem. Mater. 8, 2109 (1996) 59. S. Fan, M.G. Chapline, N.R. Franklin, T.W. Tombler, A.M. Cassell, H. Dai: Science 283, 512 (1999) 60. J. Kong, H.T. Soh, A.M. Cassel, C.F. Quate, H. Dai: Nature 395, 878 (1998) 61. X.-Y. Song, W. Cao, M.R. Ayers, A.J. Hunt: J. Mater. Res. 10, 251 (1995) 62. W.Z. Li, S.S. Xie, L.X. Qian, B.H. Chang, B.S. Zou, W.Y. Zhou, R.A. Zhao, G. Wang: Science 274, 1701 (1996) 63. H.D. Sun, Z.K. Tang, J. Chen, G. Li: Solid State Commun. 109, 365 (1999) 64. Z.K. Tang, H.D. Sun, J. Wang, J. Chen, G. Li: Appl. Phys. Lett. 73, 2287 (1998) 65. X.H. Chen, S.Q. Feng, Y. Ding, J.C. Peng, Z.Z. Chen: Thin Solid Films 339, 6 (1999) 66. M. Terrones, N. Grobert, J. Olivares, J.P. Zhang, H. Terrones, K. Kordatos, W.K. Hsu, J.P. Hare, P.D. Townsend, K. Prassides, A.K. Cheetham, H.W. Kroto, D.R.M. Walton: Nature 388, 52 (1997) 67. J.D. Klein, R.D.I. Herrick, D. Palmer, M.J. Sailor, C.J. Brunlik, C.R. Martim: Chem. Mater. 5, 902 (1993) 68. R. Dagani: C&EN June 7, 25 (1999) 69. C.M. Zelenski, P.K. Dorhout: J. Am. Chem. Soc. 120, 734 (1998) 70. N.K. Raman, M.T. Andreson, C.J. Brinker: Chem. Mater. 8, 1682 (1996) 71. T. Kyotani, L.-F. Tsai, A. Tomita: Chem. Commun. 701 (1997) 72. A. Tomita, T. Kyotani, T. Tagaki: Jpn. Kokai Takkyo Koho JP 09, 142, 819 (3 June 1997) 73. P.M. Ajayan, O. Stephan, Ph. Redlich: Nature 375, 564 (1995) 74. B.C. Satishkumar, A. Govindraj, E.M. Vogel, L. Basumallick, C.N.R. Rao: J. Mater. Res. 12, 604 (1997) 75. A. Chu, J. Cook, R.J.R. Heesom, J.L. Hutchison, M.L.H. Green, J. Sloan: Chem. Mater. 8, 2751 (1996)

376 76. W. Han, S. Fan, Q. Li, B. Gu, X. Zhang, D. Yu: Appl. Phys. Lett. 71, 2271 (1997) 77. W. Han, S. Fan, Q. Li, Y. Hu: Science 277, 1287 (1997) 78. J. Zhu, S. Fan: J. Mater. Res. 14, 7 (1999) 79. W. Han, Y. Bando, K. Kurashima, T. Sato: Chem. Phys. Lett. 299, 368 (1999) 80. W. Han, Y. Bando, K. Kurashima, T. Sato: Appl. Phys. Lett. 73, 3085 (1998) 81. H. Dai, E.W. Wong, Y.Z. Lu, S. Fan, C.M. Lieber: Nature 375, 769 (1995) 82. E.W. Wong, B.W. Maynor, L.D. Burns, C.M. Lieber: Chem. Mater. 8, 2041 (1996) 83. M.W. Anderson, J. Shi, D.A. Leigh, A.E. Moody, F.A. Wade, B. Hamilton, S.W. Carr: Chem. Commun. 533 (1993) 84. P.W. Murray, I.M. Brookes, S.A. Haycock, G. Thornton: Phys. Rev. Lett. 80, 988 (1998) 85. B.W. Smith, M. Monthioux, D.E. Luzzi: Nature 396, 323 (1998) 86. A.M. Cassel, W.A. Scrivens, J.M. Tour: Angew. Chem. Int. Ed. 37, 1528 (1998) 87. N. Sonobe, T. Kyotani, Y. Hishiyama, M. Shiraishi, A. Tomita: J. Phys. Chem. 92, 7029 (1998) 88. T. Kyotani, N. Sonobe, A. Tomita: Nature 331, 331 (1988) 89. T.J. Bandosz, J. Jagiello, K. Putyera, J.A. Schwarz: Chem. Mater. 8, 2023 (1996) 90. J. Cook, J. Sloan, M.L.H. Green: Chem. Industry 600 (19 August 1996) 91. M. Lin, J.M. Cowley: Carbon 33, 225 (1995) 92. S.C. Tsang, Y.K. Chen, P.J.F. Harris, M.L.H. Green: Nature 372, 159 (1994) 93. R.M. Lago, S.C. Tsang, K.L. Lu, Y.K. Chen, M.L.H. Green: Chem. Commun. 1355 (1995) 94. E. Dujardin, T.W. Ebbesen, H. Hiura, K. Tanigaki: Science 265, 1850 (1994) 95. P.M. Ajayan, S. Iijima: Nature 361, 333 (1994) 96. N. Demoncy, O. Stephan, N. Brun, C. Colliex, A. Loiseau, H. Pascard: Eur. Phys. J. B 4, 147 (1998) 97. R.V. Parthasarathy, K.L.N. Phani, C.R. Martin: Adv. Mater. 7, 896 (1995) 98. V.M. Cepak, J.C. Hulteen, G. Che, K.B. Jirage, B.B. Lakshmi, E.R. Fischer, C.R. Martin: Chem. Mater. 9, 1065 (1997) 99. L. Piraux, S. Dubois, S. Demoustier-Champagne: Nucl. Instr. Meth. Phys. Res. B 131, 357 (1997) 100. C. Schoenenberger, B.M.I. van der Zande, L.G.J. Fokkink, M. Henny, C. Schmid, M. Krueger, A. Bachtold. R. Huber, H. Birk, U. Staufer: J. Phys. Chem. B 101, 5497 (1997) 101. G.E. Possin: Rev. Sci. Instrum. 41, 772 (1970) 102. R.L. Fleisher, P.B. Price, R.M. Walker: Nuclear Tracks in Solids (University of California Press, Berkeley, CA 1975) 103. S.N. Dimitryev, L.I. Krawets, W.W. Sleptsov, N.W. Simakina, O.L. Orelovitsch: Khim. Vys. Energ. 31, 286 (1997) 104. D. Routkevitchi, J. Chan, J.M. Xu, M. Moskovits: Proc. Electrochem. Soc. 97-7, 350 (1997) 105. D. Almawiawi, N. Coombs, M. Moskovits: J. Appl. Phys. 70, 4421 (1991) 106. F. Li, L. Zhang, R.M. Metzger: Chem. Mat. 10, 2470 (1998) 107. R.L. Smith, S.D. Collins: J. Appl. Phys. 71, R1 (1992) 108. S. Jonas, J. Gruszczynski, A, Kielski, E. Walasek, A. Czyzewska, G. Krupa: Szklo i Ceramika (in Polish) 46, 25 (1995) 109. F.H. Dickey: Proc. Natl. Acad. Sci. USA 35, 227 (1949) 110. T.R. Anthony, J.C. Bradley, P.J. Horoyski, M.L.W. Thewalt: Carbon 34, 1323 (1996) 111. M. Freemantle: C&EN 75(33), 11 (1997) 112. Z. Cai, C.R. Martin: J. Am. Chem. Soc. III, 4138 (1989) 113. Z. Cai, J. Jei, W. Liang, V. Menon, C.R. Martin: Chem. Mater. 3, 960 (1991) 114. Z.J. Karpinski, R.A. Osteryoung: J. Electroanal. Chem. 349, 285 (1993) 115. S.M. Drew, R.M. Wrightman: J. Electroanal. Chem. 317, 117 (1991) 116. C.T. White, T.N. Todorov: Nature 393, 240 (1998) 117. H. Ajiki, T. Ando: Solid State Commun. 102, 135 (1997) 118. J.I. Pascual, J. Mendez, J. Gomez-Herrero, A.M. Baro, N. Garcia, U. Landman, W.D. Luedtke, E.N. Bogachek, H.-P. Cheng: Science 267, 1793 (1995) 119. M.N. Baibich, J.M. Broto, A. Fert, F. Nguyen Van Dan, F. Petroff, P. Etienne, G. Creuzet, A. Friederich, J. Chazelas: Phys. Rev. Lett. 61, 2472 (1988) 120. H. Daimon, O. Kitakami: J. Appl. Phys. 73, 5391 (1993) 121. R.F. Service: Science 281, 940 (1998) 122. N.M. Rodriguez: J. Mater. Res. 8, 3233 (1993) 123. L.A. Chernozatonskii: Chem. Phys. Lett. 297, 257 (1998) 124. B. Wei, J. Zhang, J. Liang, W. Liu, Z. Gao, D. Wu: J. Mat. Sci. Lett. 16, 402 (1997) 125. E. Frackowiak, S. Gautier, H. Gaucher, S. Bonnamy, F. Beguin: Carbon 37, 61 (1999) 126. S.S. Wong, E. Joselevich, A.T. Woolley, C.L. Cheung, C.M. Lieber: Nature 394, 52 (1998) 127. H. Dai, J.H. Hafner, A.G. Rinzler, D.T. Colbert, R.E. Smalley: Nature 384, 147 (1996) 128. G.E. Gadd, M. Blackford, S. Moricca, N. Webb, P.J. Evans, A.M. Smith, G. Jacobsen, S. Leung, A. Day, Q. Hua: Science 277, 933 (1997) 129. A.C. Dillon, K.M. Jones, T.A. Bekkedahl, C.H. Kiang, D.S. Bethune, M.J. Heben: Nature 386, 377 (1997) 130. P.G. Collins, A. Zettl, H. Bando, A. Thess, R.E. Smalley: Science 278, 100 (1997) 131. S. Frank, P. Poncharal, Z.L. Wang, W.A. de Heer: Science 280, 1744 (1998) 132. W.A. de Heer, A. Chatelain, D. Ugarte: Science 270, 1179 (1995) 133. Y. Saito, K. Hamaguchi, S. Uemura, K. Uchida, Y. Tasaka, F. Ikazaki, M. Yumura, A. Kasuya, Y. Nishina: Appl. Phys. A 67, 95 (1998) 134. W.A. de Heer, W.S. Bacsa, A. Chatelain, T. Gern, R. HumphreyBaker, L. Forro, D. Ugarte: Science 268, 845 (1995) 135. P.M. Ajayan, O. Stephan, C. Colliex, D. Trauth: Science 265, 1212 (1994) 136. Z.F. Ren, Z.P. Huang, J.W. Xu, J.H. Wang, P. Bush, M.P. Siegal, P.N. Provencio: Science 282, 1105 (1998) 137. D.L. Feldheim, C.D. Keating: Chem. Soc. Rev. 27, 1 (1998) 138. K. Mullen, E. Ben-Jacob, R.C. Jaklevic, Z. Schuss: Phys. Rev. B 37, 98 (1988) 139. K.B. Jirage, J.C. Hulteen, C.R. Martin: Science 278, 655 (1997) 140. C.M. Zelenski, P.K. Dorhout: J. Am. Chem. Soc. 120, 734 (1998) 141. R.W. Matthew: J. Phys. Chem. 91, 238 (1987)