Electrochemical Fabrication of Metal Nanowires - Arizona State ...

Electrochemical Fabrication of Metal Nanowires Huixin He Chemistry Department, Rutgers University, Newark, New Jersey, USA

Nongjian J. Tao Department of Electrical Engineering, Arizona State University, Tempe, Arizona, USA

CONTENTS 1. Introduction 2. Classical Nanowires 3. Quantum Wires 4. Summary Glossary Acknowledgments References

1. INTRODUCTION The development of ever more powerful electronics depends on continued progress in miniaturizing their components. However, the laws of quantum mechanics, the limitations of fabrication techniques, and the increasing cost of the fabrication facilities may soon prevent us from the further scaling down of conventional silicon technology. The quest for alternative technologies has stimulated a surge of interest in nanometer-scale materials and devices in recent years. Metal nanowires are one of the most attractive materials because of their unique properties that may lead to a variety of applications. Examples include interconnects for nanoelectronics, magnetic devices, chemical and biological sensors, and biological labels. Metal nanowires are also attractive because they can be readily fabricated with various techniques. An important fabrication technique that will be discussed in this article is the electrochemical method. The diameters of metal nanowires range from a single atom to a few hundreds of nm, and the lengths vary over even a greater range: from a few atoms to many microns. Because of the large variation in the aspect ratio (length-todiameter ratio), different names have been used in literature to describe the wires in order to reflect the different shapes. For example, wires with large aspect ratios (e.g., >20) are called nanowires, while those with small aspect ratios are ISBN: 1-58883-001-2/$35.00 Copyright © 2003 by American Scientific Publishers All rights of reproduction in any form reserved.

called nanorods. When short “wires” are bridged between two larger electrodes, they are often referred to as nanocontacts. These definitions are intuitive, but somewhat arbitrary. For this reason and also because of the fact that all the wires have diameters on the nanometer scale, they are sometimes all loosely referred to as nanowires. In terms of electron transport properties, metal wires have been described as classical wires and quantum wires. The electron transport in a classical wire obeys the classical relation G=

A L

(1)

where G is the wire conductance, and L and A are the length and the cross-sectional area of the wire, respectively. in Eq. (1) is the conductivity, which depends on the material of the wire. The classical behavior arises because the wires are much longer than the electron mean-free path, and much thicker than the electron Fermi wavelength. The former condition means that conduction electrons experience many collisions with phonons, defects, and impurities when they traverse along a wire. The second condition smears out the effects due to the quantum-size confinement in the transverse direction of the wire. For a typical metal, such as Cu, at room temperature, the mean-free path is a few tens of nm and the electron wavelength is only a fraction of nm, comparable to the size of an atom. Many metal nanowires behave like a classical conductor despite their nanometerscale diameters. When the wire is shorter than the electron mean-free path, the electron transport is ballistic, that is, without collisions along the wire. If, in addition, the diameter of the wire is comparable to the electron wavelength, quantumsize confinement becomes important in the transverse direction, which results in well-defined quantum modes. The Encyclopedia of Nanoscience and Nanotechnology Edited by H. S. Nalwa Volume X: Pages (1–18)

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Electrochemical Fabrication of Metal Nanowires

conductance of the system measured between two bulk electrodes is described by the Landauer formula [1] G=

N 2e2 T h i j=1 ij

(2)

where e is the electron charge, h is Planck’s constant, and Tij is the transmission probability of an electron from ith mode at one side of the wire to the jth mode at the other side. The summation is overall the quantum modes, and N is the total number of modes with nonzero Tij values, which is determined by the number of standing waves at the narrowest portion of the wire. In the ideal case, Tij is 1 for i = j and 0 for all other cases, so Eq. (2) is simplified as G = NG0 , where G0 = 2e2 /h ∼775 S is the conductance quantum. So the conductance is quantized and the wire is referred to as a quantum wire. In this article, we provide an overview of electrochemical fabrication and discuss some applications of both classical and quantum wires. While we focus mainly on electrochemical or related fabrication techniques, we would like to point out that many other methods have also been rapidly developed in recent years. Examples include wet chemistry [2–14], electron beam lithography [15–20], focused ion beam techniques [21], and atomic-beam holography [17, 22, 23]. We divide the rest of the article into the following sections. In Section 2, we describe the fabrications and applications of classical nanowires. Because rather different approaches are used to fabricate metallic quantum wires, we discuss the fabrication of quantum wires separately in Section 3. In Section 4, a brief summary is provided.

2. CLASSICAL NANOWIRES We divide this section into two parts. The first part is focused on the electrochemical fabrication of the nanowires. In this part, we discuss the fabrication of various templates first, and then the fabrication of metal nanowires with the templates. The second part discusses various applications of the nanowires.

2.1. Electrochemical Fabrication of Classical Nanowires A widely used approach to fabricate metal nanowires is based on various templates, which include negative, positive, and surface step templates. We discuss each of the approaches below.

2.1.1. Negative Template Methods Negative template methods use prefabricated cylindrical nanopores in a solid material as templates. By depositing metals into the nanopores, nanowires with a diameter predetermined by the diameter of the nanopores are fabricated. There are several ways to fill the nanopores with metals or other materials to form nanowires, but the electrochemical method is a general and versatile method. If one dissolves away the host solid material, free-standing nanowires are obtained. This method may be regarded as a “brute-force”

method because the diameter of the nanowires is determined by the geometrical constraint of the pores rather than by elegant chemical principles [24]. However, it is one of the most successful methods to fabricate various nanowires that are difficult to form by conventional lithographic process. Fabrication of suitable templates is clearly a critical first step. To date, a number of methods have been developed to fabricate various negative templates. Examples include alumina membranes, polycarbonate membranes, mica sheets, and diblock polymer materials. These materials contain a large number of straight cylindrical nanopores with a narrow distribution in the diameters of the nanopores. The Templates Track-Etched Membranes When a heavy-charged particle from a nuclear radiation resource passes through certain materials, such as a mica film, it leaves a track of radiation damage in the mica film via a so-called Coulomb explosion phenomenon (Fig. 1A). The minimum width of the track is only 2.5 nm. The track can be selectively etched in a suitable reagent, such as hydrofluoric acid, a technique that was originally introduced for the detection of charged radiation particles [25, 26]. The reagent “develops” and “fixes” the tracks, which results in fine cylindrical pores in the mica along the tracks, while leaving the rest of the material essentially unchanged (Figs. 1B and 1C). The pores are randomly distributed in the mica film but with a rather uniform diameter along their entire length. The diameter of the pores can be controlled by controlling the etching time. In 1969, Possin used the mica film with nanopores to fabricate metal nanowires with a diameter as small as 40 nm [27]. The fabrication technique was refined later by Williams and Giordano who obtained Ag wires with diameters as thin as 8 nm [28]. The works by Martin et al. marked the beginning of a surge in the development and application of the methods in recent years [29–51]. They have demonstrated that various nanostructures, including metal and conducting polymer nanowires and nanotubes, can be fabricated using the negative templates, which may lead to many novel applications [29–51]. The ion-track method has been applied to create nanopores in plastic membranes, such as polycarbonate and polyester [52, 53]. Instead of using acid, alkaline solvent is used to “develop” the ion tracks in polycarbonate membranes [54]. Membranes with pore diameters as small as 10 nm have been fabricated and become commercially available. An important advantage of these plastic templates over the mica films is that their surface wetting properties can be A

B C

Proofs Only Figure 1. Track-etch process for nanoporous membranes. (A) Tracks of the high-energy fission fragments. (B) Nanopores formed after developing the damaged tracks. (C) Top view of the nanopore membrane.


tailored, which is important for many applications. Another advantage is that they can be more easily dissolved without affecting the nanowires formed in the pores. Despite the great success, these track-etched membranes have some drawbacks when they are used to fabricate nanowires. First, the pore density is rather low (109 pores/cm2 ), which limits the yield of the nanowires. The pores are randomly positioned and not always parallel to each other (Fig. 1C). While these problems may be tolerable in many applications, they can complicate the interpretations of measured properties [55]. To circumvent the problems, Sun et al. have fabricated nanoporous templates using mica single crystals [56, 57]. The pores in the crystals are diamond-shaped with welldefined crystal axes that are related to the crystal structure of the mica. The improved collimation of the pores, the uniform pore cross-section, and the low density of overlapping pores resulted in significant enhancement in the magnetic anisotropy, in comparison to nanowires of the same dimension formed in polycarbonate membranes. Anodic Porous Alumina Anodic porous alumina is another commonly used negative template. The nanopores in the template are formed by anodizing aluminum films in an acidic electrolyte. The individual nanopores in the alumina can be ordered into a close-packed honeycomb structure (Fig. 2). The diameter of each pore and the separation between two adjacent pores can be controlled by changing the anodization conditions. The fabrication method of anodic porous alumina can be traced back to the work done in the 1950’s, which involves a one-step anodization process. This original one-step anodization method is still used to fabricate most commercial alumina membranes [58, 59]. The anodic porous alumina has a much higher pore density (∼1011 pores/cm2 ), which allows one to fabricate a large number of nanowires at one time. Another interesting feature of the porous alumina template is that the chemistry of the pore walls can be altered via reaction with silane compounds [60]. The distribution of nanopores in anodic porous alumina is usually not as perfect as the one shown in Figure 2. To achieve highly ordered pores, high-purity aluminum films (99.999%) are used. In addition, they are first preannealed to remove mechanical stress and enhance the grain size. Subsequently, the films are electropolished in a 4:4:2 (by

Proofs Only Figure 2. Schematic drawing of an anodic porous alumina template. Reprinted with permission from [71], H. Asoh et al., J. Electrochem. Soc. 148, B152 (2001). © 2001, The Electrochemical Society, Inc.

3 weight) mixture of H3 PO4 , H2 SO4 , and H2 O to create homogeneous surfaces. Without the preannealing and electropolishing steps, it is hard to form well-ordered pores [61]. The order of the pores depends also on other anodization conditions, such as anodization voltage and electrolyte. It has been reported that anodization over a long period at an appropriate constant voltage can produce an almost ideal honeycomb structure over an area of several m [61, 62]. The optimal voltage depends on the electrolyte used for the anodization [61–64]. For example, the optimal voltage for long-range ordering is 25 V in sulfuric acid, 40 V in oxalic acid, and 195 V in phosphoric acid electrolyte, respectively [61, 65, 66]. The diameter and depth of each pore, as well as the spacing between adjacent pores can be also controlled by the anodizing conditions. Both the pore diameter and the pore spacing are proportional to the anodizing voltage with proportional constants of 1.29 nm V−1 and 2.5 nm V−1 , respectively. The dependence of the diameter and the spacing on the voltage is not sensitive to the electrolyte, which is quite different from the optimal voltage for ordered distribution of the pores as discussed above [67–69]. This property has been exploited to make size-selective microfiltration membranes and to control the diameter of nanowires formed in the pores. By properly controlling the anodization voltage and choosing the electrolyte, one can make highly ordered nanopores in alumina with desired pore diameter and spacing. The order of the pores achieved by anodizing an aluminum film over a long period is often limited to a domain of several m. The individual ordered domains are separated by regions of defects. Recently, a novel approach has been reported to produce a nearly ideal hexagonal nanopore array that can extend over several millimeters [70, 71]. The approach uses a pretexturing process of Al in which an array of shallow concave features is initially formed on Al by indentation. These concave features serve as nucleation sites for the formation of pores during the initial stage of anodization. The pore spacing can be controlled by the pretextured pattern and the applied voltage. Another widely used method to create highly ordered nanopore arrays is a two-step anodization method [65, 72–75]. The first step involves a long-period anodization of high purity aluminum to form a porous alumina layer. Subsequent dissolution of the porous alumina layer leads to a patterned aluminum substrate with an ordered array of concaves formed during the first anodization process. The ordered concaves serve as the initial sites to form a highly ordered nanopore array in a second anodization step. Acidic anodization of Al normally results in a porous alumina structure which is separated from the aluminum substrate with a so-called barrier layer of Al2 O3 . The barrier layer and aluminum substrate can be removed to form a free-standing porous alumina membrane. The aluminum can be removed with saturated HgCl2 and the barrier layer of Al2 O3 with a saturated solution of KOH in ethylene glycol. An alternative strategy to separate the porous alumina from the substrate is to take advantage of the dependence of pore diameter on anodization voltage. By repeatedly decreasing the anodization voltage several times at 5% increments, the barrier layer becomes a tree-root-like network with fine

4 pores. Since the root-like network has a higher exposed surface area than the primary large pores, dissolution occurs there first when immersing the sample in a concentrated acid. The dissolution of the network then results in the separation of the porous oxide film from the aluminum substrate [24]. Other Nanoporous Materials Thurn-Albrecht et al. showed a simple and robust chemical route to fabricate ultra high-density arrays of nanopores with high aspect ratios using diblock copolymer [76, 77]. The method is based on self-assembly of incompatible block copolymers into wellordered structures of molecular dimension [78–80]. Block copolymers are long-chain molecules built up from different types of monomers, say A and B, that are grouped in blocks. These blocks are often incompatible and are separated into A-rich and B-rich domains. Depending on the length, connectivity, and interactions between different blocks, the domains can form periodically arranged spheres, cylinders, lamellae, and other structures. The typical repeating distance of the structures is in the range between 10–100 nm, which is attractive for applications in the area of nanotechnology [81, 82]. For the purpose of fabricating metal nanowires, the cylindrical domains are of the obvious interest. Thurn-Albrecht et al. fabricated nanopores using diblock copolymers composed of polymethylmethacrylate (PMMA) and polystyrene (PS). The molecular weight and volume fraction of styrene are chosen such that the copolymer self-assemble into arrays of 14-nm-diameter PMMA cylinders hexagonally packed in the PS matrix with a lattice constant of 24 nm in bulk. The PMMA cylinders are oriented parallel to each other by applying an electric field, while the copolymer film is heated above the glass transition temperature. Deep ultraviolet exposure degrades the PMMA domains and simultaneously cross-links the PS matrix. By rinsing the film with acetic acid, the PMMA domains are selectively removed, which results in a PS film with ordered nanopores. Similar nanopores in other diblock copolymers have also been reported [81, 83]. One of the attractive features of the diblock copolymer template method is that it is compatible with current lithographic techniques and amendable to multilayered device fabrication. Hong et al. reported that calix[4]hydroquinones (CHQs) form chessboard-like arrays of rectangular pores when they are soaked in AgNO3 aqueous solution [84]. The rich -electron density of hydroquinones (HQ) moieties in the CHQ nanopores can capture metal ions, such as Ag+ , with high affinity via cation- interactions. Once Ag+ ions are captured inside the pores, the redox process between Ag+ and CHQ takes place spontaneously. Because the reduced neutral Ag atoms do not exhibit strong interactions with the HQ moieties, single-crystalline Ag nanowire arrays with a diameter of 0.4 nm and a length of m-scale are formed. The atomically thin wires are very stable under ambient air and aqueous environments, because they are confined in the pores and protected by the organic material. Considering the oxidation potential of the HQ moieties in the CHQ and the reduction potentials of metal ions, it should be possible to prepare nanowires of other elements, such as Au, Pd, and Pt, using this method.


Tonucci et al. described a method to fabricate arrays of nanopores in glass [85]. The pores are arranged in a two-dimensional hexagonal close-packed configuration with pore diameter as small as 33 nm and pore density as high as 3 × 1010 pores/cm2 . Because of the high-temperature stability of the nanopore arrays in glass, they are well suited as hosts or templates for nanowire arrays for high temperature studies. Other porous template materials, such as mesoporous silica [86, 87] and niobium oxide [88] have been also reported. Fabrication of Metal Nanowires Using the membrane templates previously described, nanowires of various metals, semiconductors [41] and conducting polymers [51, 89], have been fabricated. These nanostructures can be deposited into the pores by either electrochemical deposition or other methods, such as chemical vapor deposition (CVD) [90], chemical polymerization [43, 47], electroless deposition [91], or by sol–gel chemistry [41]. Electrodeposition is one of the most widely used methods to fill conducting materials into the nanopores to form continuous nanowires with large aspect ratios. One of the great advantages of the electrodeposition method is the ability to create highly conductive nanowires. This is because electrodeposition relies on electron transfer, which is the fastest along the highest conductive path. Structural analysis showed that the electrodeposited nanowires tend to be dense, continuous, and highly crystalline in contrast to other deposition methods, such as CVD. Yi and Schwarzacher demonstrated that the crystallinity of superconducting Pb nanowires can be controlled by applying a potential pulse with appropriate parameters [92]. The electrodeposition method is not limited to nanowires of pure elements. It can fabricate nanowires of metal alloys with good control over stoichiometry. For example, by adjusting the current density and solution composition, Huang et al. controlled the compositions of CoPt and FePt nanowires to 50:50 in order to obtain the high anisotropic face-centered tetragonal phases [93]. Similar strategies have been used in other magnetic nanowires [94, 95] and in thermoelectronic nanowires [50, 96]. Another important advantage of the electrodeposition method is the ability to control the aspect ratio of the metal nanowires by monitoring the total amount of passed charge. This is important for many applications. For example, the optical properties of nanowires are critically dependant on the aspect ratio [37, 38, 97]. Nanowires with multiple segments of different metals in a controlled sequence can also be fabricated by controlling the potential in a solution containing different metal ions [98]. Electrodeposition often requires one to deposit a metal film on one side of the freestanding membrane to serve as a working electrode on which electrodeposition takes place. In the case of large pore sizes, the metal film has to be rather thick to completely seal the pores on one side. The opposite side of the membrane is exposed to an electrodeposition solution, which fills up the pores and allows metal ions to reach the metal film. However, one can avoid using the metal film on the backside by using anodic alumina templates with the natural supporting Al substrate. The use of the supported templates also prevents one from breaking the fragile membrane during handling. However, it requires one

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to use AC electrodeposition [99–102]. This is because of the rather thick barrier layer between the nanopore membrane and the Al substrate. Detailed studies of the electrochemical fabrication process nanowires have been carried out by a number of groups [103, 104]. The time dependence of the current curves recorded during the electrodeposition process reveal three typical stages. Stage I corresponds to the electrodeposition of metal into the pores until they are filled up to the top surface of the membrane. In this stage, the steady-state current at a fixed potential is directly proportional to the metal film area that is in contact with the solution, as found in the electrodeposition on bulk electrodes. However, the electrodeposition is confined within the narrow pores, which has a profound effect on the diffusion process of the metal ions from the bulk solution into the pores before reaching the metal film. The concentration profiles of Co ions in the nanopores of polycarbonate membranes during electrodeposition of Co have been studied by Valizadeh et al. [105]. After the pores are filled up with deposited metal, metal grows out of the pores and forms hemispherical caps on the membrane surface. This region is called stage II. Since the effective electrode area increases rapidly during this stage, the electrochemical current increases rapidly. When the hemispherical caps coalescence into a continuous film, stage III starts, which is characterized by a constant value again. By stopping the electrodeposition process before stage I ends, an array of nanowires filled in the pores is formed. The current-time curves are not always as well behaved as the one described above [103]. For example, the current may vary during the first stage, so that stages I, II, and III may merge together and become difficult to separate. One plausible explanation of this observation is that the pores in the membranes are not aligned parallel but have a considerable angular distribution (±34 ). The angular distribution means a large length distribution of the pores, such that the pores with different lengths fill up with nanowires at different times. Another possible reason is inhomogeneous growth rates in different pores, due to different degrees of wetting of different pores. The wetting problem tends to be more severe for membranes with smaller pores because of the increased difficulty to wet all the pores before electrodeposition. One way to reduce the wetting problem is to treat polycarbonate membranes with polyvinylpyrrolidone (PVP) [103]. Adding ethanol or methanol into the electrolyte is also found to reduce the wetting problem [77]. Another method is to perform the electrodeposition in an ultrasound bath to facilitate the mass transport of ions through the pores of the membrane [106]. When freely standing nanowires are desired, one has to remove the template hosts after forming the nanowires in the templates. This task is usually accomplished by dissolving away the template materials in a suitable solvent. Methylene chloride can readily dissolve away track-etched polycarbonate film and 0.1M NaOH removes anodic alumina effectively. If one wants to also separate the nanowires from the metal films on which the nanowires are grown, a common method is to first deposit a sacrificial metal. For example, in order to fabricate freely standing Au nanowires, one can deposit a thin layer of Ag onto the metal film coated on one side of

the template membrane before filling the pores with Au. The Ag layer can be etched away later in concentrated nitric acid, which separates the Au nanowires from the metal film. While DC electrodeposition can produce high-quality nanowires, it is challenging to obtain an ordered nanowire array. Normally only 10–20% of the pores in the membrane are filled up completely using the simple DC method [107]. Using AC electrodeposition with appropriate parameters [99–102], a high filling ratio can be obtained which results in a uniform nanowire array. For example, Yin et al. reported that a high filling ratio can be obtained using a sawtooth wave, triangle wave, or sine wave, but not with a square wave [108]. Furthermore, they found that the filling ratio increases with the AC frequency. A possible reason is that nuclei formed at higher frequencies are more crystalline, which makes the metal deposition easier in the pores and promotes homogeneous growth of nanowires. Nielsch and Sauer et al. developed a pulsed electrodeposition method [109, 110]. After each potential pulse, a relatively long delay follows before application of the next pulse. The rationale is that the long delay after each pulse allows ions to diffuse into the region where ions are depleted during the deposition (pulse). They demonstrated that the pulsed electrodeposition is well suited for a uniform deposition in the pores of porous alumina with a nearly 100% filling rate. It is interesting to point out that the membrane templates have also been used to fabricate other nanostructures such as nanoparticles [24] and hollow nanotubules [44]. When conducting, polymers are synthesized (either chemically or electrochemically) in the pores of the track-etched polycarbonate membranes, the polymer preferentially nucleates and grows on the pore walls. By controlling the polymerization time, tubules with different wall thickness can be obtained. By filling up the polymer tubules with a metal, metal nanowires with polymer sheaths have been fabricated [111]. Metal nanotubules can be fabricated by modifying the pore walls with molecular anchors that allow the deposited metal to form a thin skin on the pore walls [29, 31]. These metal tubules are useful for chemical separations [39, 40].

2.1.2. Positive Template Method The positive template method uses wire-like nanostructures, such as DNA and carbon nanotubes as templates, and nanowires are formed on the outer surface of the templates. Unlike negative templates, the diameters of the nanowires are not restricted by the template sizes and can be controlled by adjusting the amount of materials deposited on the templates. By removing the templates after deposition, wire-like and tube-like structures can be formed. We discuss some of the positive templates below. Carbon Nanotube Template Fullam et al. demonstrated a method to fabricate Au nanowires using carbon nanotubes as positive templates. The first step is to self-assemble Au nanocrystals along carbon nanotubes [112]. After thermal treatment, the nanocrystal assemblies are transformed into continuous polycrystalline Au nanowires over many m. Carbon nanotubes have also been used as templates to fabricate Mo-Ge superconducting nanowires [113] and other metal nanowires [114, 115]. Choi et al. [116] reported a

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highly selective electroless deposition of metal nanoparticles on single wall carbon nanotubes (SWNTs). Because HAuCl4 (Au3+ ) or Na2 PtCl4 (Pt2+ ) have much higher reduction potentials than SWNTs, they are reduced spontaneously and form Au or Pt nanoparticles on the sidewalls of SWNTs (Fig. 3). This is different from the traditional electroless deposition because no reducing agents or catalysts are required. Charge transfer during the reaction is probed electrically as it causes significant changes in the electrical conductance of the nanotubes by hole doping. The nanoparticles decorated on the nanotube can coalesce and cover the entire surface of the nanotube. By removing the nanotube via heating, a Au tube-like structure with a outer diameter 50), they exhibit an easy axis along the wires. An important parameter that describes magnetic properties of materials is the remanence ratio, which measures

the remanence magnetization after switching off the external magnetic field. The remanence ratios of the Fe, Co, and Ni nanowires can be larger than 0.9 along the wires and much smaller in the perpendicular direction of the wires. This finding clearly shows that the shape anisotropy plays an important role in the magnetism of the nanowires. Another important parameter that describes the magnetic properties is coercivity, which is the coercive field required to demagnetize the magnet after full magnetization. The magnetic nanowires exhibit greatly enhanced magnetic coercivity [164, 165]. In addition, the coercivity depends on the wire diameter and the aspect ratio, which shows that it is possible to control the magnetic properties of the nanowires by controlling the fabrication parameters. The diameter dependence of the coercivity reflects a change of the magnetization reversal mechanism from localized quasi-coherent nucleation for small diameters to a localized curling like nucleation as the diameter exceeds a critical value [100]. Another technically important novel property observed in the magnetic nanowires is giant magnetoresistance (GMR) [158, 160, 161, 166, 167]. For example, Evans et al. have studied Co-Ni-Cu/Cu multilayered nanowires and found a magnetoresistance ratio of 55% at room temperature and 115% at 77K for current perpendicular to the plane (along the direction of the wires) [167]. Giant magnetoresistance has also been observed in semimetallic Bi nanowires fabricated by electrodeposition [168–170]. Hong et al. have studied GMR of Bi with diameters between 200 nm and 2 m in magnetic fields up to 55T and found that the magnetoresistance ratio is between 600–800% for magnetic field perpendicular to the wires and ∼200% for the field parallel to the wires [169]. The novel properties and small dimensions have potential applications in the miniaturization of magnetic sensors and the high-density magnetic storage devices. The alignment of magnetic nanowires in an applied magnetic field can be used to assemble the individual nanowires [171, 172]. Tanase et al. studied the response of Ni nanowires in response to magnetic field [171]. The nanowires are fabricated by electrodeposition using alumina templates and functionalized with luminescent porphyrins so that they can be visualized with a video microscope. In viscous solvents, magnetic fields can be used to orient the nanowires. In mobile solvents, the nanowires form chains in a head-to-tail configuration when a small magnetic field is applied. In addition, they demonstrated that three-segment Pt-Ni-Pt nanowires can be trapped between lithographically patterned magnetic microelectrodes [172]. The technique has a potential application in the fabrication and measurement of nanoscale magnetic devices.

2.2.2. Optical Applications Dickson and Lyon studied surface plasmon (collective excitation of conduction electrons) propagation along 20 nmdiameter Au, Ag, and bimetallic Au-Ag nanowires with a sharp Au/Ag heterojunction over a distance of tens of m [173]. The plasmons are excited by focusing a laser with a high numerical aperture microscope objective, which propagate along a nanowire and reemerge as light at the other end of the nanowire via plasmon scattering. The propagation depends strongly on the wavelength of the incident laser

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light and the composition of the nanowire. At the wavelength of 820 nm, the plasmon can propagate in both Au and Ag nanowires, although the efficiency in Ag is much higher than that in Au. In the case of bimetallic nanowire, light emission is clearly observed from the Ag end of the nanowire when the Au end is illuminated at 820 nm. In sharp contrast, if the same bimetallic rod is excited at 820 nm via the Ag end, no light is emitted from the distal Au end. The observation suggests that the plasmon mode excited at 820 nm is able to couple from the Au portion into the Ag portion with high efficiency, but not from the Ag portion into Au. The unidirectional propagation has been explained using a simple two-level potential model. Since surface plasmons propagate much more efficiently in Ag than in Au, the Au → Ag boundary is largely transmissive, thus enabling efficient plasmon propagation in this direction. In the opposite direction, however, propagation from Ag to Au “sees” a much steeper potential wall, allowing less optical energy to couple through to the distal end. Their experiments suggest that one can initiate and control the flow of optically encoded information with nanometer-scale accuracy over distances of many microns, which may find applications in future high-density optical computing.

white-light illumination. Different metal stripes within a single nanowire selectively adsorb different molecules, such as DNA oligomers, which can be used to detect different biological molecules simultaneously. These multisegment nanowires have been used like metallic barcodes in DNA and protein bioassays. The optical scattering efficiency of the multisegment nanowires can be significantly enhanced by reducing the dimensions of the segment, such that the excitation of the surface plasmon occurs. Mock et al. [177] have studied the optical scattering of multisegment nanowires of Ag, Au, and Ni that have diameters of ∼30 nm and length up to ∼7 m. The optical scattering is dominated by the polarization-dependant plasmon resonance of Ag and Au segments. This is different from the case of the thicker nanowires used by Nicewarner-Pena et al., where the reflectance properties of bulk metals determine the contrast of the optical images [176]. Because of the large enhancement by the surface plasmon resonance, very narrow (∼30 nm diameter) nanowires can be readily observed under white light illumination and the optical spectra of the individual segments are easily distinguishable [177]. The multisegment nanowires can host a large number of segment sequences over a rather small spatial range, which promises unique applications.

2.2.3. Biological Assays

2.2.4. Nanoelectronic and Nanoelectrochemical Applications

We have mentioned that by sequentially depositing different metals into the nanopores, multisegment or striped metal nanowires can be fabricated [106]. The length of each segment can be controlled by the charge passed in each plating step and the sequence of the multiple segments is determined by the sequence of the plating steps. Due to the different chemical reactivities of the “stripe” metals, these stripes can be modified with appropriate molecules. For example, Au binds strongly to thiols and Pt has high affinity to isocyanides. Interactions between complementary molecules on specific strips of the nanowires allow different nanowires to bind to each other and form patterns on planar surfaces. Using this strategy, nanowires could assemble deterministically into cross- or T-shaped pairs, or into more complex shapes [174]. It is also possible to use specific interactions between selectively functionalized segments of these nanowires to direct the assembly of nanowire dimers and oligomers, to prepare two-dimensional assembly of nanowire-substrate epitaxy, and to prepare threedimensional colloidal crystals from nanowire-shaped objects [117, 175]. As an example, single-stranded DNA can be exclusively modified at the tip or any desired location of a nanowire, with the rest of the wire covered by an organic passivation monolayer. This opens the possibility for sitespecific DNA assembly [106]. Nicewarner-Pena et al. showed that the controlled sequence of multisegment nanowires can be used as “barcodes” in biological assays [176]. The typical dimension of the nanowire is ∼200 nm thick and ∼10 m long. Because the wavelength dependence of reflectance is different for different metals, the individual segments are easily observed as “stripes” under an optical microscope with unpolarized

In addition to multisegment metal nanowires, one can also fabricate a metal/organic film/metal junction [178] and metal/nanoparticle/metal junctions [179] in a single nanowire, which have been used to study electron transport properties of the small amount of molecules and nanoparticles. It has been demonstrated that a Au nanowire containing 4-[2-nitro-4 (phenylethynyl) phenyl ethynylbenzenethiol molecule junction exhibits negative differential resistance at room temperature [180], while a 16-mercaptohexadecanoic acid nanojunction exhibits a coherent nonresonant tunneling [178, 181, 182]. If some of the metal segments or “stripes” are being replaced with semiconductor, colloidal, and polymer layers, one can introduce rectifying junctions, electronic switching, and photoconductive elements in the composite nanowires. If selectively modifying the nanowire further, using the distinct surface chemistry of different stripes, the nanowires can be positioned on a patterned surface to fulfill nano-logic and memory circuits by self-assembling [179, 183–185]. An array of metal nanowires can be used as a nanoelectrode array for many electrochemical applications [30, 35, 46, 49, 186]. For this purpose, a large array of nanowires with long-range hexagonal order fabricated with the anodic alumina templates is particularly attractive.

2.2.5. Chemical Sensors Penner, Handley, and Dagani et al. exploited hydrogen sensor applications using arrays of Pd nanowires [187–190]. Unlike the traditional Pd-based hydrogen sensor that detects a drop in the conductivity of Pd upon exposure to hydrogen, the Pd-nanowire sensor measures an increase in the conductivity (Fig. 9A). The reason is because the Pd wire consists of

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3. QUANTUM WIRES

Proofs Only

Figure 9. Chemical sensor application of Pd nanowires. (A) Plot of sensor current versus time for the first exposure of a Pd nanowire sensor to hydrogen and one subsequent H2 /air cycle. (B) AFM image of a Pd nanowire on a graphite surface. These images were acquired either in air or in a stream of H2 gas, as indicated. A hydrogen-actuated break junction is highlighted (circle). Reprinted with permission from [188], E. C. Walter et al., Anal. Chem. 74, 1546 (2002). © 2002, American Chemical Society.

a string of Pd particles separated with nanometer-scale gaps. These gaps close to form a conductive path in the presence of hydrogen molecules as Pd particles expand in volume (Fig. 9B). The volume expansion is well known, which is due to the disassociation of hydrogen molecules into hydrogen atoms that penetrate into the Pd lattice and expand the lattice. Although macroscopic Pd-based hydrogen sensors are readily available, they have the following two major drawbacks. First, their response time is between 0.5 s to several minutes, which is too slow to monitor gas flow in real time. Second, they are prone to the poisoning of a number of gas molecules, such as methane, oxygen, and carbon monoxide, which adsorb onto the sensor surfaces and block the adsorption sites for hydrogen molecules. The Pd nanowires offer remedies to the above problems. They have a large surface-to-volume ratio, so the response time can be as fast as 20 ms. The large surface-to-volume ratio also make the nanowire sensor less prone to the poisoning by common contaminations.

The electron transport in the nanowires previously described obeys the classical behaviors as found for macroscopic metal wires. This is because the dimensions of the nanowires are still significantly greater than the characteristic lengths, the electron mean-free path, and the electron wavelength. When the length is shorter than the electron mean-free path, the electron transport is ballistic along the wire. In addition if the diameter of the wire is comparable to the electron wavelength, the effect of quantum-size confinement becomes important in the transverse direction, which results in quantum modes. Connecting such a wire to the outside world (electron reservoirs), the conductance of the system is quantized in the ideal case. The phenomenon of quantization of conductance was first clearly demonstrated in semiconductor devices containing a two-dimensional electron gas confined into a narrow constriction by the gate voltage, where F ∼ 40 nm is much larger than the atomic scale [191, 192]. A similar conductance quantization has been observed in three-dimensional metallic wires [193–197]. Since the wavelength of conduction electrons in a typical metal is only 0.1–0.3 nm, comparable to the size of an atom, a metal wire with conductance quantized at the lowest steps must be atomically thin. This conclusion has been directly confirmed by high-resolution transmission electron microscopy [198]. Because the metal wires that exhibit conductance quantization are usually very short, they are often called atomic-scale contacts or simply nanocontacts. They are also referred to as metal quantum wires or atomic-scale metal wires.

3.1. Fabrication Metal Quantum Wires There are two approaches that one can use to fabricate metal quantum wires: one is the mechanical method and the other one is based, electrochemical etching and deposition. We provide a brief description of them below.

3.1.1. Mechanical Methods Mechanical methods create a metal quantum wire by mechanically separating two electrodes in contact. During the separation process, a metal neck is formed between the electrodes due to strong metallic cohesive energy, which is stretched into an atomically thin wire before breaking. One such method is based on a scanning tunneling microscope (STM) (Fig. 10a) [193–195, 199–202], in which the STM tip is driven into the substrate and the conductance is recorded while the tip is gradually pulled out of the contact with the substrate. The first experiment of this type was reported by Gimzewski et al. to study the transition in the electron transport between tunneling and ballistic regimes [193]. Figure 10b shows several conductance traces during stretching of a Au wire with a STM setup. The conductance decreases in a stepwise fashion. The steps tend to occur near the integer multiples of G0 , indicating the origin of conductance quantization. However, they can deviate significantly from the simple integer multiples. For this reason, a conductance histogram is often constructed from thousands of individual conductance traces to show the occurrence of the steps at difference conductance values (Fig. 10c). For metals

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particularly convenient for statistical analysis, such as conductance histograms. However, the methods form one wire at a time and use piezoelectric or other mechanical transducers, which are not desirable for device applications. It has been recently demonstrated that metal wires with quantized conductance can be fabricated with electrochemical etching and deposition [207–212], which can fabricate arrays of atomic-scale wires supported on solid substrates, thus overcoming some of the drawbacks that the mechanical methods have. The electrochemical methods are discussed below.

Proofs Only Figure 10. (a) Mechanical fabrication of a metal quantum wire with a STM setup. A STM tip is first pressed into a metal substrate and then pulled out of contact during which an atomically thin wire is formed before breaking. (b) Typical conductance versus stretching distance traces that show the quantized variation in the wire conductance. (c) Conductance histogram of Au wires in 0.1M NaClO4 . The welldefined peaks near integer multiples of G0 = 2e2 /h have been attributed to conductance quantization. Each histogram was constructed from over 1000 individual conductance traces like the ones shown in (b).

such as Au, Na, and K, well-defined peaks near the integer multiples are found. For Na and K, the peaks near 2G0 and 4G0 are missing, which is expected because of the mode degeneracy for a cylindrical symmetry of a wire in free electron gas model. The observation, therefore, demonstrates beautifully that these metal wires can be described as free electron gas models in cylindrical wires. Not all metals show pronounced histogram peaks near the integer conductance values. Most other metals show only a broad first peak that is not an integer value. For example, Nb has a first peak near 25G G0 . The transition in conductance from one step to another during mechanical stretching of a wire is usually abrupt, due to sudden rearrangements of the atoms in the wire upon stretching. That is, upon stretching, the stress is accumulated in the metallic bonds between atoms. When the accumulated elastic energy is large enough, the atomic configuration becomes unstable and collapsed into a new atomic configuration that has a thinner diameter. This atomic arrangement during mechanical stretching has been directly observed by simultaneously measuring the force with the atomic force microscope (AFM) and conductance with STM [203]. Another tool to fabricate atomic-scale metal wires is to use a mechanically controllable break-junction (MCB) [204, 205]. The MCB technique creates a clean fracture surface by mechanically breaking a metal and can provide better stability than the STM method. Other methods include the use of a tip and plate [206], two macroscopic electrodes in contact [196], and mechanical relay [197]. The mechanical methods can repeatedly fabricate (and break) a large number of wires within a relatively short time, which is

3.1.2. Electrochemical Methods Snow et al. [213] reported on an AFM-based anodic oxidation method to fabricate Al point contacts. In the method, AFM is first used to anodize a 1-m-wide Al thin film into a 40-nm-wide by 500-nm-long nanowire. The anodization is similar to conventional electrochemical anodization, except that the AFM tip is used as the cathode and water from the ambient humidity is used as electrolyte. The point contacts are formed by further anodizing a section of the nanowire. In order to achieve the control necessary to fabricate atomicsized features, in situ electrical measurements are used as feedback to control the anodization. As the conductance of the point contact is reduced below ∼5 × 10−4 S, the conductance starts to decrease in discrete steps of 2e2 /h. In some of the samples, the conductance can be stabilized at the lowest few quantum steps for a long time, which corresponds to the formation of an atomic-sized wire. Li and Tao demonstrated an electrochemical method to fabricate metal quantum wires using an electrochemical STM setup [207]. In the method, a STM tip is first held at a fixed distance (10–150 nm) from a Au substrate electrode in a plating solution (Cu). Cu is then selectively electroplated onto the sharp STM tip. The selective plating onto the tip is achieved by keeping the substrate potential slightly more positive than the bulk deposition potential. When the growing Cu reaches the substrate, a contact is formed between the tip and the substrate, which is reflected by a sharp increase in the current that flows between the tip and substrate. By slowly dissolving away the deposited Cu contact, a Cu quantum wire is formed between the tip and the substrate electrodes. The conductance of the wire changes in a stepwise fashion with a preference to occur near integer multiples of G0 = 2e2 /h. The electrochemical method does not need mechanical stretching to form the wires, but the STM setup used to achieve a small initial separation between two metal electrodes makes the method prone to thermal drift and mechanical noise. The undesired instability problem is removed in an improved electrochemical method, in which the STM setup is replaced by a metal wire supported on solid substrate (Fig. 11) [208]. The metal wire with an initial diameter of a few tens of m is glued onto a glass slide. The glue covers the entire wire except for a small portion that is exposed to electrolyte for electrochemical deposition and etching. The exposed portion is less than a few m so that ionic conduction through the electrolyte is negligible compared to the electronic conduction through the wire. By electrochemical etching, the diameter of the wire is reduced to the atomic scale, at which the conductance becomes


Proofs Only Figure 11. Electrochemical fabrication of a metal quantum wire. A metal wire is attached to the bottom surface of a plexiglas solution cell. The wire is coated with wax except for a small section that is exposed to electrolyte for etching. The electrochemical potential of the wire is controlled by a bipotentiostat with a reference electrode (RE) and a counter electrode (CE).

quantized. The process can be reversed to increase the diameter by electrochemical deposition. The electrochemical etching and deposition are controlled with a bipotentiostat that can simultaneously control the etching rate and measure the conductance of the wire. In order to form a wire with a desired conductance, a feedback loop has been demonstrated to control the electrochemical etching by comparing the measured conductance with a preset value. When the conductance is greater than the preset value, etching is activated to reduce the diameter of the wire. When the conductance is smaller than the preset value, deposition is turned on to increase the diameter. These atomic-scale wires can last from minutes to days. Further improvement of the stability may be achieved by “coating” the wire with appropriate molecules. The method has been used to fabricate atomic-scale Au, Ag, Cu, and Ni wires with conductance quantized at different steps. Morpurgo et al. observed conductance quantization during the formation metal contact between two Au electrodes by electrodeposition [209]. The initial Au electrodes are fabricated with electron beam lithography and separated with a gap of a few tens nm. Nakabayashi et al. fabricated quantum wires by electrochemically growing a Zn fractal into contact with a Cu ring electrode [212]. The Zn fractal is synthesized at an immiscible interface between water and 4-methyl-2-pentanone so that it is quasi two-dimensional. Li et al. showed that Cu, Ag, Ni, Pd, and Pb quantum wires can be formed between two Au electrodes by electrochemical deposition and etching [210, 214]. A nice feature of the approach is that the Au electrodes can be reused by dissolving away the quantum wires. Their experiment indicates that while Cu, Ag, Ni, and Pd can form stable wires with conductance quantized near 1 G0 , conductance quantization of Pb wires is rather unstable. Elhoussine et al. have reported on conductance quantization in magnetic nanowires (Ni) electrodeposited in the nanopores of track-etched polymer membranes [211]. The

13 magnetic nanocontacts are formed at the extremity of a single Ni nanowire either inside or outside of the nanopores. As expected for ferromagnetic metals without spin degeneracy, their experiment shows that the conductance of the contacts is quantized in units of 0.5G0 (G0 = 2e2 /h). This system might be useful for studying ballistic spin transport through electrodeposited nanocontacts and tunneling through controllable magnetic nanogaps. The method described above can fabricate atomic-scale wires for many measurements, but a simpler method has been demonstrated by Boussaad and Tao [215]. The method does not require a bipotentiostat and feedback control, and it can simultaneously fabricate a large array of wires. The principle is illustrated in Fig. 12(a). It starts with a pair of electrodes separated with a relative large gap in an electrolyte. When applying a bias voltage between the two electrodes, metal atoms are etched off from the anode and deposited onto the cathode. The etching takes place all over the anode surface, but the deposition is localized to the sharpest point on the cathode, due to a high electric field and a metal ion concentration near the sharpest point. Consequently, the gap narrows and disappears eventually when a point contact is formed between the two electrodes. In order to control the formation of the contact between the electrodes, the etching and deposition processes must be terminated immediately after a desired contact is formed. While a feedback mechanism may be used for this purpose, they introduced a much simpler self-termination mechanism by connecting one electrode in a series with an external

Figure 12. Fabrication of metal nanowires with a self-terminated electrochemical method. (a) Metal atoms etched off the left electrode are deposited onto the right electrode by applying a voltage between the electrodes with an external resistor (Rext ) in series. As the gap between the two electrodes shrinks, the gap resistance decreases, which results in a drop in etching/deposition voltage and eventually terminates the etching/deposition processes. (b) Choosing a Rext < 127 k, a wire with quantized conductance can be fabricated. The conductance change during the formation of a contact (Rext = 3 k and V0 = 12 V). The large conductance fluctuations corresponding to constant breakdown and reformation of the contact are due to electromigration.

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resistor (Rext ). So the effective voltage (or overpotential) for etching and deposition is given by Vgap =

Rgap Rgap + Rext

V0

(3)

where Rgap is the resistance between the two electrodes, and V0 is the total applied bias voltage. Initially, the gap is large, so no tunneling current flows across it and Rgap is solely determined by ionic conduction (leakage current) between the electrodes. By coating the electrodes with an insulation layer, such as Si3 N4 , the unwanted leakage current can be reduced below 1 pA, which gives rise to a large initial Rgap ( Rext ). According to Eq. (3), Vgap ∼ V0 initially, so the etching and deposition take place at maximum speed and the gap quickly narrows. When the gap is reduced to a few nm or less, Rgap begins to decrease because of electron tunneling across the gap. Eventually, a contact with quantized conductance is formed between the two electrodes. By choosing an appropriate Rext , one can form either a small gap or a contact (quantum wire) with quantized conductance. If Rext is greater than h/2e2 , the resistance for a single atom contact between two electrodes terminates with a small tunneling gap between the electrodes. On the other hand, if Rext is smaller than h/2e2 , it terminates with an atomic-scale contact between the electrodes. Figure 12(b) shows the conductance (normalized against G0 between two Cu electrodes during electrochemical etching and deposition in water with Rext preset at 3 k (