Self-assembled nanowires on semiconductor surfaces

A number of different families of nanowires which self-assemble on semiconductor surfaces have been identified in recent years. They are particularly interesting from the standpoint of nanoelectronics, which seeks non-lithographic ways of creating interconnects at the nm scale (though possibly for carrying signal rather than current), as well as from the standpoint of traditional materials science and surface science. We survey these families and consider their physical and electronic structure, as well as their formation and reactivity. Particular attention is paid to rare earth nanowires and the Bi nanoline, both of which self-assemble on Si(001).Further information within the topic of this review article, including an up-to-date list of relevant publications, can be found on our Website. The address is:

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Single crystal GaN nanowires

Single crystal gallium nitride nanowires have been obtained by heating gallium acetylacetonate in the presence of carbon nanotubes or activated carbon in NH3 vapor at 910 degrees C. GaN nanowires also were obtained when the reaction of gallium acetylacetonate with NH3 was carried out over catalytic Fe/Ni particles dispersed over silica. The former procedure with carbon nanotubes is preferable because it avoids the presence of metal particles in the nanowire bundles.     

Catalyst-free ZnO nanowires grown on a-plane GaN

ZnO nanowires were grown on a-plane GaN templates by chemical vapor deposition (CVD) without employing a catalyst. The a-plane GaN templates were pre-deposited on an r-plane sapphire substrate by metal-organic CVD. The resulting ZnO nanowires grow in angles off- related to the GaN basal plane. X-ray diffraction (XRD) spectra showed that the ZnO layer was grown with a heteroepitaxial relationship of (110)_ZnO||(110)_GaN. Photoluminescence spectra measured at 17 K exhibited near-band-edge emission at 372 nm with a full width at half maximum of 10 nm. The growth mechanism on a-GaN was the Volmer-Weber (VW) mode and differed from the Stranski-Krastanow (SK) mode observed for growth on c-GaN. This difference results from the higher interfacial free-energy on the a-plane between ZnO and GaN than that on the c-plane orientation.     

Nanopatterning of ultrananocrystalline diamond nanowires

We report the fabrication of horizontally aligned ultrananocrystalline diamond (UNCD) nanowires (NWs) via two different approaches. First, with the top-down approach by using electron beam lithography (EBL) and reactive ion etching (RIE) with a photo resist layer as an etch mask. Using this approach, we demonstrate fabrication of 50?μm long UNCD NWs with widths as narrow as 40?nm. We further present an alternative approach to grow UNCD NWs at pre-defined positions through a selective seeding process. No RIE was needed either to etch the NWs or to remove the mask. In this case, we achieved UNCD NWs with lengths of 50?μm and smallest width of 90?nm respectively. Characterization of these nanowires by using scanning electron microscopy (SEM) and atomic force microscopy (AFM) shows that the UNCD NWs are well defined and fully released, with no indication of residual stress. Characterization using visible and ultraviolet (UV) Raman spectroscopy indicates that in both fabrication approaches, UNCD NWs maintain their intrinsic diamond structure.     

Self-assembled single-crystal ferromagnetic iron nanowires formed by decomposition

Arrays of perpendicular ferromagnetic nanowires have recently attracted considerable interest for their potential use in many areas of advanced nanotechnology. We report a simple approach to create self-assembled nanowires of alpha-Fe through the decomposition of a suitably chosen perovskite. We illustrate the principle behind this approach using the reaction 2La(0.5)Sr(0.5)FeO(3) --> LaSrFeO(4) + Fe + O(2) that occurs during the deposition of La(0.5)Sr(0.5)FeO(3) under reducing conditions. This leads to the spontaneous formation of an array of single-crystalline alpha-Fe nanowires embedded in LaSrFeO(4) matrix, which grow perpendicular to the substrate and span the entire film thickness. The diameter and spacing of the nanowires are controlled directly by deposition temperature. The nanowires show uniaxial anisotropy normal to the film plane and magnetization close to that of bulk alpha-Fe. The high magnetization and sizable coercivity of the nanowires make them desirable for high-density data storage and other magnetic-device applications.     

In situ nanomechanics of GaN nanowires

The deformation, fracture mechanisms, and the fracture strength of individual GaN nanowires were measured in real time using a transmission electron microscope-scanning probe microscope (TEM-SPM) platform. Surface mediated plasticity, such as dislocation nucleation from a free surface and plastic deformation between the SPM probe (the punch) and the nanowire contact surface were observed in situ. Although local plasticity was observed frequently, global plasticity was not observed, indicating the overall brittle nature of this material. Dislocation nucleation and propagation is a precursor before the fracture event, but the fracture surface shows brittle characteristic. The fracture surface is not straight but kinked at (10-10) or (10-11) planes. Dislocations are generated at a stress near the fracture strength of the nanowire, which ranges from 0.21 to 1.76 GPa. The results assess the mechanical properties of GaN nanowires and may provide important insight into the design of GaN nanowire devices for electronic and optoelectronic applications.     

Diameter-dependent electromechanical properties of GaN nanowires

The diameter-dependent Young's modulus, E, and quality factor, Q, of GaN nanowires were measured using electromechanical resonance analysis in a transmission electron microscope. E is close to the theoretical bulk value ( approximately 300 GPa) for a large diameter nanowire (d=84 nm) but is significantly smaller for smaller diameters. At room temperature, Q is as high as 2,800 for d=84 nm, significantly greater than what is obtained from micromachined Si resonators of comparable surface-to-volume ratio. This implies significant advantages of smooth-surfaced GaN nanowire resonators for nanoelectromechanical system (NEMS) applications. Two closely spaced resonances are observed and attributed to the low-symmetry triangular cross section of the nanowires.     

Acoustic charge transport in GaN nanowires

We present acoustic charge transport in GaN nanowires (GaN NWs). The GaN NWs were grown by molecular beam epitaxy (MBE) on silicon(111) substrates. The nanowires were removed from the silicon substrate, aligned using surface acoustic waves (SAWs) on the piezoelectric substrate LiNbO(3) and finally contacted by electron beam lithography. Then, a SAW was used to create an acoustoelectric current in the GaN NWs which was detected as a function of radio-frequency (RF) wave frequency and its power. The presented method and our experimental findings open up a route towards new acoustic charge transport nanostructure devices in a wide bandgap material such as GaN.     

The controlled growth of GaN nanowires

This paper reports a scalable process for the growth of high-quality GaN nanowires and uniform nanowire arrays in which the position and diameter of each nanowire is precisely controlled. The approach is based on conventional metalorganic chemical vapor deposition using regular precursors and requires no additional metal catalyst. The location, orientation, and diameter of each GaN nanowire are controlled using a thin, selective growth mask that is patterned by interferometric lithography. It was found that use of a pulsed MOCVD process allowed the nanowire diameter to remain constant after the nanowires had emerged from the selective growth mask. Vertical GaN nanowire growth rates in excess of 2 mum/h were measured, while remarkably the diameter of each nanowire remained constant over the entire (micrometer) length of the nanowires. The paper reports transmission electron microscopy and photoluminescence data.     

Vertically aligned nanowires from boron-doped diamond

Vertically aligned diamond nanowires with controlled geometrical properties like length and distance between wires were fabricated by use of nanodiamond particles as a hard mask and by use of reactive ion etching. The surface structure, electronic properties, and electrochemical functionalization of diamond nanowires were characterized by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) as well as electrochemical techniques. AFM and STM experiments show that diamond nanowire etched for 10 s have wire-typed structures with 3-10 nm in length and with typically 11 nm spacing in between. The electrode active area of diamond nanowires is enhanced by a factor of 2. The functionalization of nanowire tips with nitrophenyl molecules is characterized by STM on clean and on nitrophenyl molecule-modified diamond nanowires. Tip-modified diamond nanowires are promising with respect to biosensor applications where controlled biomolecule bonding is required to improve chemical stability and sensing significantly.     

High output nanogenerator based on assembly of GaN nanowires

GaN nanowires (NWs) were synthesized through a vapor-liquid-solid (VLS) process. Based on structural analysis, the c-axis of the NW was confirmed to be perpendicular to the growth direction. Nanogenerators (NGs) fabricated by rational assembly of the GaN NWs produced an output voltage up to 1.2 V and output current density of 0.16 μA cm?2. The measured performance of the GaN NGs was consistent with the calculations using finite element analysis (FEA).     

Photoinduced self-organization of gallium nanowires on a GaN surface

The mechanism of ultraviolet laser ablation of GaN epitaxial films is determined: it is found to be based on the dissociation of GaN molecules to form volatile nitrogen-containing components. The conditions of exposure under which the formation of gallium nanoclusters on the GaN surface are determined. Regimes of epitaxial growth of GaN are found in which parallel microterraces form on the surface of the samples. It is found that when samples with microterraces in the as-grown state are irradiated by high-power ultraviolet radiation, gallium nanowires are formed on the surface. It is proposed to use these phenomena to develop new UV optical lithographic techniques and to fabricate single-electron devices based on GaN. Pis’ma Zh. Tekh. Fiz. 25, 13–18 (May 26, 1999)     

Disorder effects in focused-ion-beam-deposited Pt contacts on GaN nanowires

The current-bias (I-V) characteristics at various temperatures, T, of focused-ion-beam (FIB)-deposited Pt contacts on GaN nanowires evolves from low-resistance ohmic (linear I-V) to rectifying as the diameter increases, and both exhibit strongly nonmetallic T-dependence. The small-diameter (66 nm) T-dependent resistance is explained by two-dimensional variable range hopping with a small characteristic energy, ensuring low resistance at 300 K. For large diameters (184 nm), back-to-back Schottky barriers explain the nonlinear I-V at all T values and permit an estimate of doping concentration from the bias-dependent barrier height. Both behaviors can be understood by accounting for the role of FIB-induced amorphization of GaN underneath the contact, as confirmed by cross-sectional transmission electron microscopy.     

Self-assembled diphenylalanine nanowires for cellular studies and sensor applications

In this paper we present a series of experiments showing that vertical self-assembled diphenylalanine peptide nanowires (PNWs) are a suitable candidate material for cellular biosensing. We grew HeLa and PC12 cells onto PNW modified gold surfaces and observed no hindrance of cell growth caused by the peptide nanostructures; furthermore we studied the properties of PNWs by investigating their influence on the electrochemical behavior of gold electrodes. The PNWs were functionalized with polypyrrole (PPy) by chemical polymerization, therefore creating conducting peptide/polymer nanowire structures vertically attached to a metal electrode. The electroactivity of such structures was characterized by cyclic voltammetry. The PNW/PPy modified electrodes were finally used as amperometric dopamine sensors, yielding a detection limit of 3,1 microM.     

Synthesies and properties of Tb-doped GaN nanowires

The synthesis of Tb-doped GaN nanowires on Si (111) substrates through ammoniating Ga₂O₃ films doped with Tb was investigated. X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscope, high-resolution transmission electron microscopy and photoluminescence were used to characterize the composition, structure, morphology and optical properties of the products. The results show that the as-synthesized GaN nanowires doped with 3 at % Tb are of single-crystalline hexagonal wurtzite structure. The nanowires have diameters ranging from 30 to 50 nm and the lengths up to tens of micrometers. An f-f intra-atomic transition of rare earth at 545 nm corresponding to ⁵ D ₄–⁷ F ₅ of the Tb³⁺ and other two peaks related with doping are observed in PL spectrum, confirming the doping of Tb into GaN. The growth mechanism of GaN nanowires was discussed briefly.     

Room-temperature ferromagnetism in Cu doped GaN nanowires

We report magnetism in Cu doped single-crystalline GaN nanowires. The typical diameter and the length of the Ga1-xCuxN nanowires (x = 0.01, 0.024) are 10-100 nm and tens of micrometers, respectively. The saturation magnetic moments are measured to be higher than 0.86 microB/Cu at 300 K, and the Curie temperatures are far above room temperature. Anomalous X-ray scattering and X-ray diffraction measurement make it clear that Cu atoms substitute the Ga sites, and they largely take part in the wurtzite network of host GaN. X-ray absorption and X-ray magnetic circular dichroism spectra at Cu L(2,3) edges show that doped Cu has local magnetic moment and the electronic configuration of it is mainly 3d9 but mixed with a small portion of trivalent component. It seems that the ionocovalent bonding nature of Cu 3d orbital with surrounding semiconductor medium makes Cu atom a mixed electron configuration and local magnetic moments. These outcomes suggest that the Ga1-xCuxN system is a room-temperature ferromagnetic semiconductor.     

Room-temperature photodetection dynamics of single GaN nanowires

We report on the photocurrent behavior of single GaN n-i-n nanowires (NWs) grown by plasma-assisted molecular-beam epitaxy on Si(111). These structures present a photoconductive gain in the range of 10(5)-10(8) and an ultraviolet (350 nm) to visible (450 nm) responsivity ratio larger than 6 orders of magnitude. Polarized light couples with the NW geometry with a maximum photoresponse for polarization along the NW axis. The photocurrent scales sublinearly with optical power, following a I ~ P(β) law (β < 1) in the measured range with β increasing with the measuring frequency. The photocurrent time response remains in the millisecond range, which is in contrast to the persistent (hours) photoconductivity effects observed in two-dimensional photoconductors. The photocurrent is independent of the measuring atmosphere, either in the air or in vacuum. Results are interpreted taking into account the effect of surface states and the total depletion of the NW intrinsic region.     

Mechanical elasticity of vapour-liquid-solid grown GaN nanowires

Mechanical elasticity of hexagonal wurtzite GaN nanowires with hexagonal cross sections grown through a vapour-liquid-solid (VLS) method was investigated using a three-point bending method with a digital-pulsed force mode (DPFM) atomic force microscope (AFM). In a diameter range of 57-135?nm, bending deflection and effective stiffness, or spring constant, profiles were recorded over the entire length of end-supported GaN nanowires and compared to the classic elastic beam models. Profiles reveal that the bending behaviour of the smallest nanowire (57.0?nm in diameter) is as a fixed beam, while larger nanowires (89.3-135.0?nm in diameter) all show simple-beam boundary conditions. Diameter dependence on the stiffness and elastic modulus are observed for these GaN nanowires. The GaN nanowire of 57.0?nm diameter displays the lowest stiffness (0.98?N?m(-1)) and the highest elastic modulus (400 ± 15?GPa). But with increasing diameter, elastic modulus decreases, while stiffness increases. Elastic moduli for most tested nanowires range from 218 to 317?GPa, which approaches or meets the literature values for bulk single crystal and GaN nanowires with triangular cross sections from other investigators. The present results together with further tests on plastic and fracture processes will provide fundamental information for the development of GaN nanowire devices.