Transport modulation in Ge/Si core/shell nanowires through controlled synthesis of doped Si shells

Appropriately controlling the properties of the Si shell in Ge/Si core/shell nanowires permits not only passivation of the Ge surface states, but also introduces new interface phenomena, thereby enabling novel nanoelectronics concepts. Here, we report a rational synthesis of Ge/Si core/shell nanowires with doped Si shells. We demonstrate that the morphology and thickness of Si shells can be controlled for different dopant types by tuning the growth parameters during synthesis. We also present distinctly different electrical characteristics that arise from nanowire field-effect transistors fabricated using the synthesized Ge/Si core/shell nanowires with different shell morphologies. Furthermore, a clear transition in the modification of device characteristics is observed for crystalline shell nanowires following removal of the shell using a unique trimming process of successive native oxide formation/etching. Our results demonstrate that the preferred transport path through the nanowire structure can be modulated by appropriately tuning the growth conditions.     

Growth of nickel silicides in Si and Si/SiOx core/shell nanowires

We exploited the oxide shell structure to explore the structure confinement effect on the nickel silicide growth in one-dimensional nanowire template. The oxide confinement structure is similar to the contact structure (via hole) in the thin film system or nanodevices passivated by oxide or nitride film. Silicon nanowires in direct contact with nickel pads transform into two phases of nickel silicides, Ni31Si12 and NiSi2, after one-step annealing at 550 °C. In a bare Si nanowire during the annealing process, NiSi2 grows initially through the nanowire, followed by the transformation of NiSi2 into the nickel-rich phase, Ni31Si12 starting from near the nickel pad. Ni31Si12 is also observed under the nickel pads. Although the same phase transformations of Si to nickel silicides are observed in nanowires with oxide confinement structure, the growth rate of nickel silicides, Ni31Si12 and NiSi2, is retarded dramatically. With increasing oxide thickness from 5 to 50 nm, the retarding effect of the Ni31Si12 growth and the annihilation of Ni2Si into the oxide confined-Si is clearly observed. Ni31Si12 and Ni2Si phases are limited to grow into the Si/SiOx core-shell nanowire as the shell thickness reaches 50 nm. It is experimental evidence that phase transformation is influenced by the stressed structure at nanoscale.     

Ni-silicide growth kinetics in Si and Si/SiO2 core/shell nanowires

A systematic study of the kinetics of axial Ni silicidation of as-grown and oxidized Si nanowires (SiNWs) with different crystallographic orientations and core diameters ranging from ～ 10 to 100 nm is presented. For temperatures between 300 and 440?°C the length of the total axial silicide intrusion varies with the square root of time, which provides clear evidence that the rate limiting step is diffusion of Ni through the growing silicide phase(s). A retardation of Ni-silicide formation for oxidized SiNWs is found, indicative of a stress induced lowering of the diffusion coefficients. Extrapolated growth constants indicate that the Ni flux through the silicided NW is dominated by surface diffusion, which is consistent with an inverse square root dependence of the silicide length on the NW diameter as observed for (111) orientated SiNWs. In situ TEM silicidation experiments show that NiSi(2) is the first forming phase for as-grown and oxidized SiNWs. The silicide-SiNW interface is thereby atomically abrupt and typically planar. Ni-rich silicide phases subsequently nucleate close to the Ni reservoir, which for as-grown SiNWs can lead to a complete channel break-off for prolonged silicidation due to significant volume expansion and morphological changes.     

Si/a-Si core/shell nanowires as nonvolatile crossbar switches

Radial core/shell nanowires (NWs) represent an important class of nanoscale building blocks with substantial potential for exploring fundamental electronic properties and realizing novel device applications at the nanoscale. Here, we report the synthesis of crystalline silicon/amorphous silicon (Si/a-Si) core/shell NWs and studies of crossed Si/a-Si NW metal NW (Si/a-Si x M) devices and arrays. Room-temperature electrical measurements on single Si/a-Si x Ag NW devices exhibit bistable switching between high (off) and low (on) resistance states with well-defined switching threshold voltages, on/off ratios greater than 10(4), and current rectification in the on state. Temperature-dependent switching experiments suggest that rectification can be attributed to barriers to electric field-driven metal diffusion. Systematic studies of Si/a-Si x Ag NW devices show that (i) the bit size can be at least as small as 20 nm x 20 nm, (ii) the writing time is <100 ns, (iii) the retention time is >2 weeks, and (iv) devices can be switched >10(4) times without degradation in performance. In addition, studies of dense one-dimensional and two-dimensional Si/a-Si x Ag NW devices arrays fabricated on crystalline and plastic substrates show that elements within the arrays can be independently switched and read, and moreover that bends with radii of curvature as small as 0.3 cm cause little change in device characteristics. The Si/a-Si x Ag NW devices represent a highly scalable and promising nanodevice element for assembly and fabrication of dense nonvolatile memory and programmable nanoprocessors.     

Performance analysis of a Ge/Si core/shell nanowire field-effect transistor

We ana/lyze the performance of a recently reported Ge/Si core/shell nanowire transistor using a semiclassical, ballistic transport model and an sp3d5s* tight-binding treatment of the electronic structure. Comparison of the measured performance of the device with the effects of series resistance removed to the simulated result assuming ballistic transport shows that the experimental device operates between 60 and 85% of the ballistic limit. For this approximately 15 nm diameter Ge nanowire, we also find that 14-18 modes are occupied at room temperature under ON-current conditions with ION/IOFF = 100. To observe true one-dimensional transport in a 110 Ge nanowire transistor, the nanowire diameter would have to be less than about 5 nm. The methodology described here should prove useful for analyzing and comparing on a common basis nanowire transistors of various materials and structures.     

Genomic design of strong direct-gap optical transition in Si/Ge core/multishell nanowires

Finding a Si-based material with strong optical activity at the band-edge remains a challenge despite decades of research. The interest lies in combining optical and electronic functions on the same wafer, while retaining the extraordinary know-how developed for Si. However, Si is an indirect-gap material. The conservation of crystal momentum mandates that optical activity at the band-edge includes a phonon, on top of an electron-hole pair, and hence photon absorption and emission remain fairly unlikely events requiring optically rather thick samples. A promising avenue to convert Si-based materials to a strong light-absorber/emitter is to combine the effects on the band-structure of both nanostructuring and alloying. The number of possible configurations, however, shows a combinatorial explosion. Furthermore, whereas it is possible to readily identify the configurations that are formally direct in the momentum space (due to band-folding) yet do not have a dipole-allowed transition at threshold, the problem becomes not just calculation of band structure but also calculation of absorption strength. Using a combination of a genetic algorithm and a semiempirical pseudopotential Hamiltonian for describing the electronic structures, we have explored hundreds of thousands of possible coaxial core/multishell Si/Ge nanowires with the orientation of [001], [110], and [111], discovering some "magic sequences" of core followed by specific Si/Ge multishells, which can offer both a direct bandgap and a strong oscillator strength. The search has revealed a few simple design principles: (i) the Ge core is superior to the Si core in producing strong bandgap transition; (ii) [001] and [110] orientations have direct bandgap, whereas the [111] orientation does not; (iii) multishell nanowires can allow for greater optical activity by as much as an order of magnitude over plain nanowires; (iv) the main motif of the winning configurations giving direct allowed transitions involves rather thin Si shell embedded within wide Ge shells. We discuss the physical origin of the enhanced optical activity, as well as the effect of possible experimental structural imperfections on optical activity in our candidate core/multishell nanowires.     

Nanoscale effects on heterojunction electron gases in GaN/AlGaN core/shell nanowires

The electronic properties of heterojunction electron gases formed in GaN/AlGaN core/shell nanowires with hexagonal and triangular cross sections are studied theoretically. We show that at nanoscale dimensions, the nonpolar hexagonal system exhibits degenerate quasi-one-dimensional electron gases at the hexagon corners, which transition to a core-centered electron gas at lower doping. In contrast, polar triangular core/shell nanowires show either a nondegenerate electron gas on the polar face or a single quasi-one-dimensional electron gas at the corner opposite the polar face, depending on the termination of the polar face. More generally, our results indicate that electron gases in closed nanoscale systems are qualitatively different from their bulk counterparts.     

Crystal structure transfer in core/shell nanowires

Structure engineering is an emerging tool to control opto-electronic properties of semiconductors. Recently, control of crystal structure and the formation of a twinning superlattice have been shown for III-V nanowires. This level of control has not been obtained for Si nanowires, the most relevant material for the semiconductor industry. Here, we present an approach, in which a designed twinning superlattice with the zinc blende crystal structure or the wurtzite crystal structure is transferred from a gallium phosphide core wire to an epitaxially grown silicon shell. These materials have a difference in lattice constants of only 0.4%, which allows for structure transfer without introducing extra defects. The twinning superlattices, periodicity, and shell thickness can be tuned with great precision. Arrays of free-standing Si nanotubes are obtained by a selective wet-chemical etch of the core wire.     

Spherical aberration correction using a liquid-crystal spatial-light modulator in off-axis electron holography

One can correct spherical aberration in a transmission electron microscope by using a newly developed aberration-correction method involving off-axis electron holography. In this method, a liquid-crystal spatial-light modulator (LC SLM) is employed during the holographic reconstruction step to compensate for spherical aberration. Application of this method to high-resolution off-axis electron holograms of fine gold particles is presented. The phase distribution of the corrected object wave is visualized by the Zernike phase-contrast method carried out with the same LC SLM.     

Photoluminescence polarization in strained GaN/AlGaN core/shell nanowires

The optical polarization properties of GaN/AlGaN core/shell nanowire (NW) heterostructures have been investigated using polarization resolved micro-photoluminescence (μ-PL) and interpreted in terms of a strain-dependent 6 × 6 k·p theoretical model. The NW heterostructures were fabricated in two steps: the Si-doped n-type c-axis GaN NW cores were grown by molecular beam epitaxy (MBE) and then epitaxially overgrown using halide vapor phase epitaxy (HVPE) to form Mg-doped AlGaN shells. The emission of the uncoated strain-free GaN NW core is found to be polarized perpendicular to the c-axis, while the GaN core compressively strained by the AlGaN shell exhibits a polarization parallel to the NW c-axis. The luminescence of the AlGaN shell is weakly polarized perpendicular to the c-axis due to the tensile axial strain in the shell.     

Significant reduction of thermal conductivity in Si/Ge core-shell nanowires

We report on the effect of germanium (Ge) coatings on the thermal transport properties of silicon (Si) nanowires using nonequilibrium molecular dynamics simulations. Our results show that a simple deposition of a Ge shell of only 1 to 2 unit cells in thickness on a single crystalline Si nanowire can lead to a dramatic 75% decrease in thermal conductivity at room temperature compared to an uncoated Si nanowire. By analyzing the vibrational density states of phonons and the participation ratio of each specific mode, we demonstrate that the reduction in the thermal conductivity of Si/Ge core-shell nanowire stems from the depression and localization of long-wavelength phonon modes at the Si/Ge interface and of high frequency nonpropagating diffusive modes.     

Si-CdSSe core/shell nanowires with continuously tunable light emission

Uniform Si-CdSSe core/shell nanowires were controllably synthesized by a multisource thermal evaporation route. Both the silicon core and the alloyed CdSSe shell are of high-quality and single crystalline. The silicon core is grown via the gold-catalyzed VLS route with a silicon wafer piece at the high temperature zone as the source. These preferentially grown Si nanowires further serve as templates for the afterward depositions of CdSSe shells using CdS/CdSe powders at the low temperature zone of the furnace as sources. The composition/band gap of the shells can be continuously modulated by the S/Se ratio of the evaporation sources, making these prepared heterostructures have strong and spectral position/color largely tunable light emission at the visible region. These kind of structures may have potential applications in multicolor nanoscaled light-emitting devices. This flexible growth route will also be applicable for controllable synthesis of other Si wire containing heterostructures.     

Composition and local strain mapping in Au-catalyzed axial Si/Ge nanowires

For most applications, heterostructures in nanowires (NWs) with lattice mismatched materials are required and promise certain advantages thanks to lateral strain relaxation. The formation of Si/Ge axial heterojunctions is a challenging task to obtain straight, defect free and extended NWs. And the control of the interface will determine the future device properties. This paper reports the growth and analysis of NWs consisting of an axial Si/Ge heterostructure grown by a vapor-liquid-solid process. The composition gradient and the strain distribution at the heterointerface were measured by advanced quantitative electron microscopy methods with a resolution at the nanometer scale. The transition from pure Ge to pure Si shows an exponential slope with a transition width of 21?nm for a NW diameter of 31?nm. Although diffuse, the heterointerface makes possible strain engineering along the axis of the NW. The interface is dislocation-free and a tensile out-of-plane strain is noticeable in the Ge section of the NW, indicating a lattice accommodation. Experimental results were compared to finite element calculations.     

Giant spin splitting in optically active ZnMnTe/ZnMgTe core/shell nanowires

An enhancement of the Zeeman splitting as a result of the incorporation of paramagnetic Mn ions in ZnMnTe/ZnMgTe core/shell nanowires is reported. The studied structures are grown by gold-catalyst assisted molecular beam epitaxy. The near band edge emission of these structures, conspicuously absent in the case of uncoated ZnMnTe nanowires, is activated by the presence of ZnMgTe coating. Giant Zeeman splitting of this emission is studied in ensembles of nanowires with various average Mn concentrations of the order of a few percent, as well as in individual nanowires. Thus, we show convincingly that a strong spin sp-d coupling is indeed present in these structures.     

Thermal and tensile properties of Si/Ge core-shell and superlattice nanowires

The Stillinger-Weber potential-based MD (Molecular dynamics) method is used to simulate the heating-up and axial tension of Si/Ge core-shell and superlattice nanowires; according to the simulative results, the differences in their thermal and mechanical properties are discussed. The results show the following: (1) The Si/Ge superlattice nanowire is more thermally stable than the core-shell one, and their melting points are 1160 and 1320 K, respectively. (2) The Si/Ge core-shell nanowire has higher elastic module than the super-lattice one. (3) Under tension, the super-lattice nanowire has better antideformation capability than the core-shell one but has comparative antiloading capability.     

Thermal and tensile properties of Si/Ge core-shell and superlattice nanowires

The Stillinger-Weber potential-based MD (Molecular dynamics) method is used to simulate the heating-up and axial tension of Si/Ge core-shell and superlattice nanowires; according to the simulative results, the differences in their thermal and mechanical properties are discussed. The results show the following: (1) The Si/Ge superlattice nanowire is more thermally stable than the core-shell one, and their melting points are 1160 and 1320 K, respectively. (2) The Si/Ge core-shell nanowire has higher elastic module than the super-lattice one. (3) Under tension, the super-lattice nanowire has better antideformation capability than the core-shell one but has comparative antiloading capability.     

Ultrafast electron and hole dynamics in germanium nanowires

We present the first ultrafast time-resolved optical measurements, to the best of our knowledge, on ensembles of germanium nanowires. Vertically aligned germanium nanowires with mean diameters of 18 and 30 nm are grown on (111) silicon substrates through chemical vapor deposition. We optically inject electron-hole pairs into the nanowires and exploit the indirect band structure of germanium to separately probe electron and hole dynamics with femtosecond time resolution. We find that the lifetime of both electrons and holes decreases with decreasing nanowire diameter, demonstrating that surface effects dominate carrier relaxation in semiconductor nanowires.     

Fabrication of GaN/GaN:Mn core/shell nanowires and their photoluminescences

We report on the fabrication of GaN/GaN:Mn core/shell nanowires (NWs) using a two-step metalorganic chemcial vapor deposition (MOCVD) and chloride-based chemical vapor transport (CVT) process. Structural analyses indicated that the heterostructure NWs were single crystalline and exhibited a core/shell and lozenge structure. The photoluminescence (PL) of the core/shell NWs showed a peak at a center wavelength of 454 nm, which was red-shifted compared to those of GaN and GaN:Mn NWs. This outcome indicates the accumulation of excited carriers at the interfaces that would be helpful in developing novel magnetism in diluted magnetic GaN:Mn semiconductors.     

Electrical breakdown and nanogap formation of indium oxide core/shell heterostructure nanowires

We report the electrical breakdown behavior and subsequent nanogap formation of In(2)O(3)/InO(x) core/shell heterostructure nanowires with substrate-supported and suspended structures. The radial heterostructure nanowires, composed of crystalline In(2)O(3) cores and amorphous In-rich shells, are grown by chemical vapor deposition. As the nanowires broke down, they exhibited two distinct current drops in the current-voltage characteristics. The tips of the broken nanowires were found to have a cone or a volcano shape depending on the width of the nanowire. The shape, the size, and the position of the nanogap depend strongly on the device structure and the nanowire dimensions. The substrate-supported and the suspended devices exhibit distinct breakdown behavior which can be explained by the diffusive thermal transport model. The breakdown temperature of the nanowire is estimated to be about 450?K, close to the melting temperature of indium. We demonstrated the usefulness of this technique by successful fabrication of working pentacene field-effect transistors.     

FIB/TEM characterization of the composition and structure of core/shell Cu-Ni nanowires

Characterization of composition and structure is crucial to understanding the properties and performance of nanomaterials. For nanowires and nanotubes, determining radial compositional and structural modulations is particularly challenging. Here we use a focused ion beam (FIB) lift-out technique to show that Cu-Ni core/shell nanowires fabricated by template synthesis are characterized by large, high purity (>99 atom %) copper grains surrounded by much smaller, high purity (>99 atom %) nickel grains.