The influence of surface oxide on the growth of metal/semiconductor nanowires

We report the critical effects of oxide on the growth of nanostructures through silicide formation. Under an in situ ultrahigh vacuum transmission electron microscope, it is observed from the conversion of Si nanowires into the metallic PtSi grains epitaxially through controlled reactions between lithographically defined Pt pads and Si nanowires. With oxide, instead of contact area, single crystal PtSi grains start forming either near the center between two adjacent pads or from the ends of Si nanowires, resulting in the heterostructure formation of Si/PtSi/Si. Without oxide, transformation from Si into PtSi begins at the contact area between them, resulting in the heterostructure formation of PtSi/Si/PtSi. The nanowire heterostructures have an atomically sharp interface with epitaxial relationships of Si(20-2)//PtSi(10-1) and Si[111]//PtSi[111]. Additionally, it has been observed that the existence of oxide significantly affects not only the growth position but also the growth behavior and the growth rate by two orders of magnitude. Molecular dynamics simulations have been performed to support our experimental results and the proposed growth mechanisms. In addition to fundamental science, the significance of the study matters for future processing techniques in nanotechnology and related applications as well.     

Single-crystalline Ni2Ge/Ge/Ni2Ge nanowire heterostructure transistors

In this study, we report on the formation of a single-crystalline Ni(2)Ge/Ge/Ni(2)Ge nanowire heterostructure and its field effect characteristics by controlled reaction between a supercritical fluid-liquid-solid (SFLS) synthesized Ge nanowire and Ni metal contacts. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies reveal a wide temperature range to convert the Ge nanowire to single-crystalline Ni(2)Ge by a thermal diffusion process. The maximum current density of the fully germanide Ni(2)Ge nanowires exceeds 3.5 × 10(7) A cm(-2), and the resistivity is about 88 μΩ cm. The in situ reaction examined by TEM shows atomically sharp interfaces for the Ni(2)Ge/Ge/Ni(2)Ge heterostructure. The interface epitaxial relationships are determined to be [Formula: see text] and [Formula: see text]. Back-gate field effect transistors (FETs) were also fabricated using this low resistivity Ni(2)Ge as source/drain contacts. Electrical measurements show a good p-type FET behavior with an on/off ratio over 10(3) and a one order of magnitude improvement in hole mobility from that of SFLS-synthesized Ge nanowire.     

Dopant-free GaN/AlN/AlGaN radial nanowire heterostructures as high electron mobility transistors

We report the rational synthesis of dopant-free GaN/AlN/AlGaN radial nanowire heterostructures and their implementation as high electron mobility transistors (HEMTs). The radial nanowire heterostructures were prepared by sequential shell growth immediately following nanowire elongation using metal-organic chemical vapor deposition (MOCVD). Transmission electron microscopy (TEM) studies reveal that the GaN/AlN/AlGaN radial nanowire heterostructures are dislocation-free single crystals. In addition, the thicknesses and compositions of the individual AlN and AlGaN shells were unambiguously identified using cross-sectional high-angle annular darkfield scanning transmission electron microscopy (HAADF-STEM). Transport measurements carried out on GaN/AlN/AlGaN and GaN nanowires prepared using similar conditions demonstrate the existence of electron gas in the undoped GaN/AlN/AlGaN nanowire heterostructures and also yield an intrinsic electron mobility of 3100 cm(2)/Vs and 21,000 cm(2)/Vs at room temperature and 5 K, respectively, for the heterostructure. Field-effect transistors fabricated with ZrO(2) dielectrics and metal top gates showed excellent gate coupling with near ideal subthreshold slopes of 68 mV/dec, an on/off current ratio of 10(7), and scaled on-current and transconductance values of 500 mA/mm and 420 mS/mm. The ability to control synthetically the electronic properties of nanowires using band structure design in III-nitride radial nanowire heterostructures opens up new opportunities for nanoelectronics and provides a new platform to study the physics of low-dimensional electron gases.     

Silicidation of silicon nanowires by platinum

The solid-state reaction between platinum and silicon nanowires grown by the vapor-liquid-solid technique was studied. The reaction product PtSi is an attractive candidate for contacts to p-type silicon nanowires due to the low barrier height of PtSi contacts to p-type Si in the planar geometry, and the formation of PtSi was the motivation for our study. Silicidation was carried out by annealing Pt on Si nanowires from 250 to 700 degrees C, and the reaction products were characterized by transmission electron microscopy. Strikingly different morphologies of the reacted nanowires were observed depending on the annealing temperature, platinum film thickness, silicon nanowire diameter, and level of unintentional oxygen contamination in the annealing furnace. Conversion to PtSi was successfully realized by annealing above 400 degrees C in purified N2 gas. A uniform morphology was achieved for nanowires with an appropriate combination of Si nanowire diameter and Pt film thickness to form PtSi without excess Pt or Si. Similar to the planar silicidation process, oxygen affects the nanowire silicidation process greatly.     

Core/multishell nanowire heterostructures as multicolor, high-efficiency light-emitting diodes

We report the growth and characterization of core/multishell nanowire radial heterostructures, and their implementation as efficient and synthetically tunable multicolor nanophotonic sources. Core/multishell nanowires were prepared by metal-organic chemical vapor deposition with an n-GaN core and InxGa1-xN/GaN/p-AlGaN/p-GaN shells, where variation of indium mole fraction is used to tune emission wavelength. Cross-sectional transmission electron microscopy studies reveal that the core/multishell nanowires are dislocation-free single crystals with a triangular morphology. Energy-dispersive X-ray spectroscopy clearly shows shells with distinct chemical compositions, and quantitatively confirms that the thickness and composition of individual shells can be well controlled during synthesis. Electrical measurements show that the p-AlGaN/p-GaN shell structure yields reproducible hole conduction, and electroluminescence measurements demonstrate that in forward bias the core/multishell nanowires function as light-emitting diodes, with tunable emission from 365 to 600 nm and high quantum efficiencies. The ability to synthesize rationally III-nitride core/multishell nanowire heterostructures opens up significant potential for integrated nanoscale photonic systems, including multicolor lasers.     

Multi-quantum-well nanowire heterostructures for wavelength-controlled lasers

Rational design and synthesis of nanowires with increasingly complex structures can yield enhanced and/or novel electronic and photonic functions. For example, Ge/Si core/shell nanowires have exhibited substantially higher performance as field-effect transistors and low-temperature quantum devices compared with homogeneous materials, and nano-roughened Si nanowires were recently shown to have an unusually high thermoelectric figure of merit. Here, we report the first multi-quantum-well (MQW) core/shell nanowire heterostructures based on well-defined III-nitride materials that enable lasing over a broad range of wavelengths at room temperature. Transmission electron microscopy studies show that the triangular GaN nanowire cores enable epitaxial and dislocation-free growth of highly uniform (InGaN/GaN)n quantum wells with n=3, 13 and 26 and InGaN well thicknesses of 1-3 nm. Optical excitation of individual MQW nanowire structures yielded lasing with InGaN quantum-well composition-dependent emission from 365 to 494 nm, and threshold dependent on quantum well number, n. Our work demonstrates a new level of complexity in nanowire structures, which potentially can yield free-standing injection nanolasers.     

Ultralong single-crystal metallic Ni2Si nanowires with low resistivity

Ultralong, single-crystal Ni2Si nanowires sheathed with amorphous silicon oxide were synthesized on a large scale by a chemical vapor transport (CVT) method, using iodine as the transport reagent and Ni2Si powder as the source material. Structural characterization using powder X-ray diffraction, electron microscopy, and energy-dispersive spectroscopy shows that the nanowires have Ni2Si-SiOx core-shell structure with single-crystal Ni2Si core and amorphous silicon oxide shell. The oxide shell is electrically insulating and can be removed by HF etching. Four-terminal electrical measurements show that the single-crystal nanowire has extremely low resistivity of 21 muOmega.cm and is capable of supporting remarkably high failure current density >108 A/cm2. These unique Ni2Si nanowires are very attractive nanoscale building blocks for interconnects and fully silicided (FUSI) gate applications in nanoelectronics.     

GaAs/AlGaAs nanowire heterostructures studied by scanning tunneling microscopy

We directly image the interior of GaAs/AlGaAs axial and radial nanowire heterostructures with atomic-scale resolution using scanning tunneling microscopy. We show that formation of monolayer sharp and smooth axial interfaces are possible even by vapor-phase epitaxy. However, we also find that instability of the ternary alloys formed in the Au seed fundamentally limits axial heterostructure control, inducing large segment asymmetries. We study radial core-shell nanowires, imaging even ultrathin submonolayer shells. We demonstrate how large twinning-induced morphological defects at the wire surfaces can be removed, ensuring the formation of wires with atomically flat sides.     

Si/InGaN core/shell hierarchical nanowire arrays and their photoelectrochemical properties

Three-dimensional hierarchical nanostructures were synthesized by the halide chemical vapor deposition of InGaN nanowires on Si wire arrays. Single phase InGaN nanowires grew vertically on the sidewalls of Si wires and acted as a high surface area photoanode for solar water splitting. Electrochemical measurements showed that the photocurrent density with hierarchical Si/InGaN nanowire arrays increased by 5 times compared to the photocurrent density with InGaN nanowire arrays grown on planar Si (1.23 V vs RHE). High-resolution transmission electron microscopy showed that InGaN nanowires are stable after 15 h of illumination. These measurements show that Si/InGaN hierarchical nanostructures are a viable high surface area electrode geometry for solar water splitting.     

Ultrashort channel silicon nanowire transistors with nickel silicide source/drain contacts

We demonstrate the shortest transistor channel length (17 nm) fabricated on a vapor-liquid-solid (VLS) grown silicon nanowire (NW) by a controlled reaction with Ni leads on an in situ transmission electron microscope (TEM) heating stage at a moderate temperature of 400 °C. NiSi(2) is the leading phase, and the silicide-silicon interface is an atomically sharp type-A interface. At such channel lengths, high maximum on-currents of 890 (μA/μm) and a maximum transconductance of 430 (μS/μm) were obtained, which pushes forward the performance of bottom-up Si NW Schottky barrier field-effect transistors (SB-FETs). Through accurate control over the silicidation reaction, we provide a systematic study of channel length dependent carrier transport in a large number of SB-FETs with channel lengths in the range of 17 nm to 3.6 μm. Our device results corroborate with our transport simulations and reveal a characteristic type of short channel effects in SB-FETs, both in on- and off-state, which is different from that in conventional MOSFETs, and that limits transport parameter extraction from SB-FETs using conventional field-effect transconductance measurements.     

Cover Picture: Epitaxial Growth of Indium Arsenide Nanowires on Silicon Using Nucleation Templates Formed by Self‐Assembled Organic Coatings (Adv. Mater. 14/2007)

On p. 1801, Lars Samuelson and co‐workers report on InAs nanowires that are grown directly on Si substrates by employing self‐assembled organic coatings to create an oxide template which guides nanowire nucleation. The nanowires extend vertically from the Si(111) substrate (foreground). No metal catalysts are used, and the InAs crystal extends to the nanowire tip as shown in the atomically resolved transmission electron microscopy image (dome background). The reported method constitutes a promising approach to the integration of new components into existing Si technology.     

Topographical, compositional and schottky characterization of PtSi/Si schottky diodes

PtSi ultra-thin films were grown on Si-wafer using pulsed laser deposition (PLD). As determined from X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), the compositional structures of the PtSi were discussed. Furthermore, the surface structure of these films was studied by atomic force microscopy (AFM). A possible growth mechanism is presented, on studying the variation of morphological features (i.e., roughness and size of crystallites) with annealing temperature and films thickness. In addition, by the AFM studies and schottky characterization measurements of PtSi films forming during various annealing processing, preferable preparing conditions are proposed to form the continuous and smooth PtSi thin film on Si substrate by PLD.     

The dependence of structural stability and tunable gap on the Si components of ZnSe/Si bi-coaxial nanowire heterostructures

The bare and hydrogen-passivated ZnSe/Si bi-coaxial nanowire heterostructures along [110] direction have been investigated by using the first-principle calculations within density functional theory. The structural stability and electronic property of ZnSe/Si bi-coaxial nanowire heterostructures have been shown by changing the Si components. It is found that the ZnSe/Si nanowires have zero gaps at lower Si components, and then they have the increasing gap at higher Si components. It is seen clearly that there is the transition of band gap form zero to nonzero. With increasing Si components, the ZnSe/Si nanowires can be also achieved as n-type or p-type, in agreement qualitatively with the experimental observations. In addition, the structural stabilities and the cohesive energies of ZnSe/Si bi-coaxial nanowires are changed obviously with the different Si components.     

Magnetic properties of single-crystalline CoSi nanowires

We have observed unusual ferromagnetic properties in single-crystalline CoSi nanowire ensemble, in marked contrast to the diamagnetic CoSi in bulk. High-density freestanding CoSi nanowires with B20 crystal structure are synthesized by a vapor-transport-based method. The reaction of cobalt chloride precursor with a Si substrate produces high-aspect-ratio CoSi nanowires. The high-resolution transmission electron microscopy and electron diffraction studies reveal superlattice structure in CoSi nanowires with twice the lattice parameter of simple cubic CoSi lattice. The zero-field-cooled and field-cooled (ZFC-FC) measurements from the nanowire ensemble show freezing of the disordered surface spins at low temperatures. The magnetoresistance (MR) measurements of single nanowire devices show a negative MR whose magnitude gets larger at lower temperatures.     

In-situ TEM observation of repeating events of nucleation in epitaxial growth of nano CoSi2 in nanowires of Si

The formation of CoSi and CoSi2 in Si nanowires at 700 and 800 degrees C, respectively, by point contact reactions between nanodots of Co and nanowires of Si have been investigated in situ in a ultrahigh vacuum high-resolution transmission electron microscope. The CoSi2 has undergone an axial epitaxial growth in the Si nanowire and a stepwise growth mode was found. We observed that the stepwise growth occurs repeatedly in the form of an atomic step sweeping across the CoSi2/Si interface. It appears that the growth of a new step or a new silicide layer requires an independent event of nucleation. We are able to resolve the nucleation stage and the growth stage of each layer of the epitaxial growth in video images. In the nucleation stage, the incubation period is measured, which is much longer than the period needed to grow the layer across the silicide/Si interface. So the epitaxial growth consists of a repeating nucleation and a rapid stepwise growth across the epitaxial interface. This is a general behavior of epitaxial growth in nanowires. The axial heterostructure of CoSi2/Si/CoSi2 with sharp epitaxial interfaces has been obtained. A discussion of the kinetics of supply limited and source-limited reaction in nanowire case by point contact reaction is given. The heterostructures are promising as high performance transistors based on intrinsic Si nanowires.     

Silicon nanowire transistors with a channel width of 4 nm fabricated by atomic force microscope nanolithography

The emergence of an ultrasensitive sensor technology based on silicon nanowires requires both the fabrication of nanoscale diameter wires and the integration with microelectronic processes. Here we demonstrate an atomic force microscopy lithography that enables the reproducible fabrication of complex single-crystalline silicon nanowire field-effect transistors with a high electrical performance. The nanowires have been carved from a silicon-on-insulator wafer by a combination of local oxidation processes with a force microscope and etching steps. We have fabricated and measured the electrical properties of a silicon nanowire transistor with a channel width of 4 nm. The flexibility of the nanofabrication process is illustrated by showing the electrical performance of two nanowire circuits with different geometries. The fabrication method is compatible with standard Si CMOS processing technologies and, therefore, can be used to develop a wide range of architectures and new microelectronic devices.     

Sub-100 nanometer channel length Ge/Si nanowire transistors with potential for 2 THz switching speed

Ge/Si core/shell nanowires (NWs) are attractive and flexible building blocks for nanoelectronics ranging from field-effect transistors (FETs) to low-temperature quantum devices. Here we report the first studies of the size-dependent performance limits of Ge/Si NWFETs in the sub-100 nm channel length regime. Metallic nanoscale electrical contacts were made and used to define sub-100 nm Ge/Si channels by controlled solid-state conversion of Ge/Si NWs to NiSixGe y alloys. Electrical transport measurements and modeling studies demonstrate that the nanoscale metallic contacts overcome deleterious short-channel effects present in lithographically defined sub-100 nm channels. Data acquired on 70 and 40 nm channel length Ge/Si NWFETs with a drain-source bias of 0.5 V yield transconductance values of 78 and 91 microS, respectively, and maximum on-currents of 121 and 152 microA. The scaled transconductance and on-current values for a gate and bias voltage window of 0.5 V were 6.2 mS/microm and 2.1 mA/microm, respectively, for the 40 nm device and exceed the best reported values for planar Si and NW p-type FETs. In addition, analysis of the intrinsic switching delay shows that terahertz intrinsic operation speed is possible when channel length is reduced to 70 nm and that an intrinsic delay of 0.5 ps is achievable in our 40 nm device. Comparison of the experimental data with simulations based on a semiclassical, ballistic transport model suggests that these sub-100 nm Ge/Si NWFETs with integrated high-kappa gate dielectric operate near the ballistic limit.     

Kinked p-n junction nanowire probes for high spatial resolution sensing and intracellular recording

Semiconductor nanowires and other semiconducting nanoscale materials configured as field-effect transistors have been studied extensively as biological/chemical (bio/chem) sensors. These nanomaterials have demonstrated high-sensitivity from one- and two-dimensional sensors, although the realization of the ultimate pointlike detector has not been achieved. In this regard, nanoscale p-n diodes are attractive since the device element is naturally localized near the junction, and while nanowire p-n diodes have been widely studied as photovoltaic devices, their applications as bio/chem sensors have not been explored. Here we demonstrate that p-n diode devices can serve as a new and powerful family of highly localized biosensor probes. Designed nanoscale axial p-n junctions were synthetically introduced at the joints of kinked silicon nanowires. Scanning electron microscopy images showed that the kinked nanowire structures were achieved, and electrical transport measurements exhibited rectifying behavior with well-defined turn-on in forward bias as expected for a p-n diode. In addition, scanning gate microscopy demonstrated that the most sensitive region of these nanowires was localized near the kinked region at the p-n junction. High spatial resolution sensing using these p-n diode probes was carried out in aqueous solution using fluorescent charged polystyrene nanobeads. Multiplexed electrical measurements show well-defined single-nanoparticle detection, and experiments with simultaneous confocal imaging correlate directly the motion of the nanobeads with the electrical signals recorded from the p-n devices. In addition, kinked p-n junction nanowires configured as three-dimensional probes demonstrate the capability of intracellular recording of action potentials from electrogenic cells. These p-n junction kinked nanowire devices, which represent a new way of constructing nanoscale probes with highly localized sensing regions, provide substantial opportunity in areas ranging from bio/chem sensing and nanoscale photon detection to three-dimensional recording from within living cells and tissue.     

Silicon nanowire Esaki diodes

We report on the fabrication and characterization of silicon nanowire tunnel diodes. The silicon nanowires were grown on p-type Si substrates using Au-catalyzed vapor-liquid-solid growth and in situ n-type doping. Electrical measurements reveal Esaki diode characteristics with peak current densities of 3.6 kA/cm(2), peak-to-valley current ratios of up to 4.3, and reverse current densities of up to 300 kA/cm(2) at 0.5 V reverse bias. Strain-dependent current-voltage (I-V) measurements exhibit a decrease of the peak tunnel current with uniaxial tensile stress and an increase of 48% for 1.3 GPa compressive stress along the <111> growth direction, revealing the strain dependence of the Si band structure and thus the tunnel barrier. The contributions of phonons to the indirect tunneling process were probed by conductance measurements at 4.2 K. These measurements show phonon peaks at energies corresponding to the transverse acoustical and transverse optical phonons. In addition, the low-temperature conductance measurements were extended to higher biases to identify potential impurity states in the band gap. The results demonstrate that the most likely impurity, namely, Au from the catalyst particle, is not detectable, a finding that is also supported by the excellent device properties of the Esaki diodes reported here.     

Direct observation of a noncatalytic growth regime for GaAs nanowires

We identify a new noncatalytic growth regime for molecular beam epitaxially grown GaAs nanowires (NWs) that may provide a route toward axial heterostructures with discrete material boundaries and atomically sharp doping profiles. Upon increase of the As/Ga flux ratio, the growth mode of self-induced GaAs NWs on SiO(2)-masked Si(111) is found to exhibit a surprising discontinuous transition in morphology and aspect ratio. For effective As/Ga ratios <1, in situ reflection high-energy electron diffraction measurements reveal clear NW growth delay due to formation of liquid Ga droplets since the growth proceeds via the vapor-liquid-solid mechanism. In contrast, for effective As/Ga ratios >1 an immediate onset of NW growth is observed indicating a transition to droplet-free, facet-driven selective area growth with low vertical growth rates. Distinctly different microstructures, facet formation and either the presence or absence of Ga droplets at the apex of NWs, are further elucidated by transmission electron microscopy. The results show that the growth mode transition is caused by an abrupt change from As- to Ga-limited conditions at the (111)-oriented NW growth front, allowing precise tuning of the dominant growth mode.