Abrupt degenerately-doped silicon nanowire tunnel junctions.

We have confirmed the presence of narrow, degenerately-doped axial silicon nanowire (SiNW) p-n junctions via off-axis electron holography (EH). SiNWs were grown via the vapor-solid-liquid (VLS) mechanism using gold (Au) as the catalyst, silane (SiH4), diborane (B2H6) and phosphine (PH3) as the precursors, and hydrochloric acid (HCl) to stabilize the growth. Two types of growth were carried out, and in each case we explored growth with both n/p and p/n sequences. In the first type, we abruptly switched the dopant precursors at the desired junction location, and in the second type we slowed the growth rate at the junction to allow the dopants to readily leave the Au catalyst. We demonstrate degenerately-doped p/n and n/p nanowire segments with abrupt potential profiles of 1.02 ± 0.02 and 0.86 ± 0.3 V, and depletion region widths as narrow as 10 ± 1 nm via EH. Low temperature current-voltage measurements show an asymmetric curvature in the forward direction that resemble planar gold-doped tunnel junctions, where the tunneling current is hidden by a large excess current. The results presented herein show that the direct VLS growth of degenerately-doped axial SiNW p-n junctions is feasible, an essential step in the fabrication of more complex SiNW-based devices for electronics and solar energy.

Three-Dimensional Imaging of Beam-Induced Biasing of InP/GaInP Tunnel Diodes.

Electron holographic tomography was used to obtain three-dimensional reconstructions of the morphology and electrostatic potential gradient of axial GaInP/InP nanowire tunnel diodes. Crystal growth was carried out in two opposite directions: GaInP-Zn/InP-S and InP-Sn/GaInP-Zn, using Zn as the p-type dopant in the GaInP but with changes to the n-type dopant (S or Sn) in the InP. Secondary electron and electron beam-induced current images obtained using scanning electron microscopy indicated the presence of p-n junctions in both cases and current-voltage characteristics measured via lithographic contacts showed the negative differential resistance, characteristic of band-to-band tunneling, for both diodes. Electron holographic tomography measurements confirmed a short depletion width in both cases (21 ± 3 nm) but different built-in potentials, Vbi, of 1.0 V for the p-type (Zn) to n-type (S) transition, and 0.4 V for both were lower than the expected 1.5 V for these junctions if degenerately doped. Charging induced by the electron beam was evident in phase images which showed nonlinearity in the surrounding vacuum, most severe in the case of the nanowire grounded at the p-type Au contact. We attribute their lower Vbi to asymmetric secondary electron emission, beam-induced current biasing, and poor grounding contacts.

Axial EBIC oscillations at core/shell GaAs/Fe nanowire contacts.

Electron beam induced current (EBIC) measurements were carried out in situ in the scanning electron microscope on free-standing GaAs/Fe core-shell nanowires (NWs), isolated from the GaAs substrate via a layer of aluminum oxide. The excess current as a function of the electron beam energy, position on the NW, and scan direction were collected, together with energy dispersive x-ray spectroscopy. A model that included the effects of beam energy and Fe thickness predicted an average collection efficiency of 60%. Small spatial oscillations in the EBIC current were observed, that correlated with the average Fe grain size (30 nm). These oscillations likely originated from lateral variations in the interfacial oxide thickness, affecting the resistance, barrier potentials, and density of minority carrier recombination traps.

Regrowth mechanism for oxide isolation of GaAs nanowires.

Oxide-isolated GaAs nanowires (NWs) were obtained through a lithography-free method in which axial growth of NWs coated in aluminum oxide (Al2O3) is restarted using an annealing step. NWs are grown using the vapor-liquid-solid method and coated in nanometer thin oxide films using atomic layer deposition. Continued growth at the oxide-coated nanoparticle (NP) occurs after the thermally-induced fracture of the oxide during annealing. This oxide fracture is observed to depend on NP diameter, oxide thickness and annealing temperature. A thermal expansion mismatch model for stresses on the oxide shell is put forward to explain these results.

Direct Measurement of the Electrical Abruptness of a Nanowire p-n Junction.

Electrostatic potential maps of GaAs nanowire, p-n junctions have been measured via off-axis electron holography and compared to results from in situ electrical probing, and secondary electron emission microscopy using scanning electron microscopy. The built-in potential and depletion length of an axial junction was found to be 1.5 ± 0.1 V and 74 ± 9 nm, respectively, to be compared with 1.53 V and 64 nm of an abrupt junction of the same end point carrier concentrations. Associated with the switch from Te to Zn dopant precursor was a reduction in GaAs nanowire diameter 3 ± 1 nm that occurred prior to the junction center (n = p) and was followed by a rapid increase in Zn doping. The delay in Zn incorporation is attributed to the time required for Zn to equilibrate within the Au catalyst.

Direct measurement of coherency limits for strain relaxation in heteroepitaxial core/shell nanowires.

The growth of heteroepitaxially strained semiconductors at the nanoscale enables tailoring of material properties for enhanced device performance. For core/shell nanowires (NWs), theoretical predictions of the coherency limits and the implications they carry remain uncertain without proper identification of the mechanisms by which strains relax. We present here for the Ge/Si core/shell NW system the first experimental measurement of critical shell thickness for strain relaxation in a semiconductor NW heterostructure and the identification of the relaxation mechanisms. Axial and tangential strain relief is initiated by the formation of periodic a/2 <110> perfect dislocations via nucleation and glide on {111} slip-planes. Glide of dislocation segments is directly confirmed by real-time in situ transmission electron microscope observations and by dislocation dynamics simulations. Further shell growth leads to roughening and grain formation which provides additional strain relief. As a consequence of core/shell strain sharing in NWs, a 16 nm radius Ge NW with a 3 nm Si shell is shown to accommodate 3% coherent strain at equilibrium, a factor of 3 increase over the 1 nm equilibrium critical thickness for planar Si/Ge heteroepitaxial growth.

Ultrasensitive rapid cytokine sensors based on asymmetric geometry two-dimensional MoS2 diodes.

The elevation of cytokine levels in body fluids has been associated with numerous health conditions. The detection of these cytokine biomarkers at low concentrations may help clinicians diagnose diseases at an early stage. Here, we report an asymmetric geometry MoS2 diode-based biosensor for rapid, label-free, highly sensitive, and specific detection of tumor necrosis factor-α (TNF-α), a proinflammatory cytokine. This sensor is functionalized with TNF-α binding aptamers to detect TNF-α at concentrations as low as 10 fM, well below the typical concentrations found in healthy blood. Interactions between aptamers and TNF-α at the sensor surface induce a change in surface energy that alters the current-voltage rectification behavior of the MoS2 diode, which can be read out using a two-electrode configuration. The key advantages of this diode sensor are the simple fabrication process and electrical readout, and therefore, the potential to be applied in a rapid and easy-to-use, point-of-care, diagnostic tool.

A new generation of sensors based on extraordinary optical transmission.

[Reaction: see text]. Plasmonic-based chemical sensing technologies play a key role in chemical, biochemical, and biomedical research, but basic research in this area is still attracting interest. Researchers would like to develop new types of plasmonic nanostructures that can improve the analytical figures of merit, such as detection limits, sensitivity, selectivity, and dynamic range, relative to the commercial systems. They are also tackling issues such as cost, reproducibility, and multiplexing with the goal of providing the best plasmonic-based platform for chemical analysis. In this Account, we will describe recent advances in the optical and spectroscopic properties of nanohole arrays in thin gold films and their applications for chemical sensing. These nanostructures support the unusual phenomenon of "extraordinary optical transmission" (EOT), that is, they are more transparent at certain wavelengths than expected by the classical aperture theory. The EOT is a consequence of surface plasmon (SP) excitations; hence, the resonance should respond to the adsorption of organic molecules. We explored this effect and implemented the integration of the arrays of nanoholes as sensing elements in a microfluidic architecture. We then demonstrated how these devices could be applied in biochemical affinity tests. Arrays of nanoholes offer a small sensing footprint and operate at normal transmission mode, which make them more suitable for miniaturization. This new approach for SPR sensing is more compatible with the lab-on-chip concept and offers the possibility of high-throughput analysis from a single sensing chip. We explored the field localization properties of EOT for surface-enhanced spectroscopy. We could control the enhancement factors for SERS and SEFS by adjusting the geometry of the arrays. The shape of the individual nanoholes offers another handle to tune the enhancement factor for surface-enhanced spectroscopy and SPR sensitivity. Apexes in shaped nanostructures function as optical antennas, focusing the light at extremely small regions at the tips. We observed additional surface enhancement by tuning the apexes' properties. The extra enhancement in these cases originated only from the small number of molecules in the apex regions. The arrays of nanoholes are an exciting new substrate for chemical sensing and enhanced spectroscopy. This class of nanomaterials has the potential to provide a viable alternative to the commercial SPR-based sensors. Further research could exploit this platform to develop nanostructures that support high field localization for single-molecule spectroscopy.

Magnetic phase shift reconstruction for uniformly magnetized nanowires.

A new analytical model is developed for the magnetic phase shift of uniformly magnetized nanowires with ideal cylindrical geometry. The model is applied to experimental data from off-axis electron holography measurements of the phase shift of CoFeB nanowires, and the saturation induction of a selected wire, as well as its radius, aspect ratio, position and orientation, is determined by fitting the model parameters. The saturation induction value of 1.7T of the CoFeB nanowire is found to be similar, to be within the measurement error, to values reported in the literature.

Interfacial reactions at Fe/topological insulator spin contacts.

The authors study the composition and abruptness of the interfacial layers that form during deposition and patterning of a ferromagnet, Fe on a topological insulator (TI), Bi2Se3, Bi2Te3, and SiOx/Bi2Te3. Such structures are potentially useful for spintronics. Cross-sectional transmission electron microscopy, including interfacial elemental mapping, confirms that Fe reacts with Bi2Se3 near room temperature, forming an abrupt 5 nm thick FeSe0.92 single crystalline binary phase, predominantly (001) oriented, with lattice fringe spacing of 0.55 nm. In contrast, Fe/Bi2Te3 forms a polycrystalline Fe/TI interfacial alloy that can be prevented by the addition of an evaporated SiOx separating Fe from the TI.

Aligned cuboid iron nanoparticles by epitaxial electrodeposition.

Aligned, individual iron square cuboid nanoparticles have been achieved by taking advantage of epitaxial, three-dimensional-island growth on GaAs(001) during electrodeposition at low deposition rates. The nanoparticles exhibit lateral dimensions between 10 and 80 nm and heights below 40 nm. Surface {100} facets predominate with a thin crystalline oxide shell that protects the nanoparticles during prolonged storage in air. The single crystallinity of the iron in combination with structural alignment leads to an in-plane magnetic anisotropy. These immobilized, oriented, and stable nanoparticles are promising for applications in nanoelectronic, sensor, and data storage technologies, as well as for the detailed analysis of the effect of shape and size on magnetism at the nanoscale.

Surface plasmon-quantum dot coupling from arrays of nanoholes.

The coupling of semiconductor quantum dots (QDs) to the surface plasmon (SP) modes of nanohole arrays in a metal film was demonstrated for the first time, showing enhancement in the spontaneous emission by 2 orders of magnitude. The SP-enhanced transmission resonances of the nanohole arrays were tuned around the photoluminescence (PL) peak of polystyrene-b-poly(acrylic acid) (PS-b-PAA)-stabilized cadmium sulfide (CdS) quantum dots (QDs) in contact with the arrays. As a result the overall PL from the SP-QD system was enhanced by 2 orders of magnitude, even after excluding the enhanced transmission of the nanohole array without the QDs. The maximum enhancement occurred when the resonance from the nanohole array matched the QD PL spectrum. Time-resolved PL measurements were used to estimate the relative contribution of different physical mechanisms to the enhanced spontaneous emission. The increased spontaneous emission in the SP-QD system is promising for prospective plasmonic light-emitting devices incorporating QDs.

Ballistic electron emission microscopy studies of Au/molecule/n-GaAs diodes.

We present nanometer-scale resolution, ballistic electron emission microscopy (BEEM) studies of Au/octanedithiol/n-GaAs (001) diodes. The presence of the molecule dramatically increases the BEEM threshold voltage and displays an unusual transport signature as compared to reference Au/GaAs diodes. Furthermore, BEEM images indicate laterally inhomogeneous interfacial structure. We present calculations that address the role of the molecular layer at the interface. Our results indicate that spatially resolved measurements add new insight to studies using conventional spatial-averaging techniques.

Preparation of ideal molecular junctions: depositing non-invasive gold contacts on molecularly modified silicon.

Recent advances in creating rectifying gold|monolayer|silicon (Au-M-Si) junctions (namely, molecular silicon diodes) are reviewed. It is known that direct deposition of gold contacts onto molecular monolayers covalently bonded to silicon surfaces causes notable disruption to the junction structure, resulting in deteriorated performance and poor reproducibility that are unsuitable for practical applications. In the past few years, several new experimental approaches have been explored to minimize or eliminate such damage, including the "indirect" evaporation method and the pre-deposition of a protective "non-penetrating" metal. To enhance the interactions at the gold-monolayer interface, head-groups that allow bonding to gold are used to maintain the monolayer integrity. Construction of the device via flip-chip lamination and the modified polymer-assisted lift-off techniques also prohibits monolayer damage. Refining the fabrication and design techniques towards reliable molecular junctions is crucial if they are to be used in nanoelectronics for the purpose of miniaturization.

Molecular orientation in octanedithiol and hexadecanethiol monolayers on GaAs and Au measured by infrared spectroscopic ellipsometry.

Infrared spectroscopic ellipsometry was used for determination of molecular orientation and for lateral homogeneity studies of organic monolayers on GaAs and Au, the organic layer being either octanedithiol or hexadecanethiol (HDT). The laterally resolved measurements were performed with the infrared mapping ellipsometer at the synchrotron storage ring BESSY II. The molecular orientation within the monolayers was determined by optical model simulations of the measured ellipsometric spectra. Different tilt angles were obtained for the monolayers of HDT and octanedithiol on GaAs: 19 degrees and >30 degrees , respectively. The tilt angle of the methylene chains for HDT on Au substrate (22 degrees ) is similar to the 19 degrees tilt which was obtained for the HDT monolayers on GaAs, thus suggesting similar molecular ordering of the thiolates on both substrates.

Field dependent transport properties in InAs nanowire field effect transistors.

We present detailed studies of the field dependent transport properties of InAs nanowire field-effect transistors. Transconductance dependence on both vertical and lateral fields is discussed. Velocity-field plots are constructed from a large set of output and transfer curves that show negative differential conductance behavior and marked mobility degradation at high injection fields. Two dimensional electrothermal simulations at current densities similar to those measured in the InAs NWFET devices indicate that a significant temperature rise occurs in the channel due to enhanced phonon scattering that leads to the observed mobility degradation. Scanning transmission electron microscopy measurements on devices operated at high current densities reveal arsenic vaporization and crystal deformation in the subject nanowires.

Heteroepitaxial growth of vertical GaAs nanowires on Si(111) substrates by metal-organic chemical vapor deposition.

Epitaxial growth of vertical GaAs nanowires on Si(111) substrates is demonstrated by metal-organic chemical vapor deposition via a vapor-liquid-solid growth mechanism. Systematic experiments indicate that substrate pretreatment, pregrowth alloying temperature, and growth temperature are all crucial to vertical epitaxial growth. Nanowire growth rate and morphology can be well controlled by the growth temperature, the metal-organic precursor molar fraction, and the molar V/III ratio. The as-grown GaAs nanowires have a predominantly zinc-blende crystal structure along a <111> direction. Crystallographic {111} stacking faults found perpendicular to the growth axis could be almost eliminated via growth at high V/III ratio and low temperature. Single nanowire field effect transistors based on unintentionally doped GaAs nanowires were fabricated and found to display a strong effect of surface states on their transport properties.

Enhanced fluorescence from arrays of nanoholes in a gold film.

Arrays of sub-wavelength holes (nanoholes) in gold films were used as a substrate for enhanced fluorescence spectroscopy. Seven arrays of nanoholes with distinct periodicities (distances between the holes) were fabricated. The arrays were then spin-coated with polystyrene films containing different concentrations of the fluorescent dye oxazine 720. The dye was excited via resonant extraordinary transmission of the laser source through the nanoholes. Enhanced fluorescence was observed when the geometric characteristics of the arrays allowed for an enhancement in the transmitted excitation. This enhancement occurred via surface plasmon excitation by the laser and a consequential increase in the local electromagnetic field in a sub-wavelength region at the metal-film interface. It was demonstrated that the sensitivity of the fluorescence measurement (change in signal vs change in dye concentration in the polymer film) is significantly larger at the surface plasmon resonance conditions than that obtained from equivalent films on glass substrates. Enhancement factors for the fluorescence emission were calculated for each array, with a maximum enhancement of close to 2 orders of magnitude as compared to the emission of films on glass. The results presented here indicate that arrays of nanoholes are interesting substrates for the development of fluorescence sensors based on surface plasmon resonance, as they provide a platform that allows both spatial confinement and enhancement of excitation light. Moreover, the collinear characteristics of the present optical setup, due to the resonant extraordinary transmission through the nanohole arrays, are more conducive to miniaturization and chip integration than more traditional experimental geometries.

Surface plasmon sensor based on the enhanced light transmission through arrays of nanoholes in gold films.

Arrays of nanoholes in a gold film were used to monitor the binding of organic and biological molecules to the metallic surface. This technique is particularly sensitive to surface binding events because it is based upon the resonant surface plasmon enhanced transmission through the array of nanoholes. The sensitivity was found to be 400 nm per refractive index unit, which is comparable to other grating-based surface plasmon resonance (SPR) devices. The array of nanoholes is well suited for dense integration in a sensor chip. Furthermore, the optical geometry is collinear, which simplifies the alignment with respect to the traditional Kretschmann (reflection) arrangement for SPR sensing.