Fabrication and electrical integration of robust carbon nanotube micropillars by self-directed elastocapillary densification

Vertically aligned carbon nanotube (CNT) 'forest' microstructures fabricated by chemical vapor deposition (CVD) using patterned catalyst films typically have a low CNT density per unit area. As a result, CNT forests have poor bulk properties and are too fragile for integration with microfabrication processing. We introduce a new self-directed capillary densification method where a liquid is controllably condensed onto and evaporated from the CNT forests. Compared to prior approaches, where the substrate with CNTs is immersed in a liquid, our condensation approach gives significantly more uniform structures and enables precise control of the CNT packing density. We present a set of design rules and parametric studies of CNT micropillar densification by self-directed capillary action, and show that self-directed capillary densification enhances Young's modulus and electrical conductivity of CNT micropillars by more than three orders of magnitude. Owing to the outstanding properties of CNTs, this scalable process will be useful for the integration of CNTs as a functional material in microfabricated devices for mechanical, electrical, thermal and biomedical applications. © 2011 IOP Publishing Ltd.

Taper-free and vertically oriented Ge nanowires on Ge/Si substrates grown by a two-temperature process

Taper-free and vertically oriented Ge nanowires were grown on Si (111) substrates by chemical vapor deposition with Au nanoparticle catalysts. To achieve vertical nanowire growth on the highly lattice mismatched Si substrate, a thin Ge buffer layer was first deposited, and to achieve taper-free nanowire growth, a two-temperature process was employed. The two-temperature process consisted of a brief initial base growth step at high temperature followed by prolonged growth at lower temperature. Taper-free and defect-free Ge nanowires grew successfully even at 270 °C, which is 90 °C lower than the bulk eutectic temperature. The yield of vertical and taper-free nanowires is over 90%, comparable to that of vertical but tapered nanowires grown by the conventional one-temperature process. This method is of practical importance and can be reliably used to develop novel nanowire-based devices on relatively cheap Si substrates. Additionally, we observed that the activation energy of Ge nanowire growth by the two-temperature process is dependent on Au nanoparticle size. The low activation energy (∼5 kcal/mol) for 30 and 50 nm diameter Au nanoparticles suggests that the decomposition of gaseous species on the catalytic Au surface is a rate-limiting step. A higher activation energy (∼14 kcal/mol) was determined for 100 nm diameter Au nanoparticles which suggests that larger Au nanoparticles are partially solidified and that growth kinetics become the rate-limiting step. © 2011 American Chemical Society.

Vertically oriented epitaxial germanium nanowires on silicon substrates using thin germanium buffer layers.

We demonstrate a method to realize vertically oriented Ge nanowires on Si(111) substrates. Ge nanowires were grown by chemical vapor deposition using Au nanoparticles to seed nanowire growth via a vapor-liquid-solid growth mechanism. Rapid oxidation of Si during Au nanoparticle application inhibits the growth of vertically oriented Ge nanowires directly on Si. The present method employs thin Ge buffer layers grown at low temperature less than 600 degrees C to circumvent the oxidation problem. By using a thin Ge buffer layer with root-mean-square roughness of approximately 2 nm, the yield of vertically oriented Ge nanowires is as high as 96.3%. This yield is comparable to that of homoepitaxial Ge nanowires. Furthermore, branched Ge nanowires could be successfully grown on these vertically oriented Ge nanowires by a secondary seeding technique. Since the buffer layers are grown under moderate conditions without any high temperature processing steps, this method has a wide process window highly suitable for Si-based microelectronics.

Intrinsic terahertz plasmon signatures in chemical vapour deposited graphene

Plasmonic resonance at terahertz (THz) frequencies can be achieved by gating graphene grown via chemical vapour deposition (CVD) to a high carrier concentration. THz time domain spectroscopy of such gated monolayer graphene shows resonance features around 1.6 THz, which appear as absorption peaks when the graphene is electrostatically p-doped and change to enhanced transmission when the graphene is n-doped. Superimposed on the Drude-like frequency response of graphene, these resonance features are related to the inherent poly-crystallinity of CVD graphene. An understanding of these features is necessary for the development of future THz optical elements based on CVD graphene. © 2013 AIP Publishing LLC.

Growth kinetics and uniform scaling-up of graphene synthesis

Chemical vapor deposition on copper is the most widely used method to synthesize graphene at large scale. However, the clear understanding of the fundamental mechanisms that govern this synthesis is lacking. Using a vertical-flow, cold-wall reactor with short gas residence time we observe the early growths to study the kinetics of chemical vapor deposition of graphene on copper foils and demonstrate uniform synthesis at wafer scale. Our results indicate that the growth is limited by the catalytic dissociative dehydrogenation on the surface and copper sublimation hinders the graphene growth. We report an activation energy of 3.1 eV for ethylene-based graphene synthesis. © The Electrochemical Society.

Dry oxidation and vacuum annealing treatments for tuning the wetting properties of carbon nanotube arrays.

In this article, we describe a simple method to reversibly tune the wetting properties of vertically aligned carbon nanotube (CNT) arrays. Here, CNT arrays are defined as densely packed multi-walled carbon nanotubes oriented perpendicular to the growth substrate as a result of a growth process by the standard thermal chemical vapor deposition (CVD) technique.(1,2) These CNT arrays are then exposed to vacuum annealing treatment to make them more hydrophobic or to dry oxidation treatment to render them more hydrophilic. The hydrophobic CNT arrays can be turned hydrophilic by exposing them to dry oxidation treatment, while the hydrophilic CNT arrays can be turned hydrophobic by exposing them to vacuum annealing treatment. Using a combination of both treatments, CNT arrays can be repeatedly switched between hydrophilic and hydrophobic.(2) Therefore, such combination show a very high potential in many industrial and consumer applications, including drug delivery system and high power density supercapacitors.(3-5) The key to vary the wettability of CNT arrays is to control the surface concentration of oxygen adsorbates. Basically oxygen adsorbates can be introduced by exposing the CNT arrays to any oxidation treatment. Here we use dry oxidation treatments, such as oxygen plasma and UV/ozone, to functionalize the surface of CNT with oxygenated functional groups. These oxygenated functional groups allow hydrogen bond between the surface of CNT and water molecules to form, rendering the CNT hydrophilic. To turn them hydrophobic, adsorbed oxygen must be removed from the surface of CNT. Here we employ vacuum annealing treatment to induce oxygen desorption process. CNT arrays with extremely low surface concentration of oxygen adsorbates exhibit a superhydrophobic behavior.

Characterization of a liquid crystal microlens array using multiwalled carbon nanotube electrodes.

Reconfigurable liquid crystal microlenses employing arrays of multiwalled carbon nanotubes (MWNTs) have been designed and fabricated. The cells consist of arrays of 2 microm high MWNTs grown by plasma-enhanced chemical vapor deposition on silicon with a top electrode of indium tin oxide coated glass positioned 20 microm above the silicon and the gap filled with the nematic liquid crystal BLO48. Simulations have found that, while its nematic liquid crystal aligns with MWNTs within a distance of 10nm, this distance is greatly enhanced by the application of an external electric field. Polarized light experiments show that light is focused with focal lengths ranging from approximately 7 microm to 12 microm.

Integrating vertically aligned carbon nanotubes on micromechanical structures

The integration of high yield, uniform and preferential growth of vertically aligned carbon nanotubes (VACNT) on low stress micromechanical structures was analyzed. A combination of electron-beam crosslinked surface micromachining and direct current plasma enhanced chemical vapor deposition of electric field aligned carbon nanotubes was used for the analysis. The selective placement of high yield and uniform VACNTs on a partially suspended Ni/SiO2/Ti microstructure was also demonstrated.

Semi-insulating layer for novel high voltage polysilicon thin film transistors

This work describes the deposition and characterisation of semi-insulating oxygen-doped silicon films for the development of high voltage polycrystalline silicon (poly-Si) circuitry on glass. The performance of a novel poly-Si High Voltage Thin Film Transistor (HVTFT) structure, incorporating a layer of semi-insulating material, has been investigated using a two dimensional device simulator. The semi-insulating layer increases the operating voltage of the HVTFT structure by linearising the potential distribution in the device offset region. A glass compatible semi-insulating layer, suitable for HVTFT applications, has been deposited by the Plasma Enhanced Chemical Vapour Deposition (PECVD) technique from silane (SiH4), nitrous oxide (N2O) and helium (He) gas mixtures. The as-deposited films are furnace annealed at 600°C which is the maximum process temperature. By varying the N2O/SiH4 ratio the conductivity of the annealed films can be accurately controlled up to a maximum of around 10-7 Ω-1cm-1. Helium dilution of the reactant gases improves both film uniformity and reproducibility. Raman analysis shows the as-deposited and annealed films to be completely amorphous. A model for the microstructure of these Semi-Insulating Amorphous Oxygen-Doped Silicon (SIAOS) films is proposed to explain the observed physical and electrical properties.

Low-temperature (≤600 °C) semi-insulating oxygen-doped silicon films by the PECVD technique for large-area power applications

This work describes the deposition, annealing and characterisation of semi-insulating oxygen-doped silicon films at temperatures compatible with polysilicon circuitry on glass. The semi-insulating layers are deposited by the plasma enhanced chemical vapour deposition technique from silane (SiH4), nitrous oxide (N2O) and helium (He) gas mixtures at a temperature of 350 °C. The as-deposited films are then furnace annealed at 600 °C which is the maximum process temperature. Raman analysis shows the as-deposited and annealed films to be completely amorphous. The most important deposition variable is the N2O SiH4 gas ratio. By varying the N2O SiH4 ratio the conductivity of the annealed films can be accurately controlled, for the first time, down to a minimum of ≈10-7Ω-1cm-1 where they exhibit a T -1 4 temperature dependence indicative of a hopping conduction mechanism. Helium dilution of the reactant gases is shown to improve both film uniformity and reproducibility. A model for the microstructure of these semi-insulating amorphous oxygen-doped silicon films is proposed to explain the observed physical and electrical properties. © 1995.

Low temperature (≤ 600°C) semi-insulating oxygen-doped silicon films by the PECVD technique for large area power applications

This work describes the annealing and characterisation of semi-insulating oxygen-doped silicon films deposited by the Plasma Enhanced Chemical Vapour Deposition (PECVD) technique from silane (SiH4), nitrous oxide (N2O) and helium (He) gas mixtures. The maximum process temperature is chosen to be compatible with large area polycrystalline silicon (poly-Si) circuitry on glass. The most important deposition variable is shown to be the N2O SiH4 gas ratio. Helium dilution results in improved film uniformity and reproducibility. Raman analysis shows the 'as-deposited' and annealed films to be completely amorphous. A model for the microstructure of these Semi-Insulating Amorphous Oxygen-doped Silicon (SIAOS) films is proposed to explain the observed physical and electrical properties. © 1995.

Material properties and tribological performance of rf-PECVD deposited DLC coatings

Diamond-like carbon (DLC) coatings were deposited on to silicon, glass and metal substrates, using an rf-plasma enhanced chemical vapour deposition (rf-PECVD) process. The resultant film properties were evaluated in respect of material and interfacial property control, based on bias voltage variation and the introduction of inert (He and Ar) and reactive (N2) diluting gases in a CH4 plasma. The analysis techniques used to assess the material properties of the films included AFM, EELS, RBS/ERDA, spectroscopic, electrical, stress, microhardness, and adhesion. These were correlated to the tribological performance of the coatings using wear measurements. The most important observation is that He dilution (>90%) promotes enhanced adhesion with respect to all substrate material studies. Coatings typically exhibit a microhardness of the order of 10-20 GPa in films 0.1chemical vapour deposition (rf-PECVD) process. The resultant film properties were evaluated in respect of material and interfacial property control, based on bias voltage variation and the introduction of inert (He and Ar) and reactive (N2) diluting gases in a CH4 plasma. The analysis techniques used to assess the material properties of the films included AFM, EELS, RBS/ERDA, spectroscopic, electrical, stress, microhardness, and adhesion. These were correlated to the tribological performance of the coatings using wear measurements. The most important observation is that He dilution (>90%) promotes enhanced adhesion with respect to all substrate materials studied. Coatings typically exhibit a microhardness of the order of 10-20 GPa in films 0.1 < d < 2 μm thick, with associated electrical resistivity in the range 108 < ρ < 1012 Ω·cm, coefficient of friction <0.1 and surface RMS roughness as low as 2 A. The results are discussed with respect to surface pre-treatment, ion surface bombardment, interfacial reactivity and changes in plasma gas breakdown processes.

Hydrogen content estimation of hydrogenated amorphous carbon by visible Raman spectroscopy

In the present study, we report the hydrogen content estimation of the hydrogenated amorphous carbon (a-C:H) films using visible Raman spectroscopy in a fast and nondestructive way. Hydrogenated diamondlike carbon films were deposited by the plasma enhanced chemical vapor deposition, plasma beam source, and integrated distributed electron cyclotron resonance techniques. Methane and acetylene were used as source gases resulting in different hydrogen content and sp2/sp3 fraction. Ultraviolet-visible (UV-Vis) spectroscopic ellipsometry (1.5-5 eV) as well as UV-Vis spectroscopy were provided with the optical band gap (Tauc gap). The sp2/sp3 fraction and the hydrogen content were independently estimated by electron energy loss spectroscopy and elastic recoil detection analysis-Rutherford back scattering, respectively. The Raman spectra that were acquired in the visible region using the 488 nm line shows the superposition of Raman features on a photoluminescence (PL) background. The direct relationship of the sp2 content and the optical band gap has been confirmed. The difference in the PL background for samples of the same optical band gap (sp2 content) and different hydrogen content was demonstrated and an empirical relationship between the visible Raman spectra PL background slope and the corresponding hydrogen content was extracted. © 2004 American Institute of Physics.

Lateral field emitters fabricated using carbon nanotubes

We report on the fabrication of lateral emitters using carbon nanotubes (CNTs) grown via plasma enhanced chemical vapour deposition (PECVD). Carbon nanotubes are dispersed randomly onto a substrate, mapped, contacted with metal, and by etching the substrate, a suspended lateral emitter structure is formed. Field emission measurements from the lateral emitters show a turn-on voltage as low as 12 V. The emission characteristics showed good fits to the Fowler-Nordheim (FN) theory indicating that conventional field emission was indeed observed from these devices. © 2003 Elsevier Science B.V. All rights reserved.

Fabrication of carbon nanotube lateral field emitters

We report on the fabrication and field emission of carbon nanotube lateral field emitters. Due to its high aspect ratio and mechanical strength, we use vertically aligned multi-wall carbon nanotubes prepared by plasma-enhanced chemical vapour deposition as cathodes, which makes the fabrication of cantilever type lateral field emitters possible. The emission characteristics show that the field emission initiates at 11-17 V. The device has high geometrical enhancement factors (9.3 × 106 cm-1) compared to standard Spindt tips, which may be due to increased field concentration at the nanotube tip and the close proximity of the anode (<1 μm). The relative ease of fabrication compared to vertical field emitters and enhanced field emission characteristics observed makes the carbon nanotube lateral field emitter a good candidate for future integrated nano-electronic devices.