Electrochemical Integration of Graphene with Light-Absorbing Copper-Based Thin Films

We present an electrochemical route for the integration of graphene with light-sensitive copper-based alloys used in optoelectronic applications. Graphene grown using chemical vapor deposition (CVD) transferred to glass is found to be a robust substrate on which photoconductive CuxS films of 1-2 mu m thickness can be deposited. The effect of growth parameters on the morphology and photoconductivity of CuxS films is presented. Current-voltage (I-V) characterization and photoconductivity decay experiments are performed with graphene as one contact and silver epoxy as the other.

Efficient carbon nanotube field emitter using electrospun carbon nanofibers as a flexible electrode

Thermal-stable, conductive, and flexible carbon fabric (CF), which is composed of thin carbon fibers prepared by electrospinning, was used for the substrate of carbon nanotube (CNT) field emitter arrays. The field emitter arrays were prepared by chemical vapor deposition (CVD). The current density-electric field characteristics revealed that the CNT field emitter arrays on CF produced a higher current density at a lower turn-on voltage compared to ones on a Si substrate. This emitter integrated with a gate electrode based on hierarchy-structured carbon materials, CNTs on CF, can be used for light sources, displays, and other electronic devices. © 2009 Materials Research Society.

A simple combinatorial method aiding research on single-walled carbon nanotube growth on substrates

Establishing fabrication methods of carbon nanotubes (CNTs) is essential to realize many applications expected for CNTs. Catalytic growth of CNTs on substrates by chemical vapor deposition (CVD) is promising for direct fabrication of CNT devices, and catalyst nanoparticles play a crucial role in such growth. We have developed a simple method called "combinatorial masked deposition (CMD)", in which catalyst particles of a given series of sizes and compositions are formed on a single substrate by annealing gradient catalyst layers formed by sputtering through a mask. CMD enables preparation of hundreds of catalysts on a wafer, growth of single-walled CNTs (SWCNTs), and evaluation of SWCNT diameter distributions by automated Raman mapping in a single day. CMD helps determinations of the CVD and catalyst windows realizing millimeter-tall SWCNT forest growth in 10 min, and of growth curves for a series of catalysts in a single measurement when combined with realtime monitoring. A catalyst library prepared using CMD yields various CNTs, ranging from individuals, networks, spikes, and to forests of both SWCNTs and multi-walled CNTs, and thus can be used to efficiently evaluate self-organized CNT field emitters, for example. The CMD method is simple yet effective for research of CNT growth methods. © 2010 The Japan Society of Applied Physics.

Graphene-passivated nickel as an oxidation-resistant electrode for spintronics.

We report on graphene-passivated ferromagnetic electrodes (GPFE) for spin devices. GPFE are shown to act as spin-polarized oxidation-resistant electrodes. The direct coating of nickel with few layer graphene through a readily scalable chemical vapor deposition (CVD) process allows the preservation of an unoxidized nickel surface upon air exposure. Fabrication and measurement of complete reference tunneling spin valve structures demonstrate that the GPFE is maintained as a spin polarizer and also that the presence of the graphene coating leads to a specific sign reversal of the magneto-resistance. Hence, this work highlights a novel oxidation-resistant spin source which further unlocks low cost wet chemistry processes for spintronics devices.

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.

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.

Band gap opening of graphene after UV/ozone and oxygen plasma treatments

Graphene grown by Chemical Vapor Deposition (CVD) on nickel subsrate is oxidized by means of oxygen plasma and UV/Ozone treatments to introduce bandgap opening in graphene. The degree of band gap opening is proportional to the degree of oxidation on the graphene. This result is analyzed and confirmed by Scanning Tunnelling Microscopy/Spectroscopy and Raman spectroscopy measurements. Compared to conventional wet-oxidation methods, oxygen plasma and UV/Ozone treatments do not require harsh chemicals to perform, allow faster oxidation rates, and enable site-specific oxidation. These features make oxygen plasma and UV/Ozone treatments ideal candidates to be implemented in high-throughput fabrication of graphene-based microelectronics. © 2011 Materials Research Society.

Ion bombardment as the initial stage of diamond film growth

It is believed that during the initial stage of diamond film growth by chemical-vapor deposition (CVD), ion bombardment is the main mechanism in the bias-enhanced-nucleation (BEN) process. To verify such a statement, experiments by using mass-separated ion-beam deposition were carried out, in which a pure carbon ion beam, with precisely defined low energy, was selected for investigating the ion-bombardment effect on a Si substrate. The results are similar to those of the BEN process, which supports the ion-bombardment-enhanced-nucleation mechanism. The formation of sp(3) bonding is based on the presumption that the time of stress generation is much shorter than the duration of the relaxation process. The ion-bombarded Si is expected to enhance the CVD diamond nucleation density because the film contains amorphous carbon embedded with nanocrystalline diamond and defective graphite. (C) 2001 American Institute of Physics.

Raman study on residual strains in thin 3C-SiC epitaxial layers grown on Si(001)

Raman scattering measurement has been used to study the residual strains in the thin 3C-SiC/Si(001) epilayers with a variation of film thickness from 0.1 to 1.2 mu m. which were prepared by chemical vapor deposition (CVD)growth. Two methods have been exploited to figure our the residual strains and the exact LO bands. The final analyzing results show that residual strains exist in the 3C-SiC epilayers. The average stress is 1.3010 GPa, and the relative change of the lattice constant is 1.36 parts per thousand. Our measurements also show that 3C-SiC phonons are detectable even for the samples with film thickness in the range of 0.1 to 0.2 mu m. (C) 2000 Published by Elsevier Science S.A. All rights reserved.

Raman study on residual strains in thin 3C-SiC epitaxial layers grown on Si(001)

Raman scattering measurement has been used to study the residual strains in the thin 3C-SiC/Si(001) epilayers with a variation of film thickness from 0.1 to 1.2 mu m. which were prepared by chemical vapor deposition (CVD)growth. Two methods have been exploited to figure our the residual strains and the exact LO bands. The final analyzing results show that residual strains exist in the 3C-SiC epilayers. The average stress is 1.3010 GPa, and the relative change of the lattice constant is 1.36 parts per thousand. Our measurements also show that 3C-SiC phonons are detectable even for the samples with film thickness in the range of 0.1 to 0.2 mu m. (C) 2000 Published by Elsevier Science S.A. All rights reserved.

Fabrication of Novel Superhydrophobic Surfaces and Water Droplet Bouncing Behavior - Part 1: Stable ZnO-PDMS Superhydrophobic Surface with Low Hysteresis Constructed Using ZnO Nanoparticles

A superhydrophobic surface has many advantages in micro/nanomechanical applications, such as low adhesion, low friction and high restitution coefficient, etc. In this paper, we introduce a novel and simple route to fabricate superhydrophobic surfaces using ZnO nanocrystals. First, tetrapod-like ZnO nanocrystals were prepared via a one-step, direct chemical vapor deposition (CVD) approach. The nanostructured ZnO material was characterized by scanning electron microscope (SEM) and X-ray diffraction (XRD) and the surface functionalized by aminopropyltriethoxysilane (APS) was found to be hydrophobic. Then the superhydrophobic surface was constructed by depositing uniformly ZnO hydrophobic nanoparticles (HNPs) on the Poly(dimethylsiloxane) (PDMS) film substrate. Water wettability study revealed a contact angle of 155.4 +/- 2 degrees for the superhydrophobic surface while about 110 degrees for pure smooth PDMS films. The hysteresis was quite low, only 3.1 +/- 0.3 degrees. Microscopic observations showed that the surface was covered by micro- and nano-scale ZnO particles. Compared to other approaches, this method is rather convenient and can be used to obtain a large area superhydrophobic surface. The high contact angle and low hysteresis could be attributed to the micro/nano structures of ZnO material; besides, the superhydrophobic property of the as-constructed ZnO-PDMS surface could be maintained for at least 6 months. (C) Koninklijke Brill NV, Leiden, 2010

碳纳米管探针的制作方法研究

碳纳米管的小直径、高纵横比、高强度和高弹性、优良的耐磨损性能以及独特的电学和化学特性,使其成为高分辨率原子力显微镜的理想探针针尖。本文根据制作工艺的特点,综述现有碳纳米管探针的代表性研究和制作方法:组装式和生长式。组装式是通过手工、电场或磁场的方式将制备好的碳纳米管粘附到常规硅探针的末端;而生长式是在常规硅探针末端或悬臂梁上定点催化生长出一定直径和长度的CNT。最后指出这些方法目前存在的主要问题。

Orthogonal orientation control of carbon nanotube growth.

Carbon nanotubes (CNTs) have attracted attention for their remarkable electrical properties and have being explored as one of the best building blocks in nano-electronics. A key challenge to realize such potential is the control of the nanotube growth directions. Even though both vertical growth and controlled horizontal growth of carbon nanotubes have been realized before, the growth of complex nanotube structures with both vertical and horizontal orientation control on the same substrate has never been achieved. Here, we report a method to grow three-dimensional (3D) complex nanotube structures made of vertical nanotube forests and horizontal nanotube arrays on a single substrate and from the same catalyst pattern by an orthogonally directed nanotube growth method using chemical vapor deposition (CVD). More importantly, such a capability represents a major advance in controlled growth of carbon nanotubes. It enables researchers to control the growth directions of nanotubes by simply changing the reaction conditions. The high degree of control represented in these experiments will surely make the fabrication of complex nanotube devices a possibility.

Compósitos CNTs/biocerâmico para a estimulação elétrica óssea in situ

The present thesis aims to develop a biocompatible and electroconductor bone graft containing carbon nanotubes (CNTs) that allows the in situ regeneration of bone cells by applying pulsed external electrical stimuli. The CNTs were produced by chemical vapor deposition (CVD) by a semi-continuous method with a yield of ~500 mg/day. The deposition parameters were optimised to obtain high pure CNTs ~99.96% with controlled morphologies, fundamental requisites for the biomedical application under study. The chemical functionalisation of CNTs was also optimised to maximise their processability and biocompatibility. The CNTs were functionalised by the Diels-Alder cycloaddition of 1,3-butadiene. The biological behaviour of the functionalised CNTs was evaluated in vitro with the osteoblastic cells line MG63 and in vivo, by subcutaneous implantation in rats. The materials did not induce an expressed inflammatory response, but the functionalised CNTs showed a superior in vitro and in vivo biocompatibility than the non-functionalised ones. Composites of ceramic matrix, of bioglass (Glass) and hydroxyapatite (HA), reinforced with carbon nanotubes (CNT/Glass/HA) were processed by a wet approach. The incorporation of just 4.4 vol% of CNTs allowed the increase of 10 orders of magnitude of the electrical conductivity of the matrix. In vitro studies with MG63 cells show that the CNT/Glass/HA composites guarantee the adhesion and proliferation of bone cells, and stimulate their phenotype expression, namely the alkaline phosphate (ALP). The interactions between the composite materials and the culture medium (α-MEM), under an applied electrical external field, were studied by scanning vibrating electrode technique. An increase of the culture medium electrical conductivity and the electrical field confinement in the presence of the conductive samples submerged in the medium was demonstrated. The in vitro electrical stimulation of MG63 cells on the conductive composites promotes the increase of the cell metabolic activity and DNA content by 130% and 60%, relatively to the non-stimulated condition, after only 3 days of daily stimulation of 15 μA for 15 min. Moreover, the osteoblastic gene expression for Runx2, osteocalcin (OC) and ALP was enhanced by 80%, 50% and 25%, after 5 days of stimulation. Instead, for dielectric materials, the stimulus delivering was less efficient, giving an equal or lower cellular response than the non-stimulated condition. The proposed electroconductive bone grafts offer exciting possibilities in bone regeneration strategies by delivering in situ electrical stimulus to cells and consequent control of the new bone tissue formation rate. It is expected that conductive smart biomaterials might turn the selective bone electrotherapy of clinical relevance by decreasing the postoperative healing times.

Production of carbon nanotubes by PECVD and their applications to supercapacitors

Màster en Nanociència i Nanotecnologia