Characterization of IrO2/CNT nanocomposites

IrO₂ nanocrystals (NCs) were grown on vertically aligned carbon nanotube (CNT) templates, forming IrO₂/CNT nanocomposites, by metal organic chemical vapour deposition using (C₆H₇)(C₈H₁₂)Ir as a source reagent. The surface morphology, structural and spectroscopic properties of the nanocomposites were characterized using field-emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Raman scattering. IrO₂ varied from particle- to tube-like NCs as the deposition time increased from 5 to 60 min. The particle-like IrO₂ NCs may be used as a protective layer on CNTs, providing stable and uniform field emission application. The tube-like structure may increase the surface-to-volume ratio which makes the IrO₂/CNT nanocomposites as an attractive candidate for the supercapacitor application.     

Surface etching effects of amorphous C:H and CNx:H films formed by supermagnetron plasma for field emission use

Supermagnetron plasma was used to deposit amorphous hydrogenated carbon (a-C:H) and hydrogenated carbon nitride (a-CN_x:H) films for field-emission devices using i-C₄H₁₀/(H₂ or N₂). It was also used to improve the field-emission characteristics by surface etching using N₂/H₂ plasma. The best emission threshold electric field (E_TH) was 13 and 12 V/μm for devices using as-deposited a-C:H and as-deposited a-CN_x:H films, respectively, while they were remarkably improved to 11 and 8 V/μm by surface etching using N₂/H₂ (120/40 sccm) gas, though surface roughness was slightly increased by the surface etching. The hardness of as-deposited films was higher than 22 GPa.     

Selective growth of well-aligned carbon nanotubes by APCVD

Well-aligned good-quality carbon nanotube (CNT) array was grown on silicon substrate by atmospheric pressure chemical vapor deposition (APCVD) through SiO₂ masking. First, the patterned substrate was pretreated with NH₃ and then CNTs were synthesized at 800 °C using Ni as the catalyst, acetylene (C₂H₂) as the carbon source material and N₂ as the carrier gas. Effects of the NH₃-pretreatment time, the flow ratio of [C₂H₂]/[NH₃] and the CNT growth time on the qualities of CNT array were analyzed in detail. It was found that good-quality CNTs with an average length of around 15 μm could be grown by pretreating the Si substrate with NH₃ for 10 min and then conducting the CNT growth with a flow ratio of [C₂H₂]/[NH₃] = 30/100. Furthermore, the field emission property of CNT array was investigated using a diode structure. It was found that the turn-on electric field decreased with increasing CNT length. The turn-on electric field as low as about 2 V/μm with an emission current density of 10 μA/cm² was achieved for a CNT-array diode with the tube length near 18 μm. For the same device, the emission current density could be elevated to 10 mA/cm² with the applied voltage of 3.26 V/μm.     

Effect of catalyst thickness and plasma pretreatment on the growth of carbon nanotubes and their field emission properties

We demonstrated that the diameter and the density of carbon nanotubes (CNTs) which had a close relation to electric-field-screening effect could be easily changed by the control of catalytic Ni thickness combined with NH3 plasma pretreatment. Since the diameter and the density of CNTs had a tremendous impact on the field-emission characteristics, optimized thickness of catalyst and application of plasma pretreatment greatly improved the emission efficiency of CNTs. In the field emission test using diode-type configuration, well-dispersed thinner CNTs exhibited lower turn-on voltage and higher field enhancement factor than the densely-packed CNTs. A CNT film grown using a plasma-pretreated 25 angstroms-thick Ni catalyst showed excellent field emission characteristics with a very low turn-on field of 1.1 V/microm @ 10 microA/cm2 and a high emission current density of 1.9 mA/cm2 @ 4.0 V/microm, respectively.     

Super-low turn-on and threshold electric fields of plasma-treated partly Fe-filled carbon nanotube films

Field emission properties of partly Fe-filled carbon nanotubes (FCNTs) treated with different plasmas have been studied. Super low turn-on (0.24 V/μm) and threshold (0.6 V/μm) electric fields are identified upon nitrogen plasma treatment for 60 min. The field-enhancement factor, as high as 4.8 × 10⁴, can be attributed to the plasma-induced structural defects and the unique characteristics of thin walled FCNTs with filled Fe nanowires. A model has been proposed to understand the effects of plasma on the CNTs.     

Improved electrochemical capacitive characteristics by controlling the carbon nanotube morphology and electrolyte solution concentration

Carbon nanotubes (CNTs) have been used as the electrochemical double layer in capacitor (EDLC) electrodes. CNTs were synthesized using thermal chemical vapor deposition (CVD) at a growth temperature of 750 °C by flowing C₂H₂. The surface morphology of the synthesized CNTs could be controlled with or without Al film deposition between the stainless (SUS) sheet and Fe catalyst film. Electrochemical measurements were performed in a three-electrode arrangement. H₂SO₄ with different concentrations was used as the electrolyte solution. The relation between the specific capacitance and the surface morphology of the CNTs and the electrolyte concentration were investigated. The results showed that the electrode formed using vertically aligned CNTs with higher electrolyte concentration exhibited higher specific capacitance.     

Enhancement of field emission characteristics of carbon nanotubes on oxidation

Vertically aligned multi-walled carbon nanotubes (CNTs) were grown on p-type silicon wafer using thermal chemical vapor deposition process and subsequently treated with oxygen plasma for oxidation. It was observed that the electron field emission (EFE) characteristics are enhanced. It showed that the turn-on electric field (E(TOE)) of CNTs decreased from 0.67 (untreated) to 0.26 V/microm (oxygen treated). Raman spectra showed that the numbers of defects are increased, which are generated by oxygen-treatment, and absorbed molecules on the CNTs are responsible for the enhancement of EFE. Scanning electron microscopy and Transmission electron microscopy images were used to identify the quality and physical changes of the nanotube morphology and surfaces; revealing the evidence of enhancement in the field emission properties after oxygen-plasma treatment.     

Effects of welding head on the carbon nanotube field emission in ultrasonic nanowelding

Ultrasonic nanowelding technique was used to improve the field emission properties of carbon nanotube (CNT) cathodes. Two kinds of welding heads were used and the effects of the head on the emission properties were studied. The results show that cathodes welded by Al₂O₃ flat head demonstrate excellent field emission properties with high emission current density and good current stability. The improved field emission performance is attributed to the reliable and low resistance contact between CNTs and metal substrates. Cathodes welded by steel matrix head show a lower turn-on electric field due to the protruding CNTs at the edge of the welded pits.     

Electron field emission from the carbon-doped TiO2 nanotube arrays

The field-emission characteristics of the carbon-doped TiO₂ nanotube arrays (TNAs), which can be obtained by a heat treatment of the as-fabricated TNAs under a continuous argon and acetylene flux, were investigated. The morphology, crystalline structure, and composition of the as-grown specimens were characterized by the use of field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. It was found that the samples' turn-on electric field is reduced from 21.9 to 5.0 V/μm and the field-emission current density rapidly reaches about 9.0 mA/cm² at 11.8 V/μm after carbon doping. The dramatically improved field-emission characteristics would be mainly attributed to the reduced work function and the enhanced conductivity due to the carbon doping into TNAs.     

Field emission properties of carbon nanotubes with different morphologies

The field emission behavior of base-model well-aligned carbon nanotubes (Base-CNTs), curled carbon nanotubes (Curled-CNTs), and tip-model well-aligned CNTs (Tip-CNTs) was examined. The nanotubes were fabricated by means of direct current plasma-enhanced chemical vapor deposition using different ammonia (NH₃) pre-treatment plasma currents. The turn-on electric field values required to obtain a 10-nA current for Base-CNTs, Curled-CNTs, and Tip-CNTs were determined at 3.8, 4.3, and 4.9 V/μm, respectively. The field enhancement factor γ of Base-CNTs, calculated from a Fowler–Nordheim plot, was higher than that for the Curled-CNTs and Tip-CNTs. In the presence of a strong electric field, argon ion irradiation permanently straightened the as-grown Curled-CNTs films. The straightening process enhanced the emission properties of the as-grown Curled-CNTs films by decreasing the turn-on field and increasing the total emission current. Thus, morphology parameters of the MWNTs significantly affect the emission properties of CNTs.     

Ar + H2 plasma etching for improved adhesion of PVD coatings on steel substrates

Ar + H₂ plasma cleaning has been described for the surface modification of the steel substrates, which removes oxides and other contaminants from substrate surface effectively leading to a better adhesion of the physical vapor deposited (PVD) coatings. Approximately 1.1-1.3 μm thick TiAlN coatings were deposited on plasma treated (Ar and Ar + H₂) and untreated mild steel (MS) substrates. A mechanism has been put forward to explain the effect of plasma treatment on the substrate surface based upon the data obtained from X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). The XPS measurements on untreated and Ar + H₂ plasma etched MS substrates indicated that the untreated substrate surface mainly consisted of Fe₃O₄, whereas, after etching the concentration of oxides decreased considerably. The FESEM and the AFM results showed changes in the surface morphology and an increase in the substrate roughness as a result of Ar + H₂ plasma etching. Removal of oxide/contaminants, formation of coarser surface and increased substrate surface roughness as a result of Ar + H₂ plasma etching facilitate good mechanical interlocking at the substrate surface, leading to a better adhesion of the deposited PVD coatings. The adhesion of TiAlN coating could be increased further by incorporating a very thin Ti interlayer.     

Enhanced field emission and improved supercapacitor obtained from plasma-modified bucky paper

The surface morphology of bucky papers (BPs) made from single-walled carbon nanotubes (CNTs) is modified by plasma treatment resulting in the formation of vertical microstructures on the surface. The shapes of these structures are either pillarlike or conelike depending on whether the gas used during plasma treatment is Ar or CH(4) . A complex interplay between different factors, such as the electric field within the plasma sheath, polarization of the CNT, intertubular cohesive forces, and ion bombardment, result in the formation of these structures. The roles played by these factors are quantitatively and qualitatively analyzed. The final material is flexible, substrate-free, composite-free, made only of CNTs, and has discrete vertically aligned structures on its surface. It shows enhanced field emission and electrochemical charge-storage capabilities. The field enhancement factor is increased by 6.8 times, and the turn-on field drops by 3.5 times from an initial value of 0.35 to 0.1 V μm(-1) as a result of the treatment. The increase in Brunauer-Emmett-Teller surface area results in about a fourfold improvement in the specific capacitance of the BP electrodes. Capacitance values before and after the treatments are 75 and 290 F g(-1) , respectively. It is predicted that this controlled surface modification technique could be put to good use in several applications based on macroscopic CNT films.     

Growth and microstructures of carbon nanotube films prepared by microwave plasma enhanced chemical vapor deposition process

Well-aligned carbon nanotubes (CNTs) were grown on iron coated silicon substrates by microwave plasma enhanced chemical vapor deposition. Effect of plasma composition on the growth and microstructures of CNTs were investigated by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy and optical emission spectroscopy. Morphology and microstructure of nanotubes were found to be strongly dependent on the plasma composition. Aligned bamboo-shaped nanotubes consisting of regular cone shaped compartments were observed for C₂H₂/NH₃/N₂ and C₂H₂/NH₃/H₂ gas mixtures. Randomly oriented or no nanotubes growth were observed in C₂H₂/H₂ and C₂H₂/N₂ gas mixtures respectively. CNTs grown in nitrogen rich plasma had more frequent short compartments while compartment length increased with decreasing nitrogen concentration in the plasma. Raman spectroscopy of CNTs samples revealed that CNTs prepared in nitrogen rich plasma had higher degree of disorder than those in low nitrogen or nitrogen free plasma. In-situ optical emission spectroscopy investigations showed that CN and H radicals play very important role in both the growth and microstructure of CNTs. Microstructure of CNTs has been correlated as a function of CN radical concentration in the plasma. It is suggested that presence of nitrogen in the plasma enhances the bulk diffusion of carbon through the iron catalyst particles which causes compartment formation. Based on our experimental observations, growth model of nanotubes under different plasma composition has been suggested using base growth mechanism.     

Oxygen plasma assisted end-opening and field emission enhancement in vertically aligned multiwall carbon nanotubes

This paper highlights the changes in micro-structural and field emission properties of vertically aligned carbon nanotubes (VACNTs) via oxygen plasma treatment. We find that exposure of very low power oxygen plasma (6 W) at 13.56 MHz for 15–20 min, opens the tip of vertically aligned CNTs. Scanning electron microscopy and transmission electron microscopy images were used to identify the quality and micro-structural changes of the nanotube morphology and surfaces. Raman spectra showed that the numbers of defects were increased throughout the oxygen plasma treatment process. In addition, the hydrophobic nature of the VACNTs is altered significantly and the contact angle decreases drastically from 110° to 40°. It was observed that the electron field emission (EFE) characteristics are significantly enhanced. The turn-on electric field (ETOE) of CNTs decreased from ∼0.80 V μm⁻¹ (untreated) to ∼0.60 V μm⁻¹ (oxygen treated). We believe that the open ended VACNTs would be immensely valuable for applications such as micro/nanofluidic based filtering elements and display devices.     

Magnetic field enhances the graphitized structure and field emission effect of carbon nanotubes

This study uses a low temperature thermal chemical vapor deposition with an applied external magnetic field to grow carbon nanotubes (CNTs) on Ni/Ag-printed glass substrates. A mixture of C₂H₂ and H₂ gas was used for the growth of the CNTs. A Ni catalyst layer was deposited on the Ag-printed glass substrate by pulse electroplating. Scanning electron micrographs as well as the presence of two sharp peaks at 1320 cm⁻¹ (D band) and 1590 cm⁻¹ (G band) in the Raman spectra indicate that the graphitized structure of CNTs synthesized under a magnetic field has higher quality (i.e., a D-band to G-band intensity ratio of 0.303) than CNTs synthesized without a magnetic field. Transmission electron micrographs show a fine Ni catalyst at the tip of the tube for CNTs synthesized under a magnetic field, exhibiting a CNT “tip-growth” model. The synthesis of CNTs in the presence of a magnetic field also generates better field emission properties and better lighting morphology than without a magnetic field.     

Single- and few-walled carbon nanotubes grown at temperatures as low as 450 degrees c: electrical and field emission characterization

Single-wall (SW-) and few-walled (FW-) carbon nanotubes (CNTs) were synthesized on aluminum/ cobalt coated silicon at temperatures as low as 450 degrees C by plasma enhanced chemical vapor deposition technique (PECVD). The SWCNTs and FWCNTs grow vertically oriented and well separated from each other. The cold field emission studies of as-grown SWCNTs and FWCNTs showed low turn-on field emission threshold voltages, strongly dependent of the nanotubes morphology. Current-voltage curves of individual CNTs, measured by conductive atomic force microscopy (CAFM), showed an electrical resistance of about 90 Komega, that is attributed mainly to the resistance of the contact between the CNTs and the conductive CAFM tip (Au and Pt).     

Field emission characteristics of fast grown nanocrystalline diamond/amorphous carbon composite films by microwave plasma-enhanced chemical deposition method

This study synthesized the nanocrystalline diamond/amorphous carbon (NCD/a-C) composite films by the microwave plasma-enhanced chemical vapor deposition (MPCVD) system with Ar/CH₄/N₂ mixtures. A localized rectangular-type jet-electrode with high density plasma was used to enhance the formation of NCD/a-C films, and a maximum growth rate of 105.6 µm/h was achieved. The content variations of sp² and sp³ phases via varying nitrogen gas flow rates were investigated by using Raman spectroscopy. The NCD/a-C film which synthesized with 6% nitrogen concentration and no hydrogen plasma etching treatment possessed a low turn-on electric field of 3.1 V/µm at the emission current of 0.01 µA.     

Electron field emission from the semimetallic TiO2 nanotube arrays

To enhance field-emission (FE) properties, as-prepared TiO₂ nanotube arrays (TNAs) successfully transformed from semiconductor into semimetal by a carbonization treatment under an argon/acetylene flux at 750 °C. After semimetallic transformation, the TNAs maintain tubular morphology, however, their surface become rougher. Especially, their electronic structures are significantly improved. A low turn-on field of 3.0 V/μm and a threshold field of 7.0 V/μm are obtained. Such improvements of FE properties can be mainly attributed to the enhancements of electrical property and rough surface morphology.     

Influence of the gas composition on the synthesis of boron-doped carbon nanotubes by ECR-CVD

Boron-doped carbon nanotubes (CNTs) were synthesized on porous silicon by electron cyclotron resonance chemical vapor deposition (ECR-CVD). CH₄, B₂H₆ and H₂ were used as the source gases and Fe₃O₄ nanoparticles as the catalyst. The effect of gas composition on the boron-doped CNTs growth characteristic was investigated. Scanning electron microscopy , transmission electron microscopy and X-ray photoelectron spectroscopy were used to evaluate the structure and composition. The results show that adding B₂H₆ influences the growth characteristic of CNTs greatly. CNTs tend to unaligned growth with boron. The increase of the B₂H₆ ratio leads to changes in the structure of CNTs from straight tubular to bamboo-like and makes the outer diameters bigger, the tube walls thicker, cause a rough surface and a decrease in the growth rate of the CNTs. An increase in the B/C ratio within the samples was detected as the B₂H₆ ratio in the precursor gas was increased.     

表面态对碳纳米管场发射的影响

采用CVD法在Ni丝上直接沉积碳纳米管,并应用二极管结构测试表面态(突出尖端和吸附)对碳纳米管场发射的影响。测试表明,突出尖端主要影响碳纳米管场发射的开启电场以及场发射电流稳定性;吸附作用的影响表现在改变碳纳米管能带结构进而改变其场发射性能。